Datasets:
Opscidia
/
patents

Dataset card Data Studio Files Community
1
patent_id
stringlengths
7
8
description
stringlengths
125
2.47M
length
int64
125
2.47M
11857888
DETAILED DESCRIPTION OF THE EMBODIMENT The following detailed description is merely exemplary in nature and is not intended to limit the described embodiments of the application and uses of the described embodiments. As used herein, the word “exemplary” or “illustrative” means “serving as an example, instance, or illustration.” Any implementation described herein as “exemplary” or “illustrative” is not necessarily to be construed as preferred or advantageous over other implementations. All of the implementations described below are exemplary implementations provided to enable persons skilled in the art to practice the disclosure and are not intended to limit the scope of the appended claims. Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary or the following detailed description. Detailed reference will now be made to one or more potential embodiments of the disclosure, which are illustrated inFIGS.1through7. The toy gas station playset100(hereinafter invention) is configured for use as an amusement. The invention100present figurines and puppets that are used to emulate the activities of a vehicle park. The emulated activities include, but are not limited to the parking and refueling of a vehicle. The invention100forms a bi-level structure within which the emulated activities are performed. The invention100comprises a pedestal structure101, a plurality of stanchions102, and an elevated platform structure103. The plurality of stanchions102elevates the elevated platform structure103above the pedestal structure101. The pedestal structure101is a pedestal. The pedestal is defined elsewhere in this disclosure. The pedestal structure101transfers the loads of the plurality of stanchions102and the elevated platform structure103to a supporting surface. The pedestal structure101forms a horizontally oriented surface that receives the figurines and puppets during play activity. The pedestal structure101comprises a pedestal plate111and a first plurality of c-channels112. The pedestal plate111is a prism-shaped structure. The pedestal plate111is a disk-shaped structure. A congruent end of the disk structure of the pedestal plate111forms the horizontally oriented surface that receives the figurines and puppets during play activity. The first plurality of c-channels112elevates the pedestal plate111above the supporting surface. The pedestal plate111further comprises a pedestal chalkboard surface141. The pedestal chalkboard surface141is a whiteboard structure formed on the superior surface of the congruent end of the pedestal plate111of the pedestal structure101. The pedestal chalkboard surface141forms a surface that allows drawing lines that emulate the images commonly used to control vehicle traffic. The pedestal chalkboard surface141is an erasable structure. In the first potential embodiment of the disclosure the pedestal chalkboard surface141is applied to the pedestal plate111as a coating of chalkboard paint. The first plurality of c-channels112forms the final link of the load path that transfers the load of the invention100to the supporting surface. Each of the first plurality of c-channels112is a prism-shaped structure. Each of the first plurality of c-channels112is formed with a slot. The slot of each c-channel selected from the first plurality of c-channels112runs parallel to the center axis of the prism structure of the selected c-channel. The span of the length of the inner dimension of the slot of each c-channel selected from the first plurality of c-channels112is greater than the span of the length of the thickness of the pedestal plate111such that the pedestal plate111will insert into the slot of the selected c-channel. The center dimension of each c-channel selected from the first plurality of c-channels112is greater than a dimension selected from the group consisting of: a) the major dimension of the pedestal plate111; and, b) the minor dimension of the pedestal plate111. The first plurality of c-channels112attach to the pedestal plate111to form a u-shaped structure. The first plurality of c-channels112comprises a first c-channel151, a second c-channel152, and a third c-channel153. The first c-channel151is a prism-shaped structure. The first c-channel151forms the first arm of the u-shaped structure formed by the first plurality of c-channels112. The first c-channel151forms a c-channel. The first c-channel151is formed with a slot. The slot of the first c-channel151runs parallel to the center axis of the prism structure of the first c-channel151. The span of the length of the inner dimension of the slot of the first c-channel151is greater than the span of the length of the thickness of the pedestal plate111such that the pedestal plate111inserts into the slot of the first c-channel151. The second c-channel152is a prism-shaped structure. The second c-channel152forms the crossbeam of the u-shaped structure formed by the first plurality of c-channels112. The second c-channel152forms a c-channel. The second c-channel152is formed with a slot. The slot the second c-channel152runs parallel to the center axis of the prism structure of the second c-channel152. The span of the length of the inner dimension of the slot of the second c-channel152is greater than the span of the length of the thickness of the pedestal plate111such that the pedestal plate111inserts into the slot of the second c-channel152. The third c-channel153is a prism-shaped structure. The third c-channel153forms the second arm of the u-shaped structure formed by the first plurality of c-channels112. The third c-channel153forms a c-channel. The third c-channel153is formed with a slot. The slot of the third c-channel153runs parallel to the center axis of the prism structure of the third c-channel153. The span of the length of the inner dimension of the slot of the third c-channel153is greater than the span of the length of the thickness of the pedestal plate111such that the pedestal plate111inserts into the slot of the third c-channel153. The elevated platform structure103is a horizontally oriented platform. The elevated platform structure103forms a horizontally oriented surface that receives the figurines and puppets during play activity. The elevated platform structure103comprises a platform plate131, a second plurality of c-channels132, and a plurality of puppet structures133. The platform plate131is a prism-shaped structure. The platform plate131is a disk-shaped structure. A congruent end of the disk structure of the platform plate131forms the horizontally oriented surface that receives the figurines and puppets during play activity. In the first potential embodiment of the disclosure, the platform plate131is geometrically similar to the pedestal plate111. The platform plate131further comprises a platform chalkboard surface142and a ramp structure161. The platform chalkboard surface142is a whiteboard structure formed on the superior surface of the congruent end of the platform plate131of the pedestal structure101. The platform chalkboard surface142forms a surface that allows drawing lines that emulate the images commonly used to control vehicle traffic. The platform chalkboard surface142is an erasable structure. In the first potential embodiment of the disclosure the platform chalkboard surface142is applied to the platform plate131as a coating of chalkboard paint. The ramp structure161is a ramp. The ramp structure161is an inclined surface that joins the pedestal plate111with the platform plate131such that the invention100can emulate the transfer of a vehicle between the pedestal structure101and the elevated platform structure103. The ramp structure161further comprises a cutout plate162and a hinge163. The cutout plate162is a disk-shaped structure that is cut out of the platform plate131of the elevated platform structure103. The hinge163is a fastening structure. The hinge163secures the cutout plate162to the platform plate131such that the cutout plate162rotates relative to the platform plate131. The hinge163allows for the adjustment of the position of the cutout plate162such that the cutout plate162forms the inclined surface of the ramp structure161. The position of the cutout plate162is formed in the edge of the platform plate131that is distal from the fifth c-channel155such that the ramp structure161is halfway between the fourth c-channel154and the sixth c-channel156. The second plurality of c-channels132attaches to the platform plate131. The second plurality of c-channels132forms the portion of the load path that transfers the load of the elevated platform structure103to the plurality of stanchions102. Each of the second plurality of c-channels132is a prism-shaped structure. Each of the second plurality of c-channels132is formed with a slot. The slot of each c-channel selected from the second plurality of c-channels132runs parallel to the center axis of the prism structure of the selected c-channel. The span of the length of the inner dimension of the slot of each c-channel selected from the second plurality of c-channels132is greater than the span of the length of the thickness of the platform plate131such that the platform plate131will insert into the slot of the selected c-channel. The center dimension of each c-channel selected from the second plurality of c-channels132is greater that a dimension selected from the group consisting of: a) the major dimension of the platform plate131; and, b) the minor dimension of the platform plate131. The second plurality of c-channels132attach to the platform plate131to form a u-shaped structure. The second plurality of c-channels132comprises a fourth c-channel154, a fifth c-channel155, and a sixth c-channel156. The fourth c-channel154is a prism-shaped structure. The fourth c-channel154forms the first arm of the u-shaped structure formed by the second plurality of c-channels132. The fourth c-channel154forms a c-channel. The fourth c-channel154is formed with a slot. The slot of the fourth c-channel154runs parallel to the center axis of the prism structure of the fourth c-channel154. The span of the length of the inner dimension of the fourth c-channel154is greater than the span of the length of the thickness of the platform plate131such that the platform plate131inserts into the slot of the fourth c-channel154. The fifth c-channel155is a prism-shaped structure. The fifth c-channel155forms the crossbeam of the u-shaped structure formed by the second plurality of c-channels132. The fifth c-channel155forms a c-channel. The fifth c-channel155is formed with a slot. The slot of the fifth c-channel155runs parallel to the center axis of the prism structure of the fifth c-channel155. The span of the length of the inner dimension of the slot of the fifth c-channel155is greater than the span of the length of the thickness of the platform plate131such that the platform plate131inserts into the slot of the fifth c-channel155. The sixth c-channel156is a prism-shaped structure. The sixth c-channel156forms the second arm of the u-shaped structure formed by the second plurality of c-channels132. The sixth c-channel156forms a c-channel. The sixth c-channel156is formed with a slot. The slot of the sixth c-channel156runs parallel to the center axis of the prism structure of the sixth c-channel156. The span of the length of the inner dimension of the slot of the sixth c-channel156is greater than the span of the length of the thickness of the platform plate131such that the platform plate131inserts into the slot of the sixth c-channel156. Each of the plurality of puppet structures133are physical models of structure that are used to emulate the activities of a vehicle park. The plurality of puppet structures133comprises a storefront171and a plurality of pumps172. The storefront171is a figurine. The storefront171has the shape of a building such that the storefront171emulates a retail establishment commonly referred to as a gas station. The applicant intends that the storefront171rests on the superior congruent end of the disk structure of the platform plate131. Each of the plurality of pumps172is a puppet. Each of the plurality of pumps172has the appearance of a structure such that the plurality of pumps172emulates a mechanical device known as a gas pump. The applicant intends that the plurality of pumps172rests on the superior congruent end of the disk structure of the platform plate131. The plurality of pumps172comprises a first pump181and a second pump191. The first pump181further comprises a first reservoir182and a first nozzle183. The second pump191further comprises a second reservoir192and a second nozzle193. The plurality of stanchions102combine to attach the elevated platform structure103to the pedestal structure101. Each of the plurality of stanchions102forms a load bearing structure. Each of the plurality of stanchions102forms a vertically oriented structure. The plurality of stanchions102elevates the elevated platform structure103above the pedestal structure101such that the elevated platform structure103forms the superior structure of the invention100. Each of the plurality of stanchions102forms a load path that transfers a portion of the load of the elevated platform structure103to the pedestal structure101. The plurality of stanchions102comprises a first stanchion121, a second stanchion122, a third stanchion123, and a fourth stanchion124. The first stanchion121is a prism-shaped structure. The first stanchion121is a vertically oriented structure. By vertically oriented is meant that the center axis of the prism structure of the first stanchion121is aligned with the force of gravity. The first stanchion121forms a portion of the load path the transfers the load of the elevated platform structure103to the pedestal structure101. The first stanchion121attaches to the lateral face of the prism structure of the first c-channel151. The position of the first stanchion121is such that the span of the distance from the first stanchion121to the free end of the first c-channel151is less than the span of the distance from the first stanchion121to the fixed end of the first c-channel151. The first stanchion121projects away from the center axis of the prism structure of the first c-channel151in the superior direction. The second stanchion122is a prism-shaped structure. The second stanchion122is a vertically oriented structure. By vertically oriented is meant that the center axis of the prism structure of the second stanchion122is aligned with the force of gravity. The second stanchion122forms a portion of the load path that transfers the load of the elevated platform structure103to the pedestal structure101. The second stanchion122attaches to the lateral face of the prism structure of the first c-channel151. The position of the second stanchion122is such that the span of the distance from the second stanchion122to the fixed end of the first c-channel151is less than the span of the distance from the second stanchion122to the free end of the first c-channel151. The second stanchion122projects away from the center axis of the prism structure of the first c-channel151in the superior direction. The fourth stanchion124is a prism-shaped structure. The fourth stanchion124is a vertically oriented structure. By vertically oriented is meant that the center axis of the prism structure of the fourth stanchion124is aligned with the force of gravity. The fourth stanchion124forms a portion of the load path that transfers the load of the elevated platform structure103to the pedestal structure101. The fourth stanchion124attaches to the lateral face of the prism structure of the third stanchion123. The position of the fourth stanchion124is such that the span of the distance from the fourth stanchion124to the free end of the third stanchion123is less than the span of the distance from the fourth stanchion124to the fixed end of the third stanchion123. The fourth stanchion124projects away from the center axis of the prism structure of the third stanchion123in the superior direction. The third stanchion123is a prism-shaped structure. The third stanchion123is a vertically oriented structure. By vertically oriented is meant that the center axis of the prism structure of the third stanchion123is aligned with the force of gravity. The third stanchion123forms a portion of the load path that transfers the load of the elevated platform structure103to the pedestal structure101. The third stanchion123attaches to the lateral face of the prism structure of the second c-channel152. The position of the third stanchion123is such that the span of the distance from the third stanchion123to the fixed end of the second c-channel152is less than the span of the distance from the third stanchion123to the free end of the second c-channel152. The third stanchion123projects away from the center axis of the prism structure of the second c-channel152in the superior direction. The first stanchion121removably attaches to the lateral face of the prism structure of the fourth c-channel154. The position of the first stanchion121is such that the span of the distance from the first stanchion121to the free end of the fourth c-channel154is less than the span of the distance from the first stanchion121to the fixed end of the fourth c-channel154. The first stanchion121projects away from the center axis of the prism structure of the fourth c-channel154in the inferior direction. The second stanchion122removably attaches to the lateral face of the prism structure of the fourth c-channel154. The position of the second stanchion122is such that the span of the distance from the second stanchion122to the fixed end of the fourth c-channel154is less than the span of the distance from the second stanchion122to the free end of the fourth c-channel154. The second stanchion122projects away from the center axis of the prism structure of the fourth c-channel154in the inferior direction. The fourth stanchion124removably attaches to the lateral face of the prism structure of the sixth c-channel156. The position of the fourth stanchion124is such that the span of the distance from the fourth stanchion124to the free end of the sixth c-channel156is less than the span of the distance from the fourth stanchion124to the fixed end of the sixth c-channel156. The fourth stanchion124projects away from the center axis of the prism structure of the sixth c-channel156in the inferior direction. The third stanchion123removably attaches to the lateral face of the prism structure of the sixth c-channel156. The position of the third stanchion123is such that the span of the distance from the third stanchion123to the fixed end of the sixth c-channel156is less than the span of the distance from the third stanchion123to the free end of the sixth c-channel156. The third stanchion123projects away from the center axis of the prism structure of the sixth c-channel156in the inferior direction. The following definitions were used in this disclosure: Align: As used in this disclosure, align refers to an arrangement of objects that are: 1) arranged in a straight plane or line; 2) arranged to give a directional sense of a plurality of parallel planes or lines; or, 3) a first line or curve is congruent to and overlaid on a second line or curve. C-Channel: As used in this disclosure, the C-channel is a structure that is formed in a U-shape. The C-channel forms a prism shape with a hollow interior and an open lateral face that forms a shape characteristic of the letter C when viewed from the congruent ends. The open space of the C-channel is often used as a track. A C-channel is a U-shaped structure. Cantilever: As used in this disclosure, a cantilever is a beam or other structure that projects away from an object and is supported on only one end. A cantilever is further defined with a fixed end and a free end. The fixed end is the end of the cantilever that is attached to the object. The free end is the end of the cantilever that is distal from the fixed end. Center: As used in this disclosure, a center is a point that is: 1) the point within a circle that is equidistant from all the points of the circumference; 2) the point within a regular polygon that is equidistant from all the vertices of the regular polygon; 3) the point on a line that is equidistant from the ends of the line; 4) the point, pivot, or axis around which something revolves; or, 5) the centroid or first moment of an area or structure. In cases where the appropriate definition or definitions are not obvious, the fifth option should be used in interpreting the specification. Center Axis: As used in this disclosure, the center axis is the axis of a cylinder or a prism. The center axis of a prism is the line that joins the center point of the first congruent face of the prism to the center point of the second corresponding congruent face of the prism. The center axis of a pyramid refers to a line formed through the apex of the pyramid that is perpendicular to the base of the pyramid. When the center axes of two cylinder, prism or pyramidal structures share the same line they are said to be aligned. When the center axes of two cylinder, prism or pyramidal structures do not share the same line they are said to be offset. Center, Major, Minor, and Thickness Dimensions: As used in this disclosure, the center dimension, the major dimension, the minor dimension, and the thickness each refer to the span of a length associated with a structure selected from the group consisting of a prism structure and a disk structure. The center dimension is the span of the length of the center axis of the selected structure. The thickness is an alternate name given to the center dimension when the selected structure is a disk structure. The major dimension is the span of the length of the major axis of the perimetrical boundary that contains the selected structure. The minor dimension is the span of the length of the minor axis of the perimetrical boundary that contains the selected structure. The terms center dimension, the major dimension, the minor dimension, and the thickness are also used to describe one or more linear axes of direction associated with the selected structure. Chalk: As used in this disclosure, chalk is a material made primarily of calcium carbonate that is used for marking on chalkboards (blackboards) or other surfaces Coating: As used in this disclosure, a coating refers to a substance that is applied to the exterior surface of an object such that the coating forms a new exterior surface of the object. A coating is commonly said to be formed as a layer. Paint is an example of a common coating material. Cutout: As used in this disclosure, a cutout refers to a first disk-shaped structure that is “cutout” of a second disk-shaped structure such that a negative space is formed in the second disk-shaped structure. The form factor of the negative space formed in the second disk-shaped structure is geometrically similar to the first disk-shaped structure such that the first disk-shaped structure can be inserted into the negative space of the second disk-shaped structure to form a “continuous disk” structure. Disk: As used in this disclosure, a disk is a prism-shaped object that is flat in appearance. The disk is formed from two congruent ends that are attached by a lateral face. The sum of the surface areas of two congruent ends of the prism-shaped object that forms the disk is greater than the surface area of the lateral face of the prism-shaped object that forms the disk. In this disclosure, the congruent ends of the prism-shaped structure that forms the disk are referred to as the faces of the disk. Elevation: As used in this disclosure, elevation refers to the span of the distance in the superior direction between a specified horizontal surface and a reference horizontal surface. Unless the context of the disclosure suggest otherwise, the specified horizontal surface is the supporting surface the potential embodiment of the disclosure rests on. The infinitive form of elevation is to elevate. Figurine: As used in this disclosure, a figurine is a three dimensional structure resembling a human, animal or symbolic image. Force of Gravity: As used in this disclosure, the force of gravity refers to a vector that indicates the direction of the pull of gravity on an object at or near the surface of the earth. Form Factor: As used in this disclosure, the term form factor refers to the size and shape of an object. Geometrically Similar: As used in this disclosure, geometrically similar is a term that compares a first object to a second object wherein: 1) the sides of the first object have a one to one correspondence to the sides of the second object; 2) wherein the ratio of the length of each pair of corresponding sides are equal; 3) the angles formed by the first object have a one to one correspondence to the angles of the second object; and, 4) wherein the corresponding angles are equal. The term geometrically identical refers to a situation where the ratio of the length of each pair of corresponding sides equals 1. Hinge: As used in this disclosure, a hinge is a device that permits the turning, rotating, or pivoting of a first object relative to a second object. A hinge designed to be fixed into a set position after rotation is called a locking hinge. A spring loaded hinge is a hinge formed as an elastic structure. The elastic structure of the spring loaded hinge is deformed under a rotating force such that the elastic structure returns the spring loaded hinge back to its relaxed shape after the rotating force is removed from the spring loaded hinge. Horizontal: As used in this disclosure, horizontal is a directional term that refers to a direction that is either: 1) parallel to the horizon; 2) perpendicular to the local force of gravity, or, 3) parallel to a supporting surface. In cases where the appropriate definition or definitions are not obvious, the second option should be used in interpreting the specification. Unless specifically noted in this disclosure, the horizontal direction is always perpendicular to the vertical direction. Inferior: As used in this disclosure, the term inferior refers to a directional reference that is parallel to and in the same direction as the force of gravity when an object is positioned or used normally. Load: As used in this disclosure, the term load refers to an object upon which a force is acting or which is otherwise absorbing energy in some fashion. Examples of a load in this sense include, but are not limited to, a mass that is being moved a distance or an electrical circuit element that draws energy. The term load is also commonly used to refer to the forces that are applied to a stationary structure. Load Path: As used in this disclosure, a load path refers to a chain of one or more structures that transfers a load generated by a raised structure or object to a foundation, supporting surface, or the earth. Major and Minor Axes: As used in this disclosure, the major and minor axes refer to a pair of perpendicular axes that are defined within a structure. The length of the major axis is always greater than or equal to the length of the minor axis. The major axis forms the longest symmetric bifurcation of the structure. The major and minor axes intersect at the center of the structure. The major axis is always parallel or perpendicular to an edge of a rectangular or rectilinear structure. Negative Space: As used in this disclosure, negative space is a method of defining an object through the use of open or empty space as the definition of the object itself, or, through the use of open or empty space to describe the boundaries of an object. Paint: As used in this disclosure, when used as a noun the term paint refers to a pigment based colloid or solution that is applied to a surface as a coating of the surface. When used as a verb, the term paint refers to the application of paint to a surface. Pedestal: As used in this disclosure, a pedestal is an intermediary load bearing structure that that forms a load path between a supporting surface and an object, structure, or load. Perimeter: As used in this disclosure, a perimeter is one or more curved or straight lines that bounds an enclosed area on a plane or surface. The perimeter of a circle is commonly referred to as a circumference. Perimetrical Boundary: As used in this disclosure, a perimetrical boundary is a hypothetical rectangular block that contains an object. Specifically, the rectangular block selected to be the perimetrical boundary is the rectangular block with the minimum volume that fully contains the object. In a two-dimensional structure, the perimetrical boundary is the rectangle with the minimum surface area. Pivot: As used in this disclosure, a pivot is a rod or shaft around which an object rotates or swings. Prism: As used in this disclosure, a prism is a three-dimensional geometric structure wherein: 1) the form factor of two faces of the prism are congruent; and, 2) the two congruent faces are parallel to each other. The two congruent faces are also commonly referred to as the ends of the prism. The surfaces that connect the two congruent faces are called the lateral faces. In this disclosure, when further description is required a prism will be named for the geometric or descriptive name of the form factor of the two congruent faces. If the form factor of the two corresponding faces has no clearly established or well-known geometric or descriptive name, the term irregular prism will be used. The center axis of a prism is defined as a line that joins the center point of the first congruent face of the prism to the center point of the second corresponding congruent face of the prism. The center axis of a prism is otherwise analogous to the center axis of a cylinder. A prism wherein the ends are circles is commonly referred to as a cylinder. Pump: As used in this disclosure, a pump is a mechanical device that uses suction or pressure to raise or move fluids, compress fluids, or force a fluid into an inflatable object. Within this disclosure, a compressor refers to a pump that is dedicated to compressing a fluid or placing a fluid under pressure. Puppet: As used in this disclosure, a puppet is a three-dimensional figure resembling a human, animal or symbolic image that is used for entertainment or educational purposes. Ramp: As used in this disclosure, a ramp is an inclined surface that joins two parallel surfaces that are: 1) of different elevations; or 2) not aligned on the same plane. Rectangular Block: As used in this disclosure, a rectangular block refers to a three-dimensional prism structure comprising six rectangular surfaces (commonly called faces) formed at right angles. Within this disclosure, a rectangular block may further comprise rounded edges and corners. Ridge: As used in this disclosure, a ridge is a rectangular block structure attaches to and projects vertically away from a first surface. Rim: As used in this disclosure, a rim is an outer edge or border that follows along the perimeter of an object. Roof: As used in this disclosure, a roof is the exterior surface of a structure that is distal from the surface upon which the structure is placed. As used in this disclosure, the exterior surface is assumed to include the supporting structures associated with the exterior surface including, but not limited to, rafters, decking, soffits and fascia. A pitched roof is a roof wherein the surface of the roof has a cant that is not perpendicular to the direction of gravity. Rounded: As used in this disclosure, the term rounded refers to the replacement of an apex, vertex, or edge or brink of a structure with a (generally smooth) curvature wherein the concave portion of the curvature faces the interior or center of the structure. Slot: As used in this disclosure, a slot is a prism-shaped negative space formed as a groove or aperture that is formed in or through an object. Superior: As used in this disclosure, the term superior refers to a directional reference that is parallel to and in the opposite direction of the force of gravity when an object is positioned or used normally. Supporting Surface: As used in this disclosure, a supporting surface is a horizontal surface upon which an object is placed and to which the load of the object is transferred. This disclosure assumes that an object placed on the supporting surface is in an orientation that is appropriate for the normal or anticipated use of the object. Stanchion: As used in this disclosure, a stanchion refers to a vertically oriented prism-shaped pole, post, or support. U-Shaped Structure: As used in this disclosure, a U-shaped structure refers to a three-sided structure comprising a crossbeam, a first arm, and a second arm. In a U-shaped structure, the first arm and the second arm project away from the crossbeam: 1) in the same direction; 2) at a roughly perpendicular angle to the crossbeam, and, 3) the span of the length of the first arm roughly equals the span of the length of the second arm. The first arm and the second arm project away from the crossbeam in the manner of a cantilever. An illiterate U-shaped structure is a U-shaped structure where the span of the length of the first arm does not equal the span of the length of the second arm Vertical: As used in this disclosure, vertical refers to a direction that is either: 1) perpendicular to the horizontal direction; 2) parallel to the local force of gravity; or, 3) when referring to an individual object the direction from the designated top of the individual object to the designated bottom of the individual object. In cases where the appropriate definition or definitions are not obvious, the second option should be used in interpreting the specification. Unless specifically noted in this disclosure, the vertical direction is always perpendicular to the horizontal direction. Whiteboard: As used in this disclosure, a whiteboard is a surface that is designed to receive non-permanent markings that can be used for communication or recordation purposes. This definition is explicitly intended to include chalkboards. Whiteboards are also commonly referred to as dry erase boards. With respect to the above description, it is to be realized that the optimum dimensional relationship for the various components of the invention described above and inFIGS.1through7include variations in size, materials, shape, form, function, and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the invention. It shall be noted that those skilled in the art will readily recognize numerous adaptations and modifications which can be made to the various embodiments of the present invention which will result in an improved invention, yet all of which will fall within the spirit and scope of the present invention as defined in the following claims. Accordingly, the invention is to be limited only by the scope of the following claims and their equivalents.
35,413
11857889
The following callout list of elements can be a useful guide in referencing the element numbers of the drawings.10Toy block18top hinge19bottom hinge20rotating panel21panel top edge22panel bottom edge23panel right edge24panel left edge30frame31first frame section32second frame section33front wall34rear wall35panel top right corner36panel top left corner37panel bottom left corner38panel bottom right corner39top hinge axle40magnets41right upper magnet42left upper magnet43upper right magnet44lower right magnet45upper left magnet46lower left magnet47right lower magnet48left lower magnet49bottom hinge axle50magnet retainers51right upper magnet retainer52left upper magnet retainer53upper right magnet retainer54lower right magnet retainer55upper left magnet retainer56lower left magnet retainer57right lower magnet retainer58left lower magnet retainer61inside frame wall62intermediate frame wall63outside frame wall64inside ring65outside ring66stop tab71right upper magnet retainer support wall72left upper magnet retainer support wall73upper right magnet retainer support wall74lower right magnet retainer support wall75upper left magnet retainer support wall76lower left magnet retainer support wall77right lower magnet retainer support wall78left lower magnet retainer support wall80joining studs81upper right stud82upper middle stud83upper left stud84right middle stud85left middle stud86lower right stud87lower middle stud88lower left stud91upper right stud chamber92upper middle stud93upper left stud chamber94right middle stud chamber95left middle stud chamber96lower right stud chamber97lower middle stud chamber98lower left stud chamber101upper right stud chamber support wall102upper middle stud chamber support wall103upper left stud chamber support wall104right middle stud chamber support wall105left middle stud chamber support wall106lower right stud chamber support wall107lower middle stud chamber support wall108lower left stud chamber support wall121upper right stop tab122upper left stop tab123lower right stop tab124lower left stop tab125right rotating panel section126left rotating panel section131Top hinge socket132right hinge socket133left hinge socket134bottom hinge socket135right upper frame stop136left upper frame stop137right lower frame stop138left lower frame stop DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT As seen inFIG.1, a toy block10can be made as a plastic injection molded block has a frame30that retains a rotating panel20. The rotating panel20has a panel top edge21and a panel bottom edge22in a rectangular shape which can be square. The rotating panel20if square has a panel top right corner35, a panel bottom right corner38, a panel bottom left corner37, and a panel top left corner36. Additionally, the rotating panel20has a panel right edge23and a panel left edge24. The rotating panel has a top hinge35at a panel top edge21and a bottom hinge19at a panel bottom edge22. The frame30can also be rectangular with a front frame portion and a rear frame portion. A first frame section31including a front wall33fits to a second frame section32including a rear wall34. The first frame section31and the second frame section32can fit together by interference fit such as a snap connection. The front wall33and the rear wall34can be translucent to allow light to pass through the frame30. The rotating panel20can also be translucent to allow light to pass through the rotating panel20. The bottom hinge19can be made using a protrusion from the panel bottom edge22. Also, the top hinge35can be made with a protrusion extending upwardly from the panel top edge21so that the protrusion extends into the frame30. As seen inFIG.2, the periphery of the frame30includes magnet retainers50retaining magnets40. The magnets40may include a right upper magnet41, a left upper magnet42, a right lower magnet47and the left lower magnet48in a horizontal orientation. The magnets40may also include an upper right magnet43, a lower right magnet44, an upper left magnet45, and a lower left magnet46in a vertical orientation. The magnet retainers50are formed as chambers in the frame30. The right upper magnet41is mounted within the right upper magnet retainer51. The left upper magnet retainer52retains of the left upper magnet42, the upper right magnet retainer53retains the upper right magnet43. The lower right magnet retainer54retains the lower right magnet44. The upper left magnet retainer55retains the upper left magnet45. The lower left magnet retainer56retains the lower left magnet46. The magnet retainers formed as rectangular chambers in a vertical or horizontal orientation are disposed along the periphery of the frame30. On the inside of the frame, the top hinge axle39of the top hinge35may extend upwardly from the rotating panel20, and the bottom hinge axle49of the bottom hinge19may extend downwardly from the rotating panel20. The top hinge axle39receives into a top hinge socket131and the bottom hinge axle49extends into the bottom hinge socket134. The rotating panel20can be removed and reinstalled sideways so that the top hinge axle39extends into the left hinge socket133while the bottom hinge axle49extends into the right hinge socket132. The rotating panel20can be removed because the frame30has flexibility. The frame has an opening that receives the rotating panel20. The opening can be square or rectangular with one side slightly longer than the other to facilitate a bimodal implementation of the rotating panel20. As seen inFIG.3, the frame30has an inside frame wall61, a outside frame wall63, and an intermediate frame wall62formed between the inside frame wall61and the outside frame wall63. The periphery of the frame30is formed between the intermediate frame wall62and the outside frame wall63. The magnet retainers50are formed between the intermediate frame wall62and the outside frame wall63in an outside ring65. Joining studs80join the first frame section31to the second frame section32. Joining studs80are formed along the intermediate frame wall62. The inside frame wall61, the outside frame wall63and the intermediate frame wall62all have some flexibility. Magnet retainer support walls70are formed in the inside ring64. The inside ring64supports the outside ring65. The right upper magnet retainer support wall71supports the right upper magnet retainer51and the left upper magnet retainer support wall72supports the left upper magnet retainer52. The upper left magnet retainer support wall75supports the upper left magnet retainer55and the lower left magnet retainer support wall76supports the lower left magnet retainer56. The upper right magnet retainer support wall73supports the upper right magnet retainer53, and the lower right magnet retainer support wall74supports the lower right magnet retainer54. The right lower magnet retainer support wall77supports the right lower magnet retainer57, and the left lower magnet retainer support wall78supports the left lower magnet retainer58. FIGS.4-7show the side views and the top and bottom views of the frame30which are congruent with each other. The hinge sockets that receive the hinge axles are also located on the left and right sides so that the rotating panel20can be removed and reinstalled sideways so that it rotates horizontally instead of vertically. The frame30is thus symmetrical in the left and right direction as well as the top and bottom direction such that it has two planes of symmetry. As seen inFIG.8, the joining studs80include an upper right stud81adjacent to an upper right stud chamber91. The upper right stud chamber91is formed between the right upper magnet retainer51and the upper right magnet retainer53. The upper middle stud82is formed adjacent to the upper middle stud chamber92. The upper middle stud chamber92is formed between the right upper magnet retainer51and the left upper magnet retainer52. The left upper stud83is formed at the upper left stud chamber93and the upper left stud chamber93is formed between the left upper magnet retainer52and the upper left magnet retainer55. The left middle stud85is formed at the left middle stud chamber95, and the left middle stud chamber95is formed between the upper left magnet retainer55and the lower left magnet retainer56. The lower left stud88is formed at the lower left stud chamber98, and the lower left stud chamber98is formed between the lower left magnet retainer56and the left lower magnet retainer58. The lower middle stud87is formed at the lower middle stud chamber97, and a lower middle stud chamber97is formed between the left lower magnet retainer58and the right lower magnet retainer57. The lower right stud86is formed at the lower right stud chamber96, and the lower right stud chamber96is formed between the right lower magnet retainer57and the lower right magnet retainer54. The right middle stud84is formed at the right middle stud chamber94, and the right middle stud chamber94is formed between the upper right magnet retainer53and the lower right magnet retainer54. As seen inFIG.9, the stud chamber support walls support the stud chambers, and the stud chamber support the joining studs. The upper right stud chamber support wall101supports the upper right stud81. The upper middle stud chamber support wall102supports the upper middle stud chamber92. The upper left stud chamber support wall103supports the upper left stud83. The left middle stud chamber support wall105supports the left middle stud85. The lower left stud chamber support wall108supports the lower left stud88. The lower middle stud chamber support wall107supports the lower middle stud87. The lower right stud chamber support wall106supports the lower right stud86. The right middle stud chamber support wall104supports the right middle stud84. The stud chamber support walls extend between the inside frame wall61and the intermediate frame wall62. The stud chamber support walls radiate outwardly to provide structural support while allowing flexibility of the inside frame wall61, the intermediate frame wall62, and the outside frame wall63. As seen inFIG.10, the rotating panel20has a binary construction with a left rotating panel section126attaching to a right rotating panel section125. Optionally, the rotating panel20has stop tabs on the left and right edges. For example, on a left or right edge, the left rotating panel section126can have an upper left stop tab122, and a lower left stop tab124. Similarly, the right rotating panel section125can have an upper right stop tab121and a lower right stop tab123. The stop tabs can be sized to engage the edges of the frame30. For example, the panel right edge23and the panel left edge24can have stop tabs that extends outwardly so that they touch the inside frame wall61. The inside frame wall61can be sized so that the rotating panel20has free spinning where the stop tabs to not substantially impede the rotation of the rotating panel20when the rotating panel20is rotating on a vertical axis as shown in the figures. When the rotating panel20is removed and reinstalled to rotate on a horizontal axis, the rotating panel can be stopped so that it forms a rigid connection with the frame30and locks in place with the frame30. Thus, the rotating panel has a pair of modes, namely a rotating mode in a vertical orientation on a vertical rotating axis, and a fixed mode in a horizontal orientation on a horizontal nonrotating axis. The rotating panel can be bimodal between a fixed position and a rotating position. The rotating panel can be reinstalled at a 90° angle for changing modes between the fixed position and the rotating position. The inside frame wall61may have a right upper frame stop135, a left upper frame stop136, a right lower frame stop137, and a left lower frame stop138. The right lower frame stop137and left lower frame stop138are configured to engage the upper right stop tab121or the upper left stop tab122, or the lower right stop tab123, or the lower left stop tab124depending on the orientation of the rotating panel20. The rotating panel20can be a spinning panel when free, and can rotate to engage the frame stops when in the engaged position. The rotating panel20can be clicked into the engaged position and clicked out of the engaged position. As seen inFIGS.11-13, the toy blocks10can be stacked in a variety of different orientations and positions to form a larger structure. The magnets in different blocks attract to each other and automatically align the blocks to each other. To provide different engagement options, user has the option of rotating the frame by 90°, or removing the panel and rotating the panel to reinstall to the frame. Thus, the fixed mode and the rotating mode can be formed in a variety of different configurations. As seen inFIGS.14-18, the toy block has a full swing of rotation in a freely rotating mode. The toy block can still rotate in the fixed position if the user manually biases the flexible frame and snaps the block out of the fixed position, but the block does not otherwise freely spin in the fixed position.
13,037
11857890
DETAILED DESCRIPTION FIG.1shows a schematic of an interactive toy system100according to one embodiment. The interactive toy system100comprises an interactive toy10and a charging device20with a transmitting coil21, in the form of conductive loops, defining a charging zone22. The interactive toy10comprises a toy housing15and, accommodated in said toy housing15, a function device14for performing user-perceptible, controllable functions140; a control circuit13for controlling the function device14; a rechargeable power source12for providing operating power32,33to the function device14and the control circuit13; and a charging circuit11for contactless receipt of electrical energy e-m and for charging (as indicated by reference numeral31) the rechargeable power source12when the interactive toy10is positioned in the charging zone22of the contactless charging device20. The control circuit is configured to receive a primary signal101indicative of an interaction stimulus110from a stimulus source99; to receive a secondary signal102indicative of a position120of the interactive toy with respect to the charging zone22; and, responsive to the primary signal101, and to produce a control signal34based on the primary signal101and the secondary signal102. The control signal is for controlling the function device14to perform a user-perceptible function140, wherein the user-perceptible function140is selected based on the secondary signal102. As mentioned, according to some embodiments, the primary and/or secondary signals101,102may be generated using sensor devices and/or communication devices, which may be arranged inside or on the toy housing15. Alternatively or in addition thereto, the primary and/or secondary signals101,102may also be generated by devices that are located elsewhere, and transmitted to the interactive toy10. The primary signal101indicative of an interaction stimulus110may also be an analogue and/or digitally encoded remote control signal received from a remote control device as the interaction source99, e.g. via infrared (IR) or radiofrequency (RF) communication. The remote control device may be a traditional IR or RF remote control device, or in an equivalent manner, a computer or a mobile device, such as a mobile phone or a tablet computer, containing software in the form of programmed instructions for generating an interaction stimulus110. The interaction stimulus110may be generated on the basis of programmed instructions alone, or on the basis of user input through a user interface of the remote control device, mobile device, or computer, etc. The housing15of interactive toy10further comprises coupling members16,17. The interactive toy10may thus be used as a modular toy element adapted to be releasably interconnected with further modular toy elements (not shown here). As mentioned above, this is useful for the use of the interactive toy10in constructing toy construction models and/or for the construction of toy construction models with advanced interactive functionality by including a plurality of modular interactive toy elements10in such a toy construction model. Operating the interactive toy system100, the interactive toy10may be controlled to detect a primary signal101indicative of an interaction stimulus110; to detect a secondary signal102indicative of a position120of the interactive toy10with respect to the charging zone22; to select a user-perceptible function140based on the secondary signal102; and, responsive to the primary signal101, to control the function device14to perform the selected user-perceptible function140. FIGS.2a,2bshow schematically an embodiment of an interactive toy system200with modular interactive toy elements210in two different operation scenarios. According to some embodiments, the interactive system200may be the embodiment100schematically shown inFIG.1. The interactive toy system200may comprise a plurality of interactive toys210. For the sake of simplicity, only one interactive toy210is shown here. The interactive toy system200further comprises a charging device220with a coiled conductive loop221defining a charging zone222. The interactive toy system200may comprise a plurality of charging zones222. For the sake of simplicity, only one charging zone222is shown here. When an interactive toy210is placed within the charging zone222, energy can be transferred from the charging device220to the interactive toy210in order to charge the rechargeable energy storage device of the interactive toy210. The interactive toy210is configured to detect a primary signal indicative of an interaction stimulus110received from an interaction source99, and a secondary signal indicative of a position120of the interactive toy210with respect to the charging zone222. When an interaction stimulus110is detected a user perceptible function240a,240bof the interactive toy210is activated, wherein a first user perceptible function240ais selected, when the position stimulus120indicates that the interactive toy210is placed within the charging zone222as seen inFIG.2a; and wherein a second user perceptible function240bis selected, when the position stimulus120indicates that the interactive toy210is placed outside the charging zone222as seen inFIG.2b. The secondary signal102indicative of a position120of the interactive toy210with respect to the charging zone222of the charging device220may be determined in any suitable manner. In some embodiments, a strength of an electromagnetic field (e.g. above a given threshold), may also be representative of a position120of the interactive toy210with respect to the charging zone222. For example, a detected or measured electromagnetic field strength above a first threshold may be equalled to placement within the charging zone222. In this context, the electromagnetic field strength may also be determined in any suitable manner. For example, a relevant measure for the electromagnetic field strength available for energy transfer from the charging device220to the interactive toy210may be developed in the charging circuit of the interactive toy210, on the basis of a detected/measured charging activity. In this way, a detected or measured charging activity may also be used to indicate a position120of the interactive toy210with respect to the charging device220, and the secondary signal102may be developed on the basis of a detection and/or measurement of a charging activity in the interactive toy210. By way of example, the first threshold t1may be determined as a level of the electromagnetic field strength above which an efficient energy transfer from the charging device220to the interactive toy210is possible. Correspondingly, when no electromagnetic field is detected or when the detected electromagnetic field strength is below a second threshold t2, this may be equalled to a placement outside the charging zone222. The first and second threshold values may be chosen to coincide: t1=t2. Alternatively, the second threshold t2may be chosen to be lower than the first threshold t1, t1>t2, and an interval between the first and second threshold values [t1;t2] may be associated with a placement of the interactive toy210in the vicinity223of the charging zone222. In this way, a signal102indicative of a position120of the interactive toy element210with respect to the charging zone222may be developed even on the basis of a detection or measurement of an electromagnetic field strength and/or a charging activity in the interactive toy210. Furthermore, according to some embodiments, the interactive toy210may communicate with the charging device220so as uniquely to identify the charging device220. Such information may in particular be useful for interactive toy systems200comprising further charging zones222(not shown inFIGS.2a,2b) in order to determine to which one of the plurality of charging zones222the detected position stimulus120relates. The information identifying the charging zone222may then be included when developing the secondary signal, and thus be used when selecting the user-perceptible function240a,240b. FIGS.3a,3bshow schematically a further embodiment of an interactive toy system300with modular interactive toy elements310A,310B. For the sake of simplicity, only two interactive toys310A,310B are shown here. The interactive toy system300further comprises a charging device320with a coiled conductive loop321defining a charging zone322. When the interactive toys310A,310B are placed within the charging zone322, energy can be transferred from the charging device320to the interactive toys310A,310B in order to charge the rechargeable energy storage device of the interactive toys310A,310B. The embodiment of an interactive toy system300shown inFIGS.3a,3bhas all the features of the embodiment of an interactive toy system200shown inFIGS.2a,2band as discussed above, with the specific modification that the interaction source99now is a second interactive toy310B. Referring toFIG.3a, a first interactive toy310A is configured to detect a primary signal indicative of an interaction stimulus110areceived from an interaction source. The first interactive toy310A is further configured to detect a first secondary signal indicative of a position120A of the first interactive toy310A with respect to the charging zone322. A second interactive toy310B is also configured to detect a primary signal indicative of an interaction stimulus110areceived from an interaction source. The second interactive toy310B is further configured to detect a second secondary signal indicative of a position120B of the second interactive toy310B with respect to the charging zone322. When an interaction stimulus110ais detected by the first interactive to310A, a user-perceptible function340aof the interactive toy310A is activated, wherein the first user-perceptible function340ais selected, when the position120A indicates that the interactive toy310A is placed within the charging zone222as seen inFIG.3a. As already mentioned, in the embodiment shown inFIGS.3a,3b, the interaction stimulus detected by the first interactive toy310A is provided by the second interactive toy310B, wherein the interaction stimulus is selected based on a second secondary signal indicative of the position120B of the second interactive toy310B, which inFIG.3ais located outside the charging zone322. Now turning toFIG.3b, the second interactive toy310B may also be placed within the charging zone322. Based on the detection of the placement120B of the second interactive toy310B within the charging zone, a different interaction stimulus110bmay be provided to the first interactive toy310A, resulting in the selection of a second user-perceptible function340b, e.g. a stronger glow of a ‘magic crystal’, even though the position stimulus120A indicates that the first interactive toy310A is still placed inside the charging zone322as seen inFIG.3b, since now the interaction stimulus provided by the interaction source has changed. The direct interaction between two interactive toys310A,310B may thus be made dependent on different combinations of placing the interactive toys310A,310B with respect to the charging zone322. Furthermore, the change in interaction can be perceived by the user as a change in the user-perceptible function performed by at least one of the interactive toy elements. It may be noted that the second interactive toy may be prompted to provide the interaction stimulus in response to a user interaction therewith, and/or automatically, e.g. in response to an automated detection of the presence of the first interactive toy in its proximity. Turning now toFIGS.4a-c, three different states of an interactive toy system400with a plurality of interactive toys411,412,413,414and multiple charging zones422A,422B are described, thereby illustrating how interactive toy systems according to embodiments of the invention generally provide the technical means for facilitating a playfully interactive game design with embedded charging. Interactive toy systems according to embodiments of the invention thus generally provide a game designer with the technical infrastructure required to configure a game for promoting a desired charging behaviour in a manner that is linked to and embedded in the playful physical interaction without disturbing the actual play experience, or even by enhancing the play experience. As described herein, a user-perceptible output response of the interactive toys is prompted by a primary signal input, wherein the user-perceptible output response is modified according to a secondary signal. Advantageously, the primary signal input is an interaction signal indicative of an interaction stimulus, i.e. a stimulus that originates from a user interaction, an interaction with the environment, or an interaction with another interactive toy. Further, advantageously, the secondary signal is indicative of a position of the interactive toy with respect to one or more charging zones. Thereby, user perceptible output is initiated by an interaction and at the same time linked to charging of the interactive toys of the toy system in one or more of the charging zones. The interactive toy system400schematically shown inFIGS.4a-ccomprises modular Interactive toy elements411,412,413,414and a charging system with charging devices420A,420B with coiled conductive loops421A,421B defining respective charging zones422A,422B. When the interactive toys411,412,413,414are placed within one of the charging zones422A,422B, energy can be transferred from the corresponding charging device420A,420B to the interactive toys411,412,413,414in order to charge the rechargeable energy storage device of the interactive toys411,412,413,414. The embodiment of an interactive toy system400shown inFIGS.4a-chas all the features of the embodiment of an interactive toy system200shown inFIGS.2a,2band as discussed above, with the specific modification that the system is now shown with a plurality of modular interactive toy elements (here four, by way of example)411,412,413,414and multiple charging zones422A,422B (here two, by way of example). Again, by way of example, the interactive toy elements411,412,413,414are capable of emitting light as a user-perceptible output, wherein the light emission may be modified in intensity, colour, and a combination thereof, which furthermore may be provided as a time varying sequence. The light output of the interactive toy elements411,412,413,414may be controlled by a control circuit to provide the user-perceptible (here visible) output responsive to a primary signal received at the control circuit, wherein the user-perceptible output may be modified according to a function that is selected based on a secondary signal received at the control circuit. As schematically shown inFIG.4A, a user99may pick up and place two of the interactive toy elements411,412in a first charging zone422A. The user's99interaction of picking up and placing selected ones of the interactive toy elements411,412in the first charging zone420A may be detected as interaction stimulus111,112, and corresponding primary signals indicative of said interaction stimulus111,112may be developed. Furthermore, the new position121A,122A of the interactive toy elements411,412inside the first charging zone422A may be detected, and a secondary signal indicative of said position121A,122A at a location inside the first charging zone422A may be developed. Receiving the primary signal the interactive toy elements411,412are prompted to produce light output upon the user interactions111,112. Further receiving the secondary signal, the light output is generated according to a function, which is determined based on the secondary signal. For example, in response to the primary signal, the light emitters in interactive toy elements411,412are controlled to emit light, wherein the light emission is selected to be a “moderate intensity” based on the secondary signal. In a game context overlay, the moderate intensity may be associated with a “magic glow” of the interactive toy elements representing “crystal assets” evoked by the user-interaction of picking up and placing the interactive toy elements411,412in the charging zone representing a “magic source” in the game. Using this control infrastructure a game designer may thus align the user-perceptible output required for an interactive play experience with the requirement for motivating a continued charging of the interactive toy elements as an embedded part of the interactive play with the toy elements. The interaction stimulus may be detected, for example, by means of suitable detection devices arranged in the housing of the selected interactive toy elements411,412, e.g. by means of a touch sensor, a proximity sensor, a gyroscopic sensor, an acceleration sensor, an optical sensor, a magnetic sensor, and/or an inductive sensor with a pick-up coil arrangement in the toy element's411,412housing. Furthermore, the position with respect to at least one of the multiple charging zones may be detected, for example, by means of suitable detection devices arranged in the housing of the interactive toy elements411,412, e.g. by means of a touch sensor, a proximity sensor, a gyroscopic sensor, an acceleration sensor, an optical sensor, a magnetic sensor, and/or an inductive sensor with a pick-up coil arrangement in the toy element's411,412housing. The remaining interactive toy elements413,414rest without detected interaction. Accordingly, no user-perceptible function is initiated, as shown inFIG.4A. However, it is further conceivable that the selected interactive toy elements411,412when placed inside the charging zone, besides the user-perceptible output, also broadcast an interaction stimulus directed to the remaining interactive toy elements413,414, thereby developing a primary signal for the remaining interactive toy elements413,414(not shown). The primary signal is indicative of an interaction stimulus received by the remaining interactive toy elements413,414from the selected interactive toy elements411,412. Reception of the primary signal may again initiate emission of a user-perceptible output. The interactive toy elements may further detect that they are positioned outside any of the charging zones422A,422B of the toy system, thereby developing a secondary signal for the remaining interactive toy elements413,414(not shown). The secondary signal is indicative of the position of the remaining interactive toy elements413,414with respect to the charging zones422A,422B. The secondary signal may then be used to determine a user-perceptible output function for the interactive toy elements413,414remaining outside the charging zones422A,422B, which is different from the user-perceptible output function used for the selected interactive toy elements411,412that are placed inside the first charging zone422A. For example, the remaining interactive toy elements413,414may attract the user's attention by a faint pulsating light emission (not shown here), thereby indicating that they are also “magic crystals” which can be activated in a “magic circle”. FIG.4Bshows the interactive toy system in a state where the user99has placed all interactive toy elements411,412,413,414in the first charging zone422A. The user's interaction stimulus is indicated by arrow113, e.g. placing the interactive toy element413as the last one to join the interactive toy elements411,412,414already present in the first charging zone422A. Detection, e.g. by interactive toy element413, of the proximity of the other interactive toy elements411,412,414may cause an interaction between interactive toy element413and the other interactive toy elements411,412,414, which may be detected as interaction stimulus131,132,134and used to develop a primary signal indicative of that interaction at the other interactive toy elements411,412,414. The interactive toy elements411,412,413,414may further develop respective secondary signals indicative of their position121A,122A,123A,124A within the first charging zone422A. Thus inferring that all interactive toy elements411,412,413,414are located inside the same charging zone422A, while a further charging zone422B is available, the user-perceptible output function initiated by the primary signal may then be adapted based on the respective secondary signals, e.g. by reducing the light emission intensity from “moderate intensity” to “low intensity”, thereby indicating to the user that a less desirable state has been produced. FIG.4Cshows the interactive toy system in a further state with a different, more even distribution of the interactive toy elements411,412,413,414over the available charging zones422A,422B, where two of the interactive toy elements411,412are placed in the first charging zone422A as indicated by position arrows121A and122A, respectively, and where two further ones of the interactive toy elements413,414are placed in the second charging zone422B as indicated by position arrows123B and124B, respectively. From a charging point of view an even distribution of the interactive toy elements over the charging zones, or more generally a distribution according to a predetermined scheme, for example reflecting the charging capacity of the different charging zones, may e.g. be desirable in order to achieve a good load balance across the different charging devices420A,420B of the charging system. Generally, the control circuits of the interactive toy construction elements may thus be configured to take into account such a distribution scheme. Advantageously, the distribution scheme is conditioned by a charging capacity of the charging devices of the toy system. In simple embodiments, the distribution scheme may be predetermined, e.g. according to a predetermined charging capacity of the charging devices. Alternatively or in addition thereto, the distribution scheme may be determined dynamically, e.g. in response to a current load of the charging device where a given interactive toy element is placed, and including information indicative of said current load in the secondary signal. User interactions114,115,116and inter-element interactions, such as interaction135may then initiate a user-perceptible function to be produced by the interactive toy elements411,412,413,414, wherein the function is adapted according to the secondary signal as developed based on the determined position information121A,122A,123B,124B. In response to this state, the control circuits of the interactive toy elements411,412,413,414may then be configured to control the light emission to an increased intensity (“high intensity”) as compared to both the first state shown inFIG.4Aand the second state shown inFIG.4B. In the interactive play, the increased intensity may reflect a “more powerful magic” being activated by occupying more “magic circles”. Thereby a status with respect to a desired distribution of the plurality of interactive toys over the multiple charging zones can be indicated to the user. A game designer may thus configure the toy system to align the requirement for a load-balanced use of the charging system with the goals of the interactive play, thereby motivating an optimized continued charging of the interactive toy elements during the play without compromising the user's interactive play experience. As indicated in all embodiments shown, the interactive toy elements advantageously are modular interactive toy elements comprising cooperating coupling elements and can be assembled to form a toy construction model, which may include further modular toy elements, such as passive or non-interactive functional modular toy elements to enhance the model building experience. According to some embodiments of the interactive toy system, any one of building related interactions, i.e. interactions related to the model building and construction play may be detected and used as interaction stimulus from which a primary signal may be developed. For example, such building and construction play related interactions may include connecting and/or disconnecting modular toy elements to construct an/or modify a toy construction model, detection of a vicinity, of a proximity, and/or of a fixed spatial relation with respect to other interactive, passive or non-interactive functional modular toy elements. In a yet further embodiment, shown inFIG.5, an interactive toy system500comprises a first charging device520A, a second charging device520B, a third charging device520C, a first set of interactive toy elements511,512,513,514associated with a first user99, and a second set of interactive toy elements515,516,517associated with a second user98. The first, second and third charging devices520A,520B,520C each have respective first, second and third inductive loops521A,521B,521C defining corresponding charging zones522A,522B,522C. Interactive toy elements511,512,513of the first set may be placed inside the first charging zone520A. The first user99may interact with each of the interactive toy elements511,512,513in the first charging zone520A, thus providing an interaction stimulus111,112,113from which a primary signal may be developed. A respective secondary signal is developed for each of the interactive toy elements based on their positions121A,122A,123A in the first charging zone522A. The positions121A,122A,123A may further reflect a distance from the wiring of the loop521A and may e.g. rely on sensing an inductive coupling between a pick-up coil arrangement in each of the interactive toy elements511,512,513and the inductive loop521A, which may depend on said distance. The primary signal may then initiate a user-perceptible function, wherein the function is determined according to the secondary signal. For example, interaction stimulus111,112,113is a physical handling of the toy construction elements according to a recognizable predetermined pattern, which in a playing context mimics a nurturing and training of playable characters, such as dragons, represented by the toy construction elements, or a model build therefrom. Position information121A,122A,123A may indicate that the toy construction elements511,512,513are placed within the first charging zone522A, which in the playing context may represent a first training base for the dragons of the first user99. In addition thereto, the position information may indicate a distance of the interactive toy elements from the windings of the first inductive loop521A, and/or vary with an inductive coupling strength as mentioned above, which thus may reflect a charging efficiency. The user-perceptible function may then be a faint glow if the position111,112,113(e.g. of a dragon model) is determined as inside the first charging loop (e.g. the dragon model's training base), thereby indicating in the above-mentioned play context that the interactive toy (dragon) thrives and strengthens under the user's interaction with the respective interactive toy elements, e.g. representing care and training of the dragon. In so far the position signal carries further detailed information, such as a distance from a predetermined position for efficient charging, the secondary signal may reflect this information and the output function may be adjusted accordingly, e.g. by varying the strength of the faint glow according to said distance. A further interactive toy element514of the first set may be placed inside the third charging zone520C. The first user99may interact with the interactive toy element514in the third charging zone520C, thus providing an interaction stimulus114from which a primary signal may be developed. A respective secondary signal is developed, which is indicative of the position124C of the interactive toy element514in the third charging zone522C. Initiated by the primary signal indicative of the user's99interaction stimulus114, a user-perceptible function may then be performed by the interactive toy element514, wherein the user-perceptible function is selected based on the secondary signal indicating that the interactive toy element is now within the third charging zone522C (rather than in any one of the first and second charging zones522A,522B). The user perceptible function in the third charging zone522C may be selected to be significantly different from the user-perceptible functions that are selected when the interactive toy elements are placed in the first or second charging zones522A,522B. For example, the interactive toy element514when placed inside the third charging zone may now produce a vibrant colour and high intensity light emission in response to the interaction stimulus114. In the above-mentioned play context, the third charging zone522C may represent a battle arena, and the physical interaction stimulus114may mimic the dragons impressive posing and moves before and during battling. Interactive toy elements515,516,517of the second set associated with user98may be configured in an analogous manner. In the state of the interactive toy system500shown inFIG.5. Interactive toy elements515,516are placed inside the second charging zone520B, where the second user98may interact with each of the interactive toy elements515,516in the second charging zone520B, thus providing an interaction stimulus115,116from which a primary signal may be developed. A respective secondary signal is developed for each of the interactive toy elements515,516based on their positions125B,126B in the charging zone522B. Furthermore, the interactive toy element517of the second set is placed inside the third charging zone520C. The second user98may interact with the interactive toy element517in the third charging zone520C, thus providing an interaction stimulus117from which a primary signal may be developed. A respective secondary signal is developed, which is indicative of the position127C of the interactive toy element517in the third charging zone522C. Again, a user-perceptible function may then be performed by the interactive toy element517, which is initiated by the primary signal indicative of the user's98interaction stimulus117, wherein the user-perceptible function is selected based on the secondary signal indicating that the interactive toy element517is now within the third charging zone522C. As for the first set of interactive toy elements, the second set of interactive toy elements may perform a significantly different user-perceptible function when placed in the third charging zone522C, as compared to being placed in one of the first and second charging zones522A,522B. The interactive toy system thereby facilitates a combined nurturing/training and competitive battling play experience with multiple players using at least a first set of interactive toy elements511,512,513,514and a second set of interactive toy elements515,516,517in combination with multiple charging zones522A,522B,522C. Exploiting the infrastructure according to embodiments of the invention the game designer is thus enabled to align goals of the play experience with goals of continued charging, thereby facilitating continued play with the interactive toy elements for durations beyond single charging cycles of the interactive toy elements.
31,217
11857891
DETAILED DESCRIPTION OF THE INVENTION For simplicity and clarity of illustration, elements in the drawings are not necessarily drawn to scale. The same reference numbers in different drawings denote the same or similar elements, and as such perform similar functionality. Also, descriptions and details of well-known steps and elements are omitted for simplicity of the description. Furthermore, in the following detailed description of the present disclosure, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be understood that the present disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail so as not to unnecessarily obscure aspects of the present disclosure. Examples of various embodiments are illustrated and described further below. It will be understood that the description herein is not intended to limit the claims to the specific embodiments described. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the present disclosure as defined by the appended claims. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms “a” and “an” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises”, “comprising”, “includes”, and “including” when used in this specification, specify the presence of the stated features, integers, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, operations, elements, components, and/or portions thereof. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expression such as “at least one of” when preceding a list of elements may modify the entire list of elements and may not modify the individual elements of the list. It will be understood that, although the terms “first”, “second”, “third”, and so on may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section described below could be termed a second element, component, region, layer or section, without departing from the spirit and scope of the present disclosure. In addition, it will also be understood that when a first element or layer is referred to as being present “on” a second element or layer, the first element may be disposed directly on the second element or may be disposed indirectly on the second element with a third element or layer being disposed between the first and second elements or layers. It will be understood that when an element or layer is referred to as being “connected to”, or “coupled to” another element or layer, it may be directly on, connected to, or coupled to the other element or layer, or one or more intervening elements or layers may be present. In addition, it will also be understood that when an element or layer is referred to as being “between” two elements or layers, it may be the only element or layer between the two elements or layers, or one or more intervening elements or layers may also be present. Further, as used herein, when a layer, film, region, plate, or the like is disposed “on” or “on a top” of another layer, film, region, plate, or the like, the former may directly contact the latter or still another layer, film, region, plate, or the like may be disposed between the former and the latter. As used herein, when a layer, film, region, plate, or the like is directly disposed “on” or “on a top” of another layer, film, region, plate, or the like, the former directly contacts the latter and still another layer, film, region, plate, or the like is not disposed between the former and the latter. Further, as used herein, when a layer, film, region, plate, or the like is disposed “below” or “under” another layer, film, region, plate, or the like, the former may directly contact the latter or still another layer, film, region, plate, or the like may be disposed between the former and the latter. As used herein, when a layer, film, region, plate, or the like is directly disposed “below” or “under” another layer, film, region, plate, or the like, the former directly contacts the latter and still another layer, film, region, plate, or the like is not disposed between the former and the latter. Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Water Vapor Generating Apparatus FIG.1is a cross-sectional view for illustrating a water vapor generating apparatus according to an embodiment of the present disclosure.FIGS.2and3are perspective views for illustrating one embodiment of an inner cage and an outer cage shown inFIG.1, respectively. FIG.4is a cross-sectional perspective view for illustrating an embodiment of each of first and second evaporation tubes shown inFIG.1.FIG.5is a cross-sectional view for illustrating a water vapor pressure-change reduction member according to an embodiment of the present disclosure. Referring toFIG.1toFIG.5, a water vapor generating apparatus100according to an embodiment of the present disclosure may provide water vapor to a fuel reformer (1200inFIG.6) which generates hydrogen necessary for reaction of a fuel cell from hydrocarbon fuel chemically containing hydrogen, such as methane (CH4), ethane (C2H6), propane (C3H8), butane (C4H10), natural gas, or coal gas. In one embodiment, when methane (CH4) is supplied as the hydrocarbon fuel, the fuel reformer1200reacts the methane with the water vapor supplied from the water vapor generating apparatus100(1100inFIG.6) according to a following Reaction Formula 1 to generate the hydrogen: 3CH4+4H2O→10H2+2CO+CO2Reaction Formula 1 Together with this reaction, a side reaction to produce carbon (C) according to a following Reaction Formula 2 may occur inside the fuel reformer (1200inFIG.6) depending on a reaction temperature and a ratio of a contents of the water vapor and a carbon component: 2CO→C+CO2Reaction Formula 2 When the carbon generated in this way is supplied to a fuel cell stack (1300inFIG.6), an fuel electrode of the fuel cell may be damaged such that performance of the fuel cell may be drastically reduced. Therefore, in order to suppress such a side reaction for producing the carbon, the water vapor should be stably supplied to the fuel reformer. The water vapor generating apparatus100according to an embodiment of the present disclosure includes a chamber110, a space partitioning member120, a first evaporation tube130, a second evaporation tube140, an inner cage150, an outer cage160and a heating device (not shown). The chamber110may have internal spaces10and20. The space partitioning member120is disposed inside the chamber110to divide an internal space of the chamber110into two spaces10and20, that is, a water vapor discharge space10and a heating space20. A water vapor outlet111through which water vapor is discharged may be formed in a portion of the chamber110defining the water vapor discharge space10. This water vapor outlet111may be connected to the fuel reformer (1200inFIG.6). The chamber110and the space partitioning member120may be made of a material stable at a high temperature. For example, each of the chamber110and the space partitioning member120may be independently made of a material that is stable at a high temperature such as a metal, an alloy, a ceramic, a metal composite, or a composite of a metal and a ceramic. In one example, the chamber110and the space partitioning member120may be made of the same material or may be made of different materials. In one embodiment, the water vapor discharge space10may include a first space10adirectly connected to the water vapor outlet111and a second space10blocated below the first space10afor temporarily storing therein water which has not changed into water vapor or is generated by cooling the water vapor. The water stored in the second space10bmay be converted into the water vapor using thermal energy supplied to the heating space20. In order to effectively supply the thermal energy provided to the heating space20to the water stored in the second space10b, the second space10bmay have a top connected to the first space10aand a side and/or a bottom which are surrounded with the heating space20. A shape of the second space10bis not particularly limited as long as the space10bmay accommodate therein the water and effectively receive the thermal energy from the heating space20. For example, the second space10bmay have a cylindrical shape, a quadrangular prism, a cone, a quadrangular pyramid, and the like whose side faces are surrounded with the heating space20. In one embodiment, in order to define the first space10and the second space20, the space partitioning member120may include a first partitioning portion121and a second partitioning portion122. The first partitioning portion121may have an opening having a predetermined shape and defined in a middle partition thereof and may be coupled to a sidewall of the chamber110and may separate the first space10aand the heating space20from each other. The second partitioning portion122may extend downward from the opening of the first partitioning portion121to define the second space10b, and may separate the second space10band the heating space20from each other. In an embodiment, the space partitioning member120may include a plurality of first guide protrusions123protruding from a surface of the second partitioning portion122toward the first evaporation tube130. Each of the first guide protrusions123may support a bottom of each of portions of the first evaporation tube130to guide a coupling position of the first evaporation tube130. The first evaporation tube130may be disposed in the heating space20and in a form of a coil surrounding the second space10b. The first evaporation tube130may have a first end disposed outside the chamber110and connected to an external water supply device (not shown) and a second end positioned within the water vapor discharge space10. The first evaporation tube130may extend through the heating space20in the same manner as described above and may extend to the water vapor discharge space10. The second evaporation tube140may be disposed in a coil shape surrounding an outer face of the first evaporation tube130. The second evaporation tube140may include a first end disposed outside the chamber110and connected to the water supply device and a second end located in the water vapor discharge space10. The second evaporation tube140may extend through the heating space20in the same manner as described above and may extend to the water vapor discharge space10. When the first and second evaporation tubes130and140are installed as described above, the water supplied to the first and second evaporation tubes130and140from the external water supply device may be converted into water vapor while moving in the heating space20. Then, the converted water vapor may be discharged into the water vapor discharge space10. In addition, the water vapor discharged from the first and second evaporation tubes130and140into the water vapor discharge space10may be supplied to the fuel reformer (1200inFIG.6) through the water vapor outlet111. Further, in accordance with the present disclosure, when two or more evaporation tubes are applied instead of a single evaporation tube, a diameter of each evaporation tube may be reduced, so that the water vapor conversion efficiency may be remarkably improved. In one embodiment, each of the first and second evaporation tubes130and140may include a bellows-type tube having a wrinkled inner face as shown inFIG.4. When each of the first and second evaporation tubes130and140is formed as the bellows type tube, water may be converted into water vapor at higher efficiency, and change in the pressure of the water vapor discharged from the first and second evaporation tubes130and140may be reduced, due to increase of a surface area resulting from the inner wrinkles of each of the first and second evaporation tubes130and140. The inner cage150may be disposed between the first evaporation tube130and the second evaporation tube140, and may press against the first evaporation tube130toward the second partitioning portion122of the space partitioning member120defining the second space10bto fix the first evaporation tube130and to support the second evaporation tube140. In one embodiment, as shown inFIG.2, the inner cage150may include a first upper frame151, a first lower frame152, a plurality of first connectors154, and a plurality of second guide protrusions155. Each of the first upper frame151and the first lower frame152may have a circular ring shape and have a constant width, and may surround and press the first evaporation tube130. The first lower frame152may be disposed below the first upper frame151and may have the same diameter as that of the first upper frame151. The plurality of first connectors154may connect the first upper frame151and the first lower frame152to each other, and may be spaced apart from each other. The plurality of first connectors154together with the first upper frame151and the first lower frame152may press against the first evaporation tube130. The plurality of second guide protrusions155may protrude from each of the plurality of first connectors154in an outward direction, that is, toward the outer cage160, and may support the second evaporation tube140. A spacing between and a protrusion length of the plurality of second guide protrusions155may be appropriately adjusted according to the diameter of the second evaporation tube140. The outer cage160may surround the second evaporation tube140, and may press against the second evaporation tube140toward the first evaporation tube130to fix the second evaporation tube140. In one embodiment, as shown inFIG.3, the outer cage160may include a second upper frame161, a second lower frame162, a middle frame163, and a plurality of second connectors164. Each of the second upper frame161, the second lower frame162, and the middle frame163may have a circular ring shape and have a constant width, and may surround and press against the second evaporation tube140. The second lower frame162may be disposed below the second upper frame161, and the middle frame163may be disposed between the second upper frame161and the second lower frame162, all of which may have the same diameter. The plurality of second connectors164may connect the second upper frame161, the second lower frame162, and the middle frame163to each other. The plurality of second connectors164together with the second upper frame161, the second lower frame162, and the middle frame163may press against the second evaporation tube140toward the first evaporation tube130. The heating device (not shown) may supply the thermal energy to the heating space20to convert water moving in and along the first and second evaporation tubes130and140into water vapor. In one embodiment, the heating device may include a high-temperature gas supplier (1400ofFIG.6) for supplying a high-temperature gas to the heating space. In this case, a gas inlet112ainto which the high-temperature gas is injected from the high-temperature gas supplier and a gas outlet112bthrough which the high-temperature gas is discharged from the heating space20may be defined in a portion of the chamber110defining the heating space20. As long as a temperature of the heating space20may be increased due to the high-temperature gas, the high-temperature gas is not particularly limited. For example, the high-temperature gas may include gas discharged from the fuel cell stack (1300inFIG.6). That is, the heating device may burn the gas discharged from the fuel cell stack using a burner (1400ofFIG.2), etc. to produce the high-temperature gas and then supply the high-temperature gas through a blower or the like to the heating space20. In another embodiment, the heating device may include an electric heater (not shown) installed in a side wall of a portion of the chamber110defining the heating space20. In one embodiment, the water vapor generating apparatus100according to the embodiment of the present disclosure may further include a temperature sensor170coupled to a bottom of the second space10bof the chamber110for measuring a temperature inside the chamber110. In one embodiment, as shown inFIG.5, the water vapor generating apparatus100according to the embodiment of the present disclosure may further include a water vapor pressure-change reduction member180disposed inside each of the first and second evaporation tubes130and140to reduce the pressure-change of the water vapor to be discharged from each of the first and second evaporation tubes130and140. The water vapor pressure-change reduction member180may be disposed in each of the first and second evaporation tubes130and140and adjacent to an end of each of the first and second evaporation tubes130and140from which the water vapor is discharged, and may have a porous structure through which water vapor may pass. For example, the water vapor pressure-change reduction member180may include a mesh structure or a foam structure inserted and disposed inside each of the first and second evaporation tubes130and140. This water vapor pressure-change reduction member180may suppress the pressure change of the water vapor due to the LeidenFrost effect. Further, in one embodiment, the water vapor generating apparatus100according to an embodiment of the present disclosure may further include a liquid water detector (not shown) disposed in the second space10bto detect liquid water present in the second space10b. As the liquid water is not converted into the water vapor in the evaporation tube130and is stored in the second space10bdue to an abnormal situation such as a decrease in the temperature of the high-temperature gas or a malfunction of the heating device, the water vapor may not be supplied to the fuel reformer (1200inFIG.2). Thus, as described above, a large amount of carbon may be produced to damage the fuel electrode of the fuel cell. The liquid water sensor may detect the liquid water present in the second space10band notify the occurrence of the above-described abnormal situation at an early stage, thereby remarkably improving the stability of the fuel cell system. When the liquid water present in the second space10bmay be sensed by the liquid water sensor, a configuration of the liquid water sensor is not particularly limited. According to the water vapor generating apparatus of the present disclosure, the first and second evaporation tubes130and140are not directly connected to the fuel reformer, but are connected to the fuel reformer (1200inFIG.6) through the water vapor discharge space10of the chamber110. Thus, the water vapor may be more uniformly supplied to the fuel reformer. In a conventional water vapor generating apparatus, in general, an external water supply device (not shown) supplies water to an evaporation tube using a pump device, and the evaporation tube is directly connected to the fuel reformer. In this case, the water vapor is non-uniformly supplied to the fuel reformer due to pulsation of the pump device. However, in accordance with the present disclosure, the first and second evaporation tubes are connected to the fuel reformer through the water vapor discharge space of the chamber, such that the water vapor discharge space may dampen the pulsation of the pump device. In addition, when the bellows-type tube is used as each of the first and second evaporation tubes, the water vapor generation efficiency may be improved, and the pressure-change of the water vapor to be supplied to the fuel reformer may be further reduced. Furthermore, when the water vapor pressure-change reduction member is disposed in each of the first and second evaporation tubes, the pressure-change of the water vapor to be supplied to the fuel reformer may be further reduced. Moreover, according to the water vapor generating apparatus of the present disclosure, the first and second evaporation tubes may be fixed using the inner cage and the outer cage. Thus, structural stability of the water vapor generating apparatus may be improved, and a diameter of each of the evaporation tubes may be reduced, thereby further improving the water vaporization efficiency. Fuel Cell System FIG.6is a view for illustrating a fuel cell system according to an embodiment of the present disclosure. Referring toFIG.6, the fuel cell system1000according to an embodiment of the present disclosure may include the water vapor generating apparatus1100, the fuel reformer1200and the fuel cell stack1300. The water vapor generating apparatus1100receives liquid water from an external water supply device (not shown), converts the liquid water into the water vapor, and supplies the water vapor to the fuel reformer1200. The water vapor generating apparatus100as described with reference toFIG.1may be applied as the water vapor generating apparatus1100. Thus, a redundant detailed description thereof will be omitted. The fuel reformer1200may generate fuel gas containing hydrogen via reaction between the hydrocarbon fuel supplied from an external fuel supply device (not shown) and the water vapor supplied from the water vapor generating apparatus1100. A known or to be developed fuel reformer may be applied as the fuel reformer1200without limitation. Thus, a detailed description thereof will be omitted. The fuel cell stack1300may generate electricity using the hydrogen of the fuel gas provided from the fuel reformer1200and oxygen of air provided from an external air supply device (not shown). The fuel cell stack1300may include a solid oxide type fuel cell stack, a solid polymer type fuel cell stack, a phosphate type fuel cell stack, a molten carbonate type fuel cell stack, etc. without limitation. In the fuel cell system1000according to an embodiment of the present disclosure, the heating device of the water vapor generating apparatus1100may include a burner1400as shown inFIG.6. The burner1400may combust the gas discharged from the fuel cell stack1300to produce the high-temperature gas and supply the as a high-temperature gas to the heating space20of the water vapor generating apparatus1100. Further, the burner1400may supply thermal energy required for the reaction of the hydrocarbon fuel and the water vapor to the fuel reformer1200. A known combustion device may be applied as the burner1400without limitation. FIG.7AandFIG.7Bare graphs showing pressure-changes measured in water vapor generating apparatuses to which a flat tube type evaporation tube and a bellows type evaporation tube are applied, respectively. Referring toFIG.7AandFIG.7B, a maximum pressure as measured in the water vapor generating apparatus to which the flat tube type evaporation tube was applied was 5.2 kPa, while a maximum pressure measured in the water vapor generating apparatus to which the bellows-type evaporation tube was applied was 3.7 kPa. That is, the maximum pressure as measured in the water vapor generating apparatus to which the bellows type evaporation tube was applied was reduced by about 1.5 kPa, compared to that in the water vapor generating apparatus to which the flat tube type evaporation tube was applied. It will be understood that although the above disclosure has been described with reference to the preferred embodiment of the present disclosure, those skilled in the art may achieve modifications and changes thereto within a range that does not deviate from the spirit and scope of the present disclosure as described in the following claims.
24,723
11857892
DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail in a non-limiting manner in the description which follows. General Presentation of the Chromatographic Separation Method The invention (in its three aspects) relates to a method for separating a mixture in a system comprising a set of several chromatography columns containing a stationary phase, wherein the method comprises successively, in a cyclic manner, in a given part of the system:a step of collecting a raffinate, a step of injecting the mixture to be separated, a step of collecting an extract and a step of injecting the mobile phase. The different steps above follow one another in this part of the system. The part of the system in question is preferably located between the outlet of one column and the inlet of the next column. Alternatively, the part of the system in question may include a column or a column part. At a given moment, one or more of the above steps may be simultaneously implemented in one or more parts of the system. For example, all of these steps may be implemented simultaneously in respective parts of the system. By “mixture to be separated” is meant a mixture of species (or compounds, including, in particular, the molecules) containing at least two species, for example at least one species of interest and at least one impurity. The mixture to be separated may be binary when it is composed of two species, or complex when it is composed of more than two species. The mixture to be separated may be diluted in a liquid phase, preferably the mobile phase used in the chromatographic method. According to embodiments, the mixture to be separated comprises one or more species chosen from:a monosaccharide sugar, for example glucose, fructose, deoxyribose, ribose, arabinose, xylose, lyxose, ribulose, xylulose, allose, altrose, galactose, gulose, idose, mannose, talose, psicose, sorbose or tagatose, and/or a polysaccharide sugar, for example a galactooligosaccharide, a fructo-oligosaccharide or a wood hydrolyzate, and/orproteins, and/oramino acids, and/ororganic acids, such as citric acid, and/ormineral salts, and/orionized species, and/oralcohols and/or glycols, and/ororganic acids from natural or enzymatic or fermentation media. This list is not exhaustive, the invention in its entirety may be carried out on any chemical species to be separated of whatever form. In certain embodiments, the mixture to be separated comprises one or more monosaccharides. Preferably, the extract and the raffinate are enriched with different monosaccharides. Advantageously, the monosaccharide has 5 or 6 carbon atoms. Preferably, the monosaccharide is chosen from glucose, fructose, deoxyribose, ribose, arabinose, xylose, lyxose, ribulose, xylulose, allose, altrose, galactose, gulose, idose, mannose, talose, psicose, sorbose, tagatose, and a mixture thereof. In certain particularly advantageous embodiments, the mixture to be separated comprises glucose and fructose. The method according to the first aspect of the invention is particularly advantageous in such a case, since the consumption of the eluent represents a significant cost in the separation of these monosaccharides. In the present application, the terms “mixture to be separated”, “feed”, “mixture to be treated”, “product to be purified” and “initial mixture” denote the same thing. The terms “mobile phase” and “eluent” are understood to mean the same thing in the present application. By “raffinate” is meant a fraction enriched in species that are less retained by the stationary phase. In the case of an initial binary mixture, this is the fraction enriched with the least retained species. By “extract” is meant a fraction enriched with species most retained by the stationary phase. In the case of an initial binary mixture, this is the fraction enriched with the most retained species. The chromatographic columns are preferably arranged in series and in a closed loop, an outlet of a column being connected to the inlet of a following column, the outlet of the last column being connected to the inlet of the first column. The columns may also be called chromatography “cells”. They may be used in a carousel system, arranged one next to the other, or even arranged one above the other within one or two towers in order to limit the footprint. The columns may contain a liquid or solid stationary phase. The eluent may be a fluid in the gaseous, liquid or even supercritical state. Injection lines for the mixture to be separated and for the eluent are provided at the inlet of the different columns, while lines for collecting extract and raffinate are provided at the outlet of the columns. Preferably the injection and collection lines are connected via connection lines between two successive columns. In certain advantageous embodiments, the system also comprises members for sequencing the injection and collection lines. In particular, the sequencing of these injection and collection lines takes place over a system operating cycle. In the present application, an “operating cycle” or “cycle” designates the time at the end of which the injection and collection lines have been sequenced until they return to their initial position in the system. At the end of a cycle, the system is again in its initial configuration. A cycle generally has as many periods as there are columns in the separation loop. Thus the cycle of a method implemented on an 8 column system is composed of 8 periods. The displacement of the collection lines (extract and raffinate) and the injection lines (loading and mobile phase) in the system is also called line switching in the present description. We can generally define four areas in the system (in particular when the method implemented is an SMB method, as described below):area1located between the eluent injection line and the line for collecting the extract,area2located between the line for collecting the extract and the line for injecting the mixture to be separated,area3located between the line for injecting the mixture to be separated and the line for collecting the raffinate, andarea4located between line for collecting the raffinate and the eluent injection line. The method according to the invention is advantageously a periodic chromatographic storage method. By “accumulation method” is meant a chromatographic method in which the injection of the mixture to be separated is inserted or added to a non-zero concentration profile passing from the outlet to the inlet of a column. Examples of such accumulation methods are the SMB method, the VariCol method, the Powerfeed method, the ModiCon method, the iSMB method or the SSMB method. The simulated moving bed method (or SMB) is a continuous multi-column method, the injection of mixture to be separated being carried out over an entire cycle. The SMB method may, in particular, be a SMB method with four areas. In this case, the system comprises a set of columns mounted in series and in a closed loop, the outlet of one column being connected to the inlet of the next column. The system comprises at least one line for injecting a mixture to be separated, a line for collecting a fraction enriched in species that is little retained by the stationary phase (the raffinate), a line for injecting an eluent and a line for collecting a fraction enriched in species that is more retained by the stationary phase (the extract). The injection lines (mixture to be separated and the eluent) and the fraction collection lines move periodically and synchronously (synchronous sequencing) within the loop in the direction of the flow of the fluid flowing through the loop. The duration between two displacements of all the injection and collection lines of a column corresponds to a period; at the end of a cycle all the points will have returned to their initial position, the system having a cyclic operation. A cycle has as many periods as there are columns. The method according to the invention may be a method of continuous injection of the mixture to be separated (i.e. a method in which the injection of the mixture to be separated is a continuous flow). The injection of the mixture to be separated is then carried out throughout the duration of the cycle. The method according to the invention may also be a method of quasi-continuous injection of the mixture to be separated. In certain particularly advantageous embodiments, the method according to the invention is an SMB method, preferably an SMB method with four areas. Alternatively, the method according to the invention may be a method in which the injection of the mixture to be separated is discontinuous. In these methods, the injection of the mixture to be separated is not carried out over the whole of a cycle but for a total duration lasting less than one cycle. Mention may be made of a discontinuous injection separation method called the iSMB method (Improved Simulated Moving Bed), as described in documents EP 0342629 and U.S. Pat. No. 5,064,539. In this method, the system operates in one step in a closed loop, without injection or product collection. We may also cite the SSMB method (Sequential Simulated Moving Bed) whose sequential multi-column method is described, for example, in document WO 2015/104464. Preferably, the method according to the invention involving a discontinuous injection of mixture to be separated, is an SSMB method. Regulation Method The method according to the first aspect of the invention comprises:the determination, in a node of the system, of the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated;the detection on said history of a characteristic point between the start of a step of collecting the extract and the end of the following step of collecting the raffinate;the comparison of the position of the characteristic point against a target position;the adjustment of the volume carrying the characteristic point, modifying the position of the characteristic point to bring the position of the characteristic point closer to the target position;the volume of the mobile phase injected per cycle being maintained above a minimum limit and/or below a maximum limit. By “system node” or “observation node” is meant a physical point of the chromatography system which may be freely chosen. In some embodiments, the observation node is located between the outlet of one column and the inlet of the next column in the system. We call “history”, the state or evolution of a variable that is representative of the concentration of one or more species contained in the mixture to be separated in motion in the system, this state being considered for a determined duration or time at the observation node. Thus, we may measure the evolution of a variable that is representative of the concentration of one or more species contained in the mixture to be separated flowing at the observation node. A history may be represented:as an evolution as a function of time, for example without limitation expressed in gross time, or in time elapsed relative to the start of the cycle or reduced to the total cycle time;as an evolution as a function of the integration over time of a liquid flow, preferably the flow flowing at the observation node, for example in a non-limiting manner expressed in gross volume, or in volume flowed compared to the beginning of the cycle or reduced to another volume (volume of a column or total cycle volume), this method being particularly advantageous in the case where the flow rates are variable during the period or cycle;as a more general evolution of an indicator of progress in the cycle. The history may thus be temporal, volumetric, or dependent on a setting the method cycle. A history is different from a concentration profile. The concentration profile of the fractions of the fluid flowing in the system is called the “concentration profile”, this state being considered at a given instant over the entire system. The document FR 2699917, cited at the beginning of this description, describes steps making it possible to reconstitute a concentration profile. The duration during which the state of the variable is determined, i.e. during which the history is determined, may be, for example, an operating cycle. At the end of the cycle, the history may be reset and restarted. The duration may also be shorter than an operating cycle. As indicated above, the abscissa of a history may be expressed in a non-limiting way in different units:the gross time: the axis then starts from 0 and ends at the effective end of the cycle time;the reduced time, defined by the gross time divided by the cycle time: in this case, the history axis is always between 0 and 1;an index of progress in the cycle: this is the generalization of the gross time divided by the cycle time; this is interesting in the case where there are scheduled stops of elution rates, whose duration may be variable;a volume index corresponding to the volume observed at the system node divided by the total volume observed at the observation node. In advantageous embodiments, the chromatographic system comprises a detector, and possibly a plurality of detectors, positioned at the node of the system where the history of the variable representative of the concentration of one or more species contained in the mixture to separate, is obtained. The detector may be, for example, a densimeter, a polarimeter, a conductometer, a refractometer, an infrared, near infrared, Raman or UV/visible spectrometer, or an on-line nuclear magnetic resonance apparatus. The detectors may be located on the system, namely on the lines of the system itself; in this case, we may consider that the fluid circulates through detectors. This is advantageous for low fluid flow rates in the system. For higher flow rates, it may be preferable to re-position the line detectors, wherein the detectors are placed on bypass lines. The method according to the invention comprises a step of determining, at a node of the system, the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated. Thus, the state of a variable that is representative of the concentration of one or more species is determined by means of one or more detectors as described above. This variable may be the concentration of one or more species of the mixture if the detectors allow it. In other embodiments, during this step, the variable representative of the concentration of one or more species is not the concentration itself nor the purity itself of the fractions. This has the advantage of regulating the operation more quickly than if a concentration or purity had to be measured (such a measurement may be complex and, therefore, take a long time). Furthermore, since it is not necessary to measure the purity or the concentration, it is not necessary to calibrate the detector, and the method according to the invention may thus tolerate a drift of the detector(s) used. It is not necessary to physically produce a history, for example by viewing or printing the history. Direct regulation without recording or viewing may be sufficient. Preferably, the step of determining the history is carried out at a single node, which makes it possible to limit the use of detectors and to avoid having to consider the synchronization of the detectors, the synchronization also being able to evolve over time in the case, for example, of a change of state of one of the columns of the system. The variables that are representative of the concentration of one or more species contained in the mixture to be separated are preferably variables that may be obtained quickly and directly, conversely, for example, to the concentration which often requires prior calibration. Thus, as an example of a specific variable, we may cite:the optical rotation, obtained, for example, by the signal returned by a polarimetric detector, which is usable in the case where the species of the mixture to be separated are optically active, for example enantiomers;absorbance or emission of spectroscopic radiation, obtained, for example, by the signal returned by a spectroscopic detector, for example with UV/visible or infrared radiation, which is usable when the species of the mixture to be separated are natural or synthetic molecules having detectable chemical groups, in particular biomolecules such as proteins or peptides;the refractive index, the density, the conductivity or the pH, which are obtained, for example, by the signal returned by detectors measuring such physical quantities, and which are usable, for example, in the case where the mixture to be separated contains sugars, ionic species, acids or bases;the combination of several specific variables mentioned above,one or more variables obtained from other detectors. The variables representative of the concentration given above by way of example, are variables for which a history may be easily obtained. The histories of these variables may be obtained in real time, which makes the method efficient. The histories translate the evolution of the concentrations at the observation node, wherein this is in the form of a signal which may easily be obtained through monitoring by a detector. The separation method according to the invention also comprises a step of detecting a characteristic point on the history, called “characteristic point of low concentration” in the present description. This step makes it possible, from the determination of the variable that is representative of the concentration, to define a revealing point of the separation method. According to certain embodiments, the characteristic point is not a precise value of the variable but is indicative of a circulation phenomenon at the observation node. The characteristic point is indicative of a relative behavior of the species circulating at the observation node. The observation node is positioned at the outlet of a column of the system. During the cycle, the lines (for collecting the raffinate, injecting the mixture to be separated, collecting the extract, and injecting the mobile phase) and the areas, move from one column to another and the said lines and areas are therefore next to (or in the vicinity of) the observation node at specific times, i.e. between the same successive columns as the observation node. On the history, it is possible to define times and durations corresponding to the passage of the lines (collection of the raffinate, injection of the mixture to be separated, collection of the extract, and injection of the mobile phase) in the vicinity of the observation node. It is then possible to locate on the history, the intervals or the mean points of the positions (also called mean positions) for collecting the raffinate, injecting the mixture to be separated, collecting the extract, and injecting the mobile phase, as well as the areas that these intervals and mean points determine. According to the invention, the characteristic point of low concentration is located between the start of a step of collecting the extract and the end of the following step of collecting the raffinate. Preferably, on the history, the said start of the extract collecting step and the said end of the following raffinate collecting step flank a mobile phase injection step. In the case of a four-area method, as described above, the characteristic point of low concentration is located either in area1, or in area4, or at the interface between these two areas (i.e. at the instant corresponding to the characteristic point, the observation node is located either in area1of the system, or in area4, or at the interface between these two areas, i.e. the mean eluent injection position). In embodiments, the detection of the characteristic point on the history takes place between the end of a step of collecting the extract and the start of the following step of collecting the raffinate. In embodiments, the detection of the characteristic point takes place in a portion of the history in which the density and/or the total concentration of the species is less than or equal to 25% of the density or, respectively, of the maximum total concentration of the mixture to be separated. The detection of the characteristic point of low concentration corresponds to the detection of the global position of the set formed by the adsorption front and the desorption front on the history, while in the document WO 2007/101944, the positions of the two fronts are individually detected and used to control the positions of the adsorption and desorption fronts. By “adsorption front” is meant an increase in concentration observed at the column outlet, in particular when the concentration increases from a low value to a value close to the maximum concentration detected over a cycle. The concentration may be the concentration of one species of the mixture to be separated, or the concentration of all the species present. By “desorption front” is meant a decrease in concentration observed at the column outlet, in particular when the concentration decreases to a low value from a value close to the maximum concentration detected on a cycle. The concentration may be the concentration of one species of the mixture to be separated, or the concentration of all the species present. The characteristic point of low concentration may be, for example:the minimum of the history, i.e. the minimum signal point as detected between the collection of the extract and the collection of the raffinate, or a local minimum; this point may be measured by a minimum signal from a densimeter, from a UV detector, but also by the minimum of the absolute value of the signal from a polarimeter;the point in the history having a determined value, for example the value zero, in particular when the variable that is representative of the concentration is the optical rotation, and the species to be separated have optical rotations of opposite signs;a point calculated as an intermediary between two points corresponding to predetermined values on the history; the predetermined values possibly corresponding, for example, to a threshold of the signal from a densimeter or a UV detector, but also to a threshold of the absolute value of the signal from a polarimeter; the characteristic point may be, for example, a barycenter and, in particular, the iso-barycenter (temporal or volumetric) of two points in the history corresponding to predetermined values;a point calculated as an intermediary between two points corresponding to values defined relatively on the history; these values may, in particular, correspond to respective fractions of the values reached in local maxima or minima of the history; thus the characteristic point may be a barycenter and, in particular, the iso-barycenter (temporal or volumetric) between two points corresponding to such defined values, and, in particular, between two points which are a characteristic point of the adsorption front and a characteristic point of the front desorption respectively; the advantage of this method is that these two characteristic points may be calculated according to two different detectors. FIGS.1and2show examples of a characteristic point of low concentration detected from a history.FIG.1corresponds to a density history (black line), obtained by a densimeter, between the collection of the extract (denoted E) and that of the raffinate (denoted R). Three examples of characteristic points of low concentration are presented. A first example of a characteristic point of low concentration, denoted1, is the point corresponding to the minimum density. A second example is the point denoted2, the abscissa of which is the iso-barycenter of the abscissas of the two points of the history corresponding to a predetermined density value of 1.05. A third example is point3whose abscissa is the iso-barycenter of the abscissas of two points obtained by threshold relative to 20%: the first point is defined by the abscissa such that the density is 20% between the minimum density observed and the density measured at the start of extract collection; the second point is defined reciprocally by the abscissa such that the density is 20% between the minimum density observed and the density measured at the end of the raffinate collection. The mean position of the mobile phase injection is denoted PM. FIG.2corresponds to a history of optical rotation, obtained by a polarimeter, between the collection of the extract (denoted E) and that of the raffinate (denoted R). Three examples of characteristic points of low concentration are presented. A first example of a characteristic point of low concentration is the point denoted1where the measured optical rotation is zero. A second example is the point denoted2whose abscissa is the iso-barycenter of the abscissas of the two points corresponding to a threshold value of the absolute value of optical rotation. A third example is the point denoted3whose abscissa is the iso-barycenter of the abscissas of the point corresponding to an optical rotation equal to 50% of the maximum optical rotation, and of the point corresponding to an optical rotation equal to 50% of the minimum optical rotation. The position of the injection of the mobile phase is denoted PM. The position of the characteristic point is data making it possible to stabilize the purities and yields of the system. As indicated above, an advantage of the method according to the invention is that the history may be determined over a duration less than one cycle. In fact, it suffices to detect the characteristic point and then proceed to the next step of regulation. Preferably, however, the determination step is carried out over a complete cycle. Furthermore, the steps of determining the history and of detecting the characteristic point may be implemented at a frequency corresponding to an integer number of cycles (all the n cycles, n being greater than or equal to 1). The more frequently are the steps of determining the history and of detecting the characteristic point, the more precise is the adjustment of the operation of the system. The method according to the invention also comprises a step of comparing the position of the characteristic point with a target position. The detection of the characteristic point may be assimilated to the determination of the time (or of the elapsed volume, the latter corresponding to the integration of the flow over time), wherein the characteristic point appears at the observation node for the duration of the history, for example a cycle; the target position then corresponds to the time (or volume) when the characteristic point should appear at the observation node to allow operation under the desired conditions. On a history corresponding to the evolution over time of a variable that is representative of the concentration of one or more species contained in the mixture to be separated, the step of comparing the position of the characteristic point with a target position, consists in comparing the abscissa of the characteristic point with a predetermined target abscissa. This helps to determine whether a disturbance has occurred in the system. In a suitably adjusted system, preferably without disturbance and in steady state, the position of the characteristic point coincides with the target position. If the system is not disturbed, the characteristic point appears at an observation node at approximately the same time during each cycle. The difference between the position of the characteristic point and the target position may then correspond to a difference in time of passage to the observation node. The target position of the characteristic point of low concentration may be defined absolutely in the cycle, or else relative to the step of injection of the mobile phase, and/or relatively to a step of collection of fraction, raffinate and/or extract. The method according to the invention also comprises a step of adjusting the volume carrying the characteristic point, modifying the position of the characteristic point to bring the position of the characteristic point closer to the target position, if there exists a difference between the position of the characteristic point and the target position. In other words, a difference between the position of the characteristic point and the target position corresponds to a deviation or a disturbance in the functioning of the system, which may be compensated by adjusting only the volume carrying the characteristic point. By “volume carrying a concentration front” is meant in the present invention, the volume carrying a front on which the characteristic point is located, or in the vicinity of which the characteristic point is located. In a four-area method as described above, it may be the carrying volume of area1(or desorption area), or the carrying volume of area4(or adsorption area). By “carrying volume of an area” is meant the volume circulating in the area in question between two line switching operations. This volume is the product of the flow of fluid circulating in the area and the period, while it may also be the integration over time of the flow between two line switching operations when the flow is not constant during the period. When the mobile phase volume of area1is modified, the position of the desorption front present in area1is also modified. Likewise, the volume of area4carries the adsorption front and a modification of the volume of area4will modify the position of the adsorption front. forehead By “volume carrying the characteristic point” is meant in the present invention a volume whose variation modifies the position of the characteristic point. As may be seen inFIGS.1and2, a modification of the volume of area1will change the position of the front between the start of the collection of the extract and the mean eluent injection point, and will modify the position of the characteristic point of the desorption front. Conversely, a modification of the volume of area4will change the position of the front between the mean eluent injection point and the end of the collection of the raffinate, thus modifying the position of the characteristic point of the adsorption front. A modification of the volume carrying the characteristic point may be performed by modifying one or more injection and/or collection flow rates; and/or by modifying the duration between line switching operations; and/or by modifying the duration of one or more injections and/or collections. Preferably, the modification of the volume carrying the characteristic point is carried out by modifying one or more injection and/or collection flow rates, or the duration between the line switching operations. To modify the volume carrying the characteristic point, one may, for example, modify the flow in area1or the flow in area4. The flow will, for example, be increased if the position of the characteristic point is located downstream of the target position (i.e. if the abscissa of the characteristic point is located downstream of the predetermined abscissa as the target position) or decreased if the position of the characteristic point is located upstream of the target position. Preferably, the volume carrying the characteristic point is adjusted without the mobile phase injection volume being modified. The volume of mobile phase injected per cycle may then remain constant during the use of the method. This is particularly useful when a mobile phase volume constraint is set. Thus, when the volume of mobile phase injected per cycle reaches the fixed extreme limit (whether it is a minimum or maximum limit), this volume remains constant at this limit. The modification of the volume carrying the adsorption area (area4), for example by a modification of the flow rate of the raffinate collection, then amounts to accordingly modifying the volume carrying the desorption area (area1), and vice versa. Thus, the adjustment of the volume carrying the characteristic point makes it possible to vary the passage of the species in the area whose carrying volume is modified. The characteristic point may be ahead of the target point (i.e. the point whose abscissa is the target position). By decreasing the volume carrying the characteristic point, we can slow down the circulation of species, and thus delay the characteristic point so as to bring it closer to the target point. Conversely, if the characteristic point is delayed with respect to the target point, the volume carrying the characteristic point is increased to accelerate the circulation of the species, and to accelerate the characteristic point so as to bring it closer to the target point. If the characteristic point is stabilized at the target point, this means that there is no adjustment to be made. It is also possible to consider providing a threshold of difference between the position of the characteristic point and the target position, wherein the adjustment is then made if the observed difference exceeds the threshold. A regulation as described above, may, for example, be a PID control (Proportional, Integral, Derivative control) acting on the volume carrying the characteristic point. In a four-area method, it is necessary to distinguish the terms “carrying volume of an area” (also called “volume of an area” or “volume of mobile phase of an area”), “volume of mobile phase” and “volume of mobile phase injected”. Thus (and as explained above), the volume of area1corresponds to the volume of the mobile phase which passes the column(s) specific to area1over a given period, and located between the eluent injection line and the extract collection line. Similarly, we may define a volume for each area of the system (for area2, for area3and for area4). As indicated above, the modification of an area volume is preferably carried out either by a modification of the flow rate, or by a modification of the duration between two switchings of the lines which frame the said area. This can modify the volume of mobile phase injected, or the volume of mobile phase of the collections. For example, a variation in the volume of area4while keeping the volumes of area3and area1constant, is equivalent to a variation of the volume of collection of the raffinate and of the volume of the mobile phase injected. The term “mobile phase volume” is a generic term for the mobile phase passing through a column. On the other hand, the “volume of mobile phase injected” or “volume of mobile phase injected per cycle” corresponds to the volume of fresh eluent injected between area4and area1(in a four-area method). It is this volume that the invention is intended to control. The regulation method described in document WO 2007/101944 makes it possible to individually regulate the mobile phase volumes of areas1and4, which are the volumes carrying the characteristic points of areas1and4(characteristic points of desorption and adsorption). This does not allow precise control of the volume of mobile phase injected per cycle. In the method according to the invention, when a volume constraint of the mobile phase injected per cycle is encountered (i.e. when a maximum and/or minimum limit is reached), the regulation is carried out by providing the same correction to the volume of area1and to the volume of area4(when the method is a four-area method). The regulation thus relates to a quantity called “volume carrying the point of low concentration” which may be, in the case of a method with four areas, the volume of area1, or the volume of area4, or a combination of the two. In such a case, a variation made to the volume of area1and area4will modify the volume of collection of the raffinate and/or of the extract, but not the volume of the mobile phase injected. The advantage of the method according to the invention is that it makes it possible both to react quickly to disturbances in the system and to control the amount of mobile phase injected during each operating cycle, unlike the methods described in the prior art. In general, methods based on the analysis of the composition of collected fractions do not allow rapid reaction to disturbances whose effects may take several cycles to stabilize. In addition, in certain cases, the time taken to analyze and obtain purity values is long. The time taken to analyze the compositions is all the longer as it is preferable to sample the fractions of the chromatographic system over an entire cycle, wherein these samples are then analyzed. Thus, the purity results may only be obtained with at least one delay cycle and with a periodicity greater than one or two cycles, which makes regulation and determining the adjustment to be applied more difficult. There is, therefore, a delay in reactivity of the accumulation systems following modifications to operating parameters or following disturbances to which an analysis delay may be added. The present method makes it possible to react as soon as a change in history is observed. The regulation implemented to restore the system is then rapid. In addition, the method according to the invention also makes it possible, by controlling a characteristic point between the start of a step of collecting the extract and the end of the following step of collecting the raffinate, to control the volume of the mobile phase used by the chromatographic method, unlike the methods regulated by the control of two characteristic points located on the adsorption front and on the desorption front. FIG.3shows a history obtained during the use of a method according to the invention in which a constraint of maximum volume of eluent injected per cycle has been set. The position of the characteristic point of low concentration coincides with its target position. In this example, the position of the characteristic point of low concentration corresponds to the position of the eluent injection. Note that the characteristic adsorption and desorption points (as described in document WO 2007/101944) have not reached their target position and that gaps persist between the adsorption and desorption points and their respective target positions. FIG.4shows a history obtained during the use of a method according to the invention in which a constraint of minimum volume of eluent injected per cycle has been set. The position of the characteristic point of low concentration coincides with its target position. In this example also, the position of the characteristic point of low concentration corresponds to the position of the eluent injection. It is to be noted that, in this case also, the characteristic points of adsorption and desorption have not reached their target position and that gaps persist between the adsorption and desorption points and their respective target positions. This regulation on the basis of the characteristic point of low concentration and not of the characteristic points of adsorption and desorption allows the imposed limits of eluent volume to be respected. According to certain embodiments, the method further comprises a step of measuring the purity of at least one collected fraction. In particular, the method comprises a step of measuring the purity of the extract and/or of the raffinate. The purity of the fraction(s) is then compared respectively with a target purity, i.e. with a predetermined purity which it is desired to achieve. It is also possible, as an alternative to measuring the purity(ies) or as a complement to these measurements, to measure a quantity of a target species in a collected fraction and determine its yield linked to the presence of target species in the fraction(s) collected. Thus, the method according to the invention may comprise a step of measuring the yield in a target species of the extract and/or of the raffinate, and a step of respectively comparing the measured yield(s) with a target yield. In the present invention, it is possible to use either purity and/or yield constraints; it is, in fact, the same type of constraints, but imposed differently. By “yield of a collected fraction” is meant in the present invention the yield of a target species contained in said collected fraction. In certain embodiments, the method according to the invention also comprises a step of modifying the volume of mixture to be separated, which is injected per cycle according to the difference between the measured purity(ies) and the target purity(ies). For example, in the case of a binary mixture, if the two purities of the extract and of the raffinate are both greater than the predetermined purities, this means that the purities are beyond specifications; the quantity of mixture may be increased to “degrade” the purities to specifications. If the extract and raffinate purities are both lower than the predetermined purities, this means that the purities are below specifications; the amount of mixture may be decreased to improve separation, and to increase purities to specifications. This operating mode may be adjusted when a single purity is of interest. As indicated above, it is also possible to measure a quantity of the target species and its yield linked to the presence of target species lost in the other collections. This yield is directly linked to the purity of the other fractions. Preferably, the steps of measuring the purity (and/or the yield) of at least one collected fraction, of comparing the measured purity(ies) (and/or the measured yield(s)) against a target purity (and/or a target yield), and modification of the volume of mixture to be separated injected per cycle, are performed at least in part, in parallel with the steps of detection on the history of the characteristic point of low concentration, of comparison of its position with a target position, and adjustment of the volume carrying the characteristic point. The modification of the quantity of mixture to be separated may be implemented by modifying the volume of mixture injected during a period. The modification of the volume of mixture to be separated may be carried out in several ways:by increasing or decreasing the mixture injection rate; and/orby increasing or decreasing the period duration. Controlling the quantity of mixture (or load) to be separated that is to be injected requires measuring at least one data item relating to purity and/or yield. The following example, which is non-limiting, illustrates a method for defining the quantity of load to be injected, and which may be used if two purities are targeted for the extract and the raffinate. Let the following variables be:P*ext: Target purity in the extract;p*raff: Target purity in the raffinate;Pext: Purity measured in the extract;Praff: Purity measured in the raffinate;εext=Pext−P*ext, i.e. the difference between the measured purity and the target purity of the extractεraff=Praff−P*raff, i.e. the difference between the measured purity and the target purity of the raffinate. The purities may be calculated by determining the mass or molar concentrations of one or more species of interest in the fraction concerned. According to a first method, PID control may be performed on a quantity obtained from the deviations of one or more purities from their target value (εextand/or εraff). Another possibility is to use the value of a function depending on the purities obtained and the target purities in order to calculate the new quantity to be injected. The modification of the quantity of mixture to be separated that is injected causes a disturbance which may cause the characteristic point of low concentration to move relative to the target position. The position of the characteristic point of low concentration is then modified by the adjustment of the volume carrying the characteristic point as has already been described above. In the present invention, the regulation of the position of the characteristic point of low concentration is carried out by the control of a single carrying volume chosen from the volume of area1, the volume of area4, or a combination of the two (for example the mean of the characteristic points of each area). The distribution of the volume carrying between area1and area4remains precisely controlled, which makes it possible to respect high and/or low threshold values of the mobile phase volume. If the high and low thresholds are equal, the volume of mobile phase injected per cycle is regulated to a precise set value according to the invention. This setpoint naturally lies between the maximum and minimum mobile phase volume limits. The control method according to the invention, therefore, makes it possible to impose the non-crossing of high and/or low threshold(s), and also to precisely control the volume of mobile phase according to other criteria than the respect of the positions of the fronts in areas1and4. In a more general description of the invention, it is possible to control the volume of the mobile phase between maximum and minimum limits which are the extremes that are never to be exceeded by using intermediate control variables which are high and low thresholds. Two extreme ways of use are possible:the high and low thresholds are fixed as being close to the maximum and minimum limits, while the mobile phase volume is controlled according to the invention when its excess value passes outside the authorized range;the high and low thresholds are modified according to the purity and/or yield measurements, while the values of the thresholds themselves remain constantly between the maximum and minimum limits of the mobile phase volume. Thus, in certain embodiments, the method according to the invention comprises a step of modifying the setpoint of the mobile phase volume injected per cycle according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s). For example, in the case of a binary mixture, if the two purities of the extract and of the raffinate are both greater than the predetermined purities, this means that the purities are beyond the specifications; the mobile phase volume may thus be decreased. If the extract and raffinate purities are both lower than the predetermined purities, this means that the purities are below specifications; the mobile phase volume may be increased. This operating mode may be adjusted when a single purity is of interest. We can also measure a quantity of the target product and its yield linked to the presence of target product lost in other collections. This yield is directly linked to the purity of the other fractions. Preferably, the steps of measuring the purity (and/or the yield) of at least one collected fraction, of comparing the measured purity(ies) (and/or the measured yield(s)) with a target purity (and/or with a target yield), and modification of the volume of mobile phase injected per cycle, are performed, at least in part, in parallel with the steps of detection on the history of the characteristic point of the low concentration, of comparison of its position with a target position, and adjustment of the volume carrying the characteristic point. In certain embodiments, during the step of modifying the volume of mobile phase injected per cycle, the volume of mixture to be separated and injected per cycle remains constant. According to other embodiments, the volume of mixture injected per cycle and the volume of mobile phase injected per cycle, are modified jointly according to the difference between the measured purities and the target purities (and/or the difference between the measured yields and the target yield(s). The possible variation of the volume of mobile phase injected is performed taking into account the maximum limit and/or the minimum limit for this volume which are/is provided for in the method of the invention. In some embodiments, the method includes a step defining the target position of the characteristic low concentration point according to of the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s)). This step makes it possible to improve the method already described, so as to optimize the target position relative to the desired purities. The purities measured may be the purity of the extract and/or of the raffinate. Preferably, the steps of measuring the purity (and/or the yield) of at least one collected fraction, of comparing the measured purity(ies) (and/or the measured yield(s)) with a target purity (and/or with a target yield), and definition of the target position are performed at least in part in parallel with the steps of detection on the history of the characteristic point of low concentration, comparison of its position with a target position, and adjustment of the volume carrying the characteristic point. The target position of the characteristic point of low concentration may be such that it is sufficiently distant (over time) from the raffinate and extract collections, if the purity of the two fractions (in the case of binary mixing) is of importance. For example, the characteristic point of low concentration may be positioned in the eluent injection step. However, the purity of a single fraction may be important. In this case, the target position may be compared to one or other of the raffinate or extract collections. For example, the characteristic point of low concentration may be positioned in area1or in area4. As indicated above, it is also possible to measure an amount of the target product and its yield linked to the presence of target product lost in the other collections. This yield is directly linked to the purity of the other fractions. It should be noted that the measurement of the purity of the fractions may be obtained with a certain delay. However, this does not penalize the method because the steps of measuring the purity of at least one collected fraction, of comparing the purity(ies) measured with a target purity, and of defining the target position, are advantageously performed in parallel with the steps of detecting the history of the characteristic point of low concentration, comparing its position against a target position, and adjusting the volume carrying the characteristic point. The definition of the new target position may then be implemented with each new measurement, or even all the cycles, by simply considering the last available measurements. During the analysis period of the purity(ies), the method continues to adjust the volume carrying the characteristic point of low concentration by comparing the position of the characteristic point with the valid target position. Several methods may be used to define the target position of the characteristic point. According to a first method, a PID type regulation is applied to the εextor εraffparameters. So if εextis negative, then the target position will be distant from the extract line (the target position is close to the raffinate line). Similarly, if εextis positive, then the target position will be brought closer to the extract line (the target position moves away from the raffinate line). The regulation is similar if applied to εraff. If εraffis negative, then the target position will be far from the raffinate line (the target position is closer to the extract line). Similarly, if εraffis positive, then the target position will be brought closer to the raffinate line (the target position moves away from the extract line). According to a second method, a PID control is applied to the combination of the εextand εraffdeviations and, more generally, to the combination of the deviations between the measured purities and/or yields and the target purities and/or yields. According to a third method, a function depending on the purities obtained and the target purities may be directly used to calculate the new position of the characteristic point. During the step of defining the target position, the target position may also be defined relative to the position of the mobile phase injection on the history. This makes it possible to adapt to changes in the position of the injection point. Optimization of the target position of the characteristic point of low concentration may be carried out automatically. In certain advantageous embodiments, the method further comprises:the determination, in a node of the system, of the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated;the detection on the history of another characteristic point, called characteristic point of high concentration in the present description, located between the beginning of a step of collecting the raffinate and the end of the following step of collecting the extract;the comparison of the position of the characteristic point of high concentration against a target position;the adjustment of the volume carrying the characteristic point of high concentration, modifying its position to bring it closer to its target position. The variable that is representative of the concentration, the observation node and the history, may, each and independently, be the same variable, observation node and history as those used for the detection of the characteristic point of low concentration; or may be a different variable, observation node and history. This characteristic point of high concentration is located between the raffinate and extract lines, in other words in area2or in area3, or at the interface of areas2and3(i.e. at the mean position of injection of the mixture to be separated), where the concentrations are high. The document WO 2007/101944 describes in detail the detection and the use of this characteristic point of high concentration, which is represented, in particular, in FIGS. 6 to 11 and 18 to 21 of the document WO 2007/101944. What has been stated above about the characteristic point of low concentration applies by analogy to the characteristic point of high concentration. The volume carrying which is adjusted to control the position of the characteristic point of high concentration may be, for example, the volume of area2, while any variation of the volume of area2is passed on identically to the volume of area3. Mobile Phase Volume Constraint In the method according to the first aspect of the invention, the volume of the mobile phase injected per cycle is kept greater than, or equal to, a minimum limit and/or less than, or equal to, a maximum limit, at least during part of the method; and preferably during the entire method. In the case where a maximum limit is imposed, when the volume of mobile phase injected per cycle reaches this maximum limit, it can no longer increase. Advantageously, when the mobile phase volume reaches the maximum limit, it remains constant at this maximum limit. In the case where a minimum limit is imposed, when the volume of mobile phase injected per cycle reaches this minimum limit, it can no longer decrease. Advantageously, when the mobile phase volume reaches the minimum limit, it remains constant at this minimum limit. In certain embodiments, the mobile phase volume is kept both greater than, or equal to, a minimum limit, and less than, or equal to, a maximum limit. In some embodiments, the upper limit and the lower limit are identical. In this case, the volume of mobile phase injected is regulated at a constant volume equal to the minimum (or maximum) limit. Triggering of the Regulation According to the Invention During the Method The regulation of the method by reference to the characteristic point of low concentration may, in certain cases, be implemented during the method, when a condition is reached, and not necessarily from the start of the method. For example, this regulation may be triggered when the volume of mobile phase injected reaches or exceeds a certain threshold. Thus, another object of the invention is a method for separating a mixture in a system comprising an assembly of one or more chromatography columns, the method successively comprising, in a cyclic manner:a step of collecting a raffinate, a step of injecting the mixture to be separated, a step of collecting an extract, and a step of injecting the mobile phase;wherein the volume of the mobile phase injected per cycle is maintained greater than, or equal to, a minimum limit and/or less than, or equal to, a maximum limit; the method being such that:as long as the volume of the mobile phase injected per cycle is greater than, or equal to, a threshold value or less than, or equal to, a threshold value, the method comprises:the determination, in a node of the system, of the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated;the detection on the history of a first characteristic point between the start of the step of collecting the extract and the end of the following step of injecting the mobile phase (also called characteristic point of desorption);the detection on the history of a second characteristic point between the start of the step of injecting the mobile phase and the end of the following step of collecting the raffinate (also called characteristic point of adsorption); the comparison of the position of each of the characteristic points against a respective target position;the adjustment of the volume carrying of the first characteristic point and the volume carrying of the second characteristic point, modifying the position of the first characteristic point and the second characteristic point so as to bring them closer to their respective target positions;when the volume of the mobile phase injected per cycle reaches a threshold value, the method is as described above: i.e. the regulation based on the first characteristic point and on the second characteristic point, is abandoned in favor of regulation based on the characteristic point of low concentration described above. For example, the threshold value may be the minimum limit and/or the maximum limit of the injected mobile phase. Alternatively, it may be a threshold value having a predetermined deviation from the minimum limit and/or the maximum limit. Thus, as long as the volume of mobile phase injected per cycle has not reached the threshold value, the chromatographic method is regulated by comparing the position of two characteristic points of adsorption and desorption with a respective target position. This allows optimal precision of the regulation. When the mobile phase volume, modified due to regulation, or for any other reason, reaches the threshold value (and, for example, the minimum limit or maximum limit), the method is then regulated less precisely using the characteristic point of low concentration, as described above, which makes it possible to avoid the drawbacks linked to an excessive increase or an excessive decrease in the injected mobile phase. Regulation by means of the two characteristic points of adsorption and desorption has been described in detail in document WO 2007/101944 as mentioned above. In addition, what has been stated above concerning the characteristic point of low concentration applies by analogy to each of the characteristic points of adsorption and desorption. Computer Program Another object of the invention consists of a computer program comprising program code instructions for executing the steps of the method according to the invention when said program is executed on a computer. The invention also relates to a computer-readable storage medium on which a computer program, as defined above, is recorded. The invention also relates to a system comprising a processor coupled to a memory on which a computer program, as defined above, is recorded. Said system may also include the chromatographic separation system as described above, or may be only a control system, connected to the separation system and distinct from it. Measurement of Purities and/or Yields by On-Line Detectors According to a second aspect, the invention relates to a method for separating a mixture in a system comprising a plurality of chromatography columns, the method successively comprising, in a cyclic manner, in a given part of the system:a step of collecting a raffinate, a step of injecting the mixture to be separated, a step of collecting an extract and a step of injecting a mobile phase; wherein the method further comprises the measurement of the purity and/or of the yield of at least one collected fraction chosen from the extract and the raffinate, said measurement of purity and/or of yield comprising the following steps:the determination, in a node of the system, of histories of at least two respective variables that are representative of the concentration of at least two species contained in the mixture to be separated, by means of at least one fast on-line detector;the determination of the concentration of at least two species of the mixture to be separated in the collected fraction, from the histories;the determination of the purity and/or yield of the collected fraction, from the concentrations. By “determination of histories of at least two respective variables representative of the concentration of at least two species contained in the mixture to be separated”, is meant the determination of histories of at least two variables, these variables each being representative of the concentration of at least two species (i.e. of the set of at least two species) contained in the mixture to be separated. Purity corresponds to the ratio of the concentration of one or more species in the collected fraction, compared to the sum of all the concentrations determined in the collected fraction. The yield corresponds to the ratio of the quantity of a species in one of the two collected fractions to the total quantity of this species of the two accumulated collected fractions. By “on-line detector” is meant within the meaning of the present invention a detector positioned at the outlet of a chromatographic column, i.e. on a connection line between two successive columns. The term “on-line detector” also means a bypass detector, the sample taking of which is positioned at the outlet of a chromatographic column, i.e. on a connection line between two successive columns. Thus, an on-line detector is not located on an outlet line of the chromatographic system (i.e. on a line for collecting the extract or the raffinate). According to the invention, a single or, alternatively, several detectors may be used. In the case where at least two detectors are used, they may be positioned at the outlet of the same column, or at the outlet of different columns. In a system in which a cyclic chromatographic method is implemented, two types of detectors may be used: fast detectors and slow detectors. In this second aspect of the invention, the at least one on-line detector used is a fast detector. By “fast detector” is meant, within the meaning of the present invention, a detector whose response time is less than one twentieth of the duration of a cycle. By “slow detector” is meant a detector whose response time is greater than one-twentieth of the duration of a cycle. A fast detector emits a signal depending on the concentration profile of the compounds moving inside the detector. It may therefore make it possible to detect a characteristic point on a history, for example for the implementation of the separation method according to the first aspect of the invention. As a fast detector, mention may be made of UV/visible absorbance detectors, measuring at one or more wavelengths, colorimeters, densimeters, conductometers, refractometers, Brix meters, polarimeters, nuclear magnetic resonance devices and NIR (near infrared), IR (infrared), FTIR (Fourier Transform Infrared Spectroscopy), and Raman spectrometers. A temperature detector may be used to correct the signal given by the above mentioned detectors. In certain embodiments, the at least one fast on-line detector is chosen from the fast detectors mentioned above, provided that the at least two variables that are representative of the concentration of at least two species contained in the mixture to be separated, are detected and different. The at least one detector can measure one or more variables representative of the concentration of at least two species contained in the mixture to be separated. Thus, for example, the spectrometric type detectors, after calibration of the absorption or emission wavelengths for the species to be separated, may make it possible to measure the concentration of said species with a single device. The use of a single fast detector sometimes does not allow precise measurement of a concentration of a species to be achieved. As illustrated in Example 6, the use of a combination of a polarimeter and a densimeter during the purification of a mixture comprising glucose, fructose and polymers of glucose in minority quantity makes it possible to obtain variables that are representative of the concentrations of the species of the mixture: the densimeter gives information on the sum of all the concentrations while the polarimeter measures a rotation of polarized light, knowing that glucose and glucose polymers present a positive contribution while fructose presents a negative contribution. In this case, the representative variables are density and polarity. The combination of the values of these variables obtained by the two detectors makes it possible to evaluate the concentrations of species of the mixture (after a calibration of the detectors). In the case of the use of a spectrometer (IR, NIR, FTIR, Raman . . . ), each measurement of the spectrometer returns an information vector made up of a set of absorption or emission values at different wavelengths. The adsorption or emission at these different wavelengths is each potentially a variable that is representative of a concentration of the species. In fact, a combination of these adsorption or emission values makes it possible to estimate the value of the concentrations of one or more of the species. The determination of such a combination is performed by standard chemometric tools. In some embodiments, at least two fast on-line detectors are used to determine the histories. Preferably, they are chosen from the fast detectors mentioned above. In some embodiments, the at least two in-line detectors are a polarimeter and a densimeter. According to other embodiments, the at least two on-line detectors are a densimeter and a conductometer. In certain embodiments, the at least two species of the mixture to be separated are monosaccharides. In these embodiments, the extract and the raffinate are enriched with different monosaccharides. In particular, the monosaccharides are chosen from the monosaccarides mentioned above. In certain embodiments, the at least two species of the mixture to be separated are glucose and fructose. In these embodiments, the mixture to be separated may contain only glucose and fructose, optionally diluted in a solvent, for example water. Alternatively, the mixture to be separated may contain one or more other compounds, such as glucose polymers. Advantageously, when the at least two species of the mixture to be separated are glucose and fructose, at least two on-line fast detectors are used, preferably a polarimeter and a densimeter. According to other embodiments, the at least two species of the mixture to be separated are an ionized species, for example in the form of a salt, and a non-ionized species. In these embodiments, the extract and the raffinate are enriched with different species, i.e. the extract is enriched with ionized species and the raffinate is enriched with non-ionized species or vice versa (the extract is enriched with non-ionized species and the raffinate is enriched with ionized species). As ionized species, mention may be made of amino acids, salts or organic acids which are in ionized form at the pH and at the operating temperature of the chromatographic separation. As a non-ionized species at the pH and at the operating temperature of the chromatographic separation, we may mention alcohols and sugars, such as the monosaccharides and polysaccharides mentioned above. Advantageously, when the at least two species of the mixture to be separated are an ionized species and a non-ionized species, at least two fast on-line detectors are used, preferably a hydrometer and a conductometer. In certain embodiments, the method according to the invention comprises, after the step of determining histories of at least two respective variables representative of the concentration of at least two species contained in the mixture to be separated, a step of determination of the mean value of each variable over a measurement interval of the histories. According to other embodiments, the method according to the invention comprises, after the step of determining histories of at least two respective variables representative of the concentration of at least two species contained in the mixture to be separated, a step of determining the value of the integration of each variable over a measurement interval of the histories. In the foregoing, each measurement interval of history may be defined in full by collecting the fraction in question. In other words, the said history measurement interval corresponds, during a cycle, to the times (or volumes) at which the collection line of the considered fraction is between the same successive columns as the detector in question. Said measurement interval may also correspond to only part of the collection of the fraction in question. Said measurement interval may also correspond to part or all of the collection of the fraction in question, and to a part of the history immediately following the collection of the fraction in question. Said measurement interval may also correspond to part or all of the collection of the fraction in question, and to a part of the history immediately preceding the collection of the fraction in question. These last three embodiments are particularly useful if asymmetry is present in the chromatography system. This measurement of purities and/or yields may be used with all prior art control methods requiring a purity measurement to perform actions. In certain embodiments, the method according to the invention further comprises:the determination, in a node of the system, of the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated;the detection on the history of a characteristic point of high concentration located between the beginning of a step of collecting the raffinate and the end of the following step of collecting the extract;the comparison of the position of the characteristic point of high concentration against a target position;the adjustment of the volume carrying the characteristic point of high concentration, modifying the position of the characteristic point of high concentration to bring it closer to its target position. What has been stated above with regard to the characteristic point of high concentration may thus apply to the second aspect of the invention. In certain embodiments, the method according to the invention further comprises:the detection on the history of a first characteristic point between the start of the step of collecting the extract and the end of the following step of injecting the mobile phase (also called characteristic point of desorption);the detection on the history of a second characteristic point between the start of the step of injecting the mobile phase and the end of the following step of collecting the raffinate (also called characteristic point of adsorption);the comparison of the position of each of the characteristic points against a respective target position;the adjustment of the volume carrying the first characteristic point and the volume carrying the second characteristic point, modifying the position of the first characteristic point and the second characteristic point to bring them closer to their respective target positions. What has been stated above with regard to the characteristic points of adsorption and desorption may thus apply to the second aspect of the invention. In certain embodiments, the method according to the invention further comprises:the determination, in a node of the system, of the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated;the detection on said history of a characteristic point of low concentration between the start of a step of collecting the extract and the end of the following step of collecting the raffinate;the comparison of the position of the characteristic point of low concentration against a target position;the adjustment of the volume carrying the characteristic point of low concentration, modifying the position of the characteristic point of low concentration to bring the position of the characteristic point of low concentration closer to its target position;preferably, the volume of the mobile phase injected per cycle is maintained greater than, or equal to, a minimum limit and/or less than, or equal to, a maximum limit. What has been stated above concerning the characteristic point of low concentration may thus apply to the second aspect of the invention. In the above embodiments, the histories on which the characteristic point of high concentration are detected, the characteristic points of adsorption and desorption, the characteristic point of low concentration, and the histories from which the concentration of at least two species of the mixture to be separated in at least one collected fraction, are determined, may independently be the same histories or different histories. The same is true for the variables that are representative of the concentration of species contained in the mixture to be separated. In some embodiments, the method also includes a step of comparing the measured purity and/or the measured yield with a target purity and/or a target yield. If the purity and/or the yield are measured in the extract and in the raffinate, the method may comprise a step of comparing the two purities and/or yields measured with their respective target purity and/or yield. In certain embodiments, the method according to the invention may also comprise a step of modifying the volume of mixture to be separated that is injected per cycle according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s)). In certain embodiments, the method according to the invention comprises a step of modifying the volume of mobile phase injected per cycle according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s)). In certain embodiments, the volume of mixture injected per cycle and the volume of mobile phase injected per cycle are modified jointly according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s)). In certain embodiments, the method comprises a step of defining the target position of the characteristic point(s) according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yields(s)). This may be the definition of the target position of the characteristic point of high concentration and/or the definition of the target position of the characteristic point of adsorption and/or that of the characteristic point of desorption and/or that of the characteristic point of low concentration. What has been stated above with regard to the comparison of a measured purity and/or a yield with a target purity and/or yield, of the modification, according to this comparison, of the volume of mixture injected and of the mobile load volume and of the definition, according to this comparison, of the target position of the characteristic point may thus be applied to the second aspect of the invention. In certain embodiments of the invention, magnitudes such as the mean operating speed of the fluid in the columns may also be modulated if it is desired to modify the production of the system, or to control the pressure on one or more columns of the system. Another object of the invention is a computer program comprising program code instructions for executing the steps of the method according to the second aspect of the invention when said program is executed on a computer. The invention also relates to a computer-readable storage medium on which a computer program as defined above, is recorded. The invention also relates to a system comprising a processor coupled to a memory on which a computer program as defined above is recorded. Said system may also include the chromatographic separation system as described above, or may only be a control system, connected to the separation system and distinct from it. Measurement of Purities and/or Yields on an Intermediate Tank According to a third aspect, the invention relates to a method for the separation of a mixture in an installation comprising:a first system comprising a plurality of chromatography columns, an outlet line for collecting a raffinate, and an outlet line for collecting an extract;at least one second system placed downstream of the first system; andat least one tank supplied by one of said outlet lines of the first system, and supplying the second system, preferably with a continuous flow; the method comprising successively, in a cyclic manner, in a given part of the first system:a step of collecting a raffinate, a step of injecting the mixture to be separated, a step of collecting an extract, and a step of injecting a mobile phase; wherein the method further comprises the measurement of the purity and/or of the yield of at least one collected fraction chosen from the extract and the raffinate, said measurement of purity and/or of yield comprising the following steps:the determination of the concentration of at least two species of the mixture to be separated in the fraction collected in the tank;the determination of the purity and/or the yield in at least one species of the fraction collected in the tank. The determination of the purity and/or of the yield in at least one species of the fraction collected in the tank is performed based on the concentrations of the at least two species of the mixture to be separated as determined in the fraction collected in the tank. The purity corresponds to the ratio of the concentration of one or more species in the fraction collected in the tank, compared to the sum of all the concentrations determined in the fraction collected in the tank. The yield corresponds to the ratio of the quantity of a species in one of the two collected fractions to the total quantity of this species of the two collected fractions taken together. The at least one second system preferably operates with a continuous supply and at stable flow and composition. The tank guarantees a continuous supply from the second system in the event of a short shutdown of the first system. The presence of the tank may, for example, allow one hour of operation of the second system in the event of a shutdown of the chromatography installation. The tank also makes it possible to make the flow rate uniform and to smoothen the composition of the fraction collected before supplying it to the second system, in the event of asymmetry in the first system from one column to another. Preferably, the tank is periodically supplied by a collected fraction and constantly emptied towards the second system. It is never purged or even completely rinsed between each cycle of the system. In the case of an equilibrium chromatography system, the fraction contained in the tank has a mean composition that is very close to the mean composition of the fraction collected over a cycle. When the chromatography system is modified or evolving, the composition of the fraction contained in the tank is not strictly equal to the composition of the fraction directly collected over a cycle of the system, as the composition of the fraction contained in the tank evolves with a delay compared to the composition of the fraction directly collected, due to the duration of the renewal of the tank. The renewal of the content of the tank is all the more delayed when the volume of the tank is large. However, this measurement remains sufficiently representative, in particular to allow regulation of the chromatography system. In the present description, the terms “outlet line” and “collection line” have the same meaning. In certain embodiments, the determination of the concentration of at least two species of the mixture to be separated in the fraction collected in the tank is performed by means of at least one detector, preferably a slow detector. As slow detectors, we may mention near infrared spectrometers, infrared spectrometers, Fourier Transform Infrared Spectrometers and Raman spectrometers, in the case where the acquisition of several spectra is necessary to obtain a signal allowing precise measurement, as the total acquisition time may then be substantial. Mention may also be made, in the context of a slow detector, of all nuclear magnetic resonance techniques. According to other embodiments, the concentration of at least two species of the mixture to be separated in the fraction collected in the tank is determined by means of an analytical chromatography system, such as High Performance Liquid Chromatography (HPLC), Ultra Performance Liquid Chromatography (UPLC), Ultra High Pressure Liquid Chromatography (UHPLC), Gas Chromatography (GC). The second system may, in particular, be a chromatography unit, an enzymatic transformation unit, a chemical transformation unit, a distillation unit, a membrane concentration unit, or an evaporation unit. In some embodiments, the second system is an evaporation unit. The installation includes a tank (or “intermediate tank”) supplied by an outlet line. The tank may, therefore, be supplied by the raffinate outlet line, or by the extract outlet line; respective tanks may be supplied by each outlet line (i.e. the outlet line of the raffinate and that of the extract). The tank is supplied with the fraction collected in the outlet line on which it is present. The tank is connected, directly or indirectly, to a second system which is supplied by the fraction contained in the tank. Preferably, the tank has a volume less than the volume of the collected fraction (i.e. the collected fraction which supplies it) over a cycle. In some embodiments, the tank contains a fraction volume equal to the volume of the fraction collected over a period of one to five periods, preferably over three periods. Particularly advantageously, when several purity and/or yield measurements are carried out successively, the tank is not cleaned and/or purged and/or rinsed between these measurements. The mixture to be separated may contain the species already mentioned above. In certain embodiments, the at least two species of the mixture to be separated whose concentration is determined, are monosaccharides. In these embodiments, the extract and the raffinate are enriched with different monosaccharides. In particular, the monosaccharides are chosen from the monosaccarides mentioned above in the description of the first aspect of the invention. In certain embodiments, the at least two species of the mixture to be separated are glucose and fructose. In certain embodiments, the method according to the invention further comprises:the determination, in a node of the system, of the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated;the detection on the history of a characteristic point of high concentration located between the beginning of a step of collecting the raffinate and the end of the following step of collecting the extract;the comparison of the position of the characteristic point of high concentration against a target position;the adjustment of the volume carrying the high concentration characteristic point, modifying the position of the characteristic point of high concentration to bring it closer to its target position. What has been stated above about the characteristic point of high concentration may be applied to the third aspect of the invention. In certain embodiments, the method according to the invention further comprises:the detection on the history of a first characteristic point between the start of the step of collecting the extract and the end of the following step of injecting the mobile phase (also called characteristic point of desorption);the detection on the history of a second characteristic point between the start of the step of injecting the mobile phase and the end of the following step of collecting the raffinate (also called characteristic point of adsorption);the comparison of the position of each of the characteristic points against a respective target position;the adjustment of the volume carrying the first characteristic point and the volume carrying the second characteristic point, modifying the position of the first characteristic point and the second characteristic point to bring them closer to their respective target positions. What has been stated above concerning the characteristic points of adsorption and desorption may be applied to the third aspect of the invention. In certain embodiments, the method according to the invention further comprises:the determination, in a node of the system, of the history of a variable that is representative of the concentration of one or more species contained in the mixture to be separated;the detection on said history of a characteristic point of low concentration between the start of a step of collecting the extract and the end of the following step of collecting the raffinate;the comparison of the position of the characteristic point of low concentration against a target position;the adjustment of the volume carrying the characteristic point of low concentration, modifying the position of the characteristic point of low concentration to bring the position of the characteristic point of low concentration closer to its target position;preferably, the volume of the mobile phase injected per cycle being maintained greater than, or equal to, a minimum limit and/or less than, or equal to, a maximum limit. What has been stated above about the characteristic point of low concentration may be applied to the third aspect of the invention. In some embodiments, the method also includes a step of comparing the measured purity and/or the measured yield with a target purity. If the purity and/or the yield are measured in the extract and in the raffinate, the method may comprise a step of comparing the two measured purities and/or yields with a respective target purity and/or yield. In certain embodiments, the method according to the invention also comprises a step of modifying the volume of mixture to be separated that is injected per cycle according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s)). In certain embodiments, the method according to the invention comprises a step of modifying the volume of mobile phase injected per cycle according to the difference between the measured purity(ies) and the target purity(ies), (and/or the difference between the measured yield(s) and the target yield(s)). In certain embodiments, the volume of mixture injected per cycle and the volume of mobile phase injected per cycle are modified jointly according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s)). In certain embodiments, the method comprises a step of defining the target position of the characteristic point(s) according to the difference between the measured purity(ies) and the target purity(ies) (and/or the difference between the measured yield(s) and the target yield(s)). It may be the definition of the target position of the characteristic point of high concentration and/or the definition of the target position of the characteristic point of adsorption and/or that of the characteristic point of desorption and/or that of the characteristic point of low concentration. What has been stated above with regard to the comparison of a measured purity and/or yield with a target purity and/or a yield, of the modification, according to this comparison, of the volume of mixture injected and the mobile load volume, and the definition, according to this comparison, of the target position of the characteristic point, may be applied to the third aspect of the invention. Another object of the invention consists of a computer program comprising program code instructions for executing the steps of the method according to the third aspect of the invention when said program is executed on a computer. The invention also relates to a computer-readable storage medium on which a computer program as defined above is recorded. The invention also relates to a system comprising a processor coupled to a memory on which a computer program as defined above is recorded. Said system may also include the chromatographic separation system as described above or may only be a control system, connected to the separation system and distinct from it. EXAMPLES The following examples illustrate the invention without limiting it. In Examples 1 to 5 which follow, a chromatographic simulation model was used with the following parameters:species present in the mixture to be separated: glucose polymers of an order greater than, or equal to, 2, glucose and fructose;stationary phase: resin XA2004/30 Ca from Novasep;mobile phase: water;elution temperature: between 55° C. and 65° C. These concentration graphs representing a loading pulse, saturation at high concentration and saturation at low concentration, in a column 2 meters long and 8.5 cm in diameter, at a flow rate of 20 mL/min, are represented respectively inFIGS.5.A,5.B and5.C. These data make it possible to reconstruct the model used, using any chromatographic simulation software, using for example the methods described in the manualPreparative Chromatography of Fine Chemicals and Pharmaceutical Agents, Henner Schmidt-Traub, Wiley-VCH, ISBN-13 978-3-527-30643-5. The method applied in Examples 1, 2, 4 and 5 is an SSMB4 with a total column height of 8 meters. The method applied in Example 3 is an SMB with a total column height of 8 meters. In Examples 6 to 7 which follow, a real chromatographic separation was carried out on a pilot, with the following parameters:species present in the mixture to be separated: glucose polymers of order greater than or equal to 2, glucose and fructose;stationary phase: resin XA2004/30 Ca from Novasep;mobile phase: water;elution temperature: between 55° C. and 65° C.;the pilot is made up of 4 columns 2 meters long and 8.5 cm in diameter;the product and eluent flow rates are between 20 and 30 mL/min;the method applied is an SSMB with a total column height of 8 meters. Example 1 A simulation of the chromatographic method as described above is carried out. Between cycle No. 1 and cycle No. 10, the system is stabilized, the volumes of the different areas are fixed and kept constant. The volume of the injected mobile phase is 0.18 BV (bed volume). From cycle No. 10, the areas are regulated with target positions of characteristic points located at +0.17 for area4(deviation of the target position from the characteristic point of adsorption in volume divided by the cycle volume, relative to the mean eluent injection position), and −0.17 for area1(deviation from the target position of the characteristic point of desorption in volume divided by the cycle volume, relative to the mean position of eluent injection). This corresponds to a target position of the characteristic point of low concentration located on the mean eluent injection point. A comparison is then made between a method regulated using the two characteristic points of adsorption and desorption, without limitation of volume of mobile phase (as described in the document WO 2007/101944), and a method regulated using the characteristic point of low concentration according to the invention in which a maximum volume threshold has been imposed. The results are summarized inFIGS.6,7,8and9. It may be seen that when the method is regulated using the two characteristic points of adsorption and desorption, wherein the two characteristic points each reach their target position. It is the same for the characteristic point of low concentration. In order to achieve these characteristic point position objectives, the mobile phase volume is increased to 0.27 BV. In the second case, the mobile phase volume is limited to 0.22 BV and the chromatographic method is regulated according to the invention using the characteristic point of low concentration. The characteristic point of low concentration remains unchanged. It is found that the target position of the point of low concentration is reached, the characteristic point reaches the position of the eluent injection point. However, the target positions of the characteristic points of adsorption and desorption are not reached. The mobile phase volume required to reach these target positions has not been reached and has been limited to the predefined maximum value. The characteristic points of adsorption and desorption are located at +0.143 and −0.143 relative to the mean position of eluent injection (in volume divided by the cycle volume), respectively. The absolute values of the deviations between each of the characteristic points of adsorption and desorption and their target position are identical and the sum of the deviations is zero. Thus, the method according to the invention makes it possible to avoid exceeding a high limit of the volume of mobile phase used, which does not allow a method regulated by taking into account two characteristic points of adsorption and desorption. Example 2 A chromatographic method simulation as described above is carried out. Between cycle No. 1 and cycle No. 10, the system is stabilized, the volumes of the different areas are fixed and kept constant. The mobile phase volume is 0.25 BV. From cycle No. 10, the areas are regulated with target positions of characteristic points located at +0.10 for area4(position of the characteristic point of adsorption in volume divided by the cycle volume, relative to the mean position of the eluent injection) and −0.10 for area1(position of the characteristic point of desorption in volume divided by the cycle volume, relative to the mean position of eluent injection). This corresponds to a target position of the characteristic point of low concentration located at the mean eluent injection point. A comparison is then made between a method regulated using the two characteristic points of adsorption and desorption, without limitation of volume of mobile phase (as described in the document WO 2007/101944), and a method regulated using the characteristic point of low concentration according to the invention in which a minimum volume threshold has been imposed. The results are summarized inFIGS.10,11,12and13. It may be seen that when the method is regulated using the two characteristic points of adsorption and desorption, the two characteristic points each reach their target position (at +0.10 and −0.10). It is the same for the characteristic point of low concentration. In order to achieve these characteristic point position objectives, the mobile phase volume is reduced to 0.18 BV. In the second case, the mobile phase volume is minimized to 0.20 and the chromatographic method is regulated according to the invention using the characteristic point of low concentration. The characteristic point of low concentration remains unchanged. It may be seen that the target position of the point of low concentration is reached at the eluent injection point. However, the target positions of the characteristic adsorption and desorption points are not reached. The mobile phase volume to reach these target positions has not been reached and has been limited to the predefined minimum value. The characteristic points of adsorption and desorption are located at +0.12 and −0.12 relative to the mean position of eluent injection (in volume divided by the volume of the cycle). The differences between each of the characteristic points of adsorption and desorption and their target position are identical. Thus, the method according to the invention makes it possible not to exceed a low limit of the volume of mobile phase used, which does not allow a method regulated by taking into account two characteristic points of adsorption and desorption. Example 3 A simulation of the chromatographic method as described above is carried out. Measurements of purity and of fructose yield in the extract and raffinate fraction are performed while these fractions are collected in tanks placed at the chromatography outlet and with continuous drawing off from each of them so that the mean volume in the tanks represents three periods Between cycle No. 1 and cycle No. 10, the system is stabilized, the volumes of the different areas are fixed and kept constant. The volume of mixture to be separated (load) injected is 0.175 BV. The yield is 90.3% and the purity is 84.9%. The target position of the characteristic point of low concentration is located on the mean eluent injection point. From cycle No. 10, the areas as well as the volume of charge injected are regulated with objectives of a purity of 90% and a yield of 85% for the extract fraction. The mobile phase volume is kept constant at the value of +0.2 BV by using the regulation using the characteristic point of low concentration of the method according to the invention. The results are summarized inFIG.14. The characteristic point of low concentration is regulated on the mean position of injection of the eluent. The volume of the mobile phase is thus kept constant and controlled. The yield and purity objectives are achieved and the volume of charge injected is increased to +0.179 BV. Example 4 A simulation of the chromatographic method as described above is carried out. Purity and fructose yield measurements in the extract fraction are carried out. Between cycle No. 1 and cycle No. 10, the system is stabilized, the volumes of the different areas are fixed and kept constant. The volume of mixture to be separated (load) injected is 0.175 BV. The yield is 90.3% and the purity is 84.9%. The mobile phase volume is constant at the value of +0.2 BV. The target position of the characteristic point of low concentration is located on the mean eluent injection point. From cycle No. 10, the method is regulated using the characteristic point of low concentration according to the method of the invention, with purity and yield targets of 90% and 85% respectively and a volume of charge injected is kept constant at the value of +0.175 BV. The results are summarized inFIG.15. The characteristic point of low concentration is regulated at the mean position of the eluent injection. The volume of the mobile phase is thus controlled. The yield and purity objectives are achieved and the volume of mobile phase is reduced to +0.194 BV. Example 5 A chromatographic method simulation as described above is carried out. Purity and fructose yield measurements in the extract fraction are carried out. The target position of the characteristic point of low concentration is optimized according to the desired purity and yield. In a first test, the target position of the characteristic point of low concentration is fixed at −0.1 BV (at the extract) relative to the mean position of injection of the eluent, while the regulation described in example 4 is applied. The results are summarized inFIG.16. A mobile phase volume of +0.198 BV is obtained. In a second test, the target position of the characteristic point of low concentration is fixed at +0.1 BV (towards the raffinate) relative to the mean position of injection of the eluent, and the regulation described in example 4 is applied. The results are summarized inFIG.17. A volume of mobile phase is obtained of +0.194 BV. It is thus possible to position the characteristic point of low concentration so as to obtain the minimum volume of mobile phase. With a characteristic point positioned at +0.04 BV towards the raffinate relative to the mean position of injection of the eluent, the minimum mobile phase volume of this separation is obtained (at a value of +0.193 BV) with an injected load volume fixed at +0.175 BV. The results are summarized inFIG.18. Example 6 An experimental chromatographic test as described above is carried out. A chromatographic method is used to treat a mixture to be separated containing glucose, fructose and a small amount of glucose polymer (with a degree of polymerization of 2 (DP2), 3 (DP3) and above). A densimeter and a polarimeter are calibrated for the two species to be separated (glucose and fructose), as a function of the temperature and as a function of the concentration of the species. The results of the polarimeter calibration are summarized inFIGS.19and20. Two histories are then measured using the previously calibrated densimeter and polarimeter positioned in line. FIGS.1and2illustrate the example because from these histories, on a cycle, the signal from each detector is integrated on the portion of the history corresponding to a fraction collection, for each fraction (the extract and the raffinate), in order to determine a “mean” density and a “mean” polarity for each fraction collected. The glucose and the mixture of glucose polymers are dextrorotatory, i.e. the angle of rotation induced by the glucose and the glucose polymers measured by a polarimeter is positive. Fructose is levorotatory, i.e. the angle of rotation induced by fructose measured by a polarimeter is negative. The angle of rotation measured by a polarimeter during a measurement on a mixture is the sum of the angles of rotation induced by the different species contained in the mixture in a unitary manner. Thus, we can establish the following equation: α=α(T)Glucose·CGlucose+α(T)Fructose·CFructose, in which:α is the angle of the glucose/fructose mixture measured by the polarimeter,α(T) is the angle of rotation of the species at the temperature applied to the measurement, obtained during the calibration of the polarimeter, andC is the concentration of the species. Measuring the density of a mixture of glucose and fructose with a densimeter as a function of the concentrations of each sugar meets the following equation: Density=β(T)·(CGlucose·CFructose)+DensityEluent(T), in which:Density is the density measured by the densimeter,DensityEluent(T) is the density of the eluent at the temperature of the measurement,β(T) is the density factor of glucose and fructose at the temperature applied to the measurement, this factor being identical for pure glucose and fructose at a given temperature, andC is the concentration of the species. These two equations allow, from the mean density and angle of rotation characterizing each fraction, the calculation, using the Gauss pivot method, of the concentration of glucose and fructose in the mixture. The purity of each fraction of glucose and fructose may then be calculated from these concentrations. This method allows the glucose and fructose concentrations of a collected fraction to be measured relatively accurately. The purities of the extract and of the raffinate may also be corrected at the margin of a corrective term depending on the distribution of other minority impurities such as glucose polymers between these two collected fractions. Example 7 An experimental chromatographic test as described above is carried out. Purity and fructose yield measurements in the extract fraction are carried out. Between cycle No. 1 and cycle No. 20, the system is stabilized and regulated. The volume of mixture to be separated (load) injected is 0.15 BV. The yield is 90% and the purity is 90%. The target position of the characteristic point of low concentration is located on the mean eluent injection point. From cycle No. 20, the areas as well as the volume of load injected are regulated with objectives of a purity of 86% and a yield of 92%. The mobile phase volume is kept constant at the value of +0.18 BV using the regulation using the characteristic point of low concentration of the method according to the invention. From cycle No. 60, oscillations on the concentration of the injected load were made, wherein the control method maintained the performance of the system. The results are summarized inFIG.21. The characteristic point of low concentration is regulated on the mean position of injection of the eluent. The volume of the mobile phase is thus kept constant and controlled. The yield and purity objectives are met and the volume of charge injected is increased to +0.16 BV.
106,042
11857893
DETAILED DESCRIPTION Tailings may contain primarily both hydrocarbons and solids, for example mineral material, such as rock, sand, silt and clay. Because of the hydrocarbon contamination of the tailings stored in tailings ponds, the process below is particularly useful in reclaiming these ponds by removing the hydrocarbon contamination, and using the decontaminated tailings to return land to its natural state. However, the apparatus and method may also be applied to any fluid having components to be separated, such as an oil-water mixture, or oil-water-solid mixture, and oil including hydrocarbons. In some embodiments the apparatus and method may treat emulsions, for example directly off of the field bypassing a free water knock out. In some embodiments feed is supplied from a tank farm on site. The fluid to be treated may comprise tailings from deep within a tailings pond, without dilution, so long as the tailings are pumpable. If the tailings are not pumpable, they may be made pumpable by dilution with water. Fluid from a skim oil tank may be treated. In general, the apparatus and method disclosed herein may be used to separate immiscible fluids such as oil and water. FIGS.1and2show a fluid treatment system100including a fluid treatment separator168(FIG.2) having a separation chamber102having an oil outlet106and a water chamber104having a water outlet108below the height of the oil outlet106. The fluid treatment separator provides an apparatus and method of fluid treatment of a feed of oil, water and solid. A fluid passage110connects between the separation and water chambers. The fluid passage110is below the height of the water outlet. As shown inFIG.1, the separation and water chambers102,104are sections of a tank of the fluid treatment separator168having a top170and bottom172(FIG.2). The separation and water chambers102,104are divided by a partition134in the tank of the fluid treatment separator168. The fluid passage110is defined by an opening between a bottom136of the partition134and the bottom172of the tank of the fluid treatment separator168. The fluid passage allows water and other liquids to travel below the partition between the two chambers. There is a second opening between a top138of the partition134and the top170of the tank of the fluid treatment separator168which allows gases to travel above the partition between the two chambers. A centrifuge flow separator112is positioned inside the separation chamber102downstream of a mixed fluid inlet142. The mixed fluid inlet142is in fluid connection with the centrifuge flow separator112for providing mixed fluids to the separation chamber102. A centrifuge flow diffuser118is connected to the mixed fluid inlet142and is oriented to direct mixed fluids into the centrifuge flow separator112. The centrifuge flow separator112has an upper opening114and a lower opening116. As shown inFIG.2, the upper opening114has an area smaller than the lower opening116. The oil outlet106includes an oil weir120, and the height of the oil outlet106is defined by a height of a top surface124of the oil weir120. The water outlet108includes a water weir122and the height of the water outlet108is defined by a height of a top surface126of the water weir122. The centrifuge flow diffuser118is positioned at the lower opening116of the centrifuge flow separator112. As shown inFIG.2, the centrifuge flow separator112is a centrifuge cone and the centrifuge flow diffuser118is a ring diffuser.FIG.4shows the cone-shape chamber112to enhance centrifuge acceleration. In other embodiments, a standard cylinder or similar component having a circular or oval cross-section may also be used instead of a centrifuge cone. In the case of low oil-content waters, cones or cylinders of different diameters can be used as the centrifuge flow separator to build a suitable oil layer thickness to avoid excess water carryover while still maintaining an acceptable downward flow velocity with respect to vessel cross sectional area. Various designs of centrifuge flow diffuser may be used in place of a diffuser ring. In another embodiment, the centrifuge flow diffuser may be any mechanism that orients the inlet flow to create a centrifugal flow pattern within the cone or cylinder. This will cause the air and oil to concentrate in the center while the clean water migrates to the outside within the cylinder and cone boundary. As shown inFIG.1, there is a phase separator128upstream of the ring diffuser118for mixing fluids prior to being diffused into the centrifuge cone112through the ring diffuser118. The phase separator128includes a pump140and a port22A for admitting gas into the phase separator. The gas may be air. A flocculant source130and a flocculant injection quill132are configured to add flocculant upstream of the phase separator128to introduce flocculants into the fluid stream entering the phase separator128. Flow stabilization vanes160(FIG.2) are arranged in the separation chamber adjacent to the upper opening114of the centrifuge cone112. A density-float sensor144is also provided adjacent to the upper opening114of the centrifuge cone112. Referring toFIG.5, the flow stabilizer vanes160are shown. The vanes160stop the centrifugal flow to allow further phase separation to happen. The air/gas releases from the working surface to the atmosphere at the top of the tank of the fluid treatment separator168. The oil droplet froth overflows the oil-weir120and flows out of the oil outlet nozzle106. The water condenses to go down outside of the cone and displaces the water in the water column104to overflow the water-weir122and flow out of water outlet nozzle108. As shown inFIG.1, a flocculant pump146is used to pump flocculant into the system. There are oil, water and solid pumps148,150and152, respectively, that discharge oil, water and solids from the system once those substances exit the oil outlet106, the water outlet108and solid outlet158, respectively. The flocculant may be, for example, an anionic polymer. Both cationic and anionic polymers can be used as flocculants. Anionic polymers for use as flocculants aids are preferred. In certain embodiments, the fluid treatment system100may operate as follows. The fluid treatment separator168may be described as a buoyancy-enhanced flotation cell or BEFC. The operation of the buoyancy-enhanced flotation cell is conducted by supplying a feed into the flotation cell168, which is specially designed to enhance the buoyancy of oil droplets to better disengage the linkage between water and oil droplets and at the same time to use a flocculant polymer and centrifugal g-force effect to demulsify the emulsion state of water and fine solid particles. The feed, having an oil concentration and fine solid content, is pumped through a number of phase separators, where the feed turns into froth, thanks to its design induced pressure-drop, which induces the ambient air or blanket gas into the working fluid in an air-liquid very fine mixing chamber. The frothed working fluid flows into the flotation cell168, which divides into 2 interconnected vessels: the water chamber, or water column,104and the separation chamber, or separation column,102, the two columns being separated by the partition wall134. This design allows separation by three different densities having the following movements:a. Less density than water: upward movement in the separation column102.b. Higher density than water: downward movement in the separation column102.c. Equal density to the water: overflows out through water weir of water column104. In the separation column102, the working fluid goes through the ring-centrifuge diffuser118to create a circulation flow inside the centrifuge cone-shape chamber112to produce the centrifuge acceleration, where the oil droplets in bubbles get higher buoyancy and move upward, whereas fine particles are pulled by g-forces and move downward. The oil froth is collected at the oil weir120after passing the flow-stabilizing vanes160at the top of the separation column102, and then flows out at oil outlet nozzle106. The clean water is separated at separation column102, moves to water column104, is collected at water weir122of water column, then overflows out at water outlet nozzle108. The cumulative fine solid particles180(FIG.2) are collected at the bottom of BEFC168, then discharged via solid outlet nozzle158. The water column and the separation column are adjacent to avoid high underflow velocities with respect to vessel cross section that can affect oil removal. The 3-phase oil-water-solid separation is occurring in the BEFC continuously and automatically with large variation of oil and solid content in the feed. The feed is supplied from a phase separator that uses energy from fluid passing through a restriction to affect a phase separation. The feed comprises a foam mixture of oil, water and gas in the froth and flocculated fine solid particles. The flow rate and pressure of the feed into the flotation cell is controlled to maintain the working fluid centrifugal flow in the separation column of the flotation cell within the predetermined range to ensure the sufficient retention time for maximizing the phase separation. The working fluid flowrate into the flotation cell is monitored by sensing the centrifugal force of working fluid in the flotation cell. The centrifugal pressure is sensed at a top of centrifuge cone of the flotation cell. The oil phase is removed from the flotation cell over a weir after being stabilized from the centrifugal flow. This allows time for the water to drop and settle down from the high dynamic centrifuge flow with oil droplets. The feed is supplied into the flotation cell at the bottom of the centrifuge cone. The feed is injected into the cone112in the form of circulation flow using the ring centrifuge diffuser118. The ring centrifuge diffuser118rotates under the supplied fluid energy to provide the centrifugal flow acceleration. As shown inFIG.6, the diffuser ring118has a central open for receiving mixed fluid, which is connected to radially extending pipes156that connect to a number of outlets154. The outlets154are oriented to direct flow perpendicularly to the circumference of the ring diffuser. The outlet can be oriented to direct flow in a clockwise or counterclockwise direction. Different numbers of fluid outlets may be used. Fluid flow in the diffuser ring118is shown with the arrows inFIG.6. In some embodiments there is a method of fluid treatment of a feed comprising oil, fine solid particles and water. The feed is supplied into the buoyancy-enhanced flotation cell (BEFC)168. The feed has an oil and solid concentration. The flotation cell168has a 2-interconnected-vessel system, one directly connected with the inlet is the separation column102and the other one is the water column104. The conical bottom outlet of the BEFC168is the cumulative solid discharge158. The separation column102has the centrifuge ring diffuser118and the centrifuge cone112, which produce the feed circulation flow movement within the centrifuge cone. The centrifugal acceleration creates g-force to separate the flocculated fine solid particles downward to the bottom solid outlet nozzle158and the centrifuge flow separates an oil phase from the working fluid where it moves closer the cone's rotational center line. At the top of the cone112, the centrifuge flow is stabilized by the vanes160and the oil phase froth becomes buoyancy-enhanced and will overflow the oil-weir120, which is higher than the water-weir122, and then can be removed from the BECF168through the oil outlet nozzle106. The separated water will displace water in the water column104, and then overflow through water-weir122to the water outlet nozzle108. The fluid treatment process may be controlled through the flow rate and pressure of the feed stream to attain the optimal centrifuge effect in the separation column of BEFC168within a large range of variations in the oil and solid concentration of the feed. Polymer flocculant is injected into the feed flow after the motive pump140, but before the phase separator128to well mix with fine solid particles in the mixing chamber of phase separator128to make them flocculated when entering the BEFC168. The feed is supplied through the phase separator128that uses energy from fluid passing through a restriction to create bubbles to demulsify the emulsion for improving the phase separation. The feed comprises a foam mixture of oil, water and gas or air. The BEFC168is designed in the shape of 2-interconnected vessels, one being the separation column102, where the feed stream comes into the BEFC and is equipped with centrifuge assembly and to collect the oil froth which over-flows the oil-weir120at the top of the separation column. The water column104allows for the collection of displaced water from the separation column102which over-flows the water-weir122at the top of the water column. The BEFC168inFIG.2is designed in the shape of conical bottom for collecting out the cumulative flocculated fine solid particles. The BEFC conical bottom solid discharge nozzle158is designed with solid level sensor178to open the solid discharge valve when the solid level reaches the level set-point. The centrifuge-ring diffuser118(FIG.6) is designed to create the circulation flow inside the centrifuge cone to produce the g-force for improving the separation as shown inFIG.7. The separation column centrifuge system of the BEFC168includes the centrifuge cone112(FIG.4) to create the circulation flow inside the centrifuge cone to produce the g-force for improving the separation as shown inFIG.7. The separation column centrifuge system of BEFC168also includes the centrifuge-flow stabilizer vanes160(FIG.5) to slow and to stop the centrifuge flow to create the oil-water phase separation at the oil-weir height level, to give separated water time to go down through the path outside of the centrifuge cone. The centrifugal circulation flow creates g-force separation and also enhances the buoyancy of the oil froth. The resulting oil froth phase is removed from the flotation cell over the oil-weir120. The feed is supplied into the flotation cell168at the bottom of the centrifuge cone112. The feed is at least partially separated across the release from centrifuge cone112due to the density difference with the water column. The less-dense-than-water objects move upward, the more-dense-than-water objects move downward, and the separated water displaces the water in the water column. As shown in the embodiment inFIG.8, the fluid treatment system includes a second flotation cell BEFC provided with an inlet of feed connected to water outlet nozzle108, to separate more oil and solid contaminants after the first BEFC168. The process disclosed inFIG.1may be repeated by supplying fluid removed from the first BEFC168into a second BEFC268, which has the same structure of the first BEFC168. A second oil froth phase is removed from oil-weir at the top of separation column of second BEFC268. The principles of operation of the second BEFC are the same as the first BEFC168. The fluid removed from the first BEFC168and supplied into the second BEFC268may first be passed through a second phase separator228, which uses energy from fluid passing through a restriction to affect a phase separation. The phase separator agitates the fluid removed from the flotation cell in the presence of a gas to cause the fluid to foam. The details of each of the first and second phase separators128,228and the first and second BEFCs168,268, may be the same as shown inFIGS.1-3, and the structure of those items are not repeated inFIG.8. When used with more than one BEFC168in series, embodiments of the apparatus and method described may affect a cascading control philosophy to ensure optimal operation of an entire system of fluid treatment cells despite variations in feed oil concentration during treatment. Such variations are inevitable when dealing with tailings feeds, and are capable of upsetting an entire separation system operated by conventional means. This is because conventional multi-separator fluid treatment devices are either calibrated to treat feeds that have a constant oil concentration or are run passively with each tank draining by gravity into a subsequent tank. In the separation of bitumen from tailings and in other cases it may be difficult or impossible to directly monitor input oil concentration as oil is adsorbed tightly to bits of clay and mud in a type of suspension and is thus difficult to measure on the fly. Thus, embodiments of the disclosed methods and apparatuses are advantageous in that they indirectly measure changes in feed oil concentration by monitoring working fluid levels in each BEFC and automatically adjusting the flux of working fluid and solids through each BEFC to maintain a relatively constant and predetermined working fluid level in each flotation cell. The number and size of phase separators may be selected independently from the vessel sizing. Vessel cross sectional area controls the amount of flow into the flotation cell. The number of phase separators will be determined based on the required process turn down ratio. For example, two phase separators may provide for a 2:1 turn down ratio. As shown inFIG.1, near the top of the tank of the fluid treatment separator168, there is an oil-water interface surface. A working separation column monitor144is sensitive to oil-water interface surface variations in the separation column. The oil-water interface monitoring device144is placed at the top of the centrifuge cone112to monitor the performance of the separation column. The oil-water interface level monitor may be a density-float sensor. The density-flow sensor that measures the density of oil froth can be used to control both the motive pump (feed pump) and underflow pump. By speeding up or slowing down these pumps will in turn affect the thickness of the oil froth layer that forms in the top of the vessel. For example, too high a froth density which is indicative of too much water in the oil froth will result in the underflow pump speeding up in relation to the motive pump (feed pump) to draw down the oil/water interface within the reactor, reducing the water carryover with oil. Too thick an oil froth layer in the reactor will result in the underflow slowing down to force more oil froth over the weir, reducing the thickness of the oil froth layer. As shown inFIG.3, the phase separator128may in operation use energy from fluid passing through a restriction18A to affect a phase separation, for example to strip oil from solids to produce an oil phase mixed with water and solids that may be dispersed on the surface of the working fluid. The oil phase may also contain water and solids, but upon dispersal on the surface of the working fluid, at least some of the water and solids, having been separated from the oil phase with the phase separator, will enter the working fluid of the flotation cell BEFC168. Embodiments of the apparatuses described are able to self-balance on feed entry of oil slugs and surges. Thus, when the inflow has a high oil fraction, more oil spills over the weir and the pumps on the outflow are controlled to reduce outflow of water to keep the water (working fluid) level within a predetermined range. When the inflow has a high-water fraction, a small amount of oil spills over the weir, and a relatively larger outflow of water is maintained by the weir height difference Δh (FIG.1). In one example, the apparatus was able to accommodate for oil percentage fluctuations in the feed of between 1 and 10%, although almost any magnitude of fluctuation may be accommodated. In some embodiments, the process control system for the BEFC168is very simple. The more flow rate and more pressure of feed, the dynamic of working fluid is increased, which means more centrifuge acceleration, more g-force and more separation occurs. The inlet feed flow is controlled by the pump140, but the separated oil and water automatically overflow the weirs to be transferred further by motive pumps. A solid level sensor178is equipped at the solid outlet158to open the solid discharge valve when the accumulated solid is higher than a defined set point. An anionic polymer flocculant additive system including the flocculant source130and the flocculant pump146is used to inject flocculant into the feed through the injection quill132installed upstream of the phase separator(s)128. In the phase separator128, the feed will be well mixed with flocculant and make the fine solid particles flocculated when entering the BEFC. Referring toFIG.3, the phase separator128may comprise a conduit, a mixing chamber20A, and the port22A. The motive pump140(FIG.1) having an inlet and an outlet may also be part of the phase separator. The inlet may be connected to a source of fluid having components to be separated. A conduit may be connected to the outlet of the motive pump. The conduit may have a discharge19A (FIG.1). A restriction18A in the conduit may form a nozzle through which the fluid flows when the motive pump is operated. The restriction18A may divide the conduit into an upstream end15A between the motive pump and nozzle and a downstream end17A that terminates at the discharge19A. The conduit may have a mixing chamber20A downstream of the nozzle and a port22A for admission of gas into the mixing chamber20A for example in an initial portion of the mixing chamber20A, to cause the feed to foam. The motive pump140, restriction18A, mixing chamber20A and port22A together comprise the phase separator128. By mixing air or blanket gas with the feed in a turbulent manner, the feed may be foamed, which facilitates removal of the oil phase from the surface of the working fluid. Induction of air/gas may produce bubbles in the stream that attach to each droplet of oil to remove the oil from the water or solid phases. In the example shown, the mixing chamber20A may terminate downstream at a transition26A in the conduit17A to a larger diameter portion of the conduit. The mixing chamber20A may have a length to internal diameter ratio of at least 20:1 or 40:1, preferably in the range 50:1 to 60:1. Improved separation of the fluid components has been found to occur as the length to internal diameter of the mixing chamber20A increases from 20:1 to 60:1. For example, by comparison with a conventional jet pump under the same testing conditions, a jet separator of the type disclosed here with a mixing chamber having a 40:1 length to diameter ratio (actual diameter; 43 mm) had an approximately 40% higher mass production of froth during treatment of oil sands tailings. The conventional jet pump had a mixing chamber with a length to diameter ratio of approximately 5:1 and actual diameter 44 mm. By same test conditions is meant: same feed material, same diameter piping on either side of the jet separator/jet pump, same flow rate and same pressure. The only difference, other than the minor difference in mixing chamber diameter between the two set ups, was the replacement of the jet separator described here with a conventional jet pump. It has been found that improved performance in terms of froth generation is obtained from a jet separator when the mixing chamber has a length to diameter ratio larger than a conventional jet pump, which generally have a mixing chamber with a length to diameter ratio of less than 20:1. Large improvements in the effectiveness of the mixing chamber20A have not been measured for length to internal diameter ratios greater than 60:1. The mixing chamber20A preferably has constant internal diameter along the length of the mixing chamber20A. When the mixing chamber20A does not have constant internal diameter, the internal diameter of the mixing chamber20A, for the purpose of calculating the length to internal diameter ratio, may be the mean internal diameter. The internal diameter of the mixing chamber20A may be selected so that the fluid exiting the restriction18A undergoes turbulence and collision with all parts of the internal wall of the mixing chamber20A. The mixing chamber20A may need only begin after the fluid exiting the restriction18A has expanded sufficiently to contact the walls of the mixing chamber20A. Although the phase separator may not pump anything other than air from the port22A, it may have the general design of a jet pump in terms of the relationship of the size of the mixing chamber to the restriction. In one embodiment, the phase separator pumps natural gas instead of air through port22A. For example, the phase separator may induce entry, into the stream, of gas such as natural gas or nitrogen from the gas blanket (not shown) that may be provided over the components of the apparatus described herein during use. A gas blanket is conventionally set up using piping to all tanks and lines to exclude oxygen and ensure a non-explosive atmosphere. The port22A may be located downstream of the restriction18A and before the mixing chamber20A. The conduit immediately after the restriction18A should have a diameter sufficient to accommodate the jet exiting the restriction18A. The mixing chamber20A may have an internal diameter that is less than the internal diameter of the conduit15A (before the restriction18A) and greater than the diameter of the restriction18A. Hence, if the conduit15A is a 16-inch pipe, and the restriction is 6 inches, then the mixing chamber may have an internal diameter between 6 inches and 16 inches, for example 12 inches. For a 12-inch internal diameter mixing chamber20A, the mixing chamber20A may be 40 feet long. For treatment of tailings, the diameter of the restriction18A may be selected to provide a pressure in the conduit15A before the restriction18A of 75 psi to 150 psi. The conduit14A after the transition26A may have an internal diameter equal to the internal diameter of the upstream portion15A of the conduit. The feed or fluid having components to be treated may comprise solids such as tailings from a tailings pond, such as a tailings pond at a heavy oil mining facility. In an example, the fluid source may comprise a first submersible pump connected to pump fluid from a first portion of a tailings pond and a second submersible pump connected to pump fluid from a second portion of a tailing pond. The pumps respectively have outlets connected to the inlet of the motive pump140. The 2nd pump may be deeper in the tailings pond than the 1st pump so that the weight percent of solids of fluid in the first portion of the tailings pond is less than the weight percent of solids of fluid in the second portion of the tailings pond. The port22A preferably comprises a valve, which may be controlled manually or automatically such as by a controller. When the port22A is not open, a vacuum created in the conduit downstream of the pump may cause vibration within the pipe and poor separation of the fluid components. When the port22A is opened sufficiently for the vibration to stop, the fluid components may be agitated and a phase separation may occur within the fluid so that oil may be stripped from solids. Gas, for example air, introduced through the port22A may become entrained with the fluid components and tends to adhere to oil in the fluid. Thus, the phase separator agitates the fluid removed from the flotation cell in the presence of a gas to cause the fluid to foam. The discharge19A (FIG.1) is disposed to discharge treated fluid into the BEFC168. In some embodiments, other separation apparatus may be used instead of or in addition to the BEFC168, such as a centrifuge, hydro-cyclone or another fluid treatment apparatus comprising an additional motive pump, restriction18A, mixing chamber20A and port22A. Any number of additional such secondary apparatus may be used as necessary to affect an adequate phase separation. Thus, the fluid treatment system may comprise a series of connected combinations of motive pump10A, restriction18A, mixing chamber20A and port22A connected together between a source of fluid16and may include multiple BEFCs168. Fluid supplied into the fluid treatment separator168should be mixed fluid and supplied to the separator under motive force. A cumulative slightly wet solid phase may be extracted from conical base of BEFC168and then pumped further to a solid collection bay. The wet solids may be allowed to dry or dried in various ways, such as with the addition of heat, but may also be allowed to drain. Once dried, the solids may be returned to a reclaimed mine site or subject to further processing, for example to extract minerals from the solids. Exemplary minerals that may be extracted include gold and titanium. Oil may be extracted from the BEFC168for example by spillover from the oil weir120. The oil may be delivered to a pipeline or subject to further processing. The disclosed fluid treatment devices may operate by pumping fluid using the motive pump140through the restriction18A in the conduit14A into the mixing chamber20A downstream of the restriction18A. Gas may be added into the fluid downstream of the restriction18A in an initial portion of the mixing chamber20A. The fluid is discharged from the conduit14A into the flotation tank168. A standard jet pump may be used as a phase separator prior to the flotation tank168. The fluid having components to be separated, such as tailings, may be supplied to the mixing chamber20A through the port22A from a source of the fluid such as from one of the submersible pumps. Motive fluid to be pumped by pump140may be water, for example supplied from a portion of a tailings pond through other pumps. The port22A may comprise one or more openings in the conduit downstream of the restriction18A but upstream of the mixing chamber20A. If more than one opening is used, gas, for example air, may be supplied through one opening and the fluid to be treated through another opening. As many openings as required may be used. Flow through the port22A may be regulated by a valve or valves. The term opening may be used here to denote a port. While air may be injected simply through the valve, a further conduit leading to a source of the fluid that is being treated may be required for the delivery of fluid to the port22A. Referring toFIG.7, there is shown the cross-section of the centrifuge cone112, showing the phase distribution under the centrifugal effect: the oil phase162is at the center line of the cone, and water phase164is in the middle and solid phase166is furthest out. Embodiments of the apparatus described herein may be portable, for example if loaded as a module on a skid (not shown) with or without wheels, for transport to a work site. The apparatus may include a housing (not shown) such as a shed to protect system components from the elements. Oil removed from the BEFC or plural BEFCs may be combined and stored in a collection vessel (not shown), which may itself supply an on-site oil treater or disc stack centrifuge, for example. Embodiments of the methods and apparatuses disclosed herein may be implemented with little or no chemical and heat addition, and thus are expected to reduce the costs of implementation and make the process more environmentally friendly. In fact, the apparatuses and methods may be run at ambient temperature. Hydrocarbons separated during the process may be used to power the apparatus. Fluid entering the apparatus may have for example 10 000 ppm oil, and when finished the oil percentage in working fluids (water) may be 50 ppm or less. In demonstrations, each pass through a BEFC has been found to remove 80-95% of residual oil in the feed, although higher or lower removal percentages may be achieved. Embodiments of the apparatuses and methods disclosed have been found to reduce the amount of oil and water sent for disposal. Although not intended to be limiting, various applications of the apparatuses and methods disclosed herein include treating fluids used in water/polymer flooding to facilitate water disposal, water recovery or reuse, treating fluids used in in-situ heavy oil batteries to facilitate deep well brine injection, treating fluids intended for third party disposal wells to reduce oil injection into disposal wells as well as enhance oil and water separation to facilitate water deep well injection and reduce contaminated solids for disposal to extend the life of the well, and treating fluids from enhanced oil recovery to achieve a higher percentage of oil that can be sent to treatment resulting in increased sales oil production. Applications also include treatment of fluids from oil sands mining, heavy oil water disposal streams, and SAGD. The apparatuses disclosed herein may include a Fugitive Emission Management system. Benefits of embodiments of the apparatus and methods may include, inter alia, the following. Oil may be extracted from an oily water/slurry at a low operating cost as the system processes the waste stream at ambient temperatures. A substantial reduction in chemical consumption for the client may be achieved. The self-balancing aspect of the apparatus and method allows handling of wide fluctuations of oil content with little effect on process efficiency or effluent quality which equates to less down time. The system may be simple and very robust, reducing maintenance issues. The system and method may be configured for a new installation or inserted into the clients existing infrastructure in most cases. The retention of oil from existing production may be increased and the percentage of oil to be re-injected as waste into disposal wells may be reduced. The apparatus and method may address existing waste stream accumulations as well as minimizing future issues. The apparatus and method may clean both the fines and accompanying process water immediately, recovering most of the available water for process recycling or release. Immaterial modifications may be made to the embodiments described here without departing from what is covered by the claims. In the claims, the word “comprising” is used in its inclusive sense and does not exclude other elements being present. The indefinite articles “a” and “an” before a claim feature do not exclude more than one of the feature being present. Each one of the individual features described here may be used in one or more embodiments and is not, by virtue only of being described here, to be construed as essential to all embodiments as defined by the claims.
34,579
11857894
DETAILED DESCRIPTION Referring to the figures generally, various coalescing filter media (e.g., filter media, etc.) having perforations are described. The coalescing filter media is generally described herein as “filter media.” The filter media is structured to separate a dispersed phase from a continuous phase of a mixture. In various embodiments described herein, the filter media is implemented within a FWS and structured to separate water (e.g., a dispersed phase, etc.) from a fuel (e.g., a continuous phase, etc.) within a fuel water mixture. However, the filter media may also be implemented in other applications where separation of a dispersed phase from a continuous phase is desirable. For example, the filter media may be implemented in a crankcase to facilitate crankcase ventilation to separate oil and water droplets from blowby gas, in an oil (e.g., lube, hydraulic oil, etc.) circulation system to separate water from the oil, and in a natural gas system to remove water or oil mist from natural gas. The coalescing filter media is a perforated filter media that includes a number of holes (e.g., perforations) arranged in a geometric or random pattern to enhance removal of the dispersed phase from the mixture. The filter media may be woven (e.g., sieve, screen, etc.) or nonwoven. In some arrangements, the filter media is polymeric. The holes or perforations may be arranged in a geometric pattern near a bottom endplate of the filter element with respect to the direction of gravity (e.g., at the bottom-half of the filter element). For example, the geometric pattern may include one or more linear rows oriented approximately normal with respect to gravity. In this example, the holes in adjacent rows may be circumferentially or horizontally offset from one another, as in a staggered array. The perforated filter media may be used as the filter media in a coalescing filter element. The perforated filter media may be used individually, or as a layer in a multimedia or multilayer filter media with any combination and number of perforated and unperforated layers. In some arrangements where the perforated filter media is a layer in a multimedia or multilayer filter media, a gap or space may exist between the perforated layer and the filter media layer immediately upstream of the perforated filter media. In some arrangements, the filter element can be implemented with a non-perforated filter media layer downstream of a perforated filter media layer. In arrangements where a gap or space exists, the gap may be a variable gap such that the gap can be present at some areas between the layers and not present at other areas between the layers. In some arrangements, the perforated layer is the downstream-most layer in a multilayer configuration. As described herein, a FWS is a subset (e.g., a particular type, etc.) of a filter. A FWS can include a single-stage, barrier type, water separator or a fuel-water coalescing filter. The FWS may include features different from other filters described herein. For example, the FWS described herein provides a draining function that the filter described herein does not so provide. Referring toFIG.1, a cross-sectional view of a filter element100is shown according to an example embodiment. The filter element100includes a first endplate102, a second endplate104, and filter media106. In some arrangements, the filter element100is a cylindrical filter element. In other arrangements, the filter element100can be arranged as a panel filter element, a flatsheet filter element, or the like. The filter element100may be, for example, a fuel filter element, an oil filter element, an air filter element, a crankcase ventilation filter element, a water filter, or the like. The filter media106is coalescing filter media. The filter media106is structured to separate two immiscible phases of a mixture107(represented by the flow arrows ofFIG.1upstream of the filter media106): a continuous phase108(primarily represented by the flow arrows ofFIG.1downstream of the filter media106) and a dispersed phase110(represented by the round or oval dots ofFIG.1). InFIG.1, it is understood that, while the flow arrows downstream of the filter media106represent the continuous phase108, some of the dispersed phase110may be entrained therewith. In some arrangements, the continuous phase108is fuel or lubricant and the dispersed phase110is water. Accordingly, as the mixture passes through the filter media106, the dispersed phase110is captured and coalesced by the filter media106. The coalesced dispersed phase110falls along the filter media106in the direction of gravity112. As the coalesced dispersed phase110falls, the coalesced dispersed phase110may or may not contact the filter media106. The filter media106may be, for example, a porous filter media, such as a nonwoven fabric, a woven filter media, an extruded screen, or the like. In some arrangements, the filter media106is a square weave screen that has a uniform (e.g., well-defined, consistent, etc.) pore size. For example, the filter media106may be a screen with thirty percent (30%) open area and squares with fifty (50) micron (“μm”) sides, made from monofilament polyester or nylon fibers. In another example, the filter media106may be a square weave screen with a thirty-one percent (31%) open area and fifty-five (55) μm sides. In other arrangements, the filter media106includes extruded mesh which has a uniform pore size. In further arrangements, the filter media106includes nonwoven filter media having a broader pore size distribution than extruded mesh filter media, such as spun-bond and melt blown nonwoven filter media, microglass filter media, and/or cellulose filter media. The filter media106may be hydrophobic such that water (i.e., the dispersed phase110in the arrangements) tends to accumulate on its upstream face or surface. In other arrangements, the filter media106is hydrophilic or has intermediate wetting characteristics. The filter media106may also be polymeric filter media. In an example embodiment, the filter media106includes one or more perforations114. The perforations114are created by incorporating holes into an unperforated layer of filter media. The perforations114may be produced as the filter media106is produced or processed, or added later when the filter media106is formed into the final filter element or formed by creating gaps or openings in an otherwise continuous sheet of filter media. In this way, the filter media106is textured. The perforations114facilitate the drainage of the coalesced dispersed phase110through the filter media106. In some embodiments, the perforations114are omitted from the filter media106. The perforations114are large relative to the pore size distribution of the filter media106. In some arrangements, the perforations114are greater than or equal to one-hundred and fifty (150) μm in diameter (or other opening dimension). In some arrangements, the perforations114are greater than or equal to two-hundred (200) μm in diameter (or other opening dimension). In further arrangements, the perforations114are greater than or equal to five-hundred (500) μm in diameter (or other opening dimension). In still further arrangements, the perforations114are greater than or equal to one-thousand (1,000) μm in diameter (or other opening dimension). For example, the perforations114may have a diameter (or other opening dimension) between one-thousand one-hundred (1,100) μm and one-thousand six-hundred (1,600) When the diameter (or other opening dimension) of the perforations114is on the order of one-thousand one-hundred (1,100) μm or less, the perforations114may be formed by a laser where removed material is substantially vaporized or burned off thereby simplifying the manufacturing process associated with the perforations114. In another example, the perforations114have a diameter (or other opening dimension) of three-thousand (3,000) μm. While the diameter of the perforations114has been described herein, the perforations114may be non-circular, and the dimension of a perforation114may instead be a length of a side of the perforation114, a distance between vertices of sides of the perforation114, or other similar measurement. The diameter of the perforations114may be determined using, among other methods and mechanisms, an optical or electron microscope (e.g., microscopy, etc.), or calculated from bubble point data as described in ASTM F-316-03 Standard Test Methods for Pore Size Characteristics of Membrane Filters by Bubble Point and Mean Flow Pore Test. In some arrangements, the bubble point of the filter media106in 2-propanol as per ISO 2942 “Hydraulic fluid power—Filter elements—Verification of fabrication integrity and determination of first bubble point” (2004) is less than 1.5 inches of water, less than 0.7 inches of water, and less than 0.3 inches of water. In some arrangements, a steady stream of bubbles is observed from multiple locations at applied air pressures of 1.5 inches of water, 0.7 inches of water, and 0.3 inches of water when the filter media106, either as a flat sheet, pleat pack or filter element is tested using a bubble point apparatus and 2-propanol as described in ISO 2942. The bubble point of the filter media106is specifically selected such that pores within the filter media106are distinguished from the perforations114such that the coalesced dispersed phase110may be removed though the perforations114. Flow restriction across the perforations114is relatively low, compared to flow restriction across the pores in the filter media106, such that the flow of the coalesced dispersed phase110through the perforations114is not substantially impeded. The desirable bubble point of the filter media106may result when the perforations114have a diameter (or other opening dimension) between one-hundred (100) and two-hundred (200) microns. In an example embodiment, the filter media106is capable of removing up to, and including, ninety-nine percent of the coalesced dispersed phase110from the mixture107. Equation 1 sets forth a relationship that is useful for determining bubble points associated with filter media106that is capable of such removal of the dispersed phase110. 3.2=B1B2(1) In Equation 1, B1is the first bubble point of an unperforated portion of the filter media106and B2is the bubble point of a perforated portion of the filter media106. This relationship between the unperforated portion of the filter media106and the perforated portion of the filter media106may be obtained by varying the number and/or diameter (or other opening dimension) of the perforations114. In some arrangements, the perforations114are positioned, spaced, and/or arranged in an identifiable location (e.g., near the top or bottom end of the filter element100, etc.) or in a geometric pattern (e.g., one or more linear rows oriented approximately normal with respect to gravity112, etc.). In other arrangements, the perforations114are randomly arranged across at least a portion of the filter media106. In further arrangements, the perforations114are arranged in adjacent rows that are circumferentially or horizontally offset from one another (e.g., as in a staggered array). When the dispersed phase is more dense than the continuous phase, the perforations114may be positioned in the bottom half of the filter media106(with respect to the direction of gravity112) near the second endplate104. In alternate arrangements, the perforations114may be positioned above the mid-point of the filter media106(with respect to the direction of gravity112) (e.g., in arrangements where the filter media is an intermediate layer in a multi-layer coalescer or when the dispersed phase110is less dense than the continuous phase108). The term “perforation” refers to an opening in the filter media that may have a cross-section of any target shape. For example, a perforation may be round in cross-section, irregularly shaped, a slot, a slit, or puncture of another shape as previously defined. The term “perforations” refers to the larger openings in the filter media106that serve the primary purpose of permitting the coalesced dispersed phase110to drain through the filter media106, while the term “pores” refers to the smaller openings that capture the fine dispersed phase110in the mixture and are present in any unperforated filter media layers (e.g., as described below with respect toFIGS.2A through2F). However, it should be understood that a small amount of coalesced dispersed phase110may also drain through the pores just as a small amount of the fine dispersed phase110may be captured by the perforations114. The perforations114in the filter media106may be produced, for example, by puncturing filter media with needles, puncturing filter media using a rotating spoked or star wheel, making slits of short length with a (flat) bladed object, burning holes in the media with an infrared laser, ultrasonic wave, using water jets, melting filter media using hot pins, using a length of filter media106that is shorter than the distance between the first endplate102and the second endplate104, or other device(s)/means. As described in further detail below with respect toFIGS.8A through8G, although the filter media106is shown as being the only layer in the filter element100with respect toFIG.1, the filter media106may be used in combination with other layers of filter media, as a composite filter media, or in conjunction with other filter/separator stages. In multi-layer arrangements, there may be one or more gaps or spaces between a perforated layer of filter media and the other layer of filter media immediately upstream of the perforated layer. These gaps may be formed between the perforated layer of filter media and the other layer of filter media even if a portion of the perforated layer of filter media is in contact with (or otherwise bonded to) a portion of the other layer of filter media. In these instances, the gaps may be non-uniform (e.g., there may be varied spacing between the perforated layer of filter media and the other layer of filter media, etc.). In some other multi-layer arrangements, the other layer of filter media is downstream of the perforated layer and there may be one or more gaps or spaces between the perforated layer of filter media and the other layer of filter media. These gaps may facilitate removal of the dispersed phase and may assist in distinguishing the pores in the filter media106from the perforations114. In some arrangements, the maximum separation between the two layers of filter media is greater than zero (0) μm. In such arrangements, the maximum separation distance may be greater than one (1) μm. In further arrangements, the maximum separation distance may be greater than one-hundred (100) μm. In some arrangements, the gap is varied between zero (0) and one-thousand (1,000) μm. In other arrangements, the gap is varied between zero (0) and one-hundred (100) μm. In further arrangements, the maximum separation between the two layers is less than five-thousand (5,000) μm. In still further arrangements, the maximum separation between the two layers is less than three-thousand (3,000) μm. In further arrangements, the maximum separation between the two layers is less than one-thousand (1,000) μm. In such arrangements, the downstream-most layer in the multilayer configuration is a perforated layer of filter media, and the upstream layers can be perforated or non-perforated. Referring toFIGS.2A through2F, micrographs showing magnified views of perforations114created in different types of filter media106are shown. The magnified views ofFIGS.2A through2Fare shown at one-hundred (100) times magnification.FIG.2Ashows a perforation114in polymeric woven screen filter media.FIG.2Bshows a perforation114in polymeric nonwoven filter media.FIG.2Cshows a perforation114in another polymeric nonwoven filter media.FIG.2Dshows a perforation114in a further nonwoven polymeric filter media.FIG.2Eshows a perforation114in a further nonwoven filter media.FIG.2Fshows a plurality of perforations114in another nonwoven filter media. The perforations114ofFIGS.2A,2B,2C, and2Dhave a diameter of five-hundred (500) μm. Other diameters are also possible. Each of the perforations114ofFIGS.2A through2Dare created by punching holes in the filter media using non-barbed needle-like devices. Other mechanisms for creating the perforations114can also be utilized. The perforations114ofFIGS.2A,2B,2C, and2Dare relatively open and essentially unblocked by fibers, threads, or other extraneous material of the media and thus are clearly visible. In the case of the filter media shown inFIGS.2E and2F, barbed needles having diameters of approximately five-hundred (500) μm and seventy-five (75) μm, respectively, were used to create the perforations114. The barbed needles displace and orient some of the fiber in a vertical direction (i.e., normal to the plane of the figure). As the barbed needle is pulled from the filter media, the needle pulls fibers along with it and partially refills the perforations114with fibers oriented in a more vertical direction. In each of the arrangements, the number of perforations114per unit area of filter media (i.e., the perforation density) is selected to be high enough that the rate of water accumulation by the coalescer does not exceed the drainage rate through the perforations114. Referring again toFIG.1, as the mixture flows through the filter element100, the dispersed phase110and the continuous phase108are transported to the filter media106where dispersed phase110droplets are captured. As captured droplets of the dispersed phase110accumulate, the droplets coalesce and grow in size. The accumulation of the dispersed phase110in the filter media106increases the restriction across the filter media106. The captured droplets of the dispersed phase110tend to be moved in the direction of gravity112(e.g., parallel to the surface or face of the filter media106). In some arrangements, the captured droplets of the dispersed phase110are moved by drag forces from the flowing continuous phase108. Accordingly, the coalesced dispersed phase110accumulates in a lower portion (with respect to the direction of gravity112) of the filter element100when the dispersed phase110is more dense than the continuous phase108(e.g., as in fuel-water separation), which can contribute to increased pressure drop. As described above, in some arrangements, the perforations114of the filter media106are located at the lower portion of the filter media106so as to minimize the accumulation of the captured dispersed phase110. In some arrangements, placing the perforations114at the lower portion of the filter media also ensures that the coalesced dispersed phase110drops are released in downstream portions of the filter element100where fluid velocity and turbulence are low. The placement of the perforations114in the lower portion (with respect to the direction of gravity112) of the filter media106and away from the filter's clean fluid outlet, ensures that coalesced drops of the dispersed phase110are not broken up by turbulence of the fluid flow downstream of the filter media106thereby facilitating removal by settling of the dispersed phase110. In other arrangements, such as where the perforated layer is an intermediate layer where coalesced dispersed phase movement parallel to the media surface is limited, the perforations114are located where the coalesced dispersed phase collects, such as just above a bond point in the filter media or just above a support rib that restricts coalesced dispersed phase drainage. As noted above, the perforations114are significantly larger than the pores of the filter media106. Since the perforations114are larger than the mean flow pore size, there is preferential flow towards and through the perforations114compared to the rest of the pores of the filter media106. For example, the perforations114each have a diameter that is at least three times a mean flow pore size of the filter media106. In another example, the perforations114each have a diameter that is at least five times a mean flow pore size of the filter media106. In yet another example, the perforations114each have a diameter that is at least ten times a mean flow pore size of the filter media106. The preferential flow supplements gravity112in transporting the dispersed phase110towards the perforations114. The net result is that the amount of captured dispersed phase110near the perforations114is increased relative to the rest of the filter media106, which produces a localized increase in the rate of coalescence. Coalesced dispersed phase110drops pass through the perforations114and exit as enlarged drops that are large enough to be removed from the mixture by settling, or by a downstream water barrier such as a hydrophobic media or screen. The continuous phase108(e.g., fuel from a fuel water mixture) continues to flow to its intended destination (e.g., engine fuel injectors). It is counterintuitive that adding the perforations114to the filter media106would enhance separation and overall performance because it is well known that small holes or leaks in particulate filters decreases removal, notably at larger particle sizes. In fact, ISO 2942 uses the presence of holes to identify filter element fabrication defects. However, in the filer media106, the perforation diameter, the density of the perforations114, Frazier permeability, and the perforation locations are controlled such that any minimal amount of the emulsified dispersed phase110passing through the perforations114is offset by overall increased removal of the dispersed phase110. The perforations114are designed to accumulate and coalesce the dispersed phase110. Dispersed phase110accumulation in and near the perforations114prevents emulsified dispersed phase110droplets from passing through the perforations114and ensures that enlarged coalesced drops of the dispersed phase110emerge from the perforations114. By minimizing the accumulation of the dispersed phase110within and on the perforated filter media106layer, the perforations114provide a further benefit by decreasing the interstitial velocity within the filter media106layer and enabling larger drops of the dispersed phase110to form and be released. Thus, the perforations114enhance performance by: (1) reducing the restriction caused by the excessive buildup of captured dispersed phase110, (2) providing localized collection or concentration points for captured dispersed phase110, (3) increasing the size of coalesced drops of dispersed phase110released from the filter media106, (4) minimizing the breakup of released coalesced drops of dispersed phase110into smaller droplets, and (5) enhancing overall removal efficiency of the filter media106. The perforation diameter, density of the perforations114, Frazier permeability, and perforation locations are important factors in increasing the efficiency of the filtration system. The size and number of perforations114can vary depending on application requirements. As discussed in further detail below, in some arrangements, the perforations114may particularly be located in areas of the filter media106with expected low downstream flow rate in order to reduce the drag force on drops of coalesced dispersed phase110exiting the perforations114, thus reducing the breakup of the coalesced drops of dispersed phase110, which would cause the dispersed phase110to remain entrained in the continuous phase108. The size of the perforations114impacts the size of the coalesced drops of dispersed phase110released from the downstream side of the filter media106surface. The size of these drops is a function of interfacial tension, the diameter of the perforation114, and magnitude of the drag force acting on the drop as it forms. As interfacial tension and perforation diameter increase, the size of released drops also increases. This affects removal because larger drops are easier to separate than smaller drops. In practice, released drops will be smaller due to drag forces from flowing continuous phase108and other effects. The magnitude of these drag forces in a FWS varies depending upon the location of a perforation114in the context of the filter element100structure. As such, larger perforations114may be utilized in higher velocity regions of a FWS, or a perforation diameter large enough to serve in the most challenging locations may be used. In some arrangements, it is desirable to maximize the size of coalesced dispersed phase110drops emerging from the perforations114. Turbulence within the perforations114can result in the break up or re-emulsification of coalesced dispersed phase. Turbulence is a function of media face velocity (μ; kg m−1s−1), perforation diameter (d; μm), and perforation density (D; number of perforations114per square meter). Equation 2 sets forth a relationship that is useful for defining desirable conditions for perforated coalescer design. RH=k⁢⁢ρ⁢⁢Vμπ⁢⁢dD(2) In Equation 2, k is equal to 4×106μm m−1and RH is the hypothetical Reynolds number for a condition in which all fluid flow passes through the perforations114and no flow passes through the filter media pores. During its useful life, most of the flow through a coalescer media passes through the pores in the filter media and this condition is not normally met in actual practice. For coalescer filter media without perforations114, the pores are so small and numerous that turbulence is not a concern. For perforated coalescers, however, turbulence may occur under conditions when the value of dD is excessively small. RH, as defined in Equation 2, is useful for defining the properties and design limits for perforated coalescer filter media. In some arrangements, value of RH is less than about six-thousand (6,000). In further arrangements, the value of RH is less than four-thousand (4,000). In further arrangements, the value of RH is below two-thousand (2,000) in order to minimize coalesced dispersed phase break up. For a given set of fluid and flow conditions, a limiting value of dD exists below which the performance of the perforated coalescer media is adversely impacted. For example, for fuel water separation the value of dD should be greater than 1.0×105μm m−2, particularly greater than 2.0×105μm m−2, and more particularly greater than 4.0×105μm m−2. For other fluid and flow conditions, different values of dD may be used. Further, perforation diameter, Frazier permeability, filter media106thickness, and the density of the perforations114affect the rate of dispersed phase110drainage from the filter media106. The perforation diameter should be great enough and the density of the perforations114should be large enough that excess dispersed phase110in and on the filter media106can drain, yet not so great as to cause unacceptable levels of emulsified dispersed phase110to pass through the perforations114rather than be captured. By treating the perforations114as capillaries penetrating the filter media106, the minimum perforation diameter, Frazier permeability, filter media106thickness, and the density of the perforations114needed to ensure drainage can be modeled using the Hagen-Poiseuille law. The drainage rate of dispersed phase110through the perforations114is a function of the following properties of the filter media106: perforation diameter (d; μm), Frazier permeability (F; feet/minute), perforation density (D; number of perforations114per square meter), and filter media106thickness (L; mm). These parameters can be used to define a parameter, P, as follows in Equation 3: P=d4⁢DFL(3) The above-calculated parameter P has units of μm4min m−2ft−1mm−1. For brevity purposes, the units are not discussed below. The performance of filter media is adversely affected when the value of P exceeds 3.0×1012. Accordingly, the value of P should be less than 3.0×1012. In some arrangements, the value of P should be less than or equal to 1.5×1012. In other arrangements, the value of P should be less than or equal to 3.0×1011. Alternatively, in MKS units for all parameters, the performance of the filter media is adversely affected when the value of P exceeds 6×10−7s. In some arrangements, the value of P should be less than or equal to 3×10−7s. In further arrangements, the value of P should be less than or equal to 6×10−8. In such arrangements, the filter media106may have a perforation diameter greater than or equal to 200 μm (e.g., between two-hundred (200) and three-thousand (3,000) μm) and/or a perforation density greater than 625 m−2(e.g., between two-thousand five-hundred (2,500) and forty-thousand (40,000) m−2). The density of the perforations114may also be represented as a number of occurrences (e.g., instances, etc.) of the perforations114per square meter. It should be noted that the average linear distance between the perforations114may be used as a surrogate for the density of the perforations114. This surrogate is useful for such embodiments where the perforations114are not distributed over the entire surface of the filter media106, but rather over only a portion of the entire surface of the filter media106, such as the embodiments shown inFIGS.7B,7C, and7G. In various applications, it has been found that it is advantageous to configure the filter media106such that an average linear distance between the perforations is less than or equal to fifty (50) millimeters, less than or equal to twenty-five (25) millimeters, less than or equal to ten (10) millimeters, and less than or equal to five (5) millimeters. The relationship between perforation diameter (“d”) and perforation density (“D”) is shown as a curved line inFIG.4for a typical fuel-water separation application for illustrative purposes. As shown inFIG.4, a series of seven diamonds labeled with the associated observed dispersed phase110(in the case ofFIG.4, water) removal efficiency is also shown at a perforation diameter of five-hundred and fifty (550) μm. The dispersed phase110removal is increased as the density of the perforations114increases. To ensure drainage under defined conditions, the density of the perforations114and perforation diameter should be located above the line shown inFIG.4. It has been found that dispersed phase110removal is enhanced when the value of P (e.g., as calculated via Equation 3) for the perforated filter media106is less than a value of 6×10−7s. As shown inFIG.4, there is a point at which the perforation density becomes too great and/or perforation diameter too large to achieve the full benefit of the perforated filter media106. The optimal range for perforation density and perforation diameter depends in part on the flow rate through the perforations114relative to the flow through unperforated portions of the filter media106. FIG.5shows a graph showing how water removal efficiency is influenced by Frazier Permeability for the filter media106in a fuel water mixture. Each data point inFIG.5was obtained using the same base filter media, but with differing perforation densities. By increasing the perforation density, Frazier Permeability was also increased. FromFIG.5, it can be seen that water removal efficiency increases rapidly with increasing Frazier Permeability (and increasing perforation density) before declining. The observed increase in water removal efficiency with increasing Frazier Permeability obtained by punching holes in the filter media is unexpected and contrary to established principles of filter design. At Frazier permeability values greater than about two-hundred (200) feet per minute, the benefit of the increased perforation density diminishes as water accumulation around individual perforations114is decreased and increasing amounts of emulsified water pass through the perforations114without being captured and coalesced. As previously noted, performance of the filter media is also a function of perforation diameter and filter media thickness, so two-hundred (200) feet per minute is regarded as a Frazier Permeability limit for the specific test conditions and under other conditions may be greater. The performance enhancement due to the perforated filter media106is greatest when less than ten percent of the total flow rate passes through the perforations114, and more specifically between 0.5 percent and five percent. The results can also be expressed in terms of the perforation density as shown inFIG.6. The results show that for the test conditions described above with respect toFIG.5, the performance enhancement due to the perforated filter media106layer is greatest when the perforation density is greater than six-hundred twenty-five (625) perforations m−2, and specifically between two-thousand five-hundred (2,500) and forty-thousand (40,000) perforations m−2. In these tests, the perforations114were located near the bottom on the filter element100with respect to gravity112(e.g., as described with respect toFIG.7Bbelow). Referring toFIGS.7A through7H, example spatial arrangements of the perforated filter media106of the filter element100are shown. The spatial location of the perforations114along the filter media106may be used to optimize filter element100performance.FIG.7Ashows the filter media106having the perforations114uniformly distributed across the filter media. In the arrangement ofFIG.7A, the perforations114are evenly spread over the surface of the filter media106. As such, no matter where the dispersed phase110is first captured, the captured dispersed phase110has a relatively short distance to drain to the nearest perforation114. FIG.7Bshows the filter media106being pleated and having a single circumferential row of perforations114near the bottom of the filter media106(with respect to the direction of gravity).FIG.7Cshows the filter media106as an unpleated filter media pack having a single circumferential row of perforations114near the bottom of the filter media106(with respect to the direction of gravity). In both the arrangement ofFIGS.7B and7C, the perforations114are optimized for applications where the dispersed phase110readily drains towards the bottom of the filter element. The positioning of the perforations114with respect to pleat tips (ofFIG.7B), particularly on the pleat faces as opposed to the pleat tips or pleat valleys, may be used to further optimize performance. In an alternative arrangement ofFIG.7B or7C, the perforations114are replaced with at least one layer of filter media positioned such that there is a small gap between the ends of the filter media106and filter endplate (e.g., the second endplate104). For example, if the layer of filter media106is allowed to just “touch” the endplate but not be bonded (e.g., glued) to it, or if a small gap (e.g., less than one millimeter) is present, the same effect can be observed as with the perforations114. As another alternative, cutting small slots in the filter media106edge, or creating a zig-zag cut in the end of the filter media106, such that some bypass (flow through) points remain after adhering the media to the endplate, will also work as the perforations114described herein. FIG.7Eshows the filter media106having three circumferential rows of perforations114: two near the bottom of the filter media106(with respect to the direction of gravity) and one centrally located between the top and the bottom. Similarly,FIG.7Fshows the filter media106having a two circumferential rows of perforations114near the bottom of the filter media106(with respect to the direction of gravity). The arrangement ofFIG.7Emay be advantageous compared to the arrangement ofFIG.7Fin applications where providing an intermediate dispersed phase110collection and drainage point is beneficial (e.g., in FWS applications where the fuel has a high water concentration). FIG.7Gshows the filter media106having perforations114near the top of the filter media106(with respect to the direction of gravity). The arrangement ofFIG.7Gwould be beneficial in applications, such as oil water separation, where the dispersed phase110, oil, is less dense than the continuous phase108, water. For a particular coalescer element or media pack, it is not necessary that the entire surface of the perforated layer be covered by the perforation pattern nor by the same perforation pattern. For example,FIG.7Dshows the filter media106arranged in a similar manner to that ofFIG.7A, except that the perforations114do not completely encircle the filter media106pleat pack. The arrangement ofFIG.7Dmay be advantageous to focus dispersed phase110collection in a certain portion of the filter element100or to alternatively to direct dispersed phase110water away from a certain portion of the filtration system. For example, if a filtration system is arranged in a manner that dispersed phase collects on a particular area or side of the filter media, the perforations114can be arranged to be in that area or side, and not on (or lower frequency) the other areas or sides. In some applications, it may be beneficial to have perforations114of at least two different sizes on a first layer of the filter media106. For example, the first layer of the filter media106may be configured such that perforations114having a first diameter (or other opening size) (e.g., ten (10) millimeters, etc.) are positioned proximate to a first end of the filter media106and such that perforations114having a second diameter (or other opening size) (e.g., 1.5 millimeters, etc.) are positioned proximate to a second end of the filter media106opposite the first end. In one example embodiment, the first end of the filter media106is located near the top of the filter element100and the perforations114located along the first end of the filter media106have a diameter that is larger than the perforations114located along the second end of the filter media106. In this embodiment, an increased portion of the continuous phase108is at the top of the filter element100. The filter media106also includes a second layer of the filter media106, downstream of the first layer of the filter media106. The second layer of the filter media106includes the perforations114located along a bottom end of the second layer of the filter media106, proximate to the second end of the first layer of the filter media106. The coalesced dispersed phase110may then be drained through the perforations114in the second layer of the filter media106. In this way, the perforations114located along the second end of the second layer of the filter media106function as small drain holes. Rather than the second layer of the filter media106, the filter element100may instead implement a non-perforated hydrophobic layer to perform final removal of the coalesced dispersed phase. In some arrangements, it is not necessary that there be more than one perforation114nor that the perforations114be round. For example,FIG.7Hshows the filter media106in stippled shading surrounding a conventional unperforated filter media in white for a conventional cylindrical coalescer element. The height of filter media106is less than that of the conventional filter media (e.g., the height of the filter media106as shown inFIGS.7A through7G), which results in a single “perforation” or gap at the bottom of the filter element where the filter media may be slightly lifted from an endplate of the filter element. This single perforation or gap functions in the same manner as described above with the perforations114and meets all requirements previously described for this invention and may be advantageous for certain applications. The presence of perforations114in a particular pattern is relatively easy to detect. For example, an ordered array or pattern may be discerned visually as a pattern of bubble rising from a filter or filter media while gradually increasing the pressure during a bubble point test as per SAE ARP901 “Bubble-Point Test Method” (2001), ASTM F316-03 “Standard Test Methods for Pore Size Characteristics of Membrane Filters by Bubble Point and Mean Flow Pore Test” (2011), or ISO 2942. A more random appearance would be observed from filters or filter media that have large pores or perforations114, as opposed to a pattern of perforations114. Alternatively, during a fuel water separation test, e.g., SAE J1488, a distinctive pattern of drops emerging from the filter element may be observed. Microscopy or other methods of identifying a pattern may also be used. As discussed above, improved dispersed phase110removal is obtained when the perforations114are located near the bottom of the filter element (e.g., as shown inFIGS.7B,7C and7F), where the dispersed phase110tends to accumulate (e.g., as in a conventional FWS). In some arrangements of a FWS, the best water removal efficiency was obtained when the majority of the perforations114are located in the lower half (with respect to height) of the filter element or coalescer filter media pack. In some arrangements, the perforations114are located in the bottom third of the filter element100. In further arrangements, the perforations114should be located in the bottom quarter of the filter element100(e.g., as illustrated inFIGS.7B,7C, and7F). AlthoughFIGS.7A through7Hshow cylindrical filter media106, the filter media106may be arranged in other geometric arrangements found in conventional filter elements. Further, although each ofFIGS.7A through7Gshows a single layer of filter media106with perforations114, additional layers of filter media (e.g., as shown inFIG.7H), upstream or downstream of the perforated filter media106—with or without perforations114—may also be present. Due to the effect of gravity and the previously described texturing of the media that may help create a gap between successive layers of filter media, coalesced dispersed phase110tends to accumulate in different places during use. For example, in traditional FWS or crankcase ventilation coalescers with vertical orientation, the dispersed phase110tends to accumulate at the bottom of the filter element. If the element is pleated (e.g., as shown inFIG.7B), the dispersed phase110may also collect in the valleys of pleats. As a result, these areas contribute excessively to the restriction across the FWS filter element and exhibit diminished droplet removal. As a result, the positioning of perforations114can influence the performance of the filter media106. Another consideration regarding perforation location is the downstream flow profile of continuous phase108(e.g., fuel in a FWS application). Depending on filter design, every filter element has its own flow profile downstream of the filter media. In order to maximize the size of released drops of dispersed phase110and their removal by settling, perforations114may be located in more quiescent or lower velocity regions where released drops are exposed to less shear and drag. For example, referring toFIGS.7B and7C, if the continuous phase110flows from outside to inside of the filter element and fuel leaves the element from the top, the downstream velocity near the top of the filter element will be greater than at the opposite end. In such an arrangement, the perforations114may be located closer to the bottom of the filter element than the top of the filter element. The perforated filter media106layer described above can be used in combination with other layers of filter media to further enhance performance (e.g., liquid-liquid performance, gas-liquid performance). The inclusion of a perforated layer of filter media106in any coalescer, composite media, or multistage filter may be used to enhance the performance (e.g., liquid-liquid performance, gas-liquid performance). Typically, providing perforations114in a layer of filter media as described (transforming it into a perforated layer) is most beneficial when, in their absence, dispersed phase110(e.g., water) accumulation at or in that layer of the multi-layer filter contributes significantly to the pressure drop, when the perforations114are used to direct the flow of captured dispersed phase110in a manner that increases coalescence, or when the perforated layer directly impacts the size of released drops of dispersed phase110. FIGS.8A through8Hshow example filter media arrangements having at least one layer of perforated filter media having perforations114. In the arrangements ofFIGS.8A through8G, further performance enhancements may be obtained when perforated layer(s) (e.g., as previously described above with respect to the perforated filter media106) are used in combination with other layers of filter media or independent filter media (e.g., in series filtration with multiple stages of filtration). In the arrangement ofFIG.8H, a single layer of perforated media is shown. In each of the arrangements ofFIGS.8A through8H, layers (A, B and C) refer to different layers of filter media; (S) indicates a space or gap between layers of filter media; and perforations114are indicated. Any layer (i.e., A, B, or C) that has a perforation114is referred to as a perforated layer. It should be understood that layers (A, B, or C) do not define or limit the properties of the layer of filter media (e.g., the layer (A) inFIG.8Amay be a different filter media or the same filter media as the layer (A) inFIG.8B), but are just to provide context of the layers of filter media in the flow direction. The flow direction is from left to right as drawn (i.e., layer (A) being the most upstream layer, layer (B) being downstream of layer (A) and upstream of layer (C), layer (C) being downstream of both layers (A and B), etc.). FIG.8Ashows a three filter media layers or stage configuration with each layer separated by space or gap labeled as (S), with middle layer (B) serving as the perforated layer.FIG.8Bis similar toFIG.8A, except that there is no space or gap between filter media layers.FIG.8Cis similar toFIG.8A, except that layers (B and C) are both perforated layers. In a variation of this embodiment, one of the layers (B and C) does not include the perforations114and the other of the layers (B and C) does include the perforations114.FIG.8Dis similar toFIG.8C, except that layers (A and B) are perforated layers, but not layer (C). In a variation of this embodiment, one of the layers (A and B) does not include the perforations114and the other of the layers (A and B) does include the perforations114.FIG.8Eis similar toFIGS.8B,8C, and8D, except that all three layers are perforated layers. In a variation of this embodiment, at least one of the layers (A, B, and C) does not include the perforations114and the others of the layers (A, B, and C) do include the perforations114.FIG.8Fis similar toFIG.8E, except that layer (B) is not a perforated layer. In a variation of this embodiment, one of the layers (A and C) does not include the perforations114and the other of the layers (A and C) does include the perforations114.FIG.8Gis a two layer configuration in which layer (B) is a perforated layer.FIG.8His a one layer configuration in the filter media layer is a perforated layer. It should be understood thatFIGS.8A through8Hare illustrative and not indicative of all potential filter media layer combinations; other combinations of layers and perforations114are contemplated. For example, in some arrangements, a region of filter media can consist of one layer or multiple layers of media having two different polymeric media laminated to each other. Applying this concept to the arrangement ofFIG.8G, layer (A) may be comprised of multiple layers of filter media laminated to each other, and layer (B) may comprise a single layer of media with perforations114. In each ofFIGS.8A through8H, the perforated layer(s) may be used in combination with other layers. In some arrangements, layers adjacent to a perforated layer are not tightly mated, attached, or bonded together, as previously discussed. This relative association between layers adjacent to a perforated layer creates a small space or gap and allows water to flow relatively unhindered parallel to the media layer surface towards the perforations114. The relative association between layers increases the path length and residence time of the drops of dispersed phase110in the media, as the droplets zig-zag through the media, thus providing greater opportunity for droplets to coalesce. As used with respect toFIGS.8A through8G, the terms “space” or “gap” refers to a physical separation between adjacent filter media layers, or a portion of adjacent filter media layers, but does not imply any particular minimum or maximum separation, nor does it imply the complete separation between the layers. For example, inFIG.8A, if layer (B) is crinkled or corrugated and layer (A) lies on top of and physically touching layer (B), there will be spaces between the two layers in the valleys of the corrugations or crinkles. Accordingly, inFIG.8A, layer (A) may act as a prefilter or preseparator while layer (B) (with perforations114) would facilitate drainage and release of enlarged drops readily separated by layer (C). Further, the texturing (i.e., the positioning, configuration, and number of the perforations114) may be varied for any of the layers (A, B, C) shown inFIGS.8A through8G. The arrangement ofFIG.8Bwould behave similarly, although the absence of a space upstream of (B) may hinder drainage somewhat while the absence of space downstream of (B) means that released drop size would largely be controlled by layer (C). The arrangement ofFIG.8Cis structured to behave like the arrangement ofFIG.8B, except that layer (C) provides support for layer (B) while layer (C)'s perforations114would yield larger released drops of coalesced dispersed phase110than the arrangement ofFIG.8B. The arrangement ofFIG.8Dincludes perforations114in layers (A and B), which provides enhanced drainage and accumulation of dispersed phase110at the perforations114, as well as structural support from layer (C), but released drop size would ultimately be controlled by layer (C). The arrangement ofFIG.8Eincludes three layers with each layer possessing perforations114. This arrangement provides enhanced drainage of all layers and released drop size regulated by the perforations114of layer (C), but may have increased risk of uncoalesced dispersed phase110passing through the perforations114rather than being separated by the media. The arrangement ofFIG.8Fhas the advantage of enhanced drainage for layers (A and C), as well as dispersed phase110accumulation at the perforations114in these layers and the perforations114in layer (C) controlling released drop size, while layer (B) eliminates bypass of dispersed phase110through the media. The arrangement ofFIG.8Gutilizes the perforations114in layer (B) to improve drainage and enhance the size of released drops. In the arrangements ofFIGS.8A through8G, arrangements in which more than one layer possess perforations114are illustrated as if the perforations114are aligned. However, this is done for illustrative purposes only, as particular arrangements do not require the perforations114to be aligned within the layers, nor does it require that the layers possess the same diameter for all of the perforations114or the same density of the perforations114. In fact, benefits may be obtained by intentionally misaligning the perforations114. For example, in the arrangement ofFIG.8C, the perforations114in layers (B and C) may be located axially or circumferentially out of alignment to ensure that all of the fluid must pass through at least some filter media (as opposed to bypassing the media through the perforations114) or to increase drainage time and allow greater time for coalescence to occur. In such multilayer arrangements ofFIGS.8A through8F, separation of the dispersed phase110from the continuous phase108is further enhanced when there is a separation (e.g., a space or gap) between the perforated filter media layer and any adjacent layer of filter media upstream of the perforated layer (in the flow direction). An example of this technique is illustrated inFIG.8A, where gaps (S1and S2) exist between the layers of the filter media. In multilayered or composite filter media, individual layers of filter media may be bound or attached to one another by a variety of techniques (e.g., through the use of adhesives, thermal or ultrasonic bonding, chemical bonding, needle punching, etc.). To facilitate ease of handling and production, the surfaces of the individual layers in composite filter media may be bound and fixed, so as not to move relative to one another at their interface. In some arrangements, upstream layers are not fixed relative to the perforated layer such that there be a gap or space (e.g., as inFIG.8Awith gap S1) between the two through which captured and coalesced dispersed phase110may flow to the perforations114in the perforated layer. Practically, the gap may be created in any of a number of ways, including any combination of: (1) not bonding the perforated layer to its adjacent upstream layer, (2) ultrasonically bonding the perforated layer to its adjacent upstream layer (and any other layers) with bond points separated far enough apart to enable relative movement between the layers and leave a small gap between the layers, (3) texturing the surface of either the perforated layer or its adjacent upstream layer, such as by introducing surface crinkles, creases, furrows, wrinkles or similar features, to create localized gaps between the layers, (4) pleating or corrugating the perforated layer or its adjacent upstream layer, (5) bonding only on the top and bottom edges of the non-pleated cylinder to hold the layers together during assembly, and to pot or embed these bond points in the endplates during filter element assembly, or (6) use a small number of point bonds or vertical bonding strips to hold the layers together during assembly. Some of the above-listed techniques, notably corrugations, pleats, surface roughness, and texturing, yield a secondary benefit by directing the dispersed phase110towards the perforations114, where the coalesced dispersed phase110accumulates, coalesces further, and drains, freeing up areas without the perforations114to separate the smaller droplets without accumulating excess dispersed phase110. For example, when filter media possesses vertically aligned pleats or corrugations with perforations114, the pleat valleys may be blinded off by compression of the filter media, so it may be desirable to locate the perforations114on the pleat faces in such specific cases. It is noteworthy that the gap between layers need not cover the entire upstream face of the perforated layer. In some arrangements, the gap between the layers covers at least 20% of the face area of the perforated filter media. The thickness of the gap may be small. Performance improvement may be achieved if the perforated layer and its adjacent upstream layer are in direct contact, but their surfaces not fixed relative to one another, such that some movement relative to one another is possible. Further performance improvement may be achieved with wrinkled perforated layers where the maximum separation between layers forming a gap is greater than zero μm. In some arrangements, the maximum separation between layers forming the gap is greater than one μm. In further arrangements, the maximum separation between the layers forming the gap is greater than one-hundred (100) μm. In some arrangements, the gap varies between zero and one-thousand (1,000) μm. In other arrangements, the gap varies between one and one-hundred (100) μm. In other arrangements, the maximum separation between the two layers is less than five-thousand (5,000) μm. In still further arrangements, the maximum separation between the two layers is less than three-thousand (3,000) μm. In yet further arrangements, the maximum separation between the two layers is less than one-thousand (1,000) μm. The use of small gaps (e.g., gaps of less than one-thousand (1,000) μm) is contrary to established coalescer design practices, in which gaps of greater than one millimeter between the so-called coalescer and separator layer are taught in order to ensure adequate space for coalesced water drops to settle. In contrast, the described filter media arrangements use small gaps to direct the flow of coalesced dispersed phase towards perforations114where they accumulate, further grow in size, and are released. In any of the above-described or below-described multi-layer media arrangements, the perforated layer of media may be co-pleated with a non-perforated media to secure the perforated layer of media to the non-perforated media. The co-pleated media may then be attached to filter cartridge endplates in a standard manner. In such arrangements, the perforated layer media has high permeability, intended to capture the coalesced dispersed phase droplets and drain the coalesced dispersed phase droplets through perforations114in the perforated filter media. The perforations114may be positioned anywhere along the face or pleat tips of the media (e.g., as described above with respect toFIGS.7A through7H), preferably with at least one perforation114per pleat face. The non-perforated media in the co-pleated media serves as particle removal filter and initial coalescer. Such co-pleated media provides certain benefits, including improved manufacturability. The co-pleated media results in greater media area for the perforated layer than an unpleated cylinder, which results in a lower face velocity and thereby improving removal and coalescing performance. The perforated layer of the co-pleated filter media may be placed upstream of the center tube, and is integrated into the pleat pack such that it does not require a separate tube, which provides for a simple filter element assembly process. In addition to perforation diameter, perforation density, Frazier permeability, and filter media thickness, the introduction of multilayer filter elements, and a gap upstream of the perforated layer, the location or positioning of the perforations114in the perforated layer also affects removal of the dispersed phase. Ideally, the perforations114should be arranged in linear rows (i.e., about the circumference of a cylindrical filter element), in an ordered array, or in another geometrical pattern with perforations114approximately equidistant from one another. However, it should be understood that non-uniform spacing of the perforations114(e.g., a random pattern of perforations114) also assists in draining coalesced dispersed phase from the filter media. FIGS.9A through9Eshow example perforations patterns for the perforated layer of filter media106. In each ofFIGS.9A through9E, the perforations114are shown as black circles. Dashed lines (identified by902) are used to illustrate the corresponding “base unit” used to create the pattern. The base unit is created across an area of the filter media106to create a perforation pattern (e.g., as shown inFIGS.7A through7G).FIG.9Ashows the simplest pattern and uses a line or row of perforations114as the base unit.FIG.9Buses an equilateral triangle as the base unit to create the ordered array or pattern and may be a preferred pattern for certain applications.FIG.9Cuses a base unit of an isosceles triangle.FIG.9Duses a square base unit, but other quadrilateral base units may also be used.FIG.9Euses concentric circles as the base unit. Other patterns or combinations of base units (e.g., equilateral triangles and squares, circles and lines, etc.) may also be used. Referring toFIG.10, a graph showing the improvement in water removal efficiency by a coalescer in a FWS possessing a perforated layer (e.g., a layer having the filter media106) is shown.FIG.10compares the water removal efficiency for two coalescer elements tested under identical conditions. The coalescer elements were identical, except that one possessed two perforated layers, “FWS With Perforated Layer,” while the other was the reference FWS, “Reference FWS Without Perforated Layer,” which used the same media without the additional perforated layers (e.g., the type described in U.S. Pat. No. 8,678,202, contents of which are herein incorporated by reference in the entirety and for all purposes). Both types of FWS have identical non-pleated outer cylinders of polymeric nonwoven filter media, except that the FWS with perforated layer has two downstream-most layers which are perforated layers. These layers possessed perforations114that are approximately five-hundred fifty (550) μm in diameter arranged in a zig-zag pattern as shown inFIG.7F. In the tested arrangement, the two rows of perforations114are about three millimeters apart. As shown, there is a six percent (6%) improvement in water removal efficiency when the element possesses perforated layers. FIGS.11through15each describe specific arrangements of FWS coalescer elements utilizing the above-described perforated filter media. FWS coalescer elements separate water from a fuel water mixture as descried in U.S. Pat. Nos. 8,678,202, 8,590,712, and 8,517,185, the contents of which are herein incorporated by reference in their entireties and for all purposes. However, it should be understood that the contemplated perforated filter media layer of the present disclosure can be used with other types of coalescers, FWS, and FWS systems. Referring toFIG.11, a cross-sectional view of a coalescer element1100for a FWS system is shown according to an example embodiment. The coalescer element1100is a multi-layer coalescer element that includes layered filter media arranged in a cylindrical manner between two endplates. The coalescer element1100filters a fuel water mixture to remove water (the dispersed phase) from fuel (the continuous phase). The coalescer element1100is part of the FWS system, and provides the cleaned fuel to a component (e.g., an injector of an internal combustion engine, a fuel pump of an internal combustion engine, etc.). The coalescer element1100is configured to facilitate outside-in flow. The coalescer element1100includes an inner pleated cylinder (labeled as a “Pleat Pack” inFIG.11) comprised of pleated filter media and three additional filter media layers (A, B, and C). Two of the layers (B and C) include perforations114(labeled as “Small Perforation(s)” inFIG.11). InFIG.11, the flow of the fluid through the coalescer element1100goes from left to right, passing first through the pleated filter media and then through the three media layers (A, B, C) of a non-pleated cylinder where droplets of the dispersed phase (water) coalesce and drain before being released through the perforations114in the perforated layers (B and C). The flow then passes through the center tube (T), which provides structural support for the coalescer element1100against, for example, forces created by pressure changes and gradients, into a space (labeled as a “Space” inFIG.11) between the perforated layers and an inner filter element (labeled as an “Inner Filter Element” inFIG.11). In the space, the enlarged drops settle out while the fuel (continuous phase) continues through the inner filter element to the component. The center tube (T) includes the perforations114and is not a solid tube. The improved performance of the arrangement ofFIG.11is detailed above inFIG.10. In an example arrangement, the coalescer element1100is configured to facilitate outside-in flow where the pleated filter media is positioned around a periphery of the coalescer element1100and the inner filter element is positioned around an inner periphery of the coalescer element1100. The first layer (A) may be relatively stiff so as to form a tube shape when bonded to the perforated layers (B and C). Depending on the application, the inner-most perforated layer (C) may have a permeability of greater than one-hundred (100) cubic feet per minute, greater than two hundred cubic feet per minute, or greater than three-hundred (300) cubic feet per minute. To achieve a permeability of greater than three-hundred (300) cubic feet per minute, the inner-most perforated layer (C) could be constructed from, for example, mono-filament woven screen (e.g., using polyester fibers, using nylon fibers, etc.). While inFIG.11the coalescer element1100is illustrated as including three layers (A, B, C), it is understood that any number of layers may be similarly implemented in the coalescer element1100. For example, the coalescer element1100may include four layers. Regardless of the number of layers incorporated in the coalescer element1100, according to various embodiments it is advantageous for the coalescer element1100to be configured such that the most downstream layer (e.g., the third layer (C), etc.) include the perforations114. With the arrangement ofFIG.11, the performance improvements continue over the life of the coalescer element1100and are not temporary. Additionally, the coalescer element1100, with the arrangement ofFIG.11, may exhibit approximately eighty percent water removal efficiency for relatively high surfactancy fuels (e.g., biodiesel, etc.) compared to conventional filters which may have a water removal efficiency of approximately sixty-seven percent. Further, using the same high surfactancy fuels, the coalescer element1100is capable of providing a face velocity (e.g., a velocity of fuel provided from the inner filter element, etc.) that is four times a face velocity of fuel provided by conventional filters. In some arrangements, the perforations114are located near the bottom end of the coalescer element1100with respect to gravity and a short distance (e.g., six millimeters, etc.) above the bottom endplate. In such arrangements, the clean continuous phase outlet of a corresponding filtration system is located at the top end of the filter media with respect to gravity, and away from the perforations114to maintain a low velocity region near the perforations114, thereby preventing breakup of the coalesced dispersed phase. The location of the perforations114near the bottom end of the coalescer element1100may facilitate transmission of the dispersed phase (water) through the perforations114due to buoyancy forces. In some arrangements, the perforations114are located near the top end of the coalescer element1100with respect to gravity and a short distance below the top endplate. In such arrangements, the clean continuous phase outlet of a corresponding filtration system is located at the bottom end of the filter media with respect to gravity, and away from the perforations114to maintain a low velocity region near the perforations114, thereby preventing breakup of the coalesced dispersed phase. In arrangements where the clean continuous phase outlet must be placed in the vicinity of the perforations114, the filtration system can include a standpipe that extends above the height of the perforations114such that coalesced dispersed phase does not reenter the separated continuous phase at the outlet. As such, the perforations114are located at a point where water draining from the perforated layer accumulates in a low fluid velocity region on the downstream side of the coalescer element to minimize the breakup and re-entrainment of released water drops back into the fuel. The non-pleated tube may consist of a single perforated layer, two perforated layers preceded by a non-perforated layer (e.g., as shown inFIG.11), or other combination of filter media layers bonded together or simply laid on top of one another. For fuel with low interfacial tension, coalesced drop size is decreased, and it is especially desirable in such instances to locate the perforations114so as to minimize drag forces that would otherwise entrain the drops in opposition to gravitational settling. In some arrangements, the center tube (T) may be upstream of the layers (A, B, C). In other arrangements, one of the layers (B and C) does not include the perforations114and the other of the layers (B and C) does include the perforations114. FIG.12shows another cross-sectional view of the coalescer element1100. As shown inFIG.12, the top endplate (labeled as a “Top Endplate” inFIG.12) includes an opening (labeled as a “Fuel Outlet” inFIG.12) through which the continuous phase (e.g., fuel) exits the coalescer element1100and the bottom endplate (labeled as a “Bottom endplate” inFIG.12) includes an opening (labeled as a “Water Outlet” inFIG.12) through which the dispersed phase (e.g., water) exits the coalescer element1100. The coalescer element1100also includes a lip seal (labeled as a “Lip Seal” inFIG.12) positioned along an annular recess on the bottom endplate. In arrangements where the coalescer element1100is modified for oil-water separation or any application where the dispersed phase is less dense than the continuous phase, a particular orientation is rotated one-hundred and eighty (180) degrees with respect toFIG.11such that the perforations114are near the upper endplate (with respect to gravity) and dispersed phase, removed from the top and continuous phase outlet is at the bottom. In some arrangements, the final layer of filter media in the non-pleated cylinder is perforated. Referring toFIG.13, a cross-sectional view of a coalescer element1300for a FWS system is shown according to an example embodiment. The coalescer element1300is similar to the coalescer element1100, except that the center tube (T) is placed between the pleated filter media and the non-pleated cylinder (as opposed to the coalescer element1100where the non-pleated cylinder is located radially inward from the center tube). The center tube (T) includes the perforations114and is not a solid tube. Additionally, in some arrangements, the coalescer element1300does not include the inner filter element as included in the coalescer element1100. In other arrangements, the coalescer element1300includes an inner element to provide additional separation. In the arrangement ofFIG.13, flow goes from left to right passing first through a pleated cylinder of filter media, then through the center tube, and finally through three media layers of a non-pleated cylinder where droplets coalesce and drain before being released through the perforations114(“Small Perforation(s)” inFIG.13) in the perforated layers. In the coalescer element1300, the center tube is located between the pleated and non-pleated cylinders. It should be noted that the center tube may alternatively be located downstream, radially inwards, from the non-pleated cylinder, similar to the coalescer element1100, however, in the arrangement shown inFIG.13the perforated layer is not compressed against the center tube in operation, captured water is able to drain more freely and water removal efficiency is improved. In some arrangements, the flow of filtered fuel then goes to the component (e.g., fuel injectors, internal combustion engine, etc.), while enlarged water drops settle out upon release from the perforated layer(s) of the inner filter element. The first layer (A) may be relatively stiff so as to form a tube shape when bonded to the perforated layers (B and C). The perforated layer (C) has a first end (e.g., bottom end) that includes at least one perforation114at a location where the dispersed phase collects due to buoyancy and is drained and a second end (e.g., top end) proximate to which the clean continuous phase outlet of a corresponding filtration system is located, away from the perforations114, thereby maintaining a low velocity region near the perforations114and preventing breakup of the coalesced dispersed phase. In an example embodiment, the perforated layer (C) is relatively loosely fit on the perforated layer (B) such that wrinkles or small pleats form on the perforated layer (C). These wrinkles or small pleats assist the perforations114in drainage of the dispersed phase. In these embodiments, the perforated layer (C) is not continuously bonded to the perforated layer (B). This configuration may cause gaps (e.g., non-uniform gaps, etc.) to be formed between the perforated layer (C) and the perforated layer (B) even if a portion of the perforated layer (C) is in contact with a portion of the perforated layer (B). For example, the layers (A, B, C) may only be bonded along a top edge and/or a bottom edge to hold the layers (A, B, C) together during assembly. For example, a top edge of the layers (A, B, C) may be partially encased in potting compound (e.g., uncured potting compound, etc.) or embedded into an endplate during assembly. In these applications, portions of the layers (A, B, C) are free and capable of moving with respect to adjacent layers (A, B, C) and portions of the layers (A, B, C) are potted or partially encased on potting compound. In other applications, the layers (A, B, C) are bonded via vertical bonding strips. For example, the layers (A, B, C) may be bonded via four vertical bonding strips, each vertical bonding strip disposed along the coalescer element1300and angularly offset by ninety degrees relative to two other vertical bonding strips such that the vertical bonding strips are circumferentially disposed about the coalescer element1300. This arrangement is advantageous because the layers (A, B, C) may selectively expand between the vertical bonding strips, thereby facilitating separation of the layers (A, B, C) and drainage of the dispersed phase from between the layers (A, B, C) towards the perforations114. Depending on the application, the inner-most perforated layer (C) may have a permeability of greater than one-hundred cubic feet per minute, greater than one-hundred and seventy cubic feet per minute, or greater than three-hundred cubic feet per minute. To achieve a permeability of greater than three-hundred cubic feet per minute, the inner-most perforated layer (C) could be constructed from, for example, mono-filament woven screen (e.g., using polyester fibers, using nylon fibers, etc.). Referring toFIG.14, a cross-sectional view of the coalescer element1300installed in a FWS as a spin-on element within a filter can (labeled as a “Filter Can” inFIG.14) is shown according to an example embodiment. In the arrangement ofFIG.14, flow occurs radially, from outside of the cylindrical filter element to inside the cylindrical filter element. Both the top and the bottom endplate of the coalescer element1300are open endplates (e.g., include holes, etc.). The top endplate provides a channel for substantially water-free fuel to leave the FWS and go to the component through a filter head (labeled as a “Filter Head” inFIG.14). The top endplate also receives a mixture of fuel and water from the filter head (Filter Head) into the channel. The bottom endplate is open to provide access for settling water drops to reach the collection sump. A gasket (labeled as a “Gasket” inFIG.14) is used to separate wet and dry fuel sides of the FWS. Through elimination of the inner element, gaskets interfacing with the inner element, support tube, etc., the coalescer element1300simplifies construction of the coalescer system without loss of performance (e.g., water removal efficiency, etc.) compared to the coalescer element1100. In side-by-side fuel water separation tests under identical conditions, a coalescer element1300of the type shown inFIGS.13and14(e.g., with perforated layer, center tube radially outward of non-pleated cylinder, perforated layer perforation pattern as shown ifFIG.8C, and no inner element) yielded ninety-one percent (91%) water removal efficiency, while a reference coalescer with inner element (the same type described relative toFIG.10) lacking perforated layer yielded eighty-nine percent (89%) efficiency. Statistically, there was no difference in performance between the coalescer element1100and the coalescer element1300despite the simplified arrangement of the coalescer element1300. Referring toFIG.15, a cross-sectional view a FWS1500having an inside-out coalescer element1502is shown according to an example embodiment. The top endplate of the coalescer element1502seals to the housing or filter head with a gasket. A radial seal (labeled as a “Gasket” inFIG.15) may maintain seal integrity even if the element moves downwards slightly under conditions of high differential pressure, such as when the coalescer element1502is plugged or cold start conditions. In an alternate arrangement, an axial or compression seal is used instead of the radial seal and is designed to maintain adequate seal compression under worst case pressure drop conditions (e.g., cold start conditions, when the coalescer element is plugged, etc.). The housing (labeled as a “Housing” inFIG.15) of the FWS1500defines an internal volume within which the coalescer element1502is positioned. Because of the inside-out nature of the coalescer element1502, a bottom seal, similar to the gasket of the coalescer element1300shown inFIG.14, is not required. This arrangement of the coalescer element1502eliminates a potential bypass point thereby facilitating use of the coalescer element1502in applications where high water removal efficiency is critical. Furthermore, this arrangement of the coalescer element1502provides a reduction in cost because a separate gasket and/or screen structure are not required. The coalescer element1502also may include more media (e.g., thirty percent more media, etc.) than the coalescer element1300, and therefore may have a longer filter life and provide a greater water removal efficiency than the coalescer element1300. As shown, water laden fuel (labeled as “Dirty fuel & H20 In” inFIG.15) enters the coalescer element1502through an opening (e.g., aperture, etc.) in the center of the top endplate and flow radially outward through the coalescer element1502. Alternatively, dirty fuel may enter the coalescer element1502through an open endplate (e.g., a bottom endplate with a perforation114in the center, etc.) in an in-line filter configuration of this embodiment. The fuel flows first through the coalescer element's inner pleated cylinder. The inner pleated cylinder is designed to serve as the first stage of the coalescer element1502, as well as, remove particles. In some arrangements, the arrangement of the inner pleated cylinder and the function of the inner pleated cylinder is similar to the arrangements described in U.S. Pat. No. 8,678,202. The fluid then passes through the supporting center tube, which also prevents the pleat pack from ballooning out as restriction builds. In some arrangements, the center tube is located between the non-pleated and pleated cylinders. In other arrangements, the center tube is located upstream of the pleated cylinder or downstream of the non-pleated cylinder. The fluid then passes through the outer non-pleated cylinder. The non-pleated cylinder may be formed from a single-layer of perforated filter media or from several layers of filter media in which the final layer is a perforated layer. When multiple layers are used, individual layers are designed such that each provides increased coalescence and the droplets increase in size as they progress through the layers. Water drops captured at the perforated layer drain downward and accumulate and coalesce near the perforations114before passing through the perforations114and being released as enlarged drops. Clean, relatively water-free fuel flows upwards, through at least one opening in the cover of the FWS1500, and to a component (e.g., a fuel pump, fuel injectors, an internal combustion engine, etc.). The FWS1500may also be implemented as a spin-on filter where the housing attaches to a filter head rather than the cover. The FWS1500may also be implemented as a cartridge filter. In these embodiments, the mixture enters the FWS1500through an aperture in the housing or the filter head, not directly through the cover. As shown inFIG.15, the perforations114are located near the bottom of the coalescer element and release drops in a similar manner as described above with respect toFIG.8C or8E. Thus, the enlarged drops are released in a relative quiescent zone. As such, the drops of coalesced water are not subject to breakup by turbulence and readily settle into the water collection sump. The housing of the FWS1500causes a water sump to form below the coalescer element1502and includes an opening near the bottom of the housing through which the water is provided to a water drain valve (labeled as a “Water Drain Valve” inFIG.15). From the water drain valve, the water may be provided to, for example, a reservoir or a sink (e.g., an exterior environment, etc.). The FWS1500provides superior water removal efficiency, as well as a simplified design with no need for an additional separator stage. The perforations114are located in close proximity to the bottom endplate, but not so close that the perforations114are pinched closed by adjacent layers pressing against them. In some arrangements, the perforations114are placed between six and twelve millimeters from the endplate, with an optional second row of perforations114, staggered between the first rows of perforations114(e.g., as shown inFIG.7F). In some arrangements, both rows of perforations114are within the region between three and eighteen millimeters from the endplate. In other arrangements, perforations114are positioned in other locations, such as further from the endplate. In further arrangements, the perforations114are positioned at one third or one quarter of the height of the filter media from the endplate. However, the benefit of placing the perforations114within the lowest flow region of the continuous phase where the lowest flow region results in the largest released droplets, and results in optimal settling and water removal efficiency. FIG.3shows a chart comparing the water removal efficiencies of the FWS1500, the “Fuel Water Separator,” with that of the unperforated “Reference Coalescer” previously described using a modified SAE J1488 FWS test procedure. The procedure was modified in that the test was conducted using fuels with low interfacial tension. One fuel exhibited an interfacial tension of 11.5 dyne/cm and the other 8.5 dyne/cm. The standard SAE J1488 test is run using fuel with an interfacial tension between fifteen and nineteen dyne/cm. Under the standard test conditions, both filters exhibit water removal efficiencies of nearly one-hundred percent. Under the more challenging conditions with low interfacial tension, the arrangement ofFIG.15exhibited water removal efficiencies of ninety-six percent (96%) and eighty-eight percent (88%) for fuels with interfacial tensions of 11.5 and 8.5 dyne/cm, respectively. In contrast, the reference filter exhibited a water removal efficiency of only between ninety-four percent (94%) and eighty percent (80%) for the same fuels. The superior performance of the coalescer element1502is also obtained with a second separator stage and with no seal around the bottom endplate. Referring toFIGS.16A and16B, in a filter element, the position of the perforations114(labeled as a “Perforation” inFIGS.16A and16B) relative to the end plate104and potting compound1606(labeled as “End Plate Potting material” inFIG.16A) may affect removal of the dispersed phase110and coalescer performance. Filter elements typically consist of a filter media pack (labeled as a “Media pack” inFIGS.16A and16B) embedded in the end plate (such as a polyamide end plate) or potted and cured in a potting compound (e.g., polyurethane placed on a plastic or metal end plate).FIG.16Aillustrates the bottom portion of an embedded-style filter element1602.FIG.16Billustrates the bottom of a potted-style filter element1604. Dispersed phase removal is greatest when the distance between the bottoms of lowest row of perforations114and the top of the potting compound1606or end plates is zero. For example, for flat end plates without an annular lip, such as embedded end plates, removal is greatest when the distance between the bottoms of lowest row of perforations114and the top of the end plates is zero or when the bottom row of perforations is partially (but not completely) embedded. Similarly, for end plates with an annular lip, such as in the case of filter elements with end plates that use a potting compound to attach the filter media pack to the end plate, removal is greatest when the distance between the bottoms of lowest row of perforations114and the top of the potting compound or end plate is zero. The annular lip may include at least one notch around the outer edge to allow the dispersed phase to drain from the end plate. In some arrangements, the perforations114may be aligned with notches in the annular lip. In either case and for cylindrical filter elements, it is preferable that the diameter of the end plate or potting compound's upper surface be greater than or equal to the diameter of the filter media pack. In such arrangements, coalesced drops emerging from the perforated layer are supported by the upper surface of the potting compound (labeled as “Potting material” inFIG.16B), end plate (labeled as “End Plate” inFIG.16B) or water accumulating in the end plate cavity. As a result, the drops can grow larger since their mass is supported and gravity does not tear the forming drop away from the filter media. In one arrangement, the lowest row of perforations114is defined by a boundary condition such that the distance between perforations114is zero (i.e., there is a continuous or near continuous band between the top of the potting compound or end plate and the bottom edge of the perforated layer in which there is no media in this layer thereby creating a gap between a bottom end of the filter media of this layer and the endplate). The height of this gap ranges from the minimum to the maximum perforation diameter range previously noted. While the filter element106has been variously described as including a layer of filter media having the perforations114, it is understood that the filter element106may not include any of the perforations114in any layer. For example, the filter element106may be constructed from filter media having a target porosity that facilitates separation of the coalesced dispersed phase and the continuous phase. In these embodiments, the center tube may still include perforations or openings to facilitate the transfer of the coalesced dispersed phase and the continuous phase therethrough. The above-described filter media, filter elements, and coalescer elements are described in relation to FWS. However, the same principles can be applied to other filtration systems that utilize coalescence to remove dispersed phase from a continuous phase (e.g., oil water separators or crankcase ventilation coalescer). It should be noted that any use of the term “example” herein to describe various embodiments is intended to indicate that such embodiments are possible examples, representations, and/or illustrations of possible embodiments (and such term is not intended to connote that such embodiments are necessarily extraordinary or superlative examples). It is important to note that the construction and arrangement of the various example embodiments are illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. For example, elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Additionally, features from particular embodiments may be combined with features from other embodiments as would be understood by one of ordinary skill in the art. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and arrangement of the various example embodiments without departing from the scope of the present invention.
88,527
11857895
DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE DISCLOSURE The present disclosure describes an electrostatic coalescer apparatus and associated method for separating water from water-in-oil mixtures that uses bi-phase (Scott-T) transformers to step up voltage and transmit high voltage electricity to the electrodes housed in the coalescer apparatus. The Scott-T transformer is a transformer circuit that is used to produce two-phase electric power, with a phase shift of 90 degrees, from a three-phase source. FIG.1Ais a schematic cross-sectional view an embodiment of an electrostatic coalescer apparatus100according to the present disclosure. The coalescer is housed in a vessel105that defines a cavity110and a longitudinal axis112. The vessel105features an emulsion inlet115for receiving a crude oil emulsion that can contain appreciable amounts of water, salt and other undesirable constituents. In some embodiments the emulsion inlet115is positioned at the bottom of the vessel105and the emulsion enters the vessel under positive pressure. The emulsion inlet can lead through an inlet header116that conveys the input emulsion deeper into the vessel to avoid the presence of accumulated water. At least one outlet for water is positioned at the vessel105. In the embodiment shown inFIG.1A, there are two such water outlets120,122. After water has been separated from the emulsion as described further below, the water exits from the vessel via outlets120,122by force of gravity. The crude oil from which impurities have been removed exits from the vessel via a crude outlet125that can be positioned, as shown, at the top of the vessel105. Within the vessel105, two pairs of electrodes are positioned horizontally adjacent to each other. The first pair of electrodes includes electrodes132and134and the second pair of electrodes includes electrodes136and138. In the first pair electrodes132is positioned above electrode134. In the second pair electrode136is positioned above electrode138. All of the electrodes132,134,136,138extend horizontally (in the direction of the longitudinal axis112). In some embodiments each of the electrodes132,134,136,138comprises a layer of charged grids. The first pair of electrodes132/134is connected to a first bi-phase Scott-T transformer circuit140. The second pair of electrodes136/138is connected to a second bi-phase Scott-T transformer circuit145. The coalescer apparatus100can be considered to be “double-volted” in that each electrode pair includes two layers of grids that are connected to transformers. The pairs of electrodes132/134,136/138are symmetrically positioned about a center of the vessel (along the longitudinal axis112). Together, the electrodes cover approximately the entire length of the vessel. In some embodiments, the first and second bi-phase Scott-T transformer circuits are equivalent. An enlarged view showing a configuration of the first bi-phase Scott-T transformer circuit140is shown inFIG.1B. As shown, the b-phase Scott-T transformer circuit145includes two transformers (T1, T2) that are configured perpendicularly to each other, hence the “T” nomenclature. The first transformer (T1), which is the “main” transformer, consists of primary winding that is split between a first section202and a second section204and a secondary winding216. The second transformer (T2), which is the “teaser” transformer, consists of a primary winding208and a secondary winding210. A first end212of the first second of primary winding202of the first transformer (T1) is coupled to a first phase (1)=0° of a three-phase power supply. The second end of the first section202is connected to the first end of the second section204by a conductor215. A second end of the section202of the primary winding of the first transformer (T1) is coupled to a conductor215(e.g., an electrical wire) that connects the first section to second section204. The second end218of the second section204is coupled to a second phase (Φ=120°) of a three-phase power supply. The first end222of the secondary winding206of T1 is coupled to electrode132of the first electrode pair via a high-voltage entrance bushing. The phase of the signal provided to the electrode is (Φ=90°), one phase of a two-phase system. A second end224of the secondary winding206of the first transformer (T1) is grounded. Turning to the second transformer (T2), the first end of the primary winding232taps the center of the primary winding208of T1 (i.e. between sections202,204) in a 1:1 ratio. That is, 50 percent of the windings of the primary of the first transformer (T1) are in section202, and 50 percent are in section204. The second end234of the primary winding208of transformer (T2) is coupled to a third phase (Φ=240°) of a three-phase power supply. The second end taps the primary winding208of the second transformer (T2) is an 86.6% (0.5×√3) ratio. The first end242of the secondary winding210of the second transformer (T2) is the connected to electrode134of the first electrode pair via a high-voltage entrance bushing. The phase of the signal provided to the electrode is (Φ=90°), the other phase of the two-phase system. A second end244of the secondary winding210of the first transformer (T2) is grounded. The second transformer circuit145of the coalescer apparatus is coupled to the three-phase power supply and the second pair of electrodes136/138in the same manner so that there is a symmetry between the way the first and second electrode pairs132/134,136/138are electrically energized. In the configuration shown inFIG.1B, the bi-phase Scott-T transformer is a step-up transformer and the secondary windings are at a higher voltage with respect to the primary windings. As noted, the first sides of the secondary windings of the first and second transformers (T1), (T2) are connected to the inside electrodes inside the vessel105while the other sides are grounded. This configuration generates high-voltage two-phase power signal with the same voltage and a phase shift of 90 degrees from a three-phase power supply. In each pair of electrodes132/134,136/138, the top electrode is coupled to the (Φ=0°) phase while the bottom electrode is coupled to the (Φ=90°) phase. The normalized potential difference between the electrode is equivalent to sin x−cos x, which is another sinusoidal signal. This configuration generates a more uniform and homogenous electrostatic field with same voltage density and no phase shift. In addition, in the embodiment ofFIGS.1A and1B, only two transformers need to be employed, in contrast to the conventional three-phase coalescer that uses three transformers. FIG.2Ais a schematic cross-sectional view of the same embodiment of the coalescer shown inFIG.1Abut this figure shows the waveform of voltage intensity between the symmetric electrodes supplied by the disclosed Scott-T transformer circuits. As shown, there is a first AC high voltage waveform305that represents the voltage between the first electrode132and the second electrode of the first electrode pair of the coalescer. A second AC high voltage waveform310represents the voltage between the first electrode136and the second electrode138of the second electrode pair. A similar pattern is generated between the bottom plates and the interface level that forms as water coalesces and separates from the crude oil emulsion. This water then exits from the vessel via the water outlets120,122. Some of the soluble impurities present in the original crude oil emulsion are removed with the water. As illustrated, the waveforms305,310have the same amplitude and phase, providing a uniform electric field throughout the coalescer. The uniform field, in turn, creates homogeneous condition for the aggregation of water throughout the vessel, improving the efficiency of the coalescing process.FIG.2Bis an exemplary graph showing a voltage density between the electrodes (of each pair) over time. In various implements, voltage levels in the vessel can be maintained within a range of 15 Kilovolts to 25 Kilovolts which is suitable for inducing sufficient aggregation of water molecules to ensure their separation from the crude oil emulsion. There are a number of advantages to the coalescer apparatus powered using bi-phase Scott-T transformers according to the present disclosure. The use of Scott-T Transformers for AC electrostatic coalescers reduces the number of transformers required for each vessel to 2 from 3; by this measure, the possibility of unbalanced voltage on the primary windings is reduced. The reduction of the possibility of unbalanced voltages, in turn, reduces power loses over time, avoids undesired voltage drops, and increases transformer life. This will result in a more robust and resilient design with a power cable redundancy. In some embodiments, the two bi-phase Scott-T transformer circuits coupled to the vessel can be provided with an independent power supply. Therefore, if one power supply is lost, only one of the transformer circuits will be down and the other one can keep working and provide a partial treatment of the emulsion, mitigating the upset. Importantly, the disclosed coalescer using bi-phase Scott-T transformers enables the employment of symmetric electrodes with a more uniform and synchronized (no phase shift) electrostatic field throughout the entire length of the vessel. This measure improves water droplet aggregation (coalescing) and separation. It is to be understood that any structural and functional details disclosed herein are not to be interpreted as limiting the systems and methods, but rather are provided as a representative embodiment and/or arrangement for teaching one skilled in the art one or more ways to implement the methods. It is to be further understood that like numerals in the drawings represent like elements through the several figures, and that not all components or steps described and illustrated with reference to the figures are required for all embodiments or arrangements. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and “comprising”, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof. Terms of orientation are used herein merely for purposes of convention and referencing and are not to be construed as limiting. However, it is recognized these terms could be used with reference to a viewer. Accordingly, no limitations are implied or to be inferred. Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having,” “containing,” “involving,” and variations thereof herein, is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. The subject matter described above is provided by way of illustration only and should not be construed as limiting. Various modifications and changes can be made to the subject matter described herein without following the example embodiments and applications illustrated and described, and without departing from the true spirit and scope of the invention encompassed by the present disclosure, which is defined by the set of recitations in the following claims and by structures and functions or steps which are equivalent to these recitations.
11,795
11857896
DETAILED DESCRIPTION OF THE INVENTION While this invention is illustrated and described in preferred embodiments, the fluid filters and the containers of the present invention may be produced in many different configurations, sizes, forms and materials. Referring now to the drawings,FIGS.1to4illustrate a water filter constructed consistent with a first preferred embodiment of the present invention. The water filter100is in a compact disc shape and comprises a housing110having open top and open bottom, an upper rim111adjacent to the open top, a top cover112removably placed over the upper rim111, a handle113extending upwardly from the top cover112and useful to grasp the top cover112. The top cover112is formed with a plurality of apertures which serve as water inlets114of the water filter100to allow for flow of the water into the housing110. The water inlets114are distributed over the whole top cover112, which may increase the flow rate of the water into the filter100. The housing110houses a deflector plate120snugly carried on a support member121that laterally and circumferentially extends from a side wall of the housing110, and a water impermeable plate130disposed in a vertical direction relative to the deflector plate120in spaced-apart fashion. In this embodiment, the deflector plate120is detachably carried on the support member121, and this detachable structure provides the ease of cleaning the filter100and replace the filter media. As clearly shown inFIG.4, the deflector plate120has a central aperture122to allow for flow of the water therethrough. The deflector plate120is preferably made of water impermeable material, such as water impermeable resin, to prevent the water from flowing downwardly through other regions of the deflector plate120than the central aperture122. The water impermeable plate130has a diameter smaller than an inner diameter of the housing, so that a circular gap131is defined therebetween. As illustrated, a plurality of spaced ribs140are provided to connect an underside of the support member121with a top surface of the water impermeable plate130so as to define a plurality of windows141between the deflector plate120and the water impermeable plate130(seeFIG.2). The ribs140may be connected with the support member121and the water impermeable plate130using any method known in the art, for example, they may be made of a plastic material and molded together integrally. The circular gap131is in fluid communication with the windows141. The water filter100further comprises a filter media for filtering the water to remove or reduce the concentration of bacteria, viruses and particulate matters. In particular, the filter media comprises a first filter material layer151useful as a coarse filter of the water flowing from the water inlets114into the filter. The first filter material layer151may consist of a first filter material, for instance, nylon or other suitable filtration material known in the art. The first filter material layer151is arranged in a space defined by the top cover112and the deflector plate120within the housing110. The filter media further comprises a second filter material layer152comprising the second filter material which is arranged in a space defined together by the deflector plate120and the water impermeable plate130. The second filter material is, for example, activated carbon, or ion exchange resin, or a mixture thereof. A feature of the water filter100is a third filter material layer153disposed to close the open bottom of the housing110by a method known in the art. For example, the third filter material layer153is held in a circular ring which may be fastened to the bottom of the housing110. The water coming from the circular gap131is guided to flow into the third filter material layer153and out of the water filter100. There is illustrated inFIG.3a particularly preferred embodiment of the third filter material layer153. The third filter material layer153is generally a laminated structure. In the illustrated embodiment illustrated inFIG.3, the laminated structure comprises a supporting layer1531, a prefilter layer1532, a nanofiber-coated layer1533, a nanofiber layer1534, and a protective layer1535seen in the water flow direction. The supporting layer1531may be formed with polyethylene terephthalate (PET) having a basic weight in the range of about 10 to 80 gsm, preferably about 40 gsm. The prefilter layer1532may consist of absorbent fabric having a basic weight in the range of about 10 to 150 gsm, for example about 40 to 80 gsm, preferably 65 gsm. The nanofiber layer1533may be formed with a plurality of polymer-based nanofibers having a diameter in the range of 10 to 900 nanometer, which are capable of removing or reducing bacteria, viruses and heavy metals. The nanofiber-coated layer1534and the protective layer1535may be formed with PET having a basic weight in the range of about 5 to 70 gsm, preferably about 30 gsm, respectively. The water flows from the second filter material layer152through the circular gap131into this third filter material layer153, and then runs through the nanofiber-based laminate filter layer to flow out of the water filter100. Advantageously, the three layers1532,1533,1534held between the two outer layers1531,1535are laminated together using any method known in the art, for example hot-melt laminating methods. The laminated structure is then overlaid with the top supporting layer1531, and is placed directly over the bottom protective layer1535. The water flows into the first filter material layer151via the water inlets114, and the filtered water by the first filter material layer151flows down through the central aperture122of the deflector plate120, and then is guided by the water impermeable plate130to deflect the flow of the water through transversely within the second filter material layer152towards the plurality of windows141formed by the ribs140, the water impermeable plate130and the deflector plate120. The filtered water by the second filter material layer152flows through the windows141and then into the circular gap131between the water impermeable plate130and the housing110. Through the circular gap131, the water would flow down to the third filter material layer153that is placed to close the open bottom of the housing110. The extended water flow path follows the arrow direction shown inFIG.1. Because of using the design of the deflector structure, a flow path for the water to flow in the filter100is formed by the first filter material layer151→the deflector plate120→the central aperture122of the deflector plate120→the second filter material layer152→the plurality of windows141→the circular gap131→the third filter material layer153→outside the housing110of the filter100. The deflector structure enables to deflect and guide the water to flow in the tortuous path within the housing, thereby to significantly increase the length of the flow path, which in turn increases the residence time of the water in the filter100and the contact surface of water with the filter media for improved filtration effect, at the same time to greatly decrease the thickness of the filter100. The first and second filter material layers151,152are effective to remove and intercept chlorine, heavy metals and other particulate matters. The nanofiber laminated structure plays the role of effectively filtering out most nano-particles, bacteria, viruses present in the water while maintaining a low pressure drop. The filter100is able to achieve the comprehensive depth filtration, and features the significant reduction in packing depth of the conventional filter materials like porous resin beads, activated carbon articles, due to the design of tortuous flow path. Therefore, the filter100can be of a compact configuration but still achieve reliable filtration performance. Now turning toFIG.5, there is illustrated a water pitcher1comprising a reservoir2for storing filtered water, and a pitcher top. The reservoir2has an open-top rim3. The pitcher top of the pitcher1is formed by the filter100discussed above and shown inFIGS.1-3. The upper rim111of the housing110of the filter100is removably engageable with the open-top rim3of the reservoir2, with the top cover112as the lid of the water pitcher1. It would be appreciated that an additional lid member may be provided to cover the top cover112to avoid dust. The filtered water can flow from the filter100into the reservoir2. In some cases, it is likely that air inside the water filter100would not be able escape and remains in the interior of the water filter100, which may have an impact on the water flow rate through the water filter100. In order to solve this problem, an air release device160constructed consistent with a preferred embodiment of the invention is incorporated into the water filter100as shown inFIG.8. There is clearly illustrated the air release device160inFIGS.9,10A and10B, which comprises a top portion161and an inner cavity162positioned beneath the top portion161and being in fluid communication with both the interior of the water filter100and the ambient environment. Specifically, the top portion161is a generally L-shaped, and includes a horizontal part1611and a vertical part1612attached to the side wall of the water filter100by, for example, molding together with the water filter100. The air release device160defines the inner cavity162, at least one air inlet163positioned at an upper portion of the inner cavity162, one or more apertures or channels164are formed at a bottom of the inner cavity162to allow for inflow of the water from the water filter, and an air outlet165positioned on top of the inner cavity161. The air remaining in the water filter100flows into the inner cavity162through the air inlet163. The air outlet165leads to the ambient environment through a lateral passageway166relative to a longitudinal axis of the inner cavity162. The passageway166extends through the top portion161and the side wall of the housing110, and thus opens to the ambient environment. A sealing member168is provided between the top portion161and the side wall of the housing110to create a sealing effect for the passageway166which extends through the top portion161and the side wall of the water filter100. The provision of the sealing member168can effectively prevent any unwanted leakage of air or water from the passageway166into a gap between the top portion161and the side wall of the water filter100. The air release device160further comprises a floating ball167that is located in the inner cavity162and that is sized such that at least a part of the floating ball167can completely block the air outlet165. The floating ball is able to float up and down to close or open the air outlet165. Preferably, the inner cavity162gradually tapers in a direction from bottom to top in order to confine upward movement of the floating ball167towards the air outlet165. The floating167is made of a plastic material, for example, that is capable of floating on the water. When the water level in the water filter100rises to reach the apertures or channels164at the bottom of the inner cavity162, the water enters the inner cavity162through the apertures or channels164and acts on the floating ball167which is caused to ascend towards the air outlet165until a part of the floating ball167closes or blocks the air outlet165(seeFIG.10B). The air remaining in the water filter100flows into the inner cavity162and is discharged when the inner cavity162is filling with the water. The air outlet165always keeps open and thus the fluid communication between the inside and the outside of the water filter100remains until the water level rises to a blockage location of the floating ball167to block the air outlet165. When the filter water flows down and out of the water filter100and the water level in the inner cavity162falls at the same time, the water exits from the inner cavity162through the apertures or channels164, and the floating ball167descends and falls onto the bottom of the inner cavity162, the air outlet165opens so that the fluid communication between the inside and the outside of the water filter100resumes. A vessel170may be provided to accommodate the water filter100as shown inFIG.11. The vessel170may be configured to have an open or perforated top, and an open or perforated bottom for water inflow and outflow. The vessel170comprises a lower portion171and an upper portion172. The lower portion171has a downwardly tapering conical side wall173adapted to be held on a reservoir for storing the filtered water. The water filter100snugly sits within the lower portion171. For the sake of clarity and simplicity, the internal structure of the filter media of the water filter is not shown in this figure. The upper portion172is adapted for containing a volume of water which is subject to purification treatment by the water filter100. FIGS.6A and6Bprovide in schematic manner a water filter200of more compact structure constructed consistent with the second embodiment of this invention. The water filter200comprises a filter media220provided in the disc form, and a housing210. The filter200of this embodiment comprises two or more water inlets221arranged in the vicinity of a periphery of the top of the filter200to allow the water to enter into an interior of the filter media220. The water filter200also comprises a housing210having an open top and a closed bottom211for housing the filter media220. The housing210is made of a water impermeable material, and the closed bottom serves as a water impermeable plate to guide the water flow. The closed bottom211of the housing210has an aperture centered on the bottom211, which functions as a water outlet212to allow the water to flow out of the filter media220. Because of the water impermeable housing210, the water from the filter media220cannot flow out of the filter in a vertical direction. Rather, the water is guided to flow towards and leave from the water outlet212at the bottom211of the housing (FIG.6B). As such the water inlets221are deviated in a staggered manner from the water outlet212to create an extended flow path along which the water flows in the filter media220, and the length of the flow path is maximized in the interior of the filter. Therefore, the water cannot flow directly in a thickness direction (i.e. height direction) of the filter media220, with a result of increased residence time of the water in the filter. The filter media220may comprise a same filter material, or two or more different filter materials. Preferably, the filter media220is configured to have a multi-layered structure. Specifically, the filter media220comprises a first filter material to form a first filter material layer, a second filter material to form a second filter material layer, and a third filter material to form a third filter material layer. By way of example, the first filter material is nylon or filterable non-woven fabrics; the second filter material is selected from activated carbon, ion exchange resin beads, and a mixture thereof; and the third filter material is a nanofiber layer, for example the nanofiber-based laminate discussed above in the first embodiment. The non-woven fabric may be in the form of a multi-layer structure comprising polyacrylonitrile (PAN), Polyethylene naphthalate (PEN) or the like. In some cases, the interior of the filter media220may be delimited by impermeable partitions to create a more tortuous flow path. Further, the filter media220may comprise a layer of nanofiber laminate, for example the one discussed in the first embodiment herein, to further increase the filtration efficiency. Like the water filter100of the above first embodiment, the water filter200may be constructed to form a pitcher top adapted to be removably or pivotably engageable with an open-top rim of the water pitcher10. The water is flowing into the filter media220via the water inlets221, transversely passes through the interior of the filter media220towards the water outlet212due to the water impermeable housing210, and then leaves out of the filter200into a reservoir of the pitcher10. This flow path provides the extended residence time for the water to increase the filtration efficiency. FIGS.7A and7Bprovide in schematic manner a water filter300constructed consistent with the third embodiment of this invention. The water filter300of this embodiment is substantially same in structure as the water filter200of the above second embodiment, but differs in the arrangement of water inlets and water outlets. As illustrated, the water filter300comprises a filter media320and a water impermeable housing310for housing the filter media320. Only one water inlet321is centered in the filter media320to allow for flow of the water into an interior of the filter media220. The housing310has a closed bottom311provided with two or more water outlets312arranged in the vicinity of a side wall of the housing311, and the water is guided to flow towards and leave from the water outlets312adjacent to the side wall of the housing (FIG.7B). Therefore, an extended flow path is created for the water, with a result of increased residence time of the water in the filter. Again, the water filter300may be constructed to form a pitcher top adapted to be removably or pivotably engageable with an open-top rim of the water pitcher20. The filters of the invention can be in the disc form, depending on the size and application of the water container. The filters200,300preferably have a ratio of width to depth in the range of 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 15:1, 18:1, 20:1, 25:1 to 30:1. Therefore, the present invention provides a fluid filter which is constructed compactly such that the filter does not submerge into the filtered water, and does not occupy significantly the internal space of the water container. Due to the compact structure, the fluid filter of the invention enables to increase flow rate of the fluid and maximize the space usage for the filtered fluid. In addition, the extended flow path leads to an extended period of residence time within interior of the filter media, which helps to increase the chance of interaction between the filter materials and the fluid during filtration process. Accordingly, filtration efficiency can be enhanced. While the present invention is described in connection with what is presently considered to be the most practical and preferred embodiments, it should be appreciated that the invention is not limited to the disclosed embodiments, and is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the claims. Modifications and variations in the present invention may be made without departing from the novel aspects of the invention as defined in the claims, and this application is limited only by the scope of the claims. NUMERICAL REFERENCES 1,10,20pitcher2reservoir3open-top rim100,200,300filter110,210,310housing111upper rim112top cover113handle114,221,321water inlet120deflector plate121support member130water impermeable plate122central aperture131circular gap140rib141window151first filter material layer152second filter material layer153third filter material layer1531supporting layer1532prefilter layer1533nanofiber-coated layer1534nanofiber layer1535protective layer160air release device161top portion1611horizontal part1612vertical part162inner cavity163air inlet164aperture or channel165air outlet166passageway167floating ball168sealing member170vessel171lower portion172upper portion173downwardly tapering conical side wall211,311closed bottom212,312water outlet220,320filter media
19,708
11857897
In the drawings, the reference numbers represent the following apparatus and internal parts respectively: A: gas cooling-scrubbing apparatus; B: filter;1: gas phase inlet;2: cyclone jet scrubbing monopipe;3: spray filtering pipe;4: filtering bed;5: coalescing bed;6: gas phase outlet;7: spray head;8: spray water pipe;9: scrubbing nozzle;10: scrubbing nozzle water pipe;11: spray pipe plate;12: spray overflow pipe;13: cyclone jet overflow pipe;14: cyclone jet pipe plate15: cyclone jet cooling water pipe;16: circulating water outlet;17: liquid discharge port;2-1: cyclone jet inlet;2-2: nozzle;2-3: contraction section;2-4: mixing section;2-5: diffuser section;2-6: tangential inlet;2-7: bubble cap;2-8: cyclone jet pipe;2-9: cyclone pipe;2-10: sedimentation outlet;3-1: spray inlet;3-2: filtering module;3-3: spray port. DETAILED DESCRIPTION In order to make the technical problem to be solved by the present disclosure, the technical solution and the beneficial effects clearer, the present invention is now further illustrated with reference to the following accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present disclosure, not to limit the present disclosure. After studying the collision mechanism of solid particles and water droplets, the inventor of the present application have discovered that there are three main ways for solid particles to contact and coalesce with a liquid phase: (1) inertial deposition of larger particles; (2) capture and interception by water droplets in the direction of the gas flow; and (3) the diffusion mechanism of smaller particles due to the action of the circumferential turbulence field. In order to reinforce the gas cooling-scrubbing effect and enhance the separation efficiency, the cyclone jet scrubbing, spray scrubbing, filtering spray and coalescing separation technologies may be used. Based on the above discoveries, the present invention has been accomplished. The technical concept of the present invention is as follows: The gas cooling-scrubbing apparatus according to the present disclosure comprises: a cyclone jet scrubbing unit, a spray scrubbing unit, a filtering spray unit and a coalescing dehydration unit. After a dusty gas is treated by the apparatus, solid particles are captured by the scrubbing water to form a liquid-solid combinant which is separated from the gas. The treated gas is discharged from a top exhaust port, and the waste scrubbing water is discharged from a liquid discharge port. The circulating water in the apparatus flows out from a circulating water outlet, and the solid particles in the circulating water are filtered through a filter. At the same time, fresh water is replenished to the apparatus through a circulating water outlet pipeline. While the tiny solid particles in the gas are separated, the gas is cooled by water. The apparatus is suitable for popularization and application in the field of gas scrubbing. First, the dusty gas enters the cyclone jet scrubbing unit from the gas phase inlet, enters the jetting region of the cyclone jet scrubbing monopipe from the cyclone jet inlet, and is fully mixed with the scrubbing water sprayed from the nozzle in the contraction section, the mixing section and the diffuser section. After the solid particles are captured by the atomized droplets to form a liquid-solid combinant, the combinant enters the cyclone region from the tangential inlet. Under the action of centrifugal force in the cyclone pipe, the liquid-solid combinant sinks and is discharged from the sedimentation outlet, while the gas treated by cyclone jetting rises, and is discharged into the spray scrubbing unit through the cyclone jet pipe. In the spray scrubbing unit, the gas treated by cyclone jetting enters the jet filtering pipe from the spray inlet, is further filtered by the filtering module, and then discharged upward from the spray port at a reduced rate. The high-pressure scrubbing water is sprayed downward through the scrubbing nozzle to collide with the rising gas, so as to further cool and scrub the gas. At the same time, the tiny solid particles in the filtering module are detached from the module by the backwash of the high-pressure scrubbing water to prolong the service life of the filtering module. The gas treated by spray scrubbing enters the filtering spray unit, wherein the spray head disposed above the filtering bed sprays cooling-scrubbing water downward to further reinforce the cooling-scrubbing effect. The gas treated by filtering spray enters the coalescing dehydration unit, wherein the coalescing bed can capture the tiny droplets in the gas effectively to prevent the gas phase from entraining droplets into a downstream device, and the treated gas is discharged from the gas phase outlet. Now, specific embodiments of the present disclosure will be described with reference to the accompanying drawings. FIG.1is a schematic flow chart of a gas cooling-scrubbing process according to a preferred embodiment of the present disclosure. As shown inFIG.1, a high-temperature dusty gas enters a gas cooling-scrubbing apparatus A from a gas inlet. Solid particles are captured by scrubbing water to form a liquid-solid combinant which is separated from the gas. The treated gas is discharged from an exhaust port on the top of the apparatus, and the waste scrubbing water is discharged from a liquid discharge port. The circulating water in the apparatus flows out from a circulating water outlet, and the solid particles in the circulating water are filtered through a filter B. At the same time, fresh water is replenished to the apparatus through a circulating water outlet pipeline. FIG.2is a schematic view of a gas cooling-scrubbing apparatus according to a preferred embodiment of the present disclosure. As shown inFIG.2, a high-temperature dusty gas first enters a cyclone jet scrubbing unit from a gas phase inlet1, wherein the cyclone jet scrubbing unit comprises a cyclone jet scrubbing monopipe2, a cyclone jet cooling water pipe15, a cyclone jet pipe plate14and a cyclone jet overflow pipe13. The gas treated by cyclone jetting rises and enters a spray scrubbing unit, wherein the spray scrubbing unit comprises a spray filtering pipe3, a spray pipe plate11, a spray overflow pipe12, a scrubbing nozzle9and a scrubbing nozzle water pipe10. The gas treated by spray scrubbing enters a filtering spray unit, wherein the filtering spray unit comprises a filtering bed4, a spray head7and a spray water pipe8. The gas treated by filtering spray enters a coalescing dehydration unit, wherein the coalescing dehydration unit comprises a coalescing bed5. The treated gas is discharged from a gas phase outlet6; the waste scrubbing water is discharged from a liquid discharge port17; and the circulating water in the apparatus flows out from a circulating water outlet16. FIG.3is a schematic view of a cyclone jet scrubbing monopipe according to a preferred embodiment of the present disclosure. As shown inFIG.3, the cyclone jet scrubbing monopipe includes a jetting region and a cyclone region. The jetting region is provided with a cyclone jet inlet2-1, a nozzle2-2, a contraction section2-3, a mixing section2-4and an diffuser section2-5. The cyclone region is provided with a tangential inlet2-6, a cyclone pipe2-9, a sedimentation outlet2-10, a cyclone jet nozzle2-8and a bubble cap2-7. By means of the jet principle, the cyclone jet scrubbing monopipe allows the solid particles in the gas to collide with the water droplets atomized by the nozzle and be intercepted and trapped. At the same time, the temperature is decreased by water cooling. After the solid particles are captured during the spray scrubbing, the liquid-solid combinant enters the inside of the cyclone pipe from the tangential inlet under the action of a pressure, and rotates at a high speed, so that the gas flow is accelerated, and a spiral flow state is developed. Due to further reduction of the cross-section of the flow passage, the cyclone speed continues to increase, forming a stable centrifugal force field inside the cyclone pipe. The gas phase with a light specific gravity coalesces into a gas core in the central zone of the cyclone pipe, and is discharged from the cyclone jet pipe. The liquid-solid combinant with a heavier specific gravity is discharged from the sedimentation outlet, thereby realizing rapid separation of coke-containing water droplets from flexible coking gas. FIG.4is a schematic view of a spray filtering pipe according to a preferred embodiment of the present disclosure. As shown inFIG.4, the spray filtering pipe is provided with a spray inlet3-1, a filtering module3-2and a spray port3-3. The internal filtering module in the spray filtering pipe is used to filter the residual fine solid particles in the gas phase. At the same time, a spray head is provided above the spray port to enable countercurrent contact of the sprayed water droplets with the gas to reinforce scrubbing and prevent the filtering module from clogging. EXAMPLES The invention will be further illustrated with reference to the following specific Examples. It is nevertheless to be appreciated that these Examples are only intended to exemplify the invention without limiting the scope of the invention. The test methods in the following examples for which no specific conditions are indicated will be carried out generally under conventional conditions or under those conditions suggested by the manufacturers. Unless otherwise specified, all parts are parts by weight, and all percentages are percentages by weight. Example 1 A gas cooling-scrubbing apparatus according to the present disclosure was used in a delayed coking and decoking device. A cyclone jet scrubbing unit, a spray scrubbing unit, a filtering spray unit, and a coalescing dehydration unit were provided to scrub the coke powder in the gas phase. (1) Process Conditions The average particle size of the coke powder in the gas phase was 20 μm, the mass concentration was about 250 mg/m3, and the gas intake was 200,000 m3/h. (2) Process Flow and Apparatus The process flow is shown inFIG.1, wherein the filter was a bag filter. The apparatus is shown inFIG.2, wherein 250 cyclone jet scrubbing monopipes and 250 spray filtering pipes were provided, and the fresh water supplement was 2 vol % of the gas intake. (3) Application Effect The mass concentration of the coke powder in the gas phase was reduced to no more than 10 mg/m3. Example 2 A gas cooling-scrubbing apparatus according to the present disclosure was used in a flexicoking and flexible coking gas decoking device. A cyclone jet scrubbing unit, a spray scrubbing unit, a filtering spray unit, and a coalescing dehydration unit were provided to scrub the coke powder in the gas phase. (1) Process Conditions The average particle size of the coke powder in the flexible coking gas was 10 μm, the mass concentration was about 50 mg/m3, the gas intake was 300,000 m3/h, and the gas temperature was 91° C. (2) Process Flow and Apparatus The process flow is shown inFIG.1, wherein the filter was a bag filter. The apparatus is shown inFIG.2, wherein 400 cyclone jet scrubbing monopipes and 400 spray filtering pipes were provided, and the fresh water supplement was 2 vol % of the gas intake. (3) Application Effect The mass concentration of the coke powder in the gas phase was reduced to no more than 10 mg/m3, and the temperature was decreased to not higher than 50° C. The Examples listed above are only preferred examples in the disclosure, and they are not intended to limit the scope of the disclosure. Equivalent variations and modifications according to the disclosure in the scope of the present application for invention all fall in the technical scope of the disclosure. All of the documents mentioned in the disclosure are incorporated herein by reference, as if each of them were incorporated herein individually by reference. It is to be further understood that various changes or modifications to the invention can be made by those skilled in the art after reading the above teachings of the invention, and these equivalent variations fall in the scope defined by the accompanying claims of the application as well.
12,341
11857898
DETAILED DESCRIPTION InFIG.2, reference numeral20generally indicates a liquid filter assembly according to the present disclosure. The liquid filter assembly20includes a filter head22and a filter cartridge24. The filter head22is typically installed on equipment, in a liquid line, for example a hydraulic line or lubricating fluid (oil) line. During servicing the filter head22would typically remain in place in the equipment. The filter cartridge24, on the other hand, is removably mounted on the filter head22. Servicing is provided by replacement of the media contained within the filter cartridge24. The filter cartridge24depicted herein is a spin-on type of filter cartridge. Thus, during servicing, the entire filter cartridge24, including both the media and outer housing, is removed and discarded and replaced with an entirely new filter cartridge24. In the cross section ofFIG.2, a central longitudinal axis26is depicted, around which the filter assembly20is positioned. The terms “axial”, “axially” and variants thereof, as used herein, is generally meant to refer to a feature extending in the general direction of the axis26. The terms “radial”, “radially”, and variants thereof, are meant to refer to a direction toward or away from the axis26. Still in reference toFIG.2, the filter head22includes a liquid flow inlet28and a liquid flow outlet30. During operation, liquid to be filtered is directed into the filter head22through the inlet28. Liquid is then directed through the filter cartridge24for filtration. The filtered liquid is then returned to the filter head22to exit through the outlet30. In a typical system, the filter head22comprises a cast metal part, for example, cast aluminum, with various features added thereto. While many embodiments are possible, in the one shown, the filter head22includes a flange32, which can have bolt holes34,35for securing the filter at22to the equipment. Secured to the flange32is an end wall36. The end wall36will typically include an inlet opening38in communication with the inlet28, to allow for the flow of liquid from the filter head22into the cartridge24. End wall36will also have an outlet opening40to allow for the flow of filtered liquid from the cartridge24into the filter head22to allow it to exit through the main outlet30. Extending axially from the end wall36is a circumferential band42. The band42has a surrounding wall44with an exterior surface46and an opposite interior or inner radial surface48. The inner radial surface48include a system to allow for selective attachment and detachment between the filter head22and the filter cartridge24, which is discussed further below. The filter cartridge24is shown in perspective view inFIG.2and cross section inFIG.2connected to the filter head22. The filter cartridge24includes a filter housing50. The filter housing50includes an external can or shell52that has a surrounding wall54. The surrounding wall54has an exterior surface56and an opposite interior surface58. There is a closed bottom60and an opposite mouth62that interfaces with the filter head22. The shell52can include a plurality of anti-slip dimples53circumferentially spaced about the shell52adjacent to the mouth62. The dimples53can be helpful for the user to be able to apply a grip on the cartridge24, when attaching or removing the cartridge24and the filter head22. Typically, the outer shell52comprises a metal component. The housing50defines an interior volume64. Within the interior volume64is positioned a filter media construction66. The filter media construction66comprises a filter media68positioned in extension between a second (lower) end cap70and a first (upper) end construction71. The end construction71is adjacent to a first end of the media construction66and can be part of a first end cap72secured to the media construction66. The media68can comprise a variety of materials as selected for the particular operation and conditions to be encountered. Typically, the filter media68would be provided in a pleated form, although alternatives are possible. A variety of types or shapes of media or media pleats can be used. Adhesive beads, for example, can help maintain media integrity and pleat spacing. In some alternative arrangements, the media68can be lined with a plastic or wire mesh screen, if desired. Filter media construction66can be tubular in shape and configured around, and defines, an open filter interior volume74. Positioned within the opened filter interior volume74is an internal media support76, in this example, comprising a porous liner extending along the media68between the end caps70,72and secured to the end caps70,72. Although alternatives are possible, in the example shown, the second end cap70is a closed end cap, meaning it has a closed center prohibiting passage therethrough of unfiltered liquid. The tubular filter media construction66has a first end80, which is secured to the first end cap72, and an opposite second end82, which is secured to the second end cap70. The media68is secured to the second end cap70by various methods, including adhering or potting, or by molding in place on the media68. A variety of materials can be used for the end cap70, which can include metal or plastic. The first end cap72, on the other hand, is typically an open end cap defining a central flow aperture84therethrough. The aperture84is positioned in direct flow communication with the interior74of the media68. Herein, the term “direct flow communication” is meant to refer to a passageway that allows a flow communication with the interior74in a manner that does not require passage through the media68. That is, liquid within the interior74can flow through the aperture84directly, without passing through the media68at the same time. Of course, the liquid does not reach the interior74unless it has first passed through the media68in the first instance, for an “out-to-in” flow arrangement as described. As indicated, the filter cartridge24depicted is configured for out-to-in flow, during filtering. By this, it is meant that unfiltered liquid is directed from the filter head22into an annulus86around the media68and between the interior surface58of the wall54; and then through the media68, through the support76and into the interior74. The filtered liquid is then directed upwardly through central flow aperture84in the first end cap72, back into the filter head22through the outlet opening40and then out through the outlet exit30. It is noted that many of the principles described herein can be utilized in association with a “in-to-out” flow arrangement, in which the flow direction for liquid being filtered is in the reverse direction, i.e., through the aperture84, into the interior76, through the media68, into the annulus86, and then back into the filter head22. In general, a seal arrangement is needed between the filter cartridge24and the filter head22in order to prevent liquid flow from bypassing the media68as it is directed through the filter cartridge24. Such a seal arrangement is provided by a seal member88on the cartridge24to form a seal between and against the cartridge24and the filter head22. Attention is directed toFIGS.3-7, in which the first end construction71is illustrated, either by itself or in combination with other features. The first end construction71includes an outer radial wall90. The outer radial wall90extends at least a portion of the length of the filter media construction66from the first end80in a direction toward the second end82. The outer radial wall90covers or overlaps a portion of the media construction66. While many examples are possible, in the one shown, the outer radial wall90overlaps less than 25% and greater than 5% of an overall length of the filter media construction between the first end80and second end82. InFIG.8, the outer radial wall90of the first end construction71is shown enlarged. The outer radial wall90defines a seal member seat92, which holds the seal member88. In the example shown, the seal member seat92has a pair of outward radially extending flanges94,95with a wall section96therebetween. The seal member88is positioned between the flanges94,95. Still in reference toFIG.8, it can be seen how the housing50is attached to the first end construction71. While many different techniques are available, in the example shown, the housing50is attached to the outer radial wall90. In particular, the housing50is non removably fixed or secured to the outer radial wall90by being folded over at least a first of the flanges95. The housing50can cover at least a portion of the wall section96in between the flanges94,95. In some embodiments, the housing50can also be folded over at least a portion of the second of the flanges94and completely cover the wall section96at fold97. InFIG.8, the seal member88is oriented radially outwardly in the seal member seat92and against the housing50. In the example shown, the housing50is sandwiched between and against the seal member88and the wall section96of the outer radial wall90of the first end construction71. The first end construction71further includes an axial wall100. The axial wall100covers the first end80of the media construction66. In general, the outer radial wall90extends at about a 90° angle relative to the axial wall100. The axial wall100defines the central flow aperture84. The central flow aperture84can further accommodate a seal member, such as a grommet seal member102therein for connection with the filter head22, e.g., the portion of the filter head22defining the outlet opening40. The first end construction71includes, in the example embodiment shown, a plurality of circumferentially spaced non-connecting sections107, shown in the example figures at107a,107b, and107c. The non-connecting sections107are, in general, along the outer radial wall90as either complete gaps (no wall structure at all); or smooth sections of the wall90; or sections of the wall90that are non-interfering with the filter head22, when the filter head22is attached to the cartridge24. In preferred implementations, the non-connecting sections107are both equal in circumferential length and equally spaced from each other. In this case, when there are the three non-connecting sections107a,107b, and107c, they are separated from each other by60g. In accordance with principles of this disclosure, the filter cartridge24includes a system to allow for a low friction installation of the cartridge24to the filter head22, including simply inserting and rotating the cartridge less than a full turn. In this embodiment, the system includes a connection system104. The connection system104will allow for low friction insertion and turning of the cartridge24less than 180° for example, about 60°. The connection system104eliminates cross-threading, and lends itself to having the connectors be specific to specific customers. In the example embodiment illustrated, the connection system104includes a plurality of circumferentially spaced connecting sections, illustrated herein as106,108, and110. Each connecting section106,108,110includes a plurality of helical profiles112,113. There can be at least two helical profiles112,113and more than two helical profiles, for example, three helical profiles112,113,114. In the example shown, there are four helical profiles112,113,114,115(FIG.8). Each of the helical profiles112,113,114,115extends circumferentially along and projecting from the outer radial wall90. By “helical profile”, it is meant a the geometrical outline along an outermost border which, if continued, would have a general spiral shape. A helical profile is not a screw thread. In a helical profile, a plane perpendicular to the central longitudinal axis will pass through more than one profile, whereas in a screw thread, a plane perpendicular to the central longitudinal axis will pass through only one thread profile. Reference is made toFIG.8. In the embodiment shown, there are four helical profiles112,113,114,115. As can be seen inFIG.7, the helical profiles112-115extend at a helix angle116. By the term “helix angle”, it is meant the angle of each of the helical profiles112-115relative to a plane perpendicular to the longitudinal axis26. InFIG.7, the helix angle is shown at reference numeral116. Each of the helical profiles112-115preferably has the same helix angle116, although in other embodiments, the helix angle116could be different for each helical profile112-115. InFIG.12,118cshows the amount of seal compression, which is affected by the helix angle116. Each of the helical profiles112-115is axially spaced from an adjacent helical profile112-115. By “axial spacing”, it is meant the spacing between the load bearing surfaces of each of the profiles112-115. The “load bearing” surface is the surface that will be against the thread of the filter head, when connected. The load bearing surfaces, in this embodiment, are shown at112a,113a,114a, and115ainFIG.20. The axial spacing between each of the individual helical profiles112-115can be the same or can be different. In the embodiment shown, the spacing is different. For example,FIGS.8and20illustrate the axial distance between connecting section112and113at D1; the distance between connecting section113and114at D2; and the distance between connecting section114and115at D3. While in some embodiments, each of D1, D2, and D3can be equal, in many preferred embodiments, each of D1, D2, and D3are of different values. Each of the helical profiles112-115has a cross-sectional shape. The cross sectional shape of each of the helical profiles112-115can all be identical, or preferably, can be different from each other. Preferably, each of the helical profiles112,115within each connecting section106,108,110has a different cross-sectional shape from at least one other helical profile112-115within the respective connecting section106,108,110. For example, inFIGS.8and20, the upper most helical profile112has a trapezoidal shape, in which one of the non-parallel sides112ais contained within a plane that is perpendicular to the longitudinal axis26, while the other of the non-parallel sides112bis angled relative to that same plane. The helical profile113is illustrated as being rectangular in shape, which could be square. The helical profile114is shown to be trapezoidal, in which both non-parallel sides are angled relative to a plane perpendicular to the longitudinal axis26. The helical profile115is shown to be rounded in cross section. These are just examples, and it should be understood, that there are many, many different shapes and combinations that can be used. Indeed, every customer of these cartridges24can ask for their own specific “code” of helical profiles. FIG.21illustrates an alternative helical profile combination, including differing the axial depths of the load bearing surfaces of the profiles. In the example ofFIG.21, there are 3 helical profiles312,313,314, which vary in: shape, axial spacing, and load bearing depth. All three of the helical profiles312,313,314are trapezoidal, but differently shaped trapezoids from each other. The axial spacing between profile312aand313ais shown at D1, while the axial spacing between profile313aand314ais shown at D2. D1and D2are different, with D1being greater than D2. The axial depths are shown at H1, H2, and H3. They are measured from the base of each of the axial bearing surfaces312a,313a,314aand a terminal (free) end of each of the helical profiles312,313,314. The axial depths H1, H2, H3vary between each other in this example embodiment. From a review ofFIGS.8,20, and21, it should be appreciated that when selecting the helical profile combination, the at least one (or more) of the helical profiles can vary between at least one other of the helical profiles by at least one of: profile shape, axial spacing, and/or axial depth, and/or any combination of these characteristics. Preferably, each connecting section106,108,110is identical to the other connecting sections106,108,110. This means that when mounting the cartridge24onto the filter head22, the user does not have to be concerned about matching the correct connecting section106,108,110with the particular receiving connecting segments on the filter head22. The filter cartridge24is constructed such that the filter housing50is non-removably secured to the outer radial wall90at the mouth62with the connecting sections106,108,110of the outer radial wall90being outside of the filter housing50. Indeed, the connecting sections106,108,110will be located axially above a terminal end98(FIG.8) of the housing50. Preferably, the outer radial wall90has a plurality of alternating circumferentially spaced connecting sections106,108,110and smooth non-connecting sections107a,107b,107c. While the connecting sections106,108,110can be interrupted with short sections that do not form connections with the filter head22, in general, in preferred examples, the non-connecting sections107will have no structure along the radial wall90that forms a connection or attachment with the filter head22, although alternatives are possible. Any interruptions in the connecting sections106,108,110that do not form connections with the filter head22are not considered to within the definition of “non-connecting sections.” In reference now toFIGS.9-11, the filter head22is shown in further detail. The inner radial surface48of the filter head22includes a plurality of circumferentially spaced connecting segments122,124,126constructed and arranged to mate with the connecting sections106,108,110of the filter cartridge24. Attention is directed toFIG.12. InFIG.12, it can be seen how the connecting segments122,124,126mate with the connecting sections106,108,110. In particular, each of the connecting segments122,124,126have a profile128, which is a mirror image of the profile shapes of the connecting sections106,108,110. As such, the profile128includes recesses having the same cross-sectional shape as the helical profiles112-115. For example, the profile128has an upper most profile recess130with a shape matching the trapezoidal shape of the helical profile112. Similarly, profile recess131has a rectangular shape, which matches the cross-sectional shape of the helical profile113. Profile recess132has a trapezoidal shape matching the shape of the helical profile114, while profile recess133has a rounded shape to receive the rounded shape to receive the rounded helical profile115. Of course, as the cross sectional shapes of the helical profiles112-115is changed, the corresponding profile recesses130-133would change as well. As can be seen inFIGS.9-11, the connecting segments122,124,126are circumferentially spaced along the inner radial surface48and are separated by smooth, ungrooved, portions135,136,137of the inner radial surface48. Attention is directed toFIGS.5and6, which shown one preferred first end construction71. The first end construction71is constructed and arranged to have an inlet arrangement140. The inlet arrangement140includes, in the example embodiment, a plurality of fluid flowpaths142, which can be inlet openings142, in the first end construction71. When fluid to be filtered enters the filter assembly20, it flows into the filter head22through the inlet28through the inlet opening38, where it exits the filter head22and enters the filter cartridge24. The fluid to filtered then enters the annulus86of the cartridge24by flowing through the inlet openings142in the first end construction71. In this embodiment, the outer radial wall90of the first end construction71is spaced from and attached to the axial wall100to define a plurality of circumferentially spaced gaps144therebetween. The gaps144function as the inlet openings142. In the preferred embodiment depicted, the circumferentially spaced connecting sections106,108,110alternate with the open gaps144in the outer radial wall90. The gaps144correspond to the non-connecting sections107. The outer radial wall90has a continuous walled ring146at a distal end148from the axial wall100. The continuous ring146is continuous in that it circumscribes and forms the entire outer periphery of the first end construction71. The continuous ring146holds the seal member88thereon. In the example embodiment, the gaps144forming the inlet openings142are between the ring146and the non-connecting sections107a,107b,107c. The filter cartridge24can further include a stop member150. The stop member150provides an engagement surface for a portion of the filter head22to abut or engage when the filter cartridge24is being mounted on and secured to the filter head22. The stop member150will provide feedback to the user that the cartridge24has been fully mated onto the filter head22with the mating of the connecting sections106,108,110and the connecting segments122,124,126. The engagement between the filter head22and the stop member150will prevent further rotation of the filter cartridge24relative to the filter head22. In the embodiment shown, the stop member150is radially protruding from the outer radial wall90of the first end construction71. In the example embodiment shown, the stop member150extends from the outer radial wall90at terminal ends of the helical profiles112-115of at least one of the connecting sections106,108,110. In the example shown inFIGS.5and7, there is only a single stop member150on the first end construction71. In some embodiments, the stop member150can extend from terminal ends of each of the connecting sections106,108,110. The helical profiles112-115can, in some variations, include a projecting bump toward the end of the profiles that would be engaged just prior to full attachment between the filter head22and the cartridge24. The bumps would require extra torque at the end of the attachment process between the connecting sections106,108,110from the connecting segments122,124,126. The bumps would help to prevent unintended disconnection between the filter head22and the cartridge24due to, for example, vibration. In accordance with principles of this disclosure, the filter cartridge24can further include at least one spring-loaded detent160. The detent160extends axially outwardly from the axial wall100of the first end construction71. In many preferred embodiments, and in the embodiment illustrated, there are a plurality of spring loaded detents160,161,162, each extending axially outwardly from the axial wall100of the first end construction71. The spring loaded detents160,161,162are circumferentially spaced from one another and are radially outward of the central flow aperture84, while being radially inward of the inlet openings142. Each spring loaded detent160,161,162includes a spring, such as a leaf spring171,172,173attached to the axial wall100to allow for elastic deflection of the detent160,161,162in an axial direction. The detents160,161,162are received by detent recesses164,165,166defined within an inner surface176of the end wall36of the filter head22. The interaction between the detents160-162and detent recesses164-166provide feedback, such as an audible “click” sound to inform the user that the filter cartridge24has been properly installed on the filter head22. The detents160,161,162also help to prevent the filter cartridge24from backing off of the filter head22due to vibration during operation. The feedback, in addition to being audible, can also be tactile, in that the user can also feel when the detents160-162are recesses164-166. An alternative embodiment of the filter assembly20is shown inFIGS.13-15at20′. The construction and features of the assembly20′ is the same as that of assembly20, and those descriptions and features are not again described here, but rather, are incorporated herein by reference. The difference between the assembly20and the assembly20′ is that the plurality of circumferentially spaced connecting segments122′ is on an outer radial surface200of the band42′ filter head22′, while the connecting sections106′ of the filter cartridge24′ are along an inner wall202of the end cap72′. The end cap72′ has a surrounding wall204that is radially outside of the outer diameter of the filter media68′. The surrounding wall204includes an extension206that projects axially from the first end80′ of the media68′, in a direction opposite of the media68′. The volume208within the extension206and between the end cap72′ and a terminal end210of the extension206is sized to receive the band42′ of the filter head22′. InFIGS.14and15, it can be appreciated that the surrounding wall54of the can52is non-removably attached to a remaining part of the cartridge24′. In the example shown, the can52is attached to the end cap72′ by being folded or crimped at crimp section212over the terminal end210of the end cap extension206. The axial wall100′ of the end cap72′ can include detents, such as160′,162′ projecting therefrom. The detents160′,162′ are received within the detent recesses in the filter head22′ provide feedback in the form of an audible click or a tactile click feeling. A seal member102′ can be seen inFIGS.14and15to provide a seal between unfiltered flow on the inlet side (dirty side) of the media68′ and the outlet side (clean side) of the media68′. The seal member102′ is around the outlet84′ of the cartridge24′. In the filter head22′, the unfiltered liquid flows through an unfiltered liquid port220to the cartridge24′. After flowing through the media68′, the filtered liquid returns to the head22′ through filtered liquid port222. An alternative embodiment of a bowl cartridge assembly is shown inFIGS.16-19at402. The bowl cartridge assembly402includes a filter cartridge404and a filter bowl406. The filter cartridge404is insertable and removable and replaceable within the filter bowl406. The filter bowl406removably connects/attaches to a filter head, such as filter head22ofFIGS.9and10.FIG.18shows the filter cartridge404partially installed within an interior408of the filter bowl406, andFIG.19shows the filter cartridge404fully installed and positioned within the interior408of the filter bowl408. The filter cartridge404can vary. In the example shown, the filter cartridge404has a tubular (e.g., cylindrical) section of pleated filter media410. At opposite ends of the filter media410are first and second end constructions or end caps412,414. The first end cap412is an open end cap having a through opening416, which is in communication with an interior of the pleated filter media. The second end cap414can be open or closed. There can be a seal member417circumscribing the opening416. The first end cap412can include at least one, and in the example shown, a plurality of spring loaded detents420,421,422each extending axially outwardly from the axial wall419of the first end cap412. The spring loaded detents420,421,422are analogous to the detents160,161,162, and the description of160,161,162applies to detents420,421,422and is not again repeated. The detents420,421,422are received by, for example, detent recesses164,165,166defined within an inner surface176of the end wall36of the filter head22to provide feedback, such as an audible “click” sound to inform the user that the filter cartridge404has been properly installed on the filter head22, while also preventing the filter cartridge404from backing off of the filter head22due to vibration during operation. The feedback, in addition to being audible, can also be tactile. The first end cap412includes a first plurality of circumferentially spaced radial projections430extending radially from an outer perimeter413of the first end cap412. The first plurality of radial projections430have a first longitudinal length with a terminal end431sized to engage a rim432the filter bowl406, when the cartridge404is inserted into the filter bowl406. The first plurality of radial projections430having a least one lateral (or side) portion433oriented to circumferentially abut a part of the filter bowl406when the cartridge404is inserted into the bowl406. As shown inFIGS.18and19, the lateral portion433will circumferentially engage against a lateral edge434of spaced connecting sections446,448, and450(described below), which helps to angularly locate, or clock, the spring loaded detents420,421,422relative to the filter head22. The radial projections430also will prevent rotation of the cartridge404within the bowl406by engaging against the lateral edges434of the connecting sections446,448, and450. The first end cap412further includes a second plurality of circumferentially spaced radial projections435extending from the outer radial wall413. The second plurality of radial projections435having a second longitudinal length that is shorter than the first longitudinal length of the first radial projections430. The second plurality of radial projections435are oriented to assist with correct rotational positioning of the cartridge404within the filter bowl406, when the cartridge404is inserted into the filter bowl406. The second radial projections435will interfere with connecting sections446,448, and450and thereby prevent the cartridge404from being inserted in the bowl406unless properly aligned with the bowl406. In accordance with principles of this disclosure, the filter bowl406includes an outer radial wall407, forming a surrounding wall defining the interior volume408therewithin. The filter bowl406has a system to allow for a low friction installation of the bowl cartridge assembly402to the filter head22, including simply inserting and rotating the assembly402less than a full turn. In this embodiment, the system includes a connection system440, analogous to system104described above, and not again repeated here. The connection system440works like the system104and allows for low friction insertion and turning of the assembly402less than 180° for example, about 60°. The connection system440eliminates cross-threading, and lends itself to having the connectors be specific to specific customers. The connection system440is implemented on the outer radial wall407. The connection system440includes a plurality of circumferentially spaced connecting sections, illustrated herein as446,448, and450, analogous to connecting sections106,108,110, having a plurality of helical profiles452,453,454, analogous to helical profiles112,113,114. The helical profiles452,453,454can have the various characteristics as described above in association withFIGS.8,20, and21, the description being incorporated herein by reference, and not again repeated here. When the filter cartridge404is installed in the bowl406, flow gaps462,464result between the filter cartridge404and the filter bowl406. The flow gaps462,464are also circumferentially between adjacent connecting sections446,448,450. When secured to the filter head22, the flow gaps462,464can be flow passageways for inlet fluid flow to be filtered. The fluid to be filtered flows from the filter head22, into the filter assembly402and into the flow gaps462,464. Then, it flow radially through the filter media410(removing impurities from the fluid) into the filter interior. From there, it exits the filter assembly402by flowing through the opening416in the first end cap412and back into the filter head22. After a period of use, the filter cartridge404can be removed from the bowl406and replaced with a new filter cartridge404. The bowl406is mounted on the filter head22through mating of the connection system440, as described above with respect to system104. The bowl cartridge assembly402can be used with a filter head, such as filter head22, to form a filter assembly. A method of servicing the filter assembly20can be practiced using the above principles. After a period of operation, the filter cartridge24will need servicing by replacing the cartridge24, due to the filter media68becoming clogged. To service the filter assembly20, the old filter cartridge24is removed from the filter head22and discarded. To remove the old filter cartridge24from the filter head, the cartridge24is rotated relative to the filter head22, preferably by hand and without the use of tools. The cartridge24is rotated in such a way as to unmate the connecting sections106,108,110from the connecting segments122,124,126. This also releases the seal member88, and allows the cartridge24to be pulled axially from the filter head22. A new filter cartridge24with new media68is then provided. The new filter cartridge24is mounted onto the filter head22by aligning the outlet opening40of the filter head22with the grommet seal member102of the cartridge24. The cartridge24is pushed axially toward the filter head22and then rotated less than 90°, typically no more than 60°. The cartridge24is rotated to engage or mate the connecting sections106,108,110with the connecting segments122,124,126. The cartridge24can be rotated until the stop member150prevents further rotation of the cartridge24within the filter head22. As the cartridge24is being rotated within the filter head22, the seal member88is compressed, to form the seal between and against the filter head22and the cartridge24. During the step of rotation, the cartridge24is rotated until the detents160,161,162are received within the detent recesses164,165,166, and feedback in the form of an audible click or a tactile click feeling is detected by the user. This will ensure that the filter cartridge24has been properly installed on the filter head22, and the filter assembly20is again ready for filtration. The above represents example principles. Many embodiments can be made using these principles.
33,534
11857899
DESCRIPTION OF THE PREFERRED EMBODIMENTS The principles and operation of the present invention may be better understood with reference to the drawings and the accompanying description. The following figure reference labels are used throughout the description to refer to similarly functioning components are used throughout the specification hereinbelow. 10Filter Housing;12odownstream outlet opening;10adedicated opening;14Lower housing;10Lperipheral lumen/;14cpiston assembly coupling12Upper Housing;members;12hhandle opening;14fflush exit opening;12iupstream Inlet opening;20stacked disc filter elements;22in-line mesh filter ring124o,spray orifice100,filter apparatus;224o102126,spine first end/spine110,fluid diverter/valve226base portion;210,body;226adaptor housing;310128a,spine radial support110Lvalve body open lumen;228amembers110uvalve body upper face;128b,spine longitudinal110bvalve body lower face;228bsupport members110ovalve body lower130, 230Piston assembly;central opening;132, 232compression plate;110cperipheral channel;232acompression plated110pvalve body perimeteradaptor housing;surface;232tthreading;110tupper face threading;134,compression spring;112,flow inlet portion/234212inlet aperture;236piston compression114,first open aperture/adaptor;214outlet open aperture;236ahead portion116,second open aperture/236btail portion;216spine aperture;140flush valve;116s,spine aperture sealed150valve controller/216sportion;regulator/switch;116o,spine aperture open152flow/pressure sensor;216oportion;155automated controller;118,closed aperture/156flow valves;218outlet close aperture;160flow motor;120,filter spine assembly;161housing;220162,motor inlet;120c,spine connecting162a,220cchannel;162b120Lspine lumen/164,motor outlet;inner lumen/164a,internal lumen central;164b122,spine second166flow turbine module;222end/spine top portion;165turbine vanes;122cspine leg connectors;168gear and clutch module;124,spine legs;170fluid diverter coupling224adaptor;312flow inlet portion/inlet310pressure relief fluidaperture;diverter;314first open310cperipheral channel;aperture/outlet324cspring recess;open aperture;324dholding pegs;316second open aperture/324ihousing (inner) distal end;spine aperture;324ohousing (outer) proximal;316ospine aperture openendportion;326spring;318pressure relief326aspring body;aperture;326cspring end;318ccoupling member;328piston body;318opressure relief opening;328aouter end surface;320pressure relief piston328binner end surface;assembly;328cspring housing recess;324housing;328dhousing coupling fins;324aouter surface;328fcentral body;324binner surface;328eseal recess; Referring now to the drawings,FIGS.1A-Bshow schematic block diagrams of optional configuration of a self-cleaning filter apparatus100according to embodiments of the present invention.FIG.1Ashows apparatus100where a flush valve140is incorporated within housing10such that the flush valve140may be controlled internally with apparatus100. FIG.1Bshows an optional configuration of apparatus100depicted inFIG.1Ain the form of apparatus102wherein that flush valve140is external to housing10and may be controlled externally, manually, remotely, electronically, hydraulically and/or automatically. Filter apparatus100,102are configured to receive an upstream flowing fluid within a housing10that is equipped with filtering element(s)20, for filtering the flowing fluid as it flows across filtering element(s)20. Filter apparatus100is adapted to function in at least two modes a filtering mode and a self-cleaning mode. Optionally the filtering apparatus100,102may be used as a stand-alone filtering device. Optionally filtering apparatus100,102may also be used in a filtering network and/or battery comprising a plurality of filtering apparatus100,102that are interconnected with one another and/or networked together to form a battery of filters. The filtering mode utilizes a first direction of flow through apparatus100, shown by the black arrows, and the self-cleaning mode utilizes a second direction of flow through apparatus100to clean filtering element(s)20from accumulated debris, shown by the white arrows. Filter apparatus100comprises a housing10having an open lumen that includes filtering elements20disposed on a spine assembly120, filtering element20is provided in the form of a plurality of ring disc filters that are disposed along the length of spine assembly120, in a compressed stacked formation. Embodiments of the present invention provide for stacking (compress) and de-stacking (decompressing) the plurality of ring disc filters20along the length of spine assembly120. The filtering elements20and spine assembly120are preferably centered within the lumen of housing10, and configured to maximize the filtering volume available within the internal cavity of housing10. Optionally and preferably spine assembly and filtering elements20compartmentalize housing10into two concentric lumen, an external lumen10L and an internal lumen120L. Most preferably external lumen10L provides for receiving the un-filtered flowing fluid while internal lumen120L provides for receiving the filtered flowing fluid. Housing10comprises two portions, an upper housing portion12and a lower housing portion14that may be coupled and securely sealed with one another to form housing10. Housing upper housing portions12and lower housing portions14may be coupled with one another by optional coupling means as is known in the art for example including over an external clamping ring, matching threading, nuts and bolts, snaps, male-female connection members, any combination thereof or the like. Spine assembly120and filtering elements20may span both upper housing portion12and lower housing portion14. Preferably the length of spine assembly120is maximized to fit within the internal cavity formed within housing10. Housing10comprises at least three openings provided to allow both first flow direction during filtering, and the second flow direction, during self-cleaning. Optionally the at least three openings may be dispersed on housing10in any combination or manner on upper portion housing12and lower portion housing14. Preferably the at least three openings include an inlet opening12i, an outlet opening12oand a flush exit opening14f. Optionally housing10may be fit with a fourth opening for associating a valve controller150with housing10, optionally and preferably about upper housing portion12. Most preferably valve controller150is disposed externally to housing10and provided to control the position of a fluid diverter110disposed internally to housing10. In embodiments valve controller150may be provided in the form of a bidirectional flow motor160, shown inFIG.12-14. Bidirectional flow motor160utilizes directed upstream water flow to control the position of the internal fluid diverter110that in turn control the phase of filter100. Optionally valve controller150may be controlled with a rotational motions providing for manually turning controller150to change between the different position of diverter110, therein changing between the direction of fluid flow. Optionally valve controller150may be controlled with a linear manual manipulation wherein controller150is provided in the form of a lever that may be raised up and down so as to switch the direction of fluid flow through housing10and preferably through diverter110, for example s shown inFIG.3C. An example of a valve controller150in the form of a manual lever150L is shown inFIG.3C. Optionally linearly manipulating lever150L, to cause fluid diverter110to move up and down, allows the diversion of the flowing fluid through diverter110to flow from the inlet aperture (112not shown) to aperture116(spine aperture) so as to divert flow into channel110cwhile simultaneously releasing and/or unstacking the disc filtering elements (not shown in this view) disposed along the spine120. Preferably the reverse motion of lever150L allows for stacking the disc filtering elements20along spine120while allowing upstream flowing fluid to be diverted via diverter110into housing10for filtering across the stacked disc filters. AccordinglyFIG.3Cshows an optional depiction of a controller150in the form of a lever150L that may be utilized to simultaneously control the flow of upstream flowing fluid through diverter110and to stack (compress) or unstack (release) the disc filters along spine120. Optionally lever150L may further simultaneously provide for opening or closing flush opening14fduring self-cleaning or filtering modes respectively. Optionally valve controller150may be controlled by automatic means for example by way of a mechanical valve, electronic valve, hydraulic valve or the like. Optionally housing10may be provided with optional dedicated openings, for example for associating housing10with an external fluid source, for introducing an external fluid source into housing10. Optionally such an external fluid source may be a container comprising at least one or more of an agent, a flowing fluid, an additive, a cleaning agent, a filtering additive, a cleaning fluid, a detergent, the like or any combination thereof. Optionally housing10may be provided with a further optional dedicated opening for example openings10a,12h. Optionally opening10amay be placed about upper portion12or lower portion14. Optional dedicated opening10a, for example as shown inFIG.7, preferably provides placement and replacement of an integrated in-line circular mesh filter ring22. Circular mesh filter ring22may optionally be associated over aperture116on fluid diverter110to provide coarse filtering of upstream flowing fluid utilized during the second flow direction during self-cleaning. Preferably opening10ais utilized to gain access to and/or to replace and/or maintenance of the in-line filter ring22, for example as shown inFIG.8C. Preferably opening10ais capped and/or sealed during filter use and may only be uncapped and/or unsealed for maintenance purposes of ring22when not in use. Optional dedicated opening12hmay be utilized for associating with and/or incorporating a secondary handle or manual manipulator for controlling a portion of and/or an internal member of apparatus100. For example, such a dedicated optional opening may be utilized for incorporating a spinning handle provided for manually spinning at least one of or both spine assembly120and/or filtering element20. Preferably first flow direction provides for filtering by allowing an upstream flow of an un-filtered flowing fluid to flow from an upstream source into housing10through inlet opening12iand allowing the filtered flowing fluid to exit housing10through outlet opening12o. During first flow direction and filtering, an upstream flow of an un-filtered flowing fluid is received into housing10through inlet12i, flowing into peripheral lumen10L. Due to buildup of fluid pressure within housing10, the un-filtered flowing fluid is thereafter forced to flow from peripheral lumen10L across filtering element20associated with spine assembly120, into inner lumen120L, therein filtering the flowing fluid. Preferably in the process debris and waste is trapped along filtering element20allowing the now filtered fluid to pass into inner lumen120L. During self-cleaning, second flow direction is provided by allowing a flowing fluid, preferably from an upstream source and optionally from an external fluid source, to flow into housing10through inlet12iis channeled into spine assembly120, in particular spine legs124, and out of housing10through flush exit opening14f, allowing debris and filtered waste material to be flushed from the filtering element20. Most preferably spine legs124are provided in the form of a hollow elongated tube having a plurality of spray nozzle orifices124oalong its length, therein allowing a flowing fluid to flow therethrough. In order to facilitate both direction of flow filtering apparatus100comprises a fluid diverter110disposed internally within housing10, most preferably within upper portion housing12. Fluid diverter110is provided in the form of a valve body. Optionally fluid diverter110may be provided in the form of a two way valve body. More preferably fluid diverter110is provided in the form of a three-way valve body. Optionally fluid diverter110may be provided in the form of a four-way valve body. Optionally fluid diverter110may be provided in the form of a multi-way valve body having at least two ways about the valve body, and most preferably at least three or more ways available ways in the valve body. Most preferably fluid diverter110provides for diverting the direction of flow between first flow direction and second flow direction. Therein diverter110provides for switching and determining the direction of flow within filter apparatus100. Optionally fluid diverter110may be fit with an in-line filter mesh ring22and/or screen, for example as shown inFIG.8C, to provide for in-line filtering of the upstream fluid used during the self-cleaning mode. Optionally in-line filter mesh may be securely associated and/or coupled over the fluid diverter aperture and/or opening utilized during self-cleaning mode with the second flow direction. Optionally in-line filter mesh may be associated with fluid diverter110at any point along the path of the second flow direction utilized during self-cleaning mode. Fluid diverter110is associated with and/or in fluid communication with outlet12o, inlet12iand spine assembly120particularly spine legs124. Optionally and preferably fluid diverter110may be indirectly associated with and in fluid communication with flush exit opening14f, most preferably via spine assembly120in particular via spine legs124. Flush exit opening14fis most preferably disposed about lower portion housing14. Preferably flush exit opening14fis controlled with a flush valve140. Optionally flush valve140may be provided as a valve integrated within housing10and optionally and preferably associated either directly or indirectly with fluid diverter110, for example as shown inFIG.1A. Optionally flush valve140may be provided as a valve external to housing10, for example as shown inFIG.1B. Optionally an external flush valve140may be a manually operated valve or a remotely controllable valve for example including but not limited to a hydraulic valve, electronic valve, automatic valve, piezoelectric valve, flapper valve or the like as is known in the art. Optionally a remotely controllable flush valve140may be controlled by a controller155. Optionally and more preferably flush valve140may be opened seamlessly when apparatus100is in self-cleaning mode during the second flow direction, and seamlessly closed when assuming filtering mode utilizing the first flow direction, as depicted by the position of fluid diverter110. Optionally flush valve140may be associated with, directly or indirectly, and/or integrated with, fluid diverter110and its external controller150for example, via spine assembly120. For example, manipulations of controller150may simultaneously bring about re-positioning of fluid diverter110within housing10and a movement, for example a rotation, of at least one spine assembly member, for example spine base126, that is in turn directly associated with flush valve140causing flush opening14fto change position from one position to another, open to close or close to open. Optionally flush valve140may change position from one position to another, open to close or close to open, by associating with piston assembly130that may be associated with spine assembly120. Optionally the status of the piston assembly130may be utilized to control flush exit opening14fby association with flush valve140. Optionally when piston assembly130is in compressed mode, flush valve140and flush opening14fmay assume the closed position, and while piston assembly130is in de-compressed mode flush valve140and flush opening14fmay assume the open position. Apparatus100preferably comprises a piston assembly130that may be controlled directly or indirectly by the positioning of fluid diverter110. For example, piston assembly130may be controlled by the changing fluid pressure within housing10during first flow direction and second flow direction. More preferably piston assembly130is associated with spine assembly120. Most preferably piston assembly130is controlled to be normally closed, compressed, during filtration and open (de-compressed, released) during cleaning. Most preferably assembly130is decompressed when fluid is directed into spine assembly120about spine legs124, indicative of self-cleaning flow direction through orifice124o. Optionally and more preferably piston assembly130comprises a compression plate132and compression spring134, that function to maintain filtering element20, provided in the form of a plurality of stacked ring disc filters, in compressed and/or stacked configuration along spine assembly120, during filtering mode. Piston assembly130further provides for releasing the stacked configuration of disc ring filter elements20, during cleaning mode, allowing the disc elements to separate and spin freely to enable flushing and cleaning of waste material filtered thereon. FIG.1A-Bshow optional configurations of apparatus100,102utilizing a dashed lead-line for example to show that optional sensors and/or controllers may be fit and/or associated with apparatus100. Apparatus100may be utilized without any such sensors and/or controllers depicted by the dashed lead-lines. Optionally apparatus100may be fit with and/or associated with at least one or more sensors for example including but not limited to flow meter and/or pressure sensors or the like. Optionally housing10may be fit with and/or associated with at least one or more sensors152for example in the form of a pressure sensor, flow-meter, or the like sensor provided to gauge at least one or more of pressure, flow, fluid pressure within housing10. Optionally housing10may be associated with at least two or more sensors152dispersed about housing10. Optionally a first sensor for example in the form of a flow meter152and/or pressure sensor may be associated with inlet12iand a second flow meter and/or pressure sensor152may be associated with outlet12o. Optionally filtering apparatus100may be associated with a controller and/or microprocessor155or the like electronic means and/or computerized means for remotely and/or wirelessly and/or electronically and/or automatically and/or hydraulically, therein controlling the state and position of valve body110, via valve controller150disposed externally to housing10. Optionally valve controller150may be provided in the form of a motor for example in the form of a servo motor, water motor160, or the like valve actuation means as is known in the art for example including but not limited to hydraulic, piezoelectric or the like. In embodiments controller155may be provided to control the flow through bi-directional flow motor160so as to control the direction of flow through motor160. Optionally and preferably controller155may be further functionally associated with to control at least one or more valves156to control the direction of flow through flow motor160. Optionally control of controller155may be facilitated by a computer, Personal Data Assistant (PDA), smartphone, mobile communication device, mobile processing device, server or the like utilizing optional communication means for example including but not limited to wired, wireless, cellular, optical, acoustic, ultrasound, radio frequency, contactless, near field (NFC), any combination thereof or the like. The description below collectively refers to the embodiment depicted inFIGS.2-6showing various views of filtering apparatus100according to an optional embodiment of the present invention. FIG.2A-Dprovide various views of apparatus100.FIG.2Ashows a perspective view of the assembled self-cleaning apparatus100, providing an external view of two part housing10, showing how upper housing portion12and lower housing portion14may be coupled and/or associated with one another. FIG.2Afurther shows housing10having an optional four opening configuration including the three standard opening inlet opening12i, outlet opening12o, flush exit opening14fand additional optional handle opening12h. Optionally and preferably handle opening12his provided for allowing valve controller150external to housing10to communicate with and control the position of fluid diverter110disposed internally to housing10. FIG.2Afurther shows an optional location on housing10and in particular upper portion12where a flow and/or pressure sensor may be optionally associated with apparatus10for example about inlet12iand outlet12o. FIG.2B-Cprovide see through views of apparatus100revealing the various members that may be included in apparatus100,FIG.2Bshows a perspective view whileFIG.2Cshows a side view.FIG.2B-Cshows apparatus100comprising, fluid diverter110, spine assembly120, piston assembly130, flush valve140, and fluid diverter controller150. As shown, piston assembly130is disposed within the lower housing portion14, over flush exit opening14fand associated with lower housing14utilizing a plurality of piston assembly coupling member14c. Coupling members14cprovided to center piston assembly within lower housing14. Coupling members14cfurther provide piston assembly130with the appropriate vertical positioning so as to provide sufficient room for the vertical movement required by piston assembly130to compress and decompress a plurality of disc filter elements20(not shown here) that may be stacked along the length of spine assembly120. Optionally and preferably coupling member14cfurther act as a guiding member and/or railing and/or stoppers and/or track to track and guide compression plate132during its vertical movement. FIG.2B-Cfurther show the association and coupling between piston assembly130with spine assembly120along spine base portion126and with fluid diverter110at spine top portion122. Most preferably spine assembly is centered within the open lumen of housing10, most preferably providing for compartmentalizing the open lumen of housing10into peripheral lumen10L and internal lumen120L. Most preferably this compartmentalization facilitates filtering a flowing fluid, as previously described. FIG.2Dprovides an exploded view of the view shown inFIG.2A, of apparatus100clearly revealing the members associated with and forming filtering apparatus100as previously described.FIG.2Dprovides a view of the different portion of spine assembly120comprising a base end126adapted for associating and coupling with piston assembly130and a top end122adapted for associating and coupling with fluid diverter110. Spine assembly120further comprises a plurality of spine legs124, radial support members128a, and longitudinal support members128bthat are dispersed between top portion122and base portion126. As shown most preferably spine legs124are preferably provided with cleaning spray orifices124oprovided to eject a flowing fluid under pressure toward filtering element20so as to clean it. Most preferably during self-cleaning and when filtering element20is provided in the form of a plurality of ring disc filter elements, that are un-stacked along the length spine assembly120, the flowing fluid ejected from the plurality of orifices124odisposed about the length of spine legs124causes the ring disc filter elements to spin, while cleaning the filtering elements outwardly toward the internal surface of housing10. FIG.3A-Bshow schematic illustrations of the core filtering components as assembled within housing10of self-cleaning apparatus100, housing10including upper housing12and lower housing14has been removed.FIG.3A-Bshows the core components including valve controller150, fluid diverter110, spine assembly120, filtering element20, piston assembly130and flush valve140.FIG.3Adepicts the core components with filtering elements20while inFIG.3Bfiltering element20has been removed to reveal spine assembly120. FIG.4Ashows a schematic cross section view of the lower portion assembled filtering apparatus100comprising lower housing14, filtering element20, spine assembly120and piston assembly130.FIG.4Aprovides a depiction of inner lumen120L and peripheral lumen10L formed across filtering elements and spine assembly120at the lower portion of apparatus100as defined by lower housing14. FIG.4Bprovides a close up schematic illustration of piston assembly130showing compression plate132and compression spring that are utilized to compress and maintain filter element20provided in the form of a plurality of ring disc filtering elements in compressed forming a stacked configuration about spine assembly120. FIG.5Ashows a see-through view of a schematic illustrative depiction of the upper portion assembled filtering apparatus100comprising upper housing12, fluid diverter110, valve handle150, and spine assembly120and filtering element20.FIG.5Aprovides a depiction of inner lumen120L and peripheral lumen10L formed across filtering elements and spine assembly120at the upper portion of apparatus100as defined by upper housing10. FIG.5Bprovides a sectional view taken about the through fluid diverter110revealing the continuous inner lumen120L formed from spine assembly120through to outlet12o. The continuous inner lumen120L provides for continuous flow of filtered flowing fluid from inner lumen120L up to the outlet opening12oand finally to the downstream target location. FIG.6A-Hshow various views of fluid diverter110according to a preferred embodiment of the present invention in the form of a three way valve body. The fluid diverter is characterized in that it is disposed internally within housing10within upper portion12and provides for control of the direction of fluid flow through filtering apparatus100in assuming a first flow direction during filtering and a second flow directing during self-cleaning. Fluid diverter110is configured to provide for self-cleaning from an upstream source utilizing the unfiltered fluid flow therein saving energy utilized in the filtering and cleaning process. Most preferably fluid diverter110is configured to maintain outlet10oin closed position throughout the self-cleaning process therein ensuring that filtered flowing fluid is not wasted during the self-cleaning process. The fluid diverter configuration according to the present invention overcomes the deficiencies of prior art self-cleaning filtering apparatus in that it does not utilize the downstream filtered flowing fluid for the filter cleaning operation and therefore saves water consumption require during the self-cleaning operations. Self-cleaning filter apparatus according to the prior art utilize a plurality of flow control valves that are disposed externally to a filtering assembly in order to allow appropriate control of the fluid flow for self-cleaning function. Such prior art external valves are expensive both to run and maintain utilizing energy in their operation. Furthermore by way of utilizing filtered downstream flowing fluid for the self-cleaning procedure prior art self-cleaning filtering apparatus both waste the filtered flowing fluid cleaning utilizing back flushing and therein waste the energy invested in filtering the upstream flowing fluid. Optionally the configuration of fluid diverter110and any portion thereof may be configured in relation to and/or according to optional parameters associated with the filtering process it is facilitation. Such optional parameters may for example include but is not limited to pressure, upstream flow rate, the type of flowing fluid being filtered, flowing fluid properties, viscosity of the flowing fluid, size of apparatus100, size of housing10, type of flush valve140, timing of flush valve140, timing of piston assembly130, any combination thereof or the like. FIG.6Ashows a perspective view of fluid diverter110coupled with a valve control handle150, wherein fluid diverter110is disposed within housing10while handle150is disposed externally with housing10via an optional handle opening12h, as previously described. Most preferably handle150is provided for turning fluid diverter110to control the flow there-through. As shown, optionally and preferably diverter110is a substantially cylindrical valve body having an upper face110u, a lower face110band perimeter surface110s. Most preferably the cylindrical body has a substantially open central lumen110L. Diverter upper face110umay be adapted to securely associated within housing10at an upper portion thereof; for example about upper housing12, for example with threading110t, shown inFIG.6B. Most preferably upper surface110uis provided to optionally and preferably associate with a fluid diverter controller150disposed external to housing10, for example as in the form of a handle as shown inFIG.6A. FIG.6C-D, show diverter lower face110badapted to receive and securely fit with spine assembly120at its base end122. Lower face110bhas a central opening110othat is in fluid communication with the open central lumen110L. Central opening110ois preferably surrounded by a peripheral channel110cdisposed along the perimeter of lower face110b. Peripheral channel110cis preferably configured to receive and securely couple with spine assembly120at second end122. Optionally and preferably central opening110ois configured to be in fluid communication and continuous with inner lumen120L. Peripheral channel120cis configured to be in fluid communication with a plurality of spine legs124defining the spine assembly inner lumen120L, providing for introducing a flowing fluid into the spine legs124that may flow out of orifices124o. FIG.6E-6Hshow diverter perimeter surface110pcomprising a flow inlet portion112, defined along surface110p, and at least three apertures extending from the perimeter surface110pincluding two open apertures116,114and one closed aperture118. Preferably flow inlet portion112is configured to be opposite inlet opening12iso as to allow the flow of an un-filtered flowing fluid into housing10, preferably into peripheral lumen10L, therein providing for the onset first flow direction during filtration.FIG.6Eshows a broken guiding line that outlines the area available to inlet portion112as upstream flowing fluid enters housing10. The broken guiding line shows that a substantial portion of diverter110is allotted to inlet portion112, for example up to about 50% of surface of perimeter surface110pis allotted for inlet portion112. Preferably, first open aperture114along surface110pis configured to align with and provide fluid communication between the outlet opening12oand the central opening110odefined on the diverter lower surface110bthrough the open central lumen110L, therein providing for the end portion of first flow direction during the filtering process that allows a filtered flowing fluid to flow out of housing10via outlet12o. Aperture114is only open during the first flow direction during filtration and is sealed throughout the self-cleaning process. Preferably, second open aperture116is configured to align with and provide fluid communication between the inlet opening12iand the spine legs124via peripheral channel110cdisposed along diverter lower surface110b. Such configuration preferably provides for the onset of the second flow direction during self-cleaning, and allows for the decompression of piston assembly130and optionally for the opening of flush exit opening14fand flush valve140. Optionally flush exit opening14fand flush valve140may be opened and closed manually or automatically as previously described. Optionally moving diverter110to the self-cleaning mode by associating aperture116with inlet12imay also direct the mechanical movement or hydraulic opening of flush valve140and flush exit opening14f, as previously described. Optionally flush valve140may be opened manually by a user to initiate the self-cleaning process after diverter110has been set to the self-cleaning mode by maneuvering aperture116over inlet12i. Preferably when self-cleaning mode is initiated by maneuvering aperture116over inlet12i, it allows piston assembly130to decompress as pressure is built-up down through spine legs124pushing compression plate132down and decompressing spring134. As shown inFIG.6F, aperture116is a partially open aperture having an open portion116oand a sealed portion116s. Open portion116ois in fluid communication with peripheral channel110c, therein configured to allow upstream flowing fluid to flow into channel110cand into the lumen of spine legs124and out orifice124o. Sealed portion116sis configured to quick stop the self-cleaning process ensuring sufficient recovery time when switching modes from self-cleaning mode back to filtering mode, allowing apparatus110to commence the filtering process only after flush opening14fand flush valve140are closed and after piston assembly130is re-compressed. Optionally and preferably the relative dimension, size and shape of the open portion116oand sealed portion116sof aperture116may be configured in relation to and/or according to optional parameters associated with the filtering process. Such optional parameters may for example include but is not limited to pressure, upstream flow rate, the type of flowing fluid being filtered, flowing fluid properties, viscosity of the flowing fluid, size of apparatus100, size of housing10, type of flush valve140, timing of flush valve140, timing of piston assembly130, any combination thereof or the like. Optionally the relative size and/or area of open portion116oto sealed portion116smay be controlled remotely, for example with a controllable shutter disposed about sealed portion116s, that may optionally be controlled by and optional controller155optionally associated with apparatus110, shown inFIG.1A-B. Optionally a shutter disposed about sealed portion116smay be controlled manually for example with a control handle150or via an optional member associated with handle150. FIG.6G-Hshow closed aperture118that is configured to align with outlet opening12o. Closed aperture118provides for sealing outlet opening12otherein preventing loss of and ensuring the quality of the down-stream filtered flowing fluid during the self-cleaning mode. Sealing outlet12owith aperture118therefore provides for redirecting the upstream flowing fluid from flowing into the housing; therein providing for the second flow direction during self-cleaning. As seen inFIG.6G-Hthe size of both open aperture114and closed aperture118govern about a 25% of the size of diverter110where the majority of the sealed portion is associated with aperture118provided to ensure the quality of the down-stream filtered fluid. FIG.8A-Bshow an optional embodiment of the fluid diverter according to the present invention, showing various views of fluid diverter210. Diverter210is similar to diverter110described and shown inFIG.6A-H, diverter210is characterized in that aperture216is configured to have a concentric open portion216oand sealed portion216s. Open portion216ois in fluid communication with peripheral channel210c, therein configured to allow upstream flowing fluid to flow into channel210cand into the lumen of spine legs124,224and out orifice124o,224o. Most preferably orifice216is configured to receive an annular mesh filter22, show in inFIG.8C. Preferably mesh filter ring22, is configured to securely associate with seal portion216s. Mesh filter ring22is provided to filter upstream flowing fluid flowing through the filter spine assembly120,220and in particular spine legs124,224during the self-clean mode.FIG.8Ashows a perspective view whileFIG.8Bshows a sectional view to reveal the passageway from opening216otoward channel210c. Now referring toFIG.15-17collectively showing an embodiment of a fluid diverter310that functions in a manner similar to the fluid diverter previously described110,210above. Accordingly fluid diverter310has similar structures and body features as previously described and is coupled and/or associated with all filter assembly portions as is described above for example including but not limited to spine assembly, controller, flush valve assembly, filter housing. Accordingly for brevity, conciseness and ease of understanding only the differences between the previously described fluid diverters are specifically described below in connection with fluid diverter310. For example, the apertures of all fluid diverters are similarly numbered including an inlet aperture312similar to inlet apertures112and212, outlet aperture314comparable to outlet aperture114,214and spine aperture316that is comparable to apertures116,216as previously described and peripheral channel310cthat functions in the same manner and form as that described with respect to peripheral channel110c,210c. Fluid diverter310is characterized in that it is a pressure relief fluid diverter that features a pressure relief piston assembly320. The pressure relieve piston assembly320is disposed along a pressure relief aperture318, similarly located as previously described apertures218,118. FIG.15Ashows a cross sectional perspective view of a filter assembly100,102revealing the internal pressure relief fluid diverter310that feature pressure relieve piston assembly320. In some embodiments fluid diverter310may be controlled by way of a manual valve controller150, for example in the form of a handle such as shown inFIG.15A. As previously described valve controller150provides for rotating fluid diverter310so as to control the relative position of diverter310within the filter housing. In some embodiment fluid diverter310may be controlled by way of an automated controller155, for example in the form of a motor and/or flow motor160, that is shown and described inFIG.12-14. As previously described valve controllers150,155provide for rotating fluid diverter310internally within the filter housing and therefore controlling the different states and/or phases of the filter housing. Optionally controller150may be provided in the form of optional handles and/or automated controller155may for example be provided in the form of a flow motor160. FIG.16A-Eshows different face on views of pressure relief fluid diverter310, each showing a different aperture and/or facet of diverter310.FIG.16Ashows a face on view of pressure relieve aperture318with pressure relief assembly320in place.FIG.16Bshows a similar face on view, however pressure relief assembly320has been removed to reveal pressure relief opening318oand coupling member318cof aperture318provided so as to fit with and house and/or receive pressure relief assembly320. Most preferably pressure relief piston assembly320provides for controlling the open and close status of opening3180. In embodiments coupling member318care provided to facilitate coupling and/or associating pressure relief assembly320over opening3180. In embodiments opening318omay be have a diameter of about 35 millimeter (mm). In embodiments opening318omay be have a diameter of from about 15 millimeters (mm) and up to about 50 millimeters (mm). FIG.16Cshows a face on view of spine aperture316having a spine aperture open portion316othat functions in the same manner and having similar form to apertures116,216and openings116o,216oas previously described therefore for the sake of conciseness will not be detailed here. FIG.16Eshows a face on view of inlet aperture312that functions in the same manner and having similar form to apertures112,212as previously described therefore for the sake of conciseness will not be detailed here. FIG.17A-Eshow various close up views of pressure relief piston assembly320removed form fluid diverter310.FIG.17AandFIG.17Bshow different perspective views of assembly320whileFIG.17C-17Eshow an exploded view revealing the different functioning part of piston assembly320. Pressure relief piston assembly320comprises housing324(FIG.17C), spring326(FIG.17D), piston body328(FIG.17E). In some embodiments housing324may be provided as an integrated with aperture318to form opening3180. FIG.17Dshows an optional form of spring326having the form of a torsion spring including two free ends326cand a central spring body326a. Spring326is fit across both body328and housing324wherein free ends326cfit with housing324at a dedicated spring recess324d; while spring body326afits with piston body328being received in a dedicated spring housing328c, as shown inFIG.17E. FIG.17Cshows piston assembly housing324having at least two spring recesses324c, and at least two holding pegs324. Housing324having a generally cylindrical body including a (inner) distal end324ithat is configured to be continuous with opening318oand a (outer) proximal end324oconfigured to be adjacent with the external surface of fluid diverter310more specifically the external surface of aperture318. Spring recesses324cprovide for receiving an end of spring326c. Holding pegs324dhave an outer surface324aprovided for coupling with and/or holding and/or receiving coupling member318cdisposed about opening318o, for example as shown inFIG.16B. Holding pegs324dhaving an inner surface324balong for coupling and/or associating and/receiving at least a portion of piston body328, more preferably at least one or more coupling fins328d. Accordingly holding pegs324dprovide for securing assembly320with coupling member318cover opening318oand body328via coupling fins328d. FIG.17Eshows a perspective view of piston body328. Body328having an outer end surface328a, an inner end surface328b, a spring housing recess328c, holding fins328d, a seal recess328e, and central body328f. In embodiments when body328is seated within housing324, as shown inFIG.17A-B, inner end surface328bis provided for matching with inner surface324band therefore collectively sealing and/or closing opening3180. Body328features a seal recess328eadjacent to inner end surface328b, where recess328eprovides for receiving a seal (not shown) increasing the closure over opening3180. Spring housing recess328cprovides for receiving spring body portion326a. Holding fins328dare preferably adjacent to inner end surface328band provide for coupling body328with housing324as described above. Optionally holding fins may be oriented to be normal and/or perpendicular to central body328f, for example as shown. Central body328fdefines the central body of piston body328that defines the length of piston body328and therefore spans between inner end surface328band outer end surface328a. Preferably the outer edge of central body328fdefines the outer end surface328aof body328, for example as shown. In embodiments, end surface328ais preferably configured to extends beyond the outer proximal end324oof housing324, for example as shown inFIG.17A-B, so as to allow end surface328ato extend beyond the external surface of fluid diverter310and more specifically the external surface of aperture318, so as to approximate with the inner surface of upper housing12covering fluid diverter310. In some embodiments the contour of end surface328amay be configured according to the curvature and/or geometry of the inner surface of upper housing12. A pressure relief piston assembly320, such as the one described above according to an optional non limiting embodiment of the present invention, is utilized to allow for more readily manipulating an internal fluid diverter310with optional controllers, for example a manual controller150, or a motorized and/or automated controller155, for example in the form of a flow motor160described herein, and/or the like motor assembly. More specifically pressure relief piston assembly320provides for relieving any pressure differential buildup that may be established across fluid diverter during the filter's (100,102) transition between the filtering phase to the self-cleaning phase, and vice versa. More specifically, pressure relief piston320when disposed over aperture opening318oallows a smooth and manageable transition between filtering phase and self-cleaning phase as a high pressure differential may build up in and around aperture318,118,218near the end of the filtering phase and just prior to the self-cleaning phase. Accordingly a preferable solution to the pressure build up is to alleviate the pressure build up is provided by piston assembly320that allows for pressure equalization during the filtering phase between aperture318and outlet aperture314. In so doing the resultant pressure relief allows for more readily manipulating controller150,155, for example a manual handle, lever and/or an automated motor and/or flow motor160, by way of greatly reducing the force required to turn fluid diverter310. Pressure equalization is provided by allowing piston assembly320to gradually determine the open/close status of opening318o, therein allowing a more fluid transition from an open state to a close state. Such fluid and/or gradual transition relieve the pressure buildup allowing the pressure build up to be gradually relieved, therein substantially reducing the force required to manipulate controller150,155, for example a manual handle, lever and/or an automated motor and/or flow motor160. For example, during filtering phase piston assembly320is in the open configuration where outer end surface328ais pressed against the inner surface of upper housing12therein causing central body portion328fto displace inwardly against spring326that in turn further urges inner end surface328bto displace inwardly to open opening318o, allowing for pressure equalization between outlet aperture314and aperture318as both are exposed to downstream water flow. In embodiments the displacement of piston body328relative to housing324is about 10 millimeters (mm). In embodiments piston assembly320may be configured to provide linear movement from about 5 mm and up to about 25 millimeters (mm) so as to control the open/close status of opening3180. In embodiments the displacement of piston assembly320may be configured relative to the biasing force spring326. In embodiments the displacement of piston assembly320may be configured relative to the fluid pressure available to the filter. During self-cleaning phase the opposite occurs where opening318ois closed and remains closed as spring326does not have a counter force, as was the case during the filtering phase, and therefore automatically shuts opening318owith inner end surface328b. During the transition between filtering phase and self-cleaning phase pressure relief assembly320maintains pressure equalization between outlet aperture114and aperture118until the outlet aperture114is closed. Once aperture114is closed, spring326urges central body328finwardly to close of opening118owith inner end surface328b. Therefore assembly320by maintaining pressure equalization between aperture114and118for an extended period time allows for readily turning fluid diverter310. FIG.9A-Cshow optional views of a spine assembly220according to an optional embodiment of the present invention.FIG.9Ashows a perspective view of spine assembly220that is similarly structured as spine assembly120as previously described. Spine assembly220having a plurality of spine legs224including a plurality of spray orifice224oprovided to expel flowing fluid during the self-cleaning mode. Spine assembly220further comprises support members228a,228bsimilar to support members128a,128bas previously described. Optionally radial support members228amay be configured to act as turbine blades, for example as shown in top down viewFIG.9C, to facilitate rotation of spine assembly220and the disc filter medial20associated thereon. Spine assembly220has a second end222and first end226similar to second end122and first end126of spine assembly120as previously described. Second end222, shown inFIG.9Cis provided for coupling with optional fluid diverters110,210and comprises a spine connecting channel220cto channel flowing fluid into spine legs124,224from peripheral channel110c,210c. Spine assembly first end226, best shown inFIG.9B, features an adaptor housing226p, provided for receiving at least a portion of adaptor236, shown inFIG.10. As previously described with respect to first end126, first end226functions to couple and/or associated spine assembly120,220with piston assembly130,230. Preferably adaptor housing226pprovides for receiving and housing adaptor236, an example of which is shown inFIG.10, that facilitates coupling between spine assembly120,220and piston assembly130,230. Preferably adaptor236provides for harnessing the rotational motion of diverter110,210and spine assembly120,220, provided with controller150, to actuate the configuration of piston assembly130,230. Therefore adaptor236allows piston assembly130,230to stack (compress) or un-stack (release) disc filtering elements20, during the filtering and self-cleaning modes respectively, based on the position fluid diverter110,210as depicted by controller150. FIG.10shows adaptor236having a bolt like body comprising a head portion236aand a tail portion236b. Head portion236aprovides for associating with spine assembly120,220preferably along first end126,226, for example within housing226p. Optionally head portion236amay comprise at least one or more coupling members236c, for securely associating adaptor236within housing226p. Tail portion236bprovides for associating with piston assembly130,230. Tail portion236bpreferably features threading and/or groove236tprovided for coupling with corresponding threading and/or rail guides232t,FIG.11B, disposed with piston assembly130,230to facilitate actuating the state and/or configuration of piston assembly130,230. FIG.11A-D, shows optional views of piston assembly230, that functions similar to piston assembly130, as previously described. Piston assembly230,130provide for controlling the compression state of disc filters20along spine assembly120,220while preferably controlling the flush opening14fso as to open flush opening during self-cleaning mode and closing it during filtration mode. FIG.11C-Dshow sectional views of piston assembly230as it is disposed within housing10, about lower portion14over flush opening14f.FIG.11C-Dshow piston assembly in the self-cleaning mode while flush opening14fis open. FIG.11A-Bshows different view of piston assembly230, that functions similarly to piston assembly130as previously described therein featuring a compression plate232,132and spring134,234. Optionally and preferably as previously described assembly130,230may be coupled with an internal flush valve140, for example in the form of a plug as shown, to control the state (open/close) of opening14f. Piston assembly230feature a compression plate adaptor housing232afor receiving at least a portion of adaptor236,FIG.10, as previously described. Preferably housing232ais configured to receive tail portion236b. Preferably housing232acomprises threading and/or rail track232tconfigured to correspond with rail and/or adaptor threading236t. FIG.12A-Bshow perspective views of an optional embodiment of filter assembly100,120fit with a bi-directional flow motor160provided for controlling the position of internal fluid diverter110. Preferably bi-directional flow motor160is utilized to turn fluid diverter110so as to change the direction of flow through the filter body and to effectively switch between filtering phase and self-cleaning phase as previously described. Accordingly bi-directional flow motor160can turn fluid diverter in both the clockwise and counterclockwise directions so as to control the position of the fluid diverter110. Most preferably bi-directional flow motor160utilizes controllable flow valves156that may be controlled with a controller155to determine the direction of flow through bi-directional flow motor160, as schematically depicted inFIG.1A-B. FIG.13A-Bshow a close up view bi-directional flow motor160.FIG.13Ashows a perspective view of bi-directional flow motor160having a housing161that is securely coupled with a portion of filter housing10of filter100,102so as to provide access to the location of fluid diverter110. Most preferably housing161is coupled over upper housing12so as to provide access to fluid diverter110. Flow motor160comprises at least two flow inlets162including inlet162aand162beach inlet providing an individual flow direction, clockwise or counter-clockwise. In embodiments flow through inlets162is preferably controlled with a controllable valve156that may be controlled with controller module155. Optionally each inlet may be controlled with an individual valve156. Optionally both inlets may be controlled with a multi-directional valve156such that the inlet in use162aor162bis controlled with a single multi-directional valve156. Flow motor comprises at least one flow outlet164, and optionally two flow outlets164a,164bas shown wherein each flow outlet having a corresponding to a flow inlet162a,162b. FIG.13Bshows a cross section of flow motor160revealing the internal compartments of bi-directional flow motor160including flow turbine module166; and diverter coupling adaptor170. In embodiments flow motor may optionally further comprise a gear and clutch module168. Turbine module166provides a turbine for utilizing the flow energy to generate bi-directional motion by utilizing flowing fluid entering housing161through inlet162and out through outlet164. Preferably turbine166is a bi-directional turbine that rotates both in clockwise and counterclockwise direction based on the flow inlet162utilized to rotate bi-directional turbine vanes165. Most preferably turbine166is functionally coupled with adaptor170such that the rotational motion provided by turbine module166is converted to rotational motion of adaptor170in-turn causing adaptor170to controllably rotate fluid diverter110in the required direction Optionally bi-directional turbine vanes may be provided in dual and/or “back to back” spoon and/or cup shape form, for example as shown inFIG.14A-B. In an optional embodiment the rotational energy provided by turbine module166may be amplified via an optional gear and clutch module168so as to provide adaptor170with sufficient power to controllably turn so as to cause fluid diverter110to turn in the required direction. FIG.14A-Bprovide a close up view of schematic bi-directional turbine vanes165shown in the form of dual cup vanes. Each vane165is formed from two cups and/or curved member that are coupled to one another back to back so as to form two individual surfaces configured to receive a fluid flow causing the turbine to rotate in one of two directions clockwise or counterclockwise depending on the flow inlet utilized. Accordingly bi-directional cup vanes165enable bi-directional rotation of flow motor160both in the clockwise and count-clockwise directions. In turn, the rotational motion provided by turbine module166is converted to mechanical motion of module170, optionally with gear and clutch module168, so as to cause fluid diverter110to turn in the appropriate direction to determine the direction of flow through filter housing10and the filter phase, self-cleaning or filtering as previously described. While the invention has been described with respect to a limited number of embodiment, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention. Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not described to limit the invention to the exact construction and operation shown and described and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. Having described a specific preferred embodiment of the invention with reference to the accompanying drawings, it will be appreciated that the present invention is not limited to that precise embodiment and that various changes and modifications can be effected therein by one of ordinary skill in the art without departing from the scope or spirit of the invention defined by the appended claims. It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination or as suitable in any other described embodiment of the invention. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment is inoperative without those elements. While the invention has been described with respect to a limited number of embodiments, it will be appreciated that many variations, modifications and other applications of the invention may be made.
57,326
11857900
DETAILED DESCRIPTION OF THE INVENTION While the invention will be described in connection with particular embodiments, it will be understood that the invention is not limited to these embodiments. On the contrary, it is contemplated that various alternatives, modifications and equivalents are included within the spirit and scope of the invention as described. In the description of the invention, the majority of references are to an example used as a surface mount. If otherwise, it will be stated. While surface mounted filters have significant advantages, they are often restricted to a small surface footprint. Accordingly, their main scalable feature is height. Although it is possible to increase the filtration area of sintered porous metal media by extending the height of the cylindrical filter element, the cost may be prohibitive. Embodiments of the present invention provide planar filter media elements and media retention mechanisms that may be less costly and allow the use of media materials that may not be usable in cylindrical media configurations. The height of such media elements is virtually unlimited, and filtration performance can meet or exceed that of comparable sintered metal media. Filtration devices of the invention may use a cylindrical casing similar to (but typically longer than) the casing22ofFIG.2Aand may be adapted for use with standard surface mounts like the mount10ofFIG.1. These devices use an annular center body to support planar, vertically mounted filter media elements that are held in place by clamping members. The combined media retention assembly is configured to fit within the cylindrical casing while maximizing the challenge area of the filter media. The center body is typically formed as a prism-shaped body with a polygonal cross-section. This provides flat faces on one, some, or all of the sides through which flow windows are formed. The planar filtration media elements are positioned so as to span these windows. Frame-like clamping members are attached to the center body so as to hold the media elements in place. FIGS.1-12illustrate an exemplary filtration apparatus1000according to an embodiment of the invention. While the filtration apparatus1000is illustrated in conjunction with the surface mount10ofFIG.1, it will be understood that it is usable with or may be adapted for use with other surface mount configurations. The filtration apparatus1000has a cylindrical casing1050with that has a closed upper end1054and an open base end that, upon installation of the apparatus1000on the surface mount10, is sealed by the base12of the mount10. The casing1050has an interior space1052and an inside diameter CD. The filtration apparatus1000may incorporate a filtration element assembly100according to a particular embodiment of the invention. The assembly100has a prismatic center support body110that has a constant, polygonal outside cross-section along its longitudinal axis118. In the illustrated embodiment, the polygonal cross-section is rectangular, but other shapes may also be used. Regardless of the number of sides, the polygonal cross-section defines a circumscribed circle CIthat is centered on the longitudinal axis118and has a diameter that is less than (or, in some embodiments, equal to) the inside diameter CDof the casing1050. This allows the support body110to be received into the interior space1052of the casing150. The support body110has top and bottom walls117,119and a number of rectangular side walls111equaling the number of sides in the polygonal cross-section. The top, bottom and side walls117,119,111collectively define a support body interior space112. The bottom wall119has a centerline-aligned support body exit port114formed there-through. An annular attachment flow fitting115may be attached to the bottom wall119at the exit port114to provide for aligned attachment of the support body110to the surface mount10and to provide for fluid communication between the support body exit port114and the surface mount exit port16. In the rectangular support body110, two opposing sides111b,111dof the support body110have flow windows116formed there-through to provide communication between the interior space112and the exterior of the support body110. The remaining two side walls111a,111care closed. It will be understood that, while the illustrated embodiment has two walls111with flow windows116, any number of side walls111may have a flow window116. Each wall111having a flow window116also has a recessed receiving channel113surrounding the flow window116. The receiving channel113is sized and configured to receive a filter medium structure150that fits within the recessed channel113so that the medium structure150spans across the flow window116. The filter medium structure150includes one or more filtration media elements. These media elements are each substantially self-sustaining planar members that are configured to screen particulate matter from gas flowing through the elements. The filter medium structure150may be configured to have desired flow-through, porosity, and filtration characteristics. In some embodiments, the filter medium structure150may consist of a single filtration medium layer. In other embodiments, the filter medium structure150may have multiple filtration medium layers. In the illustrated embodiment, each flow window116has an associated filtration element150that has an outer filter medium element130A,130B and an inner filter medium element140A,140B. The inner and outer filter medium elements140,130may have different materials, structures, flow and/or filtration characteristics. In some embodiments, the inner and outer filter elements140,130may be attached to one another to form a single filter element structure. The individual filtration medium layers may be or include any substantially planar screening structure formed from materials suitable to the gas environment and the desired particle removal size. Particularly suitable filtration media are or include self-sustaining fiber structures, particularly those formed from metal fibers. As used herein, “self-sustaining” means that the fiber medium has sufficient structural integrity to withstand the pressure differential across the flow window116without additional reinforcement. The integrity of such structures can be established through a high level of entanglement and compression or through bonding (e.g., by sintering) of the fibers at spaced apart points of contact. In some embodiments, a metal fiber filtration medium may be constructed from a single highly convoluted and entangled fiber or from a plurality of entangled fibers. Typical metal fiber diameters may range from 1-100 μm. Suitable materials for the metal fibers used in the above-described filter media may include stainless and other steels as well as other alloys including, but not limited to nickel alloys and Hastelloy® alloys. The specific metal(s) can be selected based on, for example, expected temperature/environment and corrosion resistance. In some embodiments, the filtration media elements may be or include structures that are formed from sintered metal powder or a sintered combination of entangled metal fiber(s) and metal powder. The filter medium structure150, generally, and the filter medium elements, in particular, can be tailored to provide desired filtration characteristics. In typical applications, the filter medium structure can be configured to remove particles having an effective diameter greater than 1.000 micron. In particular applications the filter medium structure150can be configured to remove particles having an effective diameter greater than 0.100 μm. As noted above, the inner and outer filter medium elements140,130may have varying characteristics. In some cases, the outer filter medium element130may be configured to screen only particles having a relatively high diameter, while the inner filter medium element140may be configured to screen smaller particles. In a particular example, the outer filter medium element130could have a porosity in a range of 50-80 percent (more particularly, 60-70 percent) and the inner filter medium element140could have a porosity in a range of 30-60 percent (more particularly, 40-50 percent. This form of staged filtration can serve to prevent clogging and consequent increased pressure loss through the life of the filtration apparatus100. Any number of media elements can be used to provide the desired filtration gradient. Alternatively, a single media element having a variable porosity gradient may be used. By staging filtration media, efficient filtration of particles down to 0.003 μm can be achieved without producing undesirable pressure losses or reducing the life of the device. The filter medium structure150is sized so that it completely covers the flow window116and fits into the recessed receiving channel113surrounding the flow window116. The initial thickness of the filter medium structure150may be greater than the depth of the receiving channel113so that subsequent placement of the filter retention clamping member results in compression of the portion of the filter medium structure150surrounding the flow window116. As best seen inFIG.12, the filtration element assembly100has two clamping members120A,120B that serve to hold the filter medium structures150A,150B in place within the receiving channels113of the support body110. It will be understood that embodiments having additional flow windows and filter medium structures will also have corresponding clamping members. Each clamping member120has a frame portion122having a flat, inward facing surface123that engages a support body side wall111aor111c. A flange portion124extends inwardly from the flat surface123. A clamp member window121extends through the frame portion122and the flange portion124. When the filtration assembly100is assembled, the clamp member windows121are in registration with the flow windows116of the support body110. The perimeter of the flange portion124is sized and shaped to correspond to the shape of the receiving channel113for reception therein. The frame portion122is configured so that the perimeter dimensions of the flat surface123matches those of the side walls111a,111c. The longitudinal cross-section of the flange portion124(best seen inFIG.9) is configured so that the combined support body110and clamping members120A,120B fit within the cylindrical casing1050. In particular embodiments, the flange portion124may be configured so that the combined support body110and clamping members120A,120B collectively form a polygonal cross-sectional shape that defines a circumscribed circle, which may be the same circle CIdefined by the cross-section of the support body110alone. In such embodiments, the cross-section of the flange portion124may be a trapezoid as in the illustrated embodiment. In other embodiments, the outer portion of the frame portion122may be curved to fit within the casing1050. When the filtration element assembly100is assembled, the filter medium structures150A,150B are disposed or partially disposed within the receiving channels113. The clamping members120A,120B are then mated to the support body110. In accomplishing this, the flange portions124are inserted into the receiving channels113to engage and compress the filter medium structures150A,150B. When the flange portions124are fully inserted, the flat surface123of the clamping member120A engages the surface of side wall111band the flat surface123of the clamping member120B engages the surface of side wall111d. The clamping members120may be attached to the support body110in this configuration by any suitable means such as welding or bonding. The support body110and the clamping members120may be formed from any materials that provide sufficient rigid support for the filter element structures150and that will retain structural integrity under expected environmental conditions. Such materials may include, but are not limited to stainless and other steels as well as other alloys including, but not limited to nickel alloys and Hastelloy® alloys. The filtration element assembly100may be received into the cylindrical casing1050and the two mounted to the surface mount10as shown inFIGS.5-7. In this configuration, particle laden gas may be introduced through the surface mount port18into the casing interior space1052surrounding the filtration element assembly100. The particle laden gas is then drawn through the filter element structures150A,150B into the support body interior112, thereby producing filtered gas, which then passes out through the support body exit port114and the surface mount port16. It will be understood that in some embodiments, the upstream and downstream flow directions may be reversed. In such embodiments, the in-flow of gas would be through the port16and the out-flow through port18. This would put the challenge side of the filter medium structure150inside the support structure interior112with the gas flow outward through the filter media. The filtration element assembly100may also be used in “in-line” applications gas flow line applications. With reference toFIGS.13and14, a filtration apparatus2000has a cylindrical casing2050with an upper end2054having an inlet port2055and a lower end2056having an outlet port2057. An inlet fitting2060having an inlet flow channel2062is attached to the upper end2054and an outlet fitting2070having an outlet flow channel2072is attached to the lower end. The fittings2060,2070are configured for connection to gas flow lines and to provide fluid communication from such lines into and through the filtration apparatus2000. The casing2050has an interior space2052and an inside diameter CD. While the attachment fitting115may be adapted for use in the in-line configuration, the filtration element assembly100is substantially unchanged from the configuration described above for use with a surface mount. As before, the filtration element assembly100may be sized to maximize filtration flow area within the limits of the diameter of the surrounding casing2050. If length is not a limiting factor, the casing2050and the filtration element assembly may be lengthened to increase filtration area and efficiency. In the in-line configuration, particle-laden gas is brought into the casing interior2052through the inlet fitting2070from an upstream gas line. The particle laden gas passes through the filter element structures150A,150B into the support body interior112, thereby producing filtered gas, which then passes out through the exit fitting2070to a downstream gas line. It will be understood that in some embodiments the flow direction of particle laden gas may be in the reverse direction so that the port2057through the lower end2056operates as an inlet and the port2055through the upper end2054operates as an exit. The filtration apparatus of the present invention provide significant performance advantages over prior art ‘sintered powder media’ apparatus. Exemplary test results have shown that filtration apparatus of the invention having the same challenge surface area as a comparable cylindrical sintered metal apparatus may provide lower pressure loss across the filtration media, higher flow rates, and longer life within the same cross-sectional footprint. These performance advantages may be further enhanced through the use of staged media layers. The planar filtration media used in the apparatus of the invention are also less expensive to manufacture and allow a high degree of flexibility in producing desired filtration efficiencies. The filtration apparatus of the invention are not limited to any particular size, flow rate, or environment. It will be readily understood by those persons skilled in the art that the present invention is susceptible to broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and foregoing description thereof, without departing from the substance or scope of the invention.
16,182
11857901
DETAILED DESCRIPTION Referring to the figures generally, various embodiments disclosed herein relate to an integrated expansion membrane assembly for a filter assembly which form at least one seal together. The membrane assembly, in particular, helps counter the expansion of the diesel exhaust fluid (DEF) by providing extra volume within the filter assembly for the expanded volume of DEF at low temperatures (e.g., at approximately −11° C. and below). The membrane assembly also protects the various structural components within the filter assembly from the load that arises due to the DEF volume expansion. As described further herein, the membrane assembly forms seals with both the filter head and the housing of the filter assembly, which prevents any DEF leakage to the external environment of the filter assembly (or to the threaded interface between the filter head and the housing). Furthermore, the membrane assembly is lockable onto the housing. The filter assembly creates multiple sealing regions in order to prevent any leakage, even in high pressure. Filter Assembly As shown inFIG.2, the filter assembly10comprises a filter cartridge12and a filter head50. The filter cartridge12comprises a filter element20, a housing30, and a membrane assembly70. The various elements of the filter assembly10form seals together through multiple sealing interfaces or regions (e.g., first, second, third, fourth, and fifth sealing interfaces or regions91,92,93,94,95, as shown inFIG.3Aand described further herein). The liquid DEF is used to facilitate the conversion of nitrous oxide (N2O) into nitrogen gas and water. As described further herein, the filter assembly10is configured to accommodate for the volumetric expansion of DEF at low temperatures (e.g., at a temperature of approximately −11° C. or less). As described further herein, the membrane assembly70extends along the housing inner surface34, the housing top surface32, and the housing outer surface36of the housing30in order to completely and securely form at least one seal with the housing30, even under pressure when the DEF expands. The filter head50comprises an inner extension52and an outer extension62(as described further herein) further forming at least one seal with the membrane assembly70and secure seals formed between the membrane assembly70and the housing30. Filter Element The filter element20is configured to filter a fluid and is positioned and housed at least partially (and optionally completely) within the housing30and the membrane assembly70(in particular within a membrane body72of the membrane assembly70), which is positioned at least partially within the housing30. Accordingly, at least a portion of the axial length of the filter element20is radially surrounded by the membrane side wall72aof the membrane body72of the membrane assembly70. The bottom of the filter element20is surrounded by the membrane bottom wall72bof the membrane body72. As shown inFIG.3A, the filter element20comprises a filter media22(for filtering the fluid), a top endplate24, and a bottom endplate28. The filter media22may define an inner area that can receive another portion of the filter assembly10, such as a center tube29. The top endplate24and the bottom endplate28are positioned along opposite ends of the filter media22. The bottom endplate28is positioned completely within the membrane body72of the membrane assembly70. The top endplate24may be positioned completely or partially within an inner region defined by the membrane body72of the membrane assembly70. The top endplate24defines a central aperture that allows filtered fluid to flow out of (or unfiltered fluid to flow into, depending on the desired configuration) the inner area of the filter element20and is configured to receive the center tube29extending into the inner area of the filter media22. The bottom endplate28may be completely closed in order to prevent fluid from flowing through the bottom endplate28(into or from the inner area of the filter element20). As shown inFIG.3A, the top endplate24extends comprises a base23and an inner extension25. The base23extends radially along the top end of the filter media22. The inner extension25is positioned along the inner radius of the base23and extends axially from the base23in a direction away from the filter media22. Accordingly, the inner extension25extends vertically above the filter media22and into a portion of the outlet51of the filter head50. The inner extension25extends along and further defines the central aperture of the top endplate24. Accordingly, fluid can flow through the inner extension25(from within the filter media22and into the outlet51, for example). The inner extension25comprises a groove (along the outer surface of the inner extension25) and a seal member26(e.g., an o-ring) positioned within the groove extending around the outer perimeter of the inner extension25of the top endplate24. The seal member26is configured to fluidly form a seal with a portion of the filter head50(such as the walls of the outlet51of the filter head50) about the entire circumference of the inner extension25of the top endplate24, thereby creating a sealing region (referred to herein as the “fifth sealing region95”) between the outer surface of the inner extension25of the top endplate24of the filter element20and a portion of the filter head50. The fifth sealing region95prevents fluid from flowing between the clean or filtered side of the filter element20and the dirty or unfiltered side of the filter element20. Filter Housing As shown inFIG.3A, the filter shell or housing30is defined by an axially-extending, circumferential housing side wall33and a radially-extending housing bottom wall or base35that are configured to house or contain at least a portion of the membrane assembly70and the filter element20. The base35extends in a radially direction beneath the membrane assembly70. The housing side wall33of the housing30extends axially from a top surface of the base35and extends around the entire circumference of the base35(circumferentially and axially surrounding the membrane body72). The housing side wall33is configured to attach to the filter head50. The housing side wall33and the base35are constructed as a single, continuous piece. Accordingly, the housing30comprises a single unitary component that cannot be separated without destruction. The housing side wall33of the housing30includes a housing inner surface34(which faces radially inward, directly toward the outer surface76of the membrane body72), a housing outer surface36(which faces radially outward and is opposite the housing inner surface34), and a housing top surface32(which extends radially between and connects the housing inner surface34and the housing outer surface36). The housing top surface32is the top axial end of the housing30. The housing outer surface36comprises threads38that are configured to threadably attach to the threads68on the inner surface64of the outer extension62of the filter head50, as shown inFIG.3A. The housing outer surface36comprises a groove and a seal member39(e.g., an o-ring) positioned within the groove extending around the outer perimeter of the housing30. The seal member39is configured to fluidly form a seal with the inner surface64of the outer extension62of the filter head50(as described further herein) about the entire outer circumference of the housing30and the entire inner circumference of the filter head50, thereby creating another sealing region (referred to herein as the “fourth sealing region94”) between the housing outer surface36of the housing30and the inner surface64of the outer extension62of the filter head50. The fourth sealing region94prevents debris from accumulating on or entering into the threaded interface between the threads38on the housing outer surface36and the threads68on the inner surface64of the outer extension62of the filter head50. As shown inFIG.3A, the housing30comprises an air vent31(positioned in and extending through an aperture defined by the base35of the housing30) in order to allow air to escape and vent from within the housing30when the DEF volumetrically expands, which provides more space within the inner area43of the housing30(as described further herein) for the membrane assembly70to move and expand into, thereby preventing back pressure from developing within the filter assembly10. However, according to other embodiments, the housing30may not include any air vent (and accordingly the base35may not define an aperture for the air vent31), and the membrane assembly70and the air within the inner area43of the housing30are simply compressed when the DEF expands in order to reduce cost and complexity. Filter Head As shown inFIG.3A, the housing30is configured to threadably attach with the filter head50. The filter head50comprises an inlet and an outlet51in order to allow fluid (in particular DEF) to enter into the filter assembly10through the inlet (to the dirty, unfiltered side of the filter element20), flow into and through the filter element20, and exit from the filter assembly10through the outlet51(from the clean, filtered side of the filter element20). Depending on the desired configuration, the inlet and the outlet51may be switched (thus reversing the direction of fluid flow through the filter assembly10). The filter head50may optionally comprise or attach to a pump housing. The filter head50comprises a base55positioned axially above at least a portion of the filter cartridge12(in particular above the housing30and the membrane assembly70). In order to securely attach to the housing30and form at least one seal with the membrane assembly70, the filter head50comprises an inner extension52and an outer extension62extending axially downwardly from the base55of the filter head50in a direction toward the base35of the housing30and the base of the membrane body72and in substantially the same direction (i.e., the inner extension52and the outer extension62are substantially parallel in the axial direction and extend along a portion of opposite sides of the housing side wall33of the housing30, toward the base35of the housing30). The inner extension52and the outer extension62extend radially about the entire perimeter of the filter head50and extend along at least a portion of the axial length of the filter cartridge12(in particular the housing30and the membrane assembly70). The inner extension52is positioned radially inward from the outer extension62. The inner extension52is positioned and provided in order to form a seal with the membrane body72and to also further form and reinforce a seal between the membrane body72and the housing30. The inner extension52comprises an inner surface54(which faces radially inward, toward the filter element20) and an outer surface56(which faces radially outward, directly toward the inner surface74of the membrane body72when assembled) that are opposite each other. When assembled, the inner extension52of the filter head50is positioned radially between and extends axially along at least a portion of the inner surface74of the membrane body72of the membrane assembly70and the outer surface of the filter element20(for example, at least a portion of the filter media22and the top endplate24). The inner extension52extends along the entire inner circumference of the membrane assembly70and around the entire outer circumference of the filter element20. As described further herein, the inner extension52of the filter head50fluidly forms a (inner) seal with the inner surface74of the membrane body72about the entire outer circumference of the inner extension52and the entire inner circumference of the membrane body72, thereby creating a sealing region (referred to herein as the “second sealing region92”) between the outer surface56of the inner extension52and the inner surface74of the membrane body72. The outer extension62comprises an inner surface64(which faces radially inward, toward the housing30and the membrane assembly70) and an outer surface66(which faces radially outward) that are opposite each other. The inner surface64of the outer extension62comprises threads68that are configured to threadably attach to the threads38on the housing outer surface36, as shown inFIG.3A. When assembled, the outer extension62of the filter head50is positioned radially outwardly from, extends around the entire outer circumference of, and extends axially along at least a portion of the housing outer surface36and the entire outer surface86of the lip82of the membrane assembly70(as described further herein). Furthermore, when assembled, the outer surface66of the outer extension62forms one of the outermost surfaces of the filter assembly10. The filter head50further comprises a slot surface58radially extending between the inner extension52and the outer extension62. Together, the outer surface56of the inner extension52, the inner surface54of the outer extension62, and the slot surface58define a radial gap or slot59positioned between and radially spaces apart the inner extension52and the outer extension62. The slot surface58is the innermost surface of the slot59(along the axial length of the slot59). The slot59extends completely around and along the entire outer surface56of the inner extension52and completely along the entire inner surface54of the outer extension62. When the filter assembly10is assembled, the slot59is configured to receive at least an upper portion of the housing side wall33of the housing30and at least an upper portion of the membrane assembly70(in particular an upper portion of the membrane body72and the entire lip82of the membrane assembly70). As described further herein, the slot surface58fluidly forms a (top) seal with the top surface77of the membrane assembly70about the entire top circumference of the membrane assembly70and the entire circumference of the slot surface58, thereby creating a sealing region (referred to herein as the “third sealing region93”) between the top surface77of the membrane assembly and the slot surface58. Membrane Assembly In order to account for the volumetric expansion of DEF in freezing temperatures, the membrane assembly70is configured to expand in order to allow more room for the DEF within the membrane assembly70to expand (at low temperatures), which prevents damage to other structural components within the filter assembly10. However, the membrane assembly70is configured to expand only when frozen or at a particular freezing temperature (e.g., at a temperature of approximately −11° C. or less) and not during normal use when the temperatures are not freezing. For example, the membrane assembly70does not expand when the fluid within the filter assembly10is simply pressurized during use in warmer temperatures. As shown inFIGS.3A-3C, the membrane assembly70(along with the rest of the filter assembly10) has a particular configuration in order to ensure that the various parts of the filter assembly10form complete and secure seals together, even if the DEF expands and the membrane assembly70thereby expands. The membrane assembly70may be integrated with certain components within the filter assembly10, such as the filter element20. As shown inFIG.3A, the membrane assembly70fluidly separates and is positionable between the housing30and the filter element20. The filter element20is positioned at least partially within the inner region defined by membrane assembly70(as described further herein) and may be radially (and optionally axially) spaced apart from the inner surface74of the membrane body72in order to allow fluid to flow between the filter element20and the membrane body72(along the axial length of the filter element20) for filtration. In order to form complete seals with the rest of the filter assembly10, the membrane assembly70extends axially along at least a portion of each of the housing inner surface34and the housing outer surface36of the housing30and radially along at least a portion of the housing top surface32. The membrane assembly70extends along the entire inner, top, and outer circumferences of the housing inner surface34, the housing top surface32, and the housing outer surface36, respectively. As described further herein, the membrane assembly70fluidly forms a (bottom and outer) seal with at least the housing inner surface34and the housing top surface32about the entire circumference of the membrane assembly70and the housing30, thereby creating a sealing region (referred to herein as the “first sealing region91”) between the membrane assembly70and the housing inner surface34and/or the housing top surface32of the housing30. A gap or inner area43is defined between a portion of the outer surface76of the membrane body72of the membrane assembly70and a portion of the housing inner surface34. This inner area43is delimited by the outer surface76of the membrane body72, the housing inner surface34, and the first sealing region91(where the membrane assembly70and the housing30form a seal together). The inner area43is filled with air (rather than foam) that compresses (and/or is vented out through the air vent31) in order to provide additional room for the membrane assembly70to outwardly expand as the DEF within the inner region of the membrane assembly70expands. Accordingly, as the membrane assembly70expands, the membrane assembly70extends toward the inner area43and reduces the volume of the inner area43. The membrane assembly70comprises the membrane body72and a lip82. As described further herein, the membrane body72and the lip82may be separate components that are either integrally attached or integrally-formed integral components. As shown inFIG.3A, the membrane body72comprises an axially-extending, circumferential membrane side wall72aand a radially-extending membrane base or bottom wall72b. The membrane side wall72aextends axially from a top surface of the membrane bottom wall72band extends around the entire circumference of the membrane bottom wall72b. The membrane side wall72aand the membrane bottom wall72bare constructed as a single, continuous piece. Accordingly, the membrane body72comprises a single unitary component that cannot be separated without destruction. To prevent fluid from flowing through the membrane body72, the membrane side wall72aand the membrane bottom wall72bof the membrane body72do not define any through-holes or apertures, thereby fluidly separating the inner region and the outer region of the membrane body72. The membrane bottom wall72bis positioned along and completely fluidly closes off a bottom portion of the membrane side wall72a. The top portion of the membrane side wall72adefines an opening of the membrane assembly70that is configured to receive the filter element20. The membrane side wall72aof the membrane body72completely radially surrounds at least a portion of the axial length of the filter element20. In particular, the membrane side wall72aof the membrane body72extends axially along at least a portion of or the entire axial length of the side walls of the filter element20(i.e., along the filter media22and optionally at least a portion of the top endplate24). The membrane bottom wall72bof the membrane body72extends axially along and completely surrounds one side of the bottom of the filter element20(i.e., the bottom endplate28). At least a portion of the (or the entire) axial length of the membrane body72is radially surrounded by the housing side wall33of the housing30. The membrane bottom wall72bof the membrane body72extends along and is surrounded axially on one side by the base35of the housing30. Accordingly, the membrane body72is positionable (both radially and axially) between the housing inner surface34and the filter element20. As shown inFIG.3A, the membrane body72comprises an inner surface74(which faces radially inward, toward the filter element20and the outer surface56of the inner extension52of the filter head50) and an outer surface76(which faces radially outward, directly toward the housing inner surface34when assembled) that are opposite each other. The inner surface74of the membrane body72of the membrane assembly70(in particular the membrane side wall72aand the membrane bottom wall72btogether) forms and defines an inner region of the membrane assembly70for receiving the filter element20. In particular, the inner region of the membrane assembly70is surrounded and defined by the membrane side wall72aand the membrane bottom wall72bof the membrane body72. The filter element20is at least partially positioned within the inner region of the membrane assembly70. As shown inFIG.3C, the membrane body72also comprises an extension78extending substantially horizontally (i.e., radially outwardly) from the top portion of the outer surface76of the membrane side wall72a(and is approximately perpendicular to the outer surface76of the membrane side wall72aof the membrane body72and the inner surface84of the lip82). The extension78is sized and positioned to extend radially over and along and directly abut the housing top surface32when assembled, axially surrounding the housing top surface32. Accordingly, the extension78is positioned axially between the housing top surface32and the slot surface58of the filter head50. The extension78radially spaces out the lip82from the outer surface76of the membrane body72in order to provide an area to receive the top portion (including the housing top surface32) of the housing30. The extension78comprises a top surface77(which faces axially upward, away from the filter housing30), and a bottom surface79(which faces axially downward, directly toward the housing top surface32when assembled) that are opposite each other. The top surface77extends along both the extension78and the top of the membrane side wall72aof the membrane body72. The extension78extends about the entire circumference of the membrane side wall72aof the membrane body72. The lip82extends vertically (i.e., axially) downwardly toward the membrane bottom wall72bfrom the extension78of the membrane body72(i.e., in the same direction as (relative to the extension78) and substantially parallel to the membrane side wall72aof the membrane body72) to secure the membrane assembly70to the housing outer surface36. The lip82is radially spaced apart from and positioned radially outward relative to the membrane side wall72aand the extension78of the membrane body72. The lip82extends about the entire circumference of the membrane body72. When assembled with the housing30, the lip82radially surrounds the top portion of the housing side wall33of the housing30. The lip82extends axially along at least a portion of the housing outer surface36(while the membrane side wall72aof the membrane body72extends axially along the housing inner surface34and the extension78of the membrane body72extends radially along the housing top surface32) and prevents the membrane assembly70from being pulled axially downward (inwardly further into the housing30) due to the DEF expansion forces. The lip82comprises an inner surface84(which faces radially inward, toward the housing outer surface36and the membrane side wall72a) and an outer surface86(which faces radially outward, directly toward the inner surface64of the outer extension62of the filter head50when assembled) that are opposite each other. According to various embodiments (as shown inFIGS.5A,6A,8A, and8E), the membrane assembly70, and in particular the membrane body72, may include a plurality of ribs71along the outer surface76of the membrane body72in order to provide structural support, in particular in suction applications. The ribs71extend axially along the entire axial height of the membrane side wall72aof the membrane body72and radially along the bottom surface of the membrane bottom wall72bof the membrane body72, in particular along the outer surface76of the membrane body72. The ribs71are spaced apart from each other about the circumference of the membrane side wall72a. Sealing Regions Due to the configuration and positioning of the various elements of the filter assembly10(in particular the membrane assembly70and the filter head50), the filter assembly10comprises and forms multiple sealing regions (including the fourth sealing region94and the fifth sealing region95, as described further herein). For example, the membrane assembly70forms a seal with the housing30at the first sealing region91. In particular, as shown in FIGS.3A-3C, the outer surface76of the membrane side wall72aof the membrane body72forms a seal (that includes an outer seal and a bottom seal) with the housing30at the first sealing region91. The first sealing region91may extend along different areas of the membrane body72(i.e., along the outer surface76of the membrane side wall72aand/or the bottom surface79of the extension78) and the housing30(i.e., along the housing inner surface34of the housing side wall33and/or the housing top surface32). For example, the outer surface76of the membrane side wall72aof the membrane body72may form a (outer) seal to the top portion of the housing inner surface34, and the bottom surface79of the extension78of the membrane body72form a (bottom) seal with the housing top surface32, both of which provide portions of the first sealing region91. The first sealing region91extends continuously and uninterrupted along and between the top portion of outer surface76of the membrane side wall72aof the membrane body72and the bottom surface79of the extension78of the membrane body72(and therefore also along and between the top portion of the housing side wall33of the housing inner surface34and the housing top surface32). The membrane assembly70forms a seal with the inner extension52of the filter head50at the second sealing region92. In particular, as shown inFIGS.3A-3C, the inner surface74of the membrane side wall72aof the membrane body72of the membrane assembly70forms a (inner) seal with the outer surface56of the inner extension52of the filter head50. At least a portion of the second sealing region92is directly opposite a portion of the first sealing region91(in particular the portion of the first sealing region91along the outer surface76of the membrane side wall72aof the membrane body72and the housing inner surface34) through the membrane body72. Accordingly, the inner seal (of the second sealing region92) and the outer seal (of the first sealing region91) are directly opposite each other through the membrane side wall72aof the membrane body72. The inner extension52of the filter head50presses against the inner surface74of the membrane body72(which presses the outer surface76of the membrane body72and the housing30closer), thereby forming a seal among the filter head50, the membrane assembly70, and the housing30(and improving both the first sealing region91and the second sealing region92). At least a portion of the first sealing region91and the second sealing region92together form a primary sealing region that prevents DEF leakage, even when the DEF is expanded in low temperature conditions. The membrane assembly70forms a seal with the slot surface58of the filter head50at the third sealing region93. In particular, the top surface77of the membrane body72forms a (top) seal with the slot surface58of the filter head50(extending radially directly between the inner extension52and the outer extension62of the filter head50). At least a portion of the third sealing region93is directly opposite a portion of the first sealing region91(in particular the portion of the first sealing region91along the bottom surface79of the extension78and the housing top surface32) through the extension78of the membrane body72. Accordingly, the formed top seal (of the third sealing region93) and the formed bottom seal (of the first sealing region91) are directly opposite each other through the extension78. As the filter head50is threaded onto the housing30, the slot surface58presses axially downward against the top surface77of the extension78of the membrane body72(which presses the extension78of the membrane body72and the housing top surface32closer), thereby further forming seals among the filter head50, the membrane assembly70, and the housing30together (and improving the first sealing region91and the third sealing region93). At least a portion of the first sealing region91and the third sealing region93together form a secondary sealing region that also prevents DEF leakage, in addition to the primary sealing region. Housing Notches and Membrane Assembly Projections As shown inFIGS.4-5B, at least one of the extension78of the membrane body72and the housing top surface32comprises at least one projection81, and the other of the extension78of the membrane body72and the housing top surface32defines at least one notch41that is complementary to the at least one projection81. For example, the housing top surface32defines at least one groove or notch41(and preferably a plurality of notches41along its circumference), and the bottom surface79of the extension78of the membrane assembly70comprises at least one projection81(and preferably a plurality of projections81along its circumference). The notch41and the projection81are complementary to each other (in size, position, number, and shape), such that the projection81fits securely into and within the notch41when the membrane assembly70is positioned at least partially within the housing30, thereby locking (in particular rotatably locking) the housing30and the membrane assembly70together. For example, the notches41and the projections81interlock together to prevent the housing30and the membrane assembly70from rotating relative to each other once assembled. The notches41of the housing30are positioned along the housing top surface32and extend axially vertically downward, toward the base35of the housing30. The projections81of the membrane assembly70are positioned along the outer surface76of the membrane side wall72aof the membrane body72and also extend axially vertically downward in order to interlock with the notches41upon assembly. As shown inFIG.5B, the projections81may be positioned along and extend axially downwardly from the bottom surface79of the extension78of the membrane body72(between the outer surface76of the membrane body72and the inner surface84of the lip82(not shown inFIGS.5A-5B)). Membrane Body and Lip According to one embodiment as shown inFIGS.3A-3C and6A-7B, the membrane assembly70is constructed as two separate pieces (forming the membrane body72and the lip82) that are integrated together. Once the membrane body72and the lip82are formed together, they create a single unitary component that cannot be separated without destruction. Accordingly, the membrane body72and the lip82may optionally be two different materials. For example, the membrane body72may be a flexible rubber, and the lip82may be a rigid plastic or metal. The lip82may comprise a ring88, a portion of which is over-molded into the membrane body72. As shown inFIG.3C(in view ofFIG.7B), the ring88comprises a horizontal, radially-extending portion (that is over-molded into the extension78of the membrane body72) and a vertical, axially-extending portion (extending out from the membrane body72, along the housing outer surface36). As shown inFIGS.7A-7B, the ring88may include a plurality of through-holes or apertures89extending completely through the radially-extending portion of the ring88and are positioned and spaced apart from each other regularly about the circumference of the ring88. The apertures89allow a portion of the membrane body72to be overmolded into and through the ring88for a secure attachment between the ring88and the membrane body72(as shown inFIG.3C). As shown inFIGS.8A-8E, the membrane assembly70(including both the membrane body72and the lip82) may be constructed as a single piece. Accordingly, the membrane assembly70comprises (and is initially constructed as) a single unitary component that cannot be separated without destruction. For example, the membrane assembly70may be constructed as a single plastic molded part. Accordingly, the membrane body72and the lip82may be the same material as each other and are molded together at the same time. As shown inFIGS.8E-8F, the membrane assembly70may still comprises at least one projection81extending downwardly from the bottom surface79of the extension78(between the outer surface76of the membrane body72and the inner surface84of the lip82). The various embodiments disclosed herein may have any features, configurations, and components of the other embodiments disclosed herein, except where noted otherwise. Calculations and Experimental Results In order to calculate the pressure within the filter assembly10, the ideal gas equation (PV=nRT) is used, where P is the pressure, V is the volume, n is number of moles of gas (in this case, 1 mole), R is the ideal gas constant, and T is the temperature. At the initial condition, the equation is modeled as P1V1=ρ1RT1(which may be when T1is −10° C., which is equal to 263.15 K and P1is atmospheric pressure, which is 1 bar). When the DEF is frozen, the equation is modeled as P2V2=ρ2RT2(which may be when T2is −25° C., which is equal to 248.15 K). Combining the two equations results in the following equation: P2/P1=(V1/V2)*(T2/T1). Assuming that the volume of DEF is 100 milliliters (mL), that V1(the volume of air) is 40% of the volume of DEF (i.e., 40 mL), that T1is 295.15 K, and that T2is 233.25 K, the volume of air is reduced to 32 mL (i.e., V2) when the DEF is frozen, due to 8% compression caused by the expansion of DEF. In this scenario, P2is equal to (40/32)*(248.15/263.15), which is 1.2 bar. The deformation of the membrane assembly70, in particular the percentage of volume expansion, due to an increase of pressure (induced by a low temperature) was simulated and tested. The setup is shown inFIG.9A, and the results are shown inFIGS.9B-9C. In this test, the temperature was approximately −40° C., assuming the maximum pressure will be generated during DEF expansion. Since the membrane assembly70has ribs71, a 2D axisymmetric analysis on the deformed shape of the membrane assembly70was performed for two different sections (i.e., through the ribs71and without the ribs71), and the expanded volume of the membrane assembly70was subsequently calculated for both sections based on their angles (i.e., the width). Due to the symmetry of the membrane assembly70, a quarter section of the filter assembly10was considered (as shown inFIG.9A) with symmetric boundary conditions along the height of the filter assembly10(i.e., the “cut” faces of the filter assembly10). In the simulation, the filter head50was vertically displaced downward to compress the membrane assembly70, and pressure was applied (in an outward direction) on the internal surfaces of the membrane assembly70(in particular along the inner surface74of the membrane body72). As shown in the results inFIGS.9B-9C, by expanding, the membrane assembly70can accommodate the expansion of the DEF at low temperature. For example, at a very low pressure (i.e., 0.5 bar), the membrane assembly70can deform more than 10% to provide a larger volume for the expanded DEF. FIGS.10A-10Bshow a finite element analysis (FEA) of the membrane assembly70during deformation. In particular,FIG.10Ashows the directional deformation of the membrane assembly70after 2 bars of pressure, andFIG.10Bshows the directional deformation of the membrane assembly70after 5 bars of pressure. As utilized herein, the term “approximately” and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. The term “approximately” as used herein refers to ±5% of the referenced measurement, position, or dimension. It should be understood by those of skill in the art who review this disclosure that these terms are intended to allow a description of certain features described and claimed without restricting the scope of these features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations of the subject matter described and claimed are considered to be within the scope of the invention as recited in the appended claims. The terms “coupled,” “connected,” “attached,” and the like as used herein mean the joining of two members directly to one another. Such joining may be stationary (e.g., permanent) or moveable (e.g., removable or releasable). References herein to the positions of elements (e.g., “top,” “bottom,” “above,” “below,” etc.) are merely used to describe the orientation of various elements in the FIGURES. It should be noted that the orientation of various elements may differ according to other exemplary embodiments, and that such variations are intended to be encompassed by the present disclosure. It is important to note that the construction and arrangement of the various exemplary embodiments are illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described herein. For example, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may also be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the scope of the present invention.
38,068
11857902
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present disclosure is further described in detail hereinafter with reference to the drawings and the specific embodiments. As shown inFIG.1toFIG.13, a high-stability shale gas desanding device with a gravel storage mechanism comprises a shale gas desanding assembly1, a driving assembly2, a flow stirring assembly3and a flow guide assembly4. The shale gas desanding assembly1comprises an outer side gas-solid separation tank101, an inner side gas-solid separation tank102is sleeved inside the outer side gas-solid separation tank101, the inner side gas-solid separation tank102is communicated with a shale gas mixture ingress pipe401of the flow guide assembly4, a top portion of the shale gas desanding assembly1is communicated with an interior of the outer side gas-solid separation tank101through a first pressure balance pipe106, the outer side gas-solid separation tank101is communicated with the shale gas mixture ingress pipe401through a second pressure balance pipe5, a pressure regulation and control assembly6is arranged on the second pressure balance pipe5, the liftable and rotatable flow stirring assembly3is further arranged inside the inner side gas-solid separation tank102, and an input end of the flow stirring assembly3is connected with an output end of the driving assembly2. Preferably, the inner side gas-solid separation tank102and the outer side gas-solid separation tank101are fixedly connected through a bridge-type connecting frame103, and top portions of the outer side gas-solid separation tank101and the inner side gas-solid separation tank102are fixedly and hermetically connected with a same tank cover104, an exhaust channel105is clamped in the tank cover104, a side end surface of the exhaust channel105is clamped with the first pressure balance pipe106, the other end of the first pressure balance pipe106is clamped on a side end surface of the outer side gas-solid separation tank101, and the first pressure balance pipe106is further provided with a one-way valve107. In the embodiment, an interlayer formed by combining the outer side gas-solid separation tank101with the inner side gas-solid separation tank102is communicated with the exhaust channel105through the first pressure balance pipe106, and the first pressure balance pipe106is further provided with the one-way valve107, which means that the airflow can only flow to the interlayer along the exhaust channel105, so that an air pressure intensity in the interlayer will always keep a maximum value of the air pressure intensity. Preferably, the driving assembly2comprises a first support mesh panel201, an arc surface of the first support mesh panel201is fixedly connected with an inner side wall of the inner side gas-solid separation tank102, a top portion of the first support mesh panel201is clamped with a first bearing202, a first adapter cylinder203is sleeved in the first bearing202, a first threaded cylinder209is sleeved in the first adapter cylinder203, a first threaded rod210is threadedly connected on an internal thread surface of the first threaded cylinder209, and a bottom portion of the first threaded rod210is fixedly connected to a top portion of the first support mesh panel201. Preferably, an outer surface of the first threaded cylinder209is fixedly connected with a first slidably connecting seat212, the first slidably connecting seat212is slidably connected in a first slidably connecting groove211formed on an inner circular surface of the first adapter cylinder203, a surface of the first adapter cylinder203is fixedly connected with a first driven bevel gear204, and a surface of the first driven bevel gear204is meshed with a first driving bevel gear205. The first driving bevel gear205is fixedly connected to a surface of a second adapter cylinder206, the surface of the second adapter cylinder206is further sleeved with a second bearing207, the second bearing207is clamped on wall bodies of the outer side gas-solid separation tank101and the inner side gas-solid separation tank102respectively, an end portion of the second adapter cylinder206is fixedly connected with an output end of an electric motor208, and a side end surface of a body of the electric motor208is fixedly connected with the side end surface of the outer side gas-solid separation tank101through a shock absorbing seat. In the technical solution above, before introducing mixed shale gas into the inner side gas-solid separation tank102through the shale gas mixture ingress pipe401, the electric motor208is controlled to be operated, and during operation of the electric motor208, an output shaft of the electric motor may drive the first driving bevel gear205to rotate in the second bearing207through the second adapter cylinder206, a torque is transferred to the first adapter cylinder203by using a linkage effect between the first driving bevel gear205and the first driven bevel gear204, and the first threaded cylinder209is driven to rotate in the first bearing202through the first adapter cylinder203. Preferably, the flow stirring assembly3comprises a connecting sleeve301, the connecting sleeve301is sleeved and fixed on a surface of the first threaded cylinder209, an upper layer wheel disc302and a lower layer wheel disc303are sequentially fixed and connected on a circumferential surface of the connecting sleeve301from top to bottom, and an arc connecting seat304is slidably connected between the upper layer wheel disc302and the lower layer wheel disc303. Preferably, a bottom portion of the arc connecting seat304is provided with a second slidably connecting groove306, a second slidably connecting seat305is slidably connected in the second slidably connecting groove306, an end surface inside the second slidably connecting groove306is further fixedly connected with a side surface of the second slidably connecting seat305through a first supporting spring307, and a bottom portion of the second slidably connecting seat305is fixedly connected to a top portion of the lower layer wheel disc303. Preferably, a top portion of the arc connecting seat304is provided with a retracting groove309, a bottom portion inside the retracting groove309is connected with a movable flow stirring plate308through a second supporting spring310, a bottom portion of the upper layer wheel disc302is further provided with an implanting groove312matched with the movable flow stirring plate308, one surfaces of the upper layer wheel disc302and the lower layer wheel disc303far away from each other are both fixedly connected with a fixed flow stirring plate311, the fixed flow stirring plates311and the movable flow stirring plates308are staggered, and corners of the movable flow stirring plates308are designed to be circular arcs. In the technical solution above, the fixed flow stirring plate311located on the upper layer wheel disc302, the movable flow stirring plate308and the upper layer wheel disc302will drive an airflow in the inner side gas-solid separation tank102to flow quickly and generate a violent vortex during rotation of the upper layer wheel disc302and the lower layer wheel disc303on the connecting sleeve301, thus enhancing a rotating flow generated by the mixed shale gas entering the inner side gas-solid separation tank102. During reciprocating lifting movements of the upper layer wheel disc302and the lower layer wheel disc303on the connecting sleeve301along a vertical direction, since the arc connecting seat304is supported by an elastic force of the first supporting spring307through the second slidably connecting seat305and limited by the inner side gas-solid separation tank102, self-regulation and control of an effective number of the movable flow stirring plates308are realized by using a particularity of a conical structure of the inner side gas-solid separation tank102for changing a state of the vortex of the airflow inside the inner side gas-solid separation tank102. An elastic supporting effect of the first supporting spring307acts on the arc connecting seat304through the second slidably connecting seat305for ensuring a basic stability of the arc connecting seat304. When the arc connecting seat304is not affected by a centrifugal force, a restoring effect may be realized automatically under the supporting effect of the first supporting spring307, and when the arc connecting seat304is affected by the centrifugal force, due to an elastic connection relationship between the arc connecting seat304and the second slidably connecting seat305, an outward extension degree of the arc connecting seat304can be automatically controlled according to the centrifugal force and an inner diameter of the inner side gas-solid separation tank102. By the second supporting spring310designed, the second supporting spring310exerts supporting and fixing effects on the movable flow stirring plate308. When the arc connecting seat304extends outwardly under an action of the centrifugal force, a corresponding number of movable flow stirring plates308will automatically extend out of the retracting groove309under the drive of a restoring elastic force of the second supporting spring310. When the arc connecting seat304is driven to restore under an action of the restoring elastic force of the first supporting spring307, due to an elastic connection relationship between the movable flow stirring plates308and the retracting groove309, the movable flow stirring plates308will automatically retract into the retracting groove309, thus effectively ensuring smooth outward extension and inward retraction of the arc connecting seat304. However, in order to reduce collision friction between the movable flow stirring plates308during retraction and the upper layer wheel disc302or collision friction between the movable flow stirring plates during outward extension and the implanting groove312, corners of the movable flow stirring plates308are designed to be circular arcs, so that the movable flow stirring plates308may retract into the retracting groove309or withdraw from the implanting groove312more easily. Preferably, the flow guide assembly4comprises the shale gas mixture ingress pipe401, the shale gas mixture ingress pipe401is provided with a first spherical valve402, the shale gas mixture ingress pipe401sequentially passes through wall bodies of the outer side gas-solid separation tank101and the inner side gas-solid separation tank102and extends inside the inner side gas-solid separation tank102, and an upper portion of the first spherical valve402is provided with a control knob403. By opening the first spherical valve402, the shale gas mixture may enter the inner side gas-solid separation tank102from the shale gas mixture ingress pipe401generally along a tangential direction close to the inner side gas-solid separation tank102. Preferably, the pressure regulation and control assembly6comprises a connecting pipe601, the connecting pipe601is sleeved on the second pressure balance pipe5, an inner side wall of the second pressure balance pipe5is fixedly connected with a conical body602, the conical body602is connected with a second spherical valve603in an embedded mode, a spherical surface of the second spherical valve603is fixedly connected with a guide rod604, a surface of the guide rod604is sleeved with a second threaded cylinder606, and an outer circumferential surface of the second threaded cylinder606is fixedly connected with an inner pipe wall of the connecting pipe601through a fixing rib607. Preferably, one side inside the second threaded cylinder606is threadedly matched with one side of a second threaded rod608, an end portion of the second threaded rod608is fixedly connected with one end of the guide rod604through a third supporting spring605, and a surface on the other side of the second threaded rod608is sleeved with a third adapter cylinder611slidably matched with the second threaded rod. An inner side wall of the third adapter cylinder611is provided with a third slidably connecting groove617, a third slidably connecting seat618is slidably connected in the third slidably connecting groove617, the third slidably connecting seat618is fixedly connected with the second threaded rod608, a surface of the third adapter cylinder611is sleeved with a third bearing610, the third bearing610is clamped on a second support mesh panel609, and an outer cambered surface of the second support mesh panel609is fixedly connected with the inner pipe wall of the connecting pipe601. A surface of the third adapter cylinder611is fixedly connected with a second driven bevel gear612, a surface of the second driven bevel gear612is meshed with a second driving bevel gear613, the second driving bevel gear613is fixedly connected at a bottom portion of a fourth adapter cylinder614, a surface of the fourth adapter cylinder614is further sleeved with a fourth bearing615, the fourth bearing615is clamped on a top pipe wall of the connecting pipe601, and a top end of the fourth adapter cylinder614is fixedly connected with a knob616. A working principle of the embodiment is as follows. The first spherical valve402is opened to make the shale gas mixture enter the inner side gas-solid separation tank102from the shale gas mixture ingress pipe401, and the mixed shale gas will rotate violently after entering the inner side gas-solid separation tank102. In addition, before introducing the mixed shale gas into the inner side gas-solid separation tank102through the shale gas mixture ingress pipe401, the electric motor208is controlled to be operated, and during operation of the electric motor208, an output shaft of the electric motor will drive the first driving bevel gear205to rotate in the second bearing207through the second adapter cylinder206, a torque is transferred to the first adapter cylinder203by using a linkage effect between the first driving bevel gear205and the first driven bevel gear204, and the first threaded cylinder209is driven to rotate in the first bearing202through the first adapter cylinder203. On one hand, the first threaded cylinder209will drive the connecting sleeve301connected onto the surface of the first threaded cylinder to rotate, and on the other hand, under a combined effect of a torsion and a thread bite force, the first threaded cylinder209will be displaced on the surface of the first threaded rod210, so that the upper layer wheel disc302and the lower layer wheel disc303on the connecting sleeve301will also move up and down in a reciprocating mode during rotation. Under the drive of the first threaded cylinder209, the fixed flow stirring plate311located on the upper layer wheel disc302, the movable flow stirring plate308and the upper layer wheel disc302will drive an airflow in the inner side gas-solid separation tank102to flow quickly and generate a violent vortex during rotation of the upper layer wheel disc302and the lower layer wheel disc303on the connecting sleeve301, thus enhancing a rotating flow generated by the mixed shale gas entering the inner side gas-solid separation tank102. During reciprocating lifting movements of the upper layer wheel disc302and the lower layer wheel disc303on the connecting sleeve301along a vertical direction, since the arc connecting seat304is supported by an elastic force of the first supporting spring307through the second slidably connecting seat305and limited by the inner side gas-solid separation tank102, self-regulation and control of an effective number of the movable flow stirring plates308are realized by using a particularity of a conical structure of the inner side gas-solid separation tank102assisted by the centrifugal force and the outward extension degree of the arc connecting seat304for changing a state of the vortex of the airflow inside the inner side gas-solid separation tank102and disturbing separation of the mixed shale gas in the inner side gas-solid separation tank102, so as to adjust a separation efficiency of the inner side gas-solid separation tank102, and then make the gas-solid separation more thorough. An acting force on the inner side gas-solid separation tank102can also be increased by changing a shape of the vortex, and the oily substance, the gravel and other impurities adhered to the inner side gas-solid separation tank102may be scratched off during lifting movements of the upper layer wheel disc302, the lower layer wheel disc303and the arc connecting seat304. An interlayer formed by combining the outer side gas-solid separation tank101with the inner side gas-solid separation tank102is communicated with the exhaust channel105through the first pressure balance pipe106, and the first pressure balance pipe106is further provided with the one-way valve107, which means that the airflow can only flow to the interlayer along the exhaust channel105, so that an air pressure intensity in the interlayer will always keep a maximum value of the air pressure intensity, and the maximum value of the air pressure intensity is an air pressure intensity in a normal operation stage inside the inner side gas-solid separation tank102. According to an air pressure intensity of the shale gas mixture ingress pipe401in the case of introducing the mixed shale gas, the knob616is turned to drive the fourth adapter cylinder614to rotate in the fourth bearing615. A torque is transferred to the third adapter cylinder611by using a linkage effect between the second driving bevel gear613and the second driven bevel gear612, and the second threaded rod608is driven to rotate in the first threaded cylinder209through the third slidably connecting seat618. Under a combined effect of the torsion and a thread bite force, the second threaded rod608will be displaced in the second threaded cylinder606, so that an initial deformation amount of the third supporting spring605may be regulated and controlled, and an elastic force of the third supporting spring605may be changed. As shown inFIG.12, the conical body602is a frustum-like cylindrical structure, with a left side contacted with the spherical surface of the second spherical valve603and a right side communicated with the interlayer (which is namely the interlayer formed by combining the outer side gas-solid separation tank101with the inner side gas-solid separation tank102) through the connecting pipe601and the second pressure balance pipe5. According to stress balance analysis, when the spherical surface of the second spherical valve603blocks the left side of the conical body602, the elastic force of the third supporting spring605and the air pressure in the shale gas mixture ingress pipe401are greater than the air pressure in the interlayer, and then the spherical surface of the second spherical valve603can tightly adhere to the conical body602, thus intercepting gas flowing from the interlayer to the second pressure balance pipe5. Therefore, when the airflow pressure inside the shale gas mixture ingress pipe401is insufficient, the elastic force of the third supporting spring605is insufficient to press the spherical surface of the second spherical valve603against the left side of the conical body602, and at the moment, the gas in the interlayer may flush through the second spherical valve603and make the second spherical valve move to the left, thus releasing the blockage of the conical body602by the spherical surface of the second spherical valve603. When the second spherical valve603releases the intercepting effect on the gas, the gas in the interlayer can enter the shale gas mixture ingress pipe401along the second pressure balance pipe5to supplement the airflow pressure in the shale gas mixture ingress pipe, which can improve a stability of the airflow to a certain extent and prevent the airflow from being stirred. In addition, the original introduced gas and the supplemented gas of the shale gas mixture ingress pipe401are the same gas, thus avoiding mutual interference between the supplemented gas and the original gas. The above embodiments are only preferred technical solutions of the present disclosure, and should not be regarded as limiting the present disclosure. The embodiments in the present application and the features in the embodiments can be arbitrarily combined with each other without conflict. The scope of protection of the present disclosure shall be the technical solutions recorded in the claims, including the equivalent alternatives of the technical features in the technical solutions recorded in the claims. Equivalent substitutions and improvements in the scope are also included in the scope of protection of the present disclosure.
20,622
11857903
DESCRIPTION OF PREFERRED EMBODIMENTS In the Figures, same or same type components are identified with same reference characters. The Figures show only examples and are not to be understood as limiting. FIGS.1to28show filter elements10with a filter bellows12that in an appropriately adapted form is suitable as a filter element10according to the invention. In particular, the filter bellows12comprises one or a plurality of notches40,44. FIGS.1to13illustrate a first filter element10(FIGS.1-6) and a filter housing102as well as a filter system100(FIGS.7to13). As can be seen inFIGS.1and2, the filter element10comprises a filter bellows12which extends along a longitudinal axis L and surrounds an interior50. The filter bellows12is formed, for example, of a folded filter material that is formed to filter bellows12, closed all around, and arranged on a support tube70. The support tube70can comprise an inwardly pointing rib. InFIGS.1and2, the folds14are indicated only in an exemplary fashion and extend across the entire length of the filter bellows12. The longitudinal edges16of the folds14are positioned on an outer circumferential surface18of the filter bellows12. The filter bellows12is formed in this example as a round element. At a first end face end20and a second end face end30, oppositely positioned thereto, of the filter element10, end disks22,32are arranged which seal the filter bellows12at its end edges. The end disks22,32can be formed in a conventional manner, for example, of foamed polyurethane. At the first end20, an end disk22is arranged which is open toward the interior50. At the oppositely positioned second end30, a closed end disk32is arranged. The closed end disk32comprises outwardly projecting circular segment-type spacer knobs34that surround at a constant radius a pin60extending into the interior50. The spacer knobs34can serve for supporting the filter element10in a housing. The open end disk22comprises an outwardly extending ring26which surrounds the opening24in the end disk22. The ring26can serve as a seal. Preferably, end disk22and ring26are formed together as one piece. In particular, the end disk can be formed together with the ring26of polyurethane. The flow direction of the fluid to be filtered is oriented through the filter bellows12. When its clean side is provided in the interior, the fluid flows from the exterior of the filter bellows12into the interior50and from there through the opening24out of the filter element10. Optionally, the flow direction can also be provided in reverse. The filter bellows12comprises at both its ends20,30a notch40,44, respectively, whose axial length42,46in the direction of the longitudinal axis L is shorter than the length extension of the filter bellows12in the direction of the longitudinal axis L. The notches40,44are locally limited and do not extend across the entire length of the folded bellows12. Preferably, the notches40,44have the greatest fold edge distance at the respective end disks22,32and taper with increasing distance away from the end disk22,32. The notches40,44widen the distance between two neighboring folds wherein the folds14as a whole extend across the entire length of the folded bellows12. Preferably, the notches40,44are arranged displaced at the circumference, for example, displaced by 180° at diametrically opposed sides of the folded bellows12. The notches can also be displaced relative to each other at angles that are different from 180°. Between the notches40,44, fixation elements90can be provided which ensure that in this region the spacing between the folds14remains constant. Optionally, conventional fixation elements90such as thread coils, glue beads, beads of hot melt, embossments (“pleatlock”) transverse to the longitudinal edges16of the folds14, and the like can be provided. The notches40,44can be produced in various ways. They can be introduced into the filter bellows12after the optional fixation elements90have already been applied. The notches40,44can be introduced during manufacture of the end disks22,32into the filter bellows12or by insertion parts or spreading elements at the support tube and the like. The two notches40,44at the filter bellows can be formed in the same manner or with different methods. It can be optionally provided that only one notch40or44is present at the filter element10. As can be seen inFIGS.3to6, the notches40,44extend from a notch in the end disk22,32.FIG.3shows a plan view of the closed end disk32of the filter element10according toFIG.1;FIG.4a detail of the filter element10at its closed end disk32; andFIG.5a detail of the filter element10at its open end disk22.FIG.6shows a longitudinal section of the filter element10according toFIG.1. When mounting the filter element10, the notch can advantageously effect frictional locking against a counter element in a housing102and reduce the risk of tilting of the filter element10during installation in the housing102. The notches40,44are kept in shape by the material of the end disk22,32. In this context, it is possible that the end disk22,32comprises within the notch a minimal protrusion relative to the folds that are spread apart by the respective notch40,44. This enables a compression of the notches40,44upon installation into a housing part that comprises a respective corresponding counter contour relative to the notches40,44. Optionally, only one or none of the end disks22,32can be provided with a notch when in the region of the filter bellows12adjoining the end disks22,32notches40,44are provided. This enables the use of the rim of the notch-free end disk for radial sealing. The closed end disk32comprises in this embodiment an inwardly curved surface having at its center a pin60projecting into the interior50. The notches40,44enable an installation of the filter element10in a correct position in a housing. In cooperation with the pin60, it can be achieved that a stable positioning of the filter element10is achieved. This is particularly advantageous when the filter element10is installed into a recumbent housing. The notches40,44and the pin60prevent a tilting of the filter element10. The filter system100with housing102is illustrated inFIGS.7to13. In this context,FIG.7shows a longitudinal section of the filter system100with housing102into which a filter element10according toFIG.1is inserted.FIG.8shows a plan view of the filter system100, andFIGS.9and10show details of the first filter system100at the closed end disk32and at the open end disk22of the filter system10.FIG.11shows an isometric view of the filter system100from a first side, andFIG.12shows an isometric view of the filter system100from a second side oppositely positioned to the first side.FIG.13shows an exploded illustration of the filter system100. The housing102is comprised of a first housing part104, for example, a housing pot, and of the second housing part106, for example, a cover. The two housing parts104,106are connected to each other, in particular detachably, at a connection105. The second housing part106comprises at its end face an inwardly curved surface which corresponds with the curved end face of the closed end disk32of the filter element10. The housing102comprises a respective corresponding notch120,122matching the notches40,44of the filter element10at its first open end disk22and at its second closed end disk32. This can be seen in the plan view of the housing102inFIG.8. The notch122is provided in the housing102corresponding to the notch44at the end30with the closed end disk32. The housing102comprises a first fluid connector110, for example, an air inlet, and a second fluid connector112, for example, an air outlet. The first fluid connector110is arranged tangentially to the first housing part104of the housing102so that the fluid can enter the housing102, for example, tangentially. The second fluid connector112is embodied as a central socket114at the first housing part104and extends in longitudinal direction L away from the filter element10. As shown inFIG.9, the spacer knobs34of the closed end disk32are resting against the inner side of the second housing part106and enable in axial direction a safe clamping of the filter element10when the housing102is closed. This enables an improvement of the stability in case of vibrations in operation of the filter element10. The notch122engages in this context at least partially the notch44of the filter element10. The open end disk22of the filter element10surrounds with the ring26a rim of the socket114projecting into the interior50and seals radially inwardly against the rim, as illustrated inFIG.10. The notch120engages in this context at least partially the notch40of the filter element10. InFIGS.11and12, the side views of the filter system100can be seen which make visible the diametrically opposed position of the notches120,122in the first and second housing part104,106. The exploded illustration inFIG.13shows the components housing pot104, filter element10, and housing cover106of the filter system100. The filter element10can be inserted into the housing102with positional orientation due to the notches40,44and the notches120,122in the housing102. FIGS.14to20show a further embodiment with a first manufacturing possibility of one or a plurality of notches40in a filter element10. In this variant, the notch40in the filter bellows12of the filter element10is produced by an insertion part250that comprises a notch structure252which engages the filter bellows12between two folds and spreads them apart. The insertion ring250can be placed, for example, when producing the foamed, for example, open end disks22, into a casting mold and can be connected with the end disk22and the filter bellows12in this way. The further elements of the filter system10correspond to those of the preceding embodiment ofFIGS.1to13, reference being had to it for avoiding unnecessary repetitions. FIG.14shows the filter element10according to a further example with a ring250for local widening of a distance between folds14of the folded bellows12prior to applying the end disk22.FIG.15shows the filter element10with foamed end disk22and embedded insertion ring250.FIG.16shows a longitudinal section through the filter element10with the insertion ring250in the open end disk22.FIG.17shows a plan view of the open end disk22of the filter element10, andFIG.18shows a detail of the filter element10in the connecting region end disk22, filter bellows12, and insertion ring250. FIGS.19and20show different views of the insertion ring250. The notch structure252is projecting in axial direction away from the annular surface of the insertion ring250. In radial direction, the notch structure252practically has no protrusion relative to the annular surface. In this way, the notch structure252can engage between two folds14and push them apart. The notch structure252is approximately wedge-shaped and comprises two curved wings251that are connected to each other and extend symmetrically away from their contact surface outwardly. The cross section through the connected wings251is approximately V-shaped and is approximately wedge-shaped wherein the two wings251of the notch structure252meet each other at the middle of the wedge shape. The front edge of the notch structure252is straight and extends parallel to the longitudinal edges16of the folds14and is aligned with the longitudinal edges16of the folds14. The rear side of the notch structure252is rounded due to a rounded shape of the wings251and tapers to a point in outward direction. Due to the rounded connecting seam and surface of the wings251, the folds14in the filter bellows12can be spread apart in a gentle manner. The filter bellows12is arranged on a support tube70. The support tube70can comprise an inwardly pointing rib. FIGS.21to28show a further variant for manufacturing at least one notch44in the folded bellows12of a filter element10, in which a notch structure72is provided at the support tube70of the filter element10. The support tube70can comprise an inwardly pointing rib. FIG.21shows the filter element10with the support tube70that is embodied for locally widening distances between folds14of the folded bellows12.FIG.22shows a longitudinal section, andFIG.23a plan view of the filter element10.FIG.24shows a detail of the filter element10at its closed end disk32.FIG.25shows a longitudinal section, andFIG.26an isometric view of the support tube70.FIG.27shows a plan view of the support tube70, andFIG.28a detail of the support tube70. The further elements of the filter element10correspond to those of the embodiment ofFIGS.1to13, reference being had to it for avoiding unnecessary repetitions. As can be seen inFIGS.21and22, the notch44in the filter bellows12at the closed end disk32of the filter element10is caused by a notch structure72of the support tube70. Generally, the support tube70is closed at its closed end by a disk74. In this example, the notch structure72is arranged at the closed end of the support tube70. The notch structure72of the support tube70engages between two folds14and widens their distance relative to each other in radial direction outwardly. In the end disk32, a notch is formed in the region of the notch structure72. The notch structure72is projecting in radial direction corresponding to the thickness of the filter bellows12away from the support tube70and projects in axial direction into the filter bellows12. The notch structure72is approximately wedge-shaped and comprises two curved wings71that are connected to each other and extend symmetrically away from their contact surface in outward direction. The cross section through the connected wings71is approximately V-shaped wherein the two wings71of the notch structure72meet each other at the middle of the wedge shape. The wings71are somewhat rounded so that the folds14in the filter bellows12can be spread apart in a gentle manner. The front edge of the notch structure72is straight and extends parallel to the longitudinal edges16of the folds14and is aligned with the longitudinal edges16of the folds14. The rear side of the notch structure72is rounded due to the rounded shape of the wings71and tapers to a point in outward direction. In this manner, the notch structure72can engage between two folds14of the filter bellows12and push them apart. Due to the rounded connecting seam and surface of the wings71, the folds14in the filter element12can be spread apart in a gentle manner. Filter bellows12with support tube70and notch structure72are intimately connected to each other during casting of the end disk32. FIGS.29to33show a filter element10according to a further embodiment of the invention with a variant of an open end disk22. FIG.29shows a longitudinal section through the filter element10,FIG.30shows a detail of the filter element10at the open end disk22.FIG.31shows a further detail of the filter element10at the open end disk22.FIG.32shows a perspective view of the filter element10viewed from its open end disk22.FIG.33shows an isometric view of the filter element10viewed from its closed end disk32. The filter element10comprises a filter bellows12which extends along a longitudinal axis L and surrounds an interior50. The filter bellows12is formed, for example, of a folded filter material that is arranged, closed all around, about the support tube70. The folds14of the filter bellows12extend across the entire length of the filter bellows12. The longitudinal edges16of the folds14are positioned on an outer circumferential surface18of the filter bellows12. The filter bellows12comprises in this example a cross section with two oppositely positioned circular arc-shaped sections that are connected to each other by straight regions. At a first end face end20and a second end face end30, oppositely positioned thereto along the longitudinal axis L, of the filter element10, end disks22,32are arranged which seal the filter bellows12at its end edges. The end disks22,32can be formed as is conventional, for example, of foamed polyurethane. At the first end20, an end disk22that is open toward the interior50is arranged. At the oppositely positioned second end30, closed end disk32is arranged. The closed end disk32comprises outwardly projecting circular segment-type spacer knobs34that surround a pin60extending into the interior50. The spacer knobs34can serve for supporting the filter element10in the housing102. The spacer knobs34are preferably formed as one piece together with the end disk32. The open end disk22comprises an outwardly facing bead28which surrounds in sections the opening24in the end disk22. The bead28is preferably formed as one piece together with the end disk22. The bead28has an approximately U-shaped form and extends approximately U-shaped about the opening24of the end disk22so that a portion of the opening24is surrounded by the bead28and a part is without bead. The bead28surrounds approximately three fourths of the circumference of the central opening24. In this context, the bead-free region of the opening24of the end disk22preferably has an edge29which is particularly strongly rounded. Through the bead-free region of the opening24, fluid can exit into a clean channel. The bead28can serve for supporting the filter element10in a housing. This is advantageous in particular in case of a housing in which the filter element10is installed in a recumbent position, i.e., with the longitudinal axis L oriented at a slant or horizontally. For manufacturing technological reasons, embossments of spacers218of a casting mold210(FIG.36), in which the first end disk22with the clean air seal25was cast onto the filter bellows12, are formed in the first end disk22. The first end disk22and the circumferential clean air seal25are comprised here of polyurethane. The second end disk32has for manufacturing technological reasons like the first end disk22an embossment, not identified in detail, which is caused by a spacer of a casting mold200(FIG.35). The embossment of the second end disk32is formed substantially continuously circumferentially and interrupted only in the region of the notch44. The flow direction of the fluid to be filtered is oriented through the filter bellows12. When its clean side is provided in the interior, the flow flows from the exterior of the filter bellows12into the interior50and from there through the opening24out of the filter element10. Optionally, the flow direction can also be provided in reverse. The filter bellows12comprises at its second end30a notch44whose axial length46in the direction of the longitudinal axis L is shorter than the length extension of the filter bellows12in the direction of the longitudinal axis L. The notch44is locally limited and does not extend across the entire length of the folded bellows12. Preferably, the notch44has the greatest fold edge distance at the end disk32and tapers with increasing spacing away from the end disk32. The notch44widens only the distance between two neighboring folds14wherein the folds14as a whole extend across the entire length of the folded bellows12. Between the notch44and the oppositely positioned open end disk22, fixation elements90can be provided which ensure that in this region the spacing between the folds14remains constant. Optionally, conventional fixation elements90such as thread coils, glue beads, beads of hot melt, embossments (“pleatlock”) transverse to the longitudinal edges16of the folds14, and the like can be provided. The notch44can be produced in different ways. It can be introduced into the filter bellows12after the optional fixation elements90have already been applied. The notch44can be introduced into the filter bellows12when producing the end disk32. Optionally, it can be provided that, as in the embodiment illustrated inFIGS.1to13, a notch40,44is provided at both ends20,30of the filter element10. The open end disk22projects radially with a protrusion23past the filter bellows12and can be used as a radial seal25(FIGS.30,31). The protrusion23preferably amounts to at least 3 mm, preferably at least 5 mm, particularly preferred at least 6 mm, further preferred at least 8 mm, further preferred at least 10 mm, particularly preferred at least 8 mm and at most 15 mm. On the side of the end disk22at which the bead28is arranged, the protrusion23of the end disk22is smaller than at the diametrically opposed side. Optionally, the end disk22can however also be embodied with circumferentially extending constant protrusion23. At the closed end disk32, a hollow, approximately T-shaped pin60projects into the interior50. The pin60can be used as a mounting aid when installing the filter element10in a housing102. At the side of the end disk32which is opposite the notch44, two spaced-apart cams36are arranged at the circumference and project in radial direction past the end disk32. They serve as mounting aid so that, upon insertion of the filter element10into its housing, the filter bellows12and the end disk32stay spaced apart from the housing wall. The support tube70comprises along its length an inwardly projecting rib78which can be utilized for positioning the support tube70in a casting bowl for the end disks22,32. At the closed end disk32, a hollow pin60projects into the interior50. The pin60can be used as a mounting aid when installing the filter element10in a housing100. This can be seen in particular inFIGS.39to46in which the filter system100is illustrated with the filter element10inserted in the housing102. FIG.34shows the support tube70for the filter element10with the inwardly projecting rib78which extends axially along the body76of the support tube70. At one end that is provided later on at the open end disk22, the support tube70comprises a folded-over broad rim80. The rim80serves as a support structure and is embodied here in the region of the first end disk22in a grid shape with radial stays and rings extending in circumferential direction between which penetrations are provided, not identified in detail. The material of the end disk22, for example, polyurethane, can engage through the penetrations and embed the rim80completely in the end disk22in this way. The pin60can be seen at the center at the end that is provided later on at the closed end disk32. The pin60can be formed of a non-elastomer material like the support tube70. The support tube70is closed off at this end by a disk74from which the pin60projects axially into the interior. FIG.35shows a casting bowl200for foaming a closed end disk32for the filter element10according toFIG.29, andFIG.36shows a casting bowl for foaming an open end disk22for the filter element according toFIG.29. At the transition of the rim80to the body76of the support tube70, cutouts75are provided where the material of the end disk22can engage. At the center in the casting bowl200for the closed end disk32, a pin contour203can be seen which is complementary to the pin60in the support tube70and onto which the support tube70can be pushed. A notch structure202is provided to engage between and spread apart two folds14of the filter bellows12arranged on the support tube70. Two cam contours204are provided for producing the cams36. Depressions206are provided as knob contour for the knobs34. The knob contours206are surrounded by a circumferential groove201which is interrupted at the notch structure. The casting bowl210for the open end disk22comprises a bead contour212in which the bead28of the end disk22is formed as well as a socket216which defines the opening24of the end disk24. At the exterior side of the socket216, a receptacle214is formed which accommodates the inwardly projecting rib78of the support tube70. Moreover, elevations218are provided which surround the socket216at a constant distance. The elements218engage the outwardly folded rim80of the support tube70. Moreover, at the socket216small projections220are distributed which engage the cutouts75of the support tube70for anchoring. By means of the support tube70, both casting bowls200,210can be aligned with each other in a defined position in that the support tube70is placed with the pin60onto the pin contour203of the casting bowl200of the closed end disk22and the inwardly positioned rib78is inserted into the receptacle214of the casting bowl210for the open end disk22. FIG.39shows a flowchart of a sequence during the manufacture of the filter element10by means of the casting bowls200,210. In step S100, a support tube70is provided at which a filter bellows12with or without notch40,44is arranged and that has an inwardly projecting axial rib78. The support tube70comprises an open end and an axially oppositely position closed end where a pin60projects into the interior of the support tube70. The end of the support tube70is closed with a disk74. In step S102, casting bowls200,210for an open end disk22and a closed end disk32are provided. In step S104, the starting material of the end disk22, in particular liquid polyurethane, is poured into the casting bowl210. The support tube70is placed in step S106with its folded-over rim80into the casting bowl210into the still liquid starting material for the open end disk22wherein the inwardly projecting rib78is inserted into the cutout214of the socket216. The elevations218engage penetrations at the rim80of the support tube70. The liquid starting material foams about and encloses the rim80of the support tube70and the end portion of the filter bellows12. After termination of the reaction of the material, the support tube70with filter bellows12and open end disk22is removed from the casting bowl210. In step S108, the starting material of the end disk32, in particular liquid polyurethane, is poured into the casting bowl200. In step S110, the support tube70is placed with the filter bellows12into the casting bowl200into the still liquid starting material for the closed end disk32and, by means of the T-shaped pin60, is positioned in correct position on the pin contour203. In this context, the notch structure202of the casting bowl200engages between two folds of the filter bellows12and spreads them apart. The liquid starting material foams about and covers the closed side of the support tube70and encloses the end portion of the filter bellows12. In this context, the spacer knobs34at the closed end disk32are formed in the depressions206. Also, the notch40in the filter bellows12is fixed. After termination of the reaction of the material, the support tube70with filter bellows12and closed end disk32is removed from the casting bowl210. FIGS.38to50show an embodiment of a filter system100according to one embodiment of the invention with a filter bellows10as it has been described above inFIGS.29to33. FIG.38shows an exploded illustration of a filter system100according to one embodiment of the invention with the filter element10according toFIG.29inserted into a housing102with a housing part104that is closed by a cover130.FIG.39shows a longitudinal section of the filter system100, andFIG.40a longitudinal section of a detail of the filter system100with mounting aids in the region of the closed end disk32of the filter element10.FIG.41shows a perspective view of the filter system100with open housing102and inserted filter element10, whileFIG.42shows the same view of the housing without filter element10.FIG.43shows a cross section of the filter system100with inserted filter element100and recognizable mounting aids in plan view. FIGS.44and45show perspective views of the open housing102of the filter system100.FIG.46shows the filter element10according toFIG.29during insertion into the housing102of the filter system100.FIGS.47and48show the cover130in detail.FIGS.49and50show in longitudinal section details in the region of the cover130at the housing part104. The housing102comprises the first housing part104, for example, a housing pot, and a second housing part in form of a cover130. At the open end of the housing part104, a circumferential collar109is formed which is interacting with a sealing element137(FIGS.49,50). The housing102comprises an inlet110and an outlet112. The inlet110is provided directly adjacent to the outlet112at the first housing part104, for example, is arranged tangentially thereat. Inlet110and outlet112of the housing102are arranged closely adjacent to each other and in the same housing part104. The fluid to be filtered experiences between inlet110and outlet112a directional deflection, in particular a deflection by 180°. As can be seen inFIGS.41and42, the second housing part104of the housing102in the installed state of the filter element10comprises below the filter element10a valve128that serves for draining water from the housing102. The valve128projects into the interior of the housing102. Also, it can be seen that inlet110and outlet112are arranged directly adjacent to each other at the same housing part104. Adjacent to the collar109, a shoulder107is provided at the inner side in the housing part104which extends between the housing-associated openings for inlet110and outlet112. The shoulder107forms a sealing surface for a seal144between cover and housing part104(FIGS.49,50). The first housing part104comprises in its bottom part a pin116which corresponds with the pin60. The corresponding pin116comprises at the contact surface to the pin60of the filter element10a locking element118that is interacting with a locking element62at the inner side of the hollow pin60. Upon insertion of the filter element10into the housing part104, the filter element10is protected thereby against tilting. When the cover130is connected to the housing part104, the pin60is separated from the corresponding pin116. When the filter element10is inserted into the first housing part104, the corresponding pin116catches the pin60of the filter element10so that the filter element10can be pushed in correct position into its end position. Subsequently, the cover130at the first housing part104is fastened. In the mounted state of the filter element10, a central longitudinal axis L of the filter element10coincides with a central longitudinal axis of the second housing part104. When the interior50of the filter element10is the clean side of the filter element10, the cover130is arranged at the clean side of the housing102. The cover130comprises in the interior a clean fluid channel134which guides the filtered fluid, for example, clean air, to the outlet122. For this purpose, at the first housing part104a socket142is arranged which provides the outlet112. The socket142projects in axial direction past the end disk22of the installed filter element10. The cover130comprises an opening132which is positioned, when the cover130is closed, below the socket142of the first housing part104. The bead28of the filter element10at the open end disk22is contacting a corresponding receptacle of the cover130and seals with the seal25of the protrusion23radially relative to the raw side of the filter element10. The bead28serves for supporting the filter element10. Since only a part of the open end disk22comprises the bead28, the bead-free region about the opening24is open toward the outlet112; the filtered fluid can flow through the cover130to the outlet112. The first housing part104comprises moreover a pin116corresponding with the pin60, as can be seen inFIGS.44and45. The corresponding pin116comprises at the contact surface to the pin60of the filter element10a locking element118that interacts with a locking element62at the inner side of the hollow pin60. The pin60predetermines the position angle of the filter element10and prevents tilting of the filter element10upon insertion of the filter element10into the housing part104. When the filter element10is pushed into the first housing part104, as indicated inFIG.46, the corresponding pin116catches the pin60of the filter element10so that the filter element10can be pushed into its end position. At the same time, the cams36at the closed end disk34ensure that the filter bellows12can glide at a safe distance across the valve128. FIG.47shows an isometric view of an exterior of the cover130, andFIG.48shows an inner side of the cover130. The cover130is wedge-shaped when viewed from the side so that its rim136rises from a region with minimal height to an oppositely positioned region with great height. In the region with great height, the opening132is arranged which opens the clean fluid channel134in the interior of the cover130. The opening132is positioned, with cover130closed, below the socket142. In the cover130, an air guide134is formed. The clean fluid channel134serves for guiding the filtered air out of the interior50of the filter element10to the outlet112of the housing102. The clean fluid channel134comprises here two regions in the opening132which in the mounted state communicate with the outlet112in the sidewall of the housing part104. The cover130comprises a circumferentially extending sealing groove141that defines a first sealing plane. Radially within the sealing groove141, a further circumferentially extending sealing groove140is arranged which defines a second sealing plane. The opening132of the cover130is positioned between the two sealing planes. A separate sealing action of the opening132is therefore not needed. As can be seen in the views ofFIGS.49and50in detail, the circumferential seal144is accommodated in the sealing groove140which is arranged between cover130and housing part104and serves for sealing between raw side and clean side. In the sealing groove141, a circumferential seal137for sealing the clean side relative to the exterior region of the filter system100is accommodated. The open end disk22comprises a radial protrusion23(FIGS.30,31) which seals as a radial seal25against a sealing region of the cover130. The sealing grooves140,141surround a circumferential collar139whose inner surface forms a sealing surface for the radial seal25of the open end disk22. When the cover130is closed, the bead28engages a receptacle138of the cover130which extends inside the collar139. This can be seen in the detail views ofFIGS.49and50in which the cover130is connected to the housing part104. The receptacle138can effect an axial clamping of the filter element10in the housing102. The cover130projects in the region of the housing102near the valve128with a rib148into the opening24of the end disk22. The valve128is arranged below the filter element10. The rib148prevents water from collecting in the clean region and returns the water into the filter element10where it can drain through the valve128. FIGS.51to57show a further embodiment of a filter system100according to a further embodiment of the invention. In this context,FIG.51shows in exploded illustration a filter system100with a housing102that comprises a first housing part104, for example, a housing pot, and a second housing part in the form of a cover130and a one-piece seal150for sealing clean side relative to raw side and against the exterior region of the filter system100.FIG.52shows an exploded illustration of the one-piece seal150and cover130of the filter system100according toFIG.51, whileFIG.53shows a perspective view of the assembly of cover130and seal150.FIG.54shows a side view of the filter system100, andFIG.55a longitudinal section of the filter system100.FIG.56shows a section through a detail of the clean fluid connector of the cover130of the filter system100, andFIG.57a section through a detail of a raw fluid side of the cover130of the filter system100. The further components and details of filter system100and filter element10are described in the previous embodiments, in particular inFIGS.29to46, reference being had to them in order to avoid unnecessary repetitions. The filter element10comprises at least one axially delimited notch44in its filter bellows12, preferably at the side of its closed end disk32. With the closed end disk32leading, the filter element10is inserted into the first housing part104wherein it can be pushed on cams36across a valve128in the first housing part104below the filter element10. The closed end disk32comprises a central, inwardly extending pin60which is pushed onto a pin116in the first housing part104. The open end disk22of the filter element10comprises a bead28which partially surrounds the opening24of the end disk22. In the bead-free region of the opening24, fluid can flow from the interior50of the filter element10through a clean fluid channel134of the cover130to the outlet112. Inlet110and outlet112are arranged directly adjacent to each other in the same housing part104. The cover130comprises a wedge-shaped rim136in whose region with the greatest height an opening132is arranged. The latter is positioned, when the cover130is closed, below the socket142of the first housing part104. The socket142projects in axial direction past the end disk22of the installed filter element10. The cover130comprises a receptacle138for the bead28. Notch44, pin60, and bead28secure the filter element10against tilting in the housing102, which is advantageous in case of a filter element10that is installed in a recumbent position. The one-piece seal150comprises a first sealing ring152and a sealing ring154which is connected thereto on both sides by flanks156and is angled thereto. The first sealing ring152is positioned at a sealing surface146at the outer rim of the inner side of the cover130, wherein the sealing surface146surrounds largely a collar139whose inner side serves as a sealing surface for the radial seal25of the end disk22. An outer groove149adjoins the sealing surface146and receives a rim of the sealing ring152. The second sealing ring154is resting on a sealing surface147which surrounds the opening132in the rim136of the cover130. The seal150is resting with the flanks156against the two transitions between the two sealing surfaces146,147. Advantageously, the sealing action between raw side and clean side about the socket142of the outlet112as well as relative to the environment in circumferential direction about the cover130is integrated in the one-piece seal150. Moreover, the cover130comprises, above the receptacle138for the bead28, a rib148that projects into the housing102and into the opening24of the open end disk22and that serves to keep away water from the clean channel134of the cover130and to guide it through the filter element10to the valve128. As can be seen in the section illustration ofFIG.55, which shows the housing ofFIG.54, and the detail illustrations inFIG.56at the clean fluid side of the filter system100and inFIG.57at the raw fluid side of the filter system100, the seal150provides the sealing action of the cover130relative to the exterior region of the cover130as well as against the raw fluid side. The sealing action clean fluid side relative to raw fluid side is effected by the first sealing ring152. The sealing action relative to the exterior side is realized by means of the second sealing ring154. The first sealing ring152comprises for this purpose an approximately Z-shaped profile in which from a central leg at each of its ends a leg is projecting in opposite direction. The second sealing ring154comprises an approximately T-shaped profile. The first sealing ring152is resting with a projecting leg in the groove149, with the central leg at the inner side of the circumferential collar109of the housing part104, and with the additionally projecting leg at the end face at the exterior side of the collar139. With the filter element10and the filter system100according to the invention, an in particular recumbently installed filter element10can be securely mounted and demounted. By elements one or a plurality of notches40,44at the filter bellows12and pin60and optionally a bead28, a positioning in correct position can be achieved and the filter element10can be protected against tilting in case of a recumbent installation. It is understood that the above described configurations in the Figures are not limited to a round cross section of the filter element10. Instead, the cross section of the filter element10can be chosen as needed, for example, round, oval, quadrangular and the like.
40,184
11857904
DETAILED DESCRIPTION In general, a frame of an element used in an air cleaner of an engine is made of a flexible material, such a rubber-based material, having a sealing function as a packing. The frame itself does not have a sufficient rigidity that allows the frame to maintain its shape. When installing such an element into a case during an operation of attaching the element, replacing the element, or the like, it is necessary for an operator to attach one half member of the case to the other half member of the case while pressing the element toward the other half member with his/her hand so that four corners of the frame can be located at regular positions. Such an operation is cumbersome and very difficult, and, for example, it is necessary for the operator to perform the operation without looking at the element because it is difficult to perform the operation while looking at the element, depending on the layout in an engine room. In consideration of the above problem, it is desirable to provide a gas filtering device that facilitates an operation of attaching an element. In the following, some embodiments of the disclosure are described in detail with reference to the accompanying drawings. Note that the following description is directed to illustrative examples of the disclosure and not to be construed as limiting to the disclosure. Factors including, without limitation, numerical values, shapes, materials, components, positions of the components, and how the components are coupled to each other are illustrative only and not to be construed as limiting to the disclosure. Further, elements in the following example embodiments which are not recited in a most-generic independent claim of the disclosure are optional and may be provided on an as-needed basis. The drawings are schematic and are not intended to be drawn to scale. Throughout the present specification and the drawings, elements having substantially the same function and configuration are denoted with the same numerals to avoid any redundant description. First Embodiment An air cleaner that is an air filtering device according to a first embodiment of the disclosure will be described. The air cleaner according to the first embodiment is, for example, a device that filters combustion air (fresh air) for an engine, which is mounted in an automobile such as a car, and reduces foreign substances such as dust in the combustion air. FIG.1is an exploded side view of an air cleaner1that is a gas filtering device according to the first embodiment. FIG.2is an enlarged view taken along line II-II ofFIG.1. The air cleaner1includes an element10and an air cleaner case20. The element10includes a frame and a filter that is held inside of the frame. The frame is made of a flexible sealing material such as a rubber-based material. The filter is made from filtering paper, sponge, or the like. The filter filters air passing therethrough, and reduces foreign substances and the like. The element10itself does not have a sufficient rigidity that allows the element10to maintain its shape. The element10has a sufficient flexibility that allows both end portions thereof to hang down due to their own weight in a case where, for example, a side edge of the frame is supported at a middle portion thereof. The element10has a rectangular shape as seen in a direction in which air flows therethrough (the up-down direction inFIG.1andFIG.2). The air cleaner case20is shaped like a box that accommodates the element10, and air to be filtered (combustion air for an engine (not illustrated)) flows through the air cleaner case20. The air cleaner case20is divided into a first member30and a second member40, in order from the engine side (downstream side). The first member30and the second member40are made from, for example, an elastic resin material such as polypropylene (PP) by, for example, injection molding or the like. The first member30is a box-shaped member into which air that has passed through the element10is introduced. The first member30has an opening31that opens toward the second member40. The first member30has a frame holder32, which holds the frame of the element10, on an inner peripheral edge of the opening31. When the air cleaner1is being used, the surface of the frame holder32is in close contact with an outer peripheral edge of the frame of the element10over the entire periphery, and is sealed by the rubber-based material of the frame. The frame holder32is disposed so that a surface of the attached element10on the second member40side (typically, a surface on a side from which air flows into the element10) faces upward or diagonally upward. The first member30is fixed to, for example, a vehicle body (not illustrated). The second member40is removable from the first member30when, for example, replacing the element10. The second member40(not illustrated) is a box-shaped member into which air introduced from an air intake port (typically, atmospheric air that flows into the engine room from the vehicle front side) is introduced, and has an opening41that opens toward the first member30. The element10is installed so as to be interposed between the first member30and the second member40in a state in which the frame is fitted into the frame holder32. Filtered air that has passed through the element10and flowed into the first member30is supplied to the engine via an intake duct (not illustrated). The first member30includes a sticking-out surface portion33that is integrated with a body portion, a ridge34, a claw35, and the like. The sticking-out surface portion33is a flat-plate-shaped portion that is provided in a region adjacent to a middle portion of each of a pair of opposing sides of the frame of the element10and that protrudes from an outer edge of the frame holder32of the first member30toward the second member40. A pair of the sticking-out surface portions33are disposed so as to face each other with the element10interposed therebetween. The ridge34protrudes from a surface of the sticking-out surface portion33on the inside of the air cleaner case20(a side facing the other sticking-out surface portion33). As illustrated inFIG.1, the ridge34extends along a circular arc that is convex toward the second member40. A plurality of the ridges34(for example, three ridges34) are concentrically arranged. As illustrated inFIG.2, in the cross-sectional shape of the ridge34taken along a plane that intersects the longitudinal direction thereof, a surface of the ridge34has a curved-surface shape along a circular arc that is convex toward the inside of the air cleaner case20. When the element10is being attached to the first member30, the ridge34interferes with the frame, and functions as a temporary holder that temporarily holds a part of the frame in a state (protruding state) in which the part is separated toward the second member40with respect to the frame holder32. The claw35protrudes further toward the second member40from the tip of the sticking-out surface portion33on the second member40side. As illustrated inFIG.2, the claw35has an inclined surface that comes into contact with a claw42of the second member40and that causes the sticking-out surface portion33to incline in a direction such that the sticking-out surface portion33falls toward the outside of the first member30. The claw42is provided on a region, which is adjacent to the sticking-out surface portion33, of the edge of the opening41of the second member40. The claw42protrudes from the edge of the opening41toward the first member30. When the second member40is being attached to the first member30, the claw42comes into contact with the claw35of the first member30and performs a function of pressing the claw35in a direction such that the claw35is opened toward the outside of the air cleaner case20in accordance with a relative displacement of the second member40toward the first member30. The claw42is a temporary-holding canceller that cancels temporary holding of the frame of the element10by the temporary holder34when the second member40is being coupled to the first member30. A recess36, which accommodates the claw42after the first member30and the second member40have been coupled to each other, is formed in an inner surface of the first member30. Next, a process of installing the element10in the air cleaner1according to the first embodiment will be described. FIG.3illustrates a state in which the element10is placed on the first member30of the air cleaner1according to the first embodiment. When an operator holds the element10at the opening31of the first member30of the air cleaner case20and presses the element10toward the frame holder32, a middle portion of each of the pair of opposing sides of the frame of the element10is temporarily held in a state of protruding from the frame holder32toward the second member in a state of being caught on the ridge34. At this time, the frame of the element10is curved along the curve of the ridge34in a direction such that the frame is convex toward the second member40. Thus, a part of an end portion of the frame of the element10(an upper end portion and a lower end portion inFIG.3) is inserted to the inside of the frame holder32in a state in which the part has a gap with respect to a corner portion of the frame holder32. Subsequently, the operator attaches the second member to the first member30. FIG.4illustrates a state in which the second member is being attached to the first member30in the air cleaner1according to the first embodiment. When the second member40is moved closer to the first member30and the claw35of the first member30and the claw42of the second member come into contact with each other, a force acting between the inclined surfaces of the claws35and42causes the sticking-out surface portion33of the first member30to deform so as to fall in a direction such that the sticking-out surface portion33opens toward the outside of the air cleaner case20(the right side inFIG.2). Thus, the ridge34displaces in a direction away from the frame of the element10, temporary holding of the frame of the element10by the ridge34is cancelled (released), and the element10enters the frame holder32while reducing the curvature thereof (while relaxing the curvature). FIG.5illustrates a state in which the first member30and the second member40have been coupled to each other in the air cleaner1according to the first embodiment. When the second member40is moved further closer to the first member30and finally the peripheral edge of the opening41of the second member40is in contact with the peripheral edge of the opening31of the first member30, the element10is held by the frame holder32in a state in which the element10is interposed between the first member30and the second member40and the element10is substantially flat. In this state, the first member30and the second member40are fixed to each other, by using, for example, a mechanical fastener (not illustrated) such as a metal clip. At this time, the claw42of the second member40is accommodated in the recess36(seeFIG.2), which is formed in the inner surface of the first member30. With the first embodiment heretofore described, it is possible to obtain the following advantageous effects. (1) Because the ridge34of the first member30holds the frame of the element10in a curved state before the second member40is attached, it is not necessary for an operator to press the element10with his/her hand, and, further, the end portions of the element10(the four corners of a rectangular shape) can easily enter the frame holder32. By attaching the second member40to the first member30in this state, temporary holding of the element10by the ridge34is cancelled and the frame of the element10becomes accommodated in the frame holder (the element10falls into the frame holder due to its own weight in a case where the opening31is facing upward or diagonally upward), and it is easy to perform the operation of attaching the element10. (2) Because the sticking-out surface portion33having the ridge34is provided at a position sticking out toward the second member40with respect to the frame holder32and the claw42of the second member40displaces the ridge34in a direction away from the frame when the second member40is moved closer to the first member30, it is possible to obtain the aforementioned advantageous effects with a simple configuration that uses elastic deformation of each member. (3) Because the frame of the element10has a rectangular shape and the ridge34temporarily holds a middle portion of each of a pair of opposing sides of the frame, it is possible to bend the element10so that both end portions thereof become closer toward the first member30with the portion where the frame is temporarily held by the ridge34as the apex, and it is possible to reliably obtain the aforementioned advantageous effects. (4) Because the ridge34, which temporarily holds the frame of the element10, has a circular arc shape that is convex toward the second member40, it is possible to appropriately control the shape of the element10so that the element10becomes curved to be convex toward the second member40, and it is possible to reliably obtain the aforementioned advantageous effects. Second Embodiment Next, an air cleaner that is an air filtering device according to a second embodiment of the disclosure will be described. In each embodiment described below, portions that are common to those of an embodiment already described will be denoted by the same numerals and descriptions of such portions will be omitted, and mainly the differences will be described. FIG.6illustrates a region around a sticking-out surface portion33of a first member30of an air cleaner according to the second embodiment (corresponding toFIG.2of the first embodiment (the element10and the second member40are not illustrated)). In the second embodiment, the cross-sectional shape of a ridge34taken along a plane perpendicular to the longitudinal direction thereof is a triangular shape (a saw-tooth shape). With the second embodiment heretofore described, in addition to the advantageous effects of the first embodiment described above, by changing the angle of the inclined surface of the ridge34in the cross-sectional shape, it is possible to appropriately adjust the resistance force when the frame of the element10is temporarily held and to appropriately adjust the easiness of cancelling temporary holding. Third Embodiment Next, an air cleaner that is an air filtering device according to a third embodiment of the disclosure will be described. FIG.7is an exploded side view of an air cleaner1that is a gas filtering device according to the third embodiment. The third embodiment has one ridge34that extends along a circular arc that is convex toward the second member as in the first embodiment and that corresponds to a radially-outermost ridge34in the first embodiment. With the third embodiment heretofore described, in addition to the advantageous effects of the first embodiment described above, by changing the number of the ridges34, it is possible to appropriately adjust the resistance force when the frame of the element10is temporarily held and to appropriately adjust the easiness of cancelling temporary holding. Fourth Embodiment Next, an air cleaner that is an air filtering device according to a fourth embodiment of the disclosure will be described. FIG.8is an exploded side view of an air cleaner1according to the fourth embodiment. FIG.9is a sectional view of a coupled portion between a first member30and a second member40in the air cleaner1according to the fourth embodiment (taken along line IX-IX inFIG.8(after the second member40has been coupled)). The fourth embodiment has a projection37and a recess38on a sticking-out surface portion33of the first member instead of the ridge34and the claw35of the first embodiment. The projection37is a temporary holder that holds the frame of the element10in a state in which the frame is curved in an arc shape that is convex toward the second member40. The projection37protrudes from a surface of the sticking-out surface portion33on the inside in the air cleaner case20. The projection37has, for example, an oval shape having a longitudinal direction that is the protruding direction in which the sticking-out surface portion33protrudes from the frame holder32. For example, three projections37are arranged along a circular arc that is convex toward the second member40. The recess38is a portion in which a projection44of the second member40is accommodated in a state in which the first member30and the second member40are coupled to each other. The recess38is formed in a surface of the sticking-out surface portion33on the inside in the air cleaner case20. The second member40has a step43and the projection44, instead of the claw42of the first embodiment. The step43is recessed, toward the inside of the air cleaner case20, in a stepped manner in a region of a peripheral edge of the opening41where the sticking-out surface portion33is formed in the first member30. The sticking-out surface portion33is disposed so as to be positioned outside of the step43in a state in which the first member30and the second member40are coupled to each other. The projection44projects from the step43toward the outside of the air cleaner case20. For example, two projections44are arranged along an edge of the opening41. The projection44is a temporary-holding canceller in the fourth embodiment. In the fourth embodiment, when the element10is placed at the opening31of the first member30, the frame of the element10is temporarily held by the projection37in a state in which the frame is curved in an arc shape that is convex toward the second member40as illustrated inFIG.8. Subsequently, when the second member40is attached to the first member30, first, the projection44presses the sticking-out surface portion33so that the sticking-out surface portion33falls toward the outside of the air cleaner case20. When the sticking-out surface portion33is pressed by the projection44and deforms so as to warp toward the outside the air cleaner case20, temporary holding of the frame of the element10by the projection37is cancelled, and the element10enters a frame holder (not illustrated) provided inside of the opening31. When the second member40is moved further toward the first member30, the projection44passes through the gap between the projections37, and, finally becomes accommodated in the recess38in a state of being fitted into the recess38. With the fourth embodiment heretofore described, in addition to the advantageous effects of the first embodiment described above, a claw or the like does not protrude from the second member40that is removed and attached when, for example, replacing the element10, and it is possible to prevent trouble such as breakage of the claw. (Modifications) The disclosure is not limited to the embodiments heretofore described, it is possible to make various modifications and changes, and the modifications and changes are within the scope of the disclosure. (1) The configuration of the gas filtering device is not limited to those of the embodiments described above, and may be changed as appropriate. For example, the shape, the structure, the material, the manufacturing method, the disposition, and the like of each member of the element and the case may be changed as appropriate. The configurations of the temporary holder and the temporary-holding canceller are not limited. (2) The gas filtering device in each embodiment is, for example, an air cleaner that filters air (fresh air) to be sucked by an engine. However, the disclosure is not limited to this, and is applicable to gas filtering devices having other uses. For example, the disclosure is applicable to purification of blow-out air in an air conditioner, a ventilator, a heater or the like, and to filtering of another gas. As heretofore described, with the disclosure, it is possible to provide a gas filtering device that facilitates an operation of attaching an element.
20,149
11857905
DETAILED DESCRIPTION Referring to the drawings, some of the reference numerals are used to designate the same or corresponding parts through several of the embodiments and figures shown and described. Corresponding parts are denoted in different embodiments with the addition of lowercase letters. Variations of corresponding parts in form or function that are depicted in the figures are described. It will be understood that variations in the embodiments can generally be interchanged without deviating from the invention. Dust collectors are used to filter dust, fumes, and other airborne particles from air handling systems typically for industrial applications.FIGS.1and2show examples of prior art dust collectors10. As best understood by comparingFIGS.1and2, the dust collectors10comprise a housing12that is connected to the air flow path of an air handling system. The housing12contains at least one cartridge14that comprises a filter16mounted to a filter pan18that seats the filter16within the housing12. The embodiment of dust collector10shown inFIG.1comprises four cartridges14within the housing12that are mounted on two pairs of rails20(also referred to as lift rails or cam bars) that raise and position the cartridges14within the housing12. In this embodiment two pairs of rails20mount two cartridges14each. A door22provides access to the cartridges14to permit a user to lower the rails20and change out the cartridges14as needed. The filter16is typically made of a pleated media folded into a shape that the air passes through. The cartridges14have gaskets24to create air-tight seals to ensure that the air flows through the filters16. The cartridges14may be horizontally or vertically oriented and each type has different structural requirements for installation of the cartridges14into the housing12. The disclosure herein is related specifically to dust collectors having vertically oriented cartridges. In prior art dust collector systems like the ones shown in the figures, there is generally no way to be certain that the cartridges14are properly seated within the housing12and that the gaskets24are properly placed to ensure all dust and fumes go through the filter16and not past the gasket24. Most vertically oriented cartridges14use a filter pan18that has a raw upward facing edge facing (as best seen inFIG.2) that creates a place for dust and debris to rest and weakens the overall strength of the filter pan18. Another issue with prior art vertical cartridges: all current manufactures use a round or panel filter with a pan style top. This does not allow them to fully utilize the surface area of the pan. The dust collector systems presented herein address many of the limitations of the prior art systems. The disclosure herein is related specifically to dust collectors having vertically oriented cartridges. As best understood by comparingFIGS.3,4,5, and6, the dust collectors10acomprise a housing12athat is connected to the air flow path of an air handling system. The housing12acontains at least one cartridge14athat comprises a filter16amounted to a filter pan18athat seats the filter16awithin the housing12a. The embodiment of dust collector10ashown inFIG.3comprises four cartridges14awithin the housing12athat are mounted on two pairs of rails20athat raise and position the cartridges14awithin the housing12a. In other embodiments, the number of rails20aand the number of cartridges14amay be varied according to the application. A door22aprovides access to the cartridges14ato permit a user to lower the rails20aand change out the cartridges14aas needed. As best seen inFIG.4, the filter16ais made of a pleated media folded into a shape that the air passes through. The cartridges14ahave gaskets24ato create air-tight seals to ensure that the air flows through the filters16a. The filter pan18ahas a generally rectangular shape that has two sides that are longer than the other two. This means that the cartridge14agenerally only has two orientations in which it can fit into the housing12a. While prior art cartridges14(shown inFIGS.1and2) have circular filter openings that can only receive filters16that have a circular cross-section, the preferred embodiment has an opening that is elliptical in shape and can therefore receive a filter16athat has an elliptical cross-section. Elliptical filters16aallow more of the surface area of the filter pan18ato be used which allows the filters16ato be larger and have more surface area for airflow treatment. This allows the use of smaller filter housings with higher air volume throughputs. Other configurations and filter geometries are possible to maximize the filter medium inclusion, but the oval shape is preferred. The filters pan18ahas at least one alignment opening26aconfigured to align the cartridge14awhen it is installed in the housing12a. The embodiment shown has alignment openings26aon two sides of the filter pan18a. This allows the cartridge to be installed in either direction within the housing12a. It is possible to have a cartridge14athat has an alignment opening26aalong each side of the filter pan18awhich would allow the cartridge14ato be loaded onto the housing12ain any orientation. In such embodiments, it is likely that the filter pan18ais sized to have the same length along each side. Referring toFIG.3, the housing12aincorporates a series of alignment blocks28asized and shaped to correspond to the alignment openings26aof the filter pan18a. In the embodiment shown, the housing incorporates two alignment blocks28aat either end of each pair of rails20a. These alignment blocks28aare positioned such that when the cartridges14aare installed in the housing12a, the alignment opening26aof the filter pan14aaligns with the alignment block28aof the housing12a. Further, the alignment blocks18aare configured such that improper installation of the cartridges14ainto the housing12aprevents the door22afrom closing which would prevent the operation of the vertically oriented dust collector10a. This ensures that a user must install the cartridges14aproperly for the system to operate. The number of alignment blocks28amay be varied so long as at least one exists to correspond to an alignment opening26ain a cartridge14a. Two alignment blocks28aper pair of rails20aallows for better alignment of the cartridges14awithin the housing. The filter pans18aare also shown to have mitered corners. This makes them easier to slide in and out of the dust collector10aand may also be incorporated to fit around structural elements in the housing10a. This also allows the filter pan18ato be made using less material than if it were squared off. The cartridges14amay also incorporate a grounding clip30athat is, as the name implies, wired to ground. This helps eliminate the buildup of static electricity in the cartridges14athat would encourage the settling of dust and particulate matter to the cartridges14a. As best seen inFIGS.5and6, the filter pan18acomprises a double walled pan with a top pan32aand a bottom pan34a. The filter16ais mounted to the filter pan18awith potting compound that acts as a glue to affix the filter16ato the filter pan18aand a sealant to prevent the passage of air at the mounting points. Potting compound may also be used to seal the top pan32aand the bottom pan34a. As best understood by comparingFIGS.3,7, and8, it can be shown how cartridges14amounted to the rails20aof the housing20aand installed within the dust collectors10a. Each pair of rails20ais mounted to a lever system36a. When a user opens the door22a, the user gains access to the lever system to lower the rails20ato the position shown inFIG.7. The cartridges14aare located within the dust collector10ahousing12aunder an upper plate38awhich has a series of openings40athat correspond to where the cartridges14amust be located within the housing12a. With the rails20ain the lower position, the user may remove and replace cartridges14aas needed. New cartridges14aare pushed back into place such that their alignment openings26aalign with the alignment blocks28aof the housing12a. The rails20aare then raised as shown inFIG.8to push the gaskets24aagainst upper plate38aand form an airtight seal between the cartridge14aand the upper plate38a. If the cartridges14aare misaligned for any reason, they will bump up against the alignment blocks28a. This would prevent the rail20afrom sealing the cartridges14ain place within the housing12aand would prevent the operation of the vertically oriented dust collector. This invention has been described with reference to several preferred embodiments. Many modifications and alterations will occur to others upon reading and understanding the preceding specification. It is intended that the invention be construed as including all such alterations and modifications in so far as they come within the scope of the appended claims or the equivalents of these claims.
8,909
11857906
DESCRIPTION OF EMBODIMENTS An air cleaner according to an aspect of the present invention is disposed inside a vehicle body frame. An intake chamber is formed in an air cleaner case of the air cleaner, and an intake air temperature of the intake chamber is detected by an intake air temperature sensor. Air is taken into the intake chamber through an inlet tube, and air is sent out from the intake chamber through an outlet tube. The outlet tube has an upstream portion protruding into the intake chamber. The upstream portion of the outlet tube has a peripheral wall formed with a through hole. The main air flow is formed from the inlet tube to the outlet tube. Air flows out from the through hole of the outlet tube, and air flow is also created at positions deviated from the main air flow. Even if the intake air temperature sensor is disposed at a position deviated from the main air flow, the detection accuracy of the intake air temperature sensor can be improved. Embodiments Hereinafter, a present embodiment will be described in detail with reference to the accompanying drawings.FIG.1is a left side view of a straddle-type vehicle according to the present embodiment in addition, in the drawings to be described later, an arrow FR indicates a vehicle front side, an arrow RE indicates a vehicle rear side, an arrow L indicates a vehicle left side, and an arrow R indicates a vehicle right side. As shown inFIG.1, a straddle-type vehicle1is formed by mounting various components such as an engine40and an electrical system on a diamond-type vehicle body frame10formed of a pipe and a sheet metal. The vehicle body frame10includes a pair of main frames12that are branched off from a head pipe11to the left and right and extend rearward, and a pair of down frames13that are branched off from the head pipe11to the left and right and extend downward. A rear portion of the engine40is supported by the pair of main frames12, and a front portion of the engine40is supported by the pair of down frames13. By supporting the engine40with the vehicle body frame10, the rigidity of an entire vehicle is secured. A front side portion of the main frame12is a tank rail14located above the engine40, and a fuel tank31is supported from below by the tank rail14. A rear side portion of the main frame12is a body frame15located behind the engine40, and a swing arm25is swingably supported by a lower half portion of the body frame15. Seat rails21each including an upper rail22and a lower rail23are attached to an upper half portion of the body frame15. A rider seat32and a pillion seat33are supported on an upper portion of the upper rail22at the rear of the fuel tank31. A pair of front forks34is steerably supported by the head pipe11via a steering shaft (not shown). A front wheel35is rotatably supported by lower portions of the front forks34, and an upper portion of the front wheel35is covered with a front fender (not shown). The swing arm25extends rearward from the body frame15. A rear wheel36is rotatably supported at the rear end of the swing arm25, and the upper side of the rear wheel36is covered with a rear fender (not shown). The engine40is coupled to the rear wheel36via a chain drive type transmission mechanism, and power from the engine40is transmitted to the rear wheel36via the transmission mechanism. An air cleaner50is disposed behind the engine40. Behind the engine40, the space for arranging the air cleaner is limited due to the frame width of the main frame12and the rail width of the seat rails21, and it is difficult to secure the capacity of the air cleaner50for securing the required output of the engine40. The intake air temperature in the air cleaner50is detected by the intake air temperature sensor. The detection accuracy is reduced when the intake air temperature sensor is arranged at a position deviated from the main air flow to satisfy the capacity of the air cleaner50and smooth air flow. Therefore, in the present embodiment, the air flow is also created at positions deviated from the main air flow of the air cleaner50to improve the detection accuracy of the intake air temperature sensor. A peripheral configuration of the engine and the air cleaner will be described with reference toFIGS.2to8.FIG.2is a left side view of the periphery of the engine according to the present embodiment.FIG.3is a top view of the periphery of the engine according to the present embodiment.FIG.4is a side view of the air cleaner according to the present embodiment.FIG.5is a top view of the air cleaner according to the present embodiment.FIG.6is a cross-sectional view of the air cleaner ofFIG.5taken along a line A-A.FIG.7is a cross-sectional perspective view of the air cleaner ofFIG.5taken along a line B-B.FIG.8is a top view of the air cleaner ofFIG.5from which an upper case is removed. As shown inFIGS.2and3, the engine40is a two-cylinder engine, and includes a crankcase41having an upper-lower divided structure. A cylinder42, a cylinder head43, and a cylinder head cover44are attached to an upper portion of the crankcase41. A magneto cover45that covers a magneto (not shown) from a side is attached to a left side surface of the crankcase41. A sprocket cover46that covers a drive sprocket (not shown) from the side is attached to the rear of the magneto cover45. A clutch cover47that covers a clutch (not shown) from the side is attached to a right side surface of the crankcase41. A throttle body48is connected to a rear surface of the cylinder head43, and the air cleaner50is connected to an upstream side (rear side) of the throttle body48. The air cleaner50is disposed behind the engine40and inside the pair of main frames12and the pair of seat rails21. As described above, the rear portions of the pair of main frames12are the pair of body frames15, and a front end portion of the air cleaner50is located inside the pair of body frames15. The upper half portion of the body frame15is inclined obliquely downward toward the rear, and an air cleaner case51behind the body frame15is also inclined obliquely downward. An upper bracket16and a lower bracket17are formed at a rear edge of the upper half portion of the body frame15. The upper rail22of the seat rail21is connected to the upper bracket16, and the lower rail23of the seat rail21is connected to the lower bracket17. The upper rail22extends rearward across a side of an upper half portion of the air cleaner case51, and the lower rail23extends obliquely rearward across a side of a lower half portion of the air cleaner case51. Front sides of the upper rail22and the lower rail23are coupled to each other via a bridge pipe24, and rear sides of the upper rail22and the lower rail23are coupled to each other at a vehicle rear portion. A front portion of the air cleaner case51protrudes upward from the upper rail22, and a protruding portion of the front portion is accommodated in a space inside the rider seat32(seeFIG.1). A rear portion of the air cleaner case51protrudes downward from the lower rail23, and a protruding portion of the rear portion serves as an expansion portion65that expands an intake chamber56(seeFIG.6) in the air cleaner case51. The expansion portion65of the air cleaner case51is located above the swing arm25(seeFIG.1), and the expansion portion65extends rearward so as to avoid a swing range of the swing arm25. A volume of the air cleaner case51is expanded by using a lower space of the seat rail21. A battery case38and a battery37are disposed above the expansion portion65of the air cleaner case51. The battery case38is supported by the pair of seat rails21via a bridge19. The battery case38is formed in a box shape having an open upper surface, and a rectangular parallelepiped battery37is held inside the battery case38. In a top view, the pair of inlet tubes62of the air cleaner50are curved, and the battery37is located between the pair of inlet tubes62. A space for arranging the battery37is secured by using a space above the expansion portion65of the air cleaner50. As shown inFIGS.4to6, the air cleaner case51of the air cleaner50includes an upper case52and a lower case53which are divided in an upper-lower direction, and a filter cover54attached to a rear surface of the upper case52. The upper case52and the lower case53extend obliquely downward from the front to the rear, and the filter cover54bulges in a dome shape on a rear side of the upper case52. Internal spaces of the upper case52and the lower case53and an internal space of the filter cover54are connected to each other through an opening55formed in the rear surface of the upper case52, and an intake chamber56is formed inside the air cleaner case51. An air filter57is disposed in the opening55in the rear surface of the upper case52, and the air filter57is covered by the filter cover54from behind. The air filter57is inclined along an upper surface of the upper case52such that an upper portion of the air filter57is located closer to the vehicle front side than a lower portion. By the air filter57, the intake chamber56is divided into a dirty side58and a clean side59. That is, the dirty side58is formed by the filter cover54on the upstream side of the air filter57, and the clean side59is formed by the upper case52and the lower case53downstream of the air filter57. A pair of inlet tubes62are attached to left and right side walls61of the filter cover54. The pair of inlet tubes62extend from the left and right side walls61of the filter cover54toward the vehicle rear side, and air is taken into the dirty side58from the rear of the vehicle by the pair of inlet tubes62. A suction port63of each inlet tube62is directed toward the rear of the vehicle, and a discharge port64of the inlet tube62is directed inward in the vehicle width direction. The pair of inlet tubes62are located inside the pair of seat rails21(seeFIG.3), and an interval between the pair of inlet tubes62is substantially equal to a lateral width of the expansion portion65. A pair of outlet tubes82are attached to a front wall81of the lower case53. The pair of outlet tubes82penetrate the front wall81of the lower case53and extend in a front-rear direction, and air is sent out from the clean side59to the engine40(seeFIG.1) by the pair of outlet tubes82. A suction port83of each outlet tube82is directed toward the rear of the vehicle, and a discharge port84of the outlet tube82is directed toward the front of the vehicle. The pair of outlet tubes82are located inside the pair of main frames12(seeFIG.3), and the pair of outlet tubes82are connected to the pair of the throttle bodies48(seeFIG.2). The inlet tubes62and the outlet tubes82are attached to an upper side of the air cleaner case51. As described above, the inlet tubes62are attached to the filter cover54, the outlet tubes82are attached to the front wall81of the lower case53, and the filter cover54and the front wall81of the lower case53face each other in the front-rear direction via the air filter57in a side view. Since the discharge port64of each inlet tube62and the suction port83of each outlet tube82are located at substantially the same height, air easily flows directly from the inlet tube62to the outlet tube82. During low rotation of the engine40and steady traveling, the main air flow from the discharge port64of the inlet tube62toward the suction port83of each outlet tube82is formed. The pair of outlet tubes82each has an upstream portion91protruding into the intake chamber56. The upstream portion91has a peripheral wall formed with a through hole92. In the air cleaner case51, an air flow from the through hole92toward the suction port83of the outlet tube82is formed in addition to the main air flow. The upper wall of the upper case52is attached with an intake air temperature sensor95that detects the intake air temperature of the air flowing out from the through hole92. The detection result of the intake air temperature sensor95is used to control the fuel injection amount. The upper wall of the upper case52protrudes upward from the upper rail22(seeFIG.2), The upper wall of the upper case52is partially recessed, and the intake air temperature sensor95is disposed in the recess of the upper case52so as to face obliquely upward. The proximal end side of the intake air temperature sensor95is exposed to the outside of the case, and a detection portion96on the distal end side of the intake air temperature sensor95is inside the case. The upper surface of the upper rail22is provided with an attachment bracket18(seeFIG.2) for the fuel tank31, and the intake air temperature sensor95is positioned below the attachment bracket18. In this way, the intake air temperature sensor95is disposed in the upper case52using the space below the attachment bracket18. In addition, a breather nipple85is formed at a front portion of the upper case52, and a breather hose (not shown) extending from the engine40is connected to the breather nipple85. A secondary air nipple87is formed at a front portion of the lower case53, and a secondary air hose (not shown) extending to an exhaust system is connected to the secondary air nipple87. A drain plug88is provided at a bottom portion of the lower case53, and water in the air cleaner case51is discharged from the drain plug88. As shown inFIGS.7and8, the pair of outlet tubes82is attached to the front wall81of the lower case53so as to be spaced apart from each other in the left-right direction. Upstream portions91(rear sides) of the pair of outlet tubes82extend toward the air filter57, and downstream portions93(front sides) of the pair of outlet tubes82are connected to the throttle body48(seeFIG.3). Lengths of the pair of outlet tubes82are different, and the outlet tube82on the left side is formed longer than the outlet tube82on the right side. The output characteristics of the engine40are adjusted by the difference in length between the pair of outlet tubes82. The suction ports83of the pair of outlet tubes82are directed toward the center of the air filter57. The pair of outlet tubes82is formed with umbrella portions94that extend toward the suction ports83, and the umbrella portions94expands the suction ports83of the outlet tubes82. Since the lengths of the pair of outlet tubes82are different from each other and the umbrella portions94of the pair of outlet tubes82are shifted in the front-rear direction, a pair of umbrella portions94do not interfere with each other at the center of the air filter57. An intake air temperature sensor95is disposed between the pair of outlet tubes82in a top view. The peripheral walls of the upstream portions91of the pair of outlet tubes82are each formed with the through hole92. In this case, among a peripheral wall on the inner side in the vehicle width direction and a peripheral wall on the outer side in the vehicle width direction of the upstream portion91of each outlet tube82, the peripheral wall on the inner side in the vehicle width direction, which is a side closer to the intake air temperature sensor95, is formed with the through hole92. The air flow from the through hole92is directed toward the intake air temperature sensor95. In addition, the intake air temperature sensor95has a detection portion96located downstream (forward) of the suction port83of the outlet tube82and upstream (rearward) of the through hole92in a top view. That is, the detection portion96of the intake air temperature sensor95is located between the suction port83and the through hole92of the outlet tube82. The main air flow from the inlet tube62toward the outlet tube82is not interfered by the intake air temperature sensor95. In the air cleaner case51, an air flow from the through hole92toward the suction port83of the outlet tube82is formed in addition to the main air flow from the inlet tube62toward the outlet tube82, The detection portion96of the intake air temperature sensor95is positioned in the middle of the flow of the intake air from the through hole92toward the suction port83, thereby improving the detection accuracy of the intake air temperature sensor95. The detection portion96of the intake air temperature sensor95is closer to the suction port83than to the through hole92. Since air is more diffused in the vehicle width direction as from the through hole92toward the suction port83in the top view, the degree of freedom in layout of the intake air temperature sensor95is improved as approaching the suction port83. Further, an umbrella portion94is formed in the vicinity of the suction port83, and the detection portion96of the intake air temperature sensor95is close to the umbrella portion94. The air flowing from the through hole92toward the suction port83is partially retained by the umbrella portion94. In particular, the umbrella portions94of the pair of outlet tubes82are close to each other, and the air is likely to be retained at the portion where the umbrella portions94are close to each other. The detection portion96of the intake air temperature sensor95is directed between the umbrella portions94of the pair of outlet tubes82. The intake air temperature of the retained air is detected by the detection portion96of the intake air temperature sensor95, thereby improving the detection accuracy of the intake air temperature sensor95. The through holes92of the pair of outlet tubes82face each other, and the air flow from the through holes92is easily directed toward the detection portion96of the intake air temperature sensor95. The intake air temperature sensor95is attached to the upper wall of the upper case52, and the detection portion96of the intake air temperature sensor95is positioned above the outlet tubes82. Since the intake air temperature sensor95is provided in the upper portion of the air cleaner case51, the intake air temperature sensor95is protected from mud, water, or the like rolled up onto the wheel. Further, by using the wide space between the pair of outlet tubes82, the air flow from the through holes92toward the suction ports83is easily detected by the detection portion96of the intake air temperature sensor95. The flow of air in the air cleaner will be described with reference toFIG.9,FIG.9is a diagram showing the flow of air in the air cleaner according to the present embodiment. As shown inFIG.9, a main air flow F1is formed between the discharge ports64of the pair of inlet tubes62and the suction ports83of the outlet tubes82in a top view. The detection portion96of the intake air temperature sensor95is disposed downstream of (forward of) the suction ports83of the pair of outlet tubes82, and the main air flow F1is not hindered by the detection portion96of the intake air temperature sensor95. When the main air flow F1enters the pair of outlet tubes82, the air flows from the through holes92toward the suction ports83of the pair of outlet tubes82. As described above, an air flow F2is also formed in the air cleaner50at a position deviated from the main air flow F1. The intake air temperature sensor95is disposed between the pair of outlet tubes82, and the detection portion96of the intake air temperature sensor95is positioned between the through holes92and the umbrella portions94of the pair of outlet tubes82in a top view. The air flow F2is partially blocked by the umbrella portions94of the pair of outlet tubes82, and is retained in the vicinity of the umbrella portions94of the pair of outlet tubes82. The detection portion96of the intake air temperature sensor95is directed toward the umbrella portions94of the pair of outlet tubes82, and the intake air temperature of the air retained in the vicinity of the pair of umbrella portions94is detected by the detection portion96of the intake air temperature sensor95, thereby improving the detection accuracy of the intake air temperature sensor95. As described above, according to the present embodiment, the main air flow is formed from the inlet tube62to the outlet tube82. Air flows out from the through hole92of the outlet tube82, and air flow is also created at positions deviated from the main air flow. Even if the intake air temperature sensor95is disposed at a position deviated from the main air flow, the detection accuracy of the intake air temperature sensor95can be improved. In the present embodiment, a two-cylinder engine is exemplified as the engine, but the type of the engine is not particularly limited. In the present embodiment, the air cleaner includes a pair of inlet tubes and a pair of outlet tubes, but the numbers of inlet tubes and outlet tubes are not limited. For example, the air cleaner may include a single inlet tube and a single outlet tube, or the air cleaner may include three or more inlet tubes and three or more outlet tubes. In the present embodiment, the air filter is inclined, but the air filter may also be not inclined. For example, the air filter may be disposed vertically. Further, in the present embodiment, the detection portion of the intake air temperature sensor is located between the through hole and the suction port in the top view, but the detection portion of the intake air temperature sensor may be located at any position as long as the main air flow is not strongly hindered. For example, the detection portion of the intake air temperature sensor may be located upstream of the suction ports of the outlet tubes, as long as at a position where the main air flow is not strongly hindered. Moreover, the detection portion of the intake air temperature sensor may be located downstream of the through holes. The umbrella portions are formed in the outlet tubes in the present embodiment, but the shape of the outlet tubes is not particularly limited as long as air can be fed from the intake chamber, For example, the outlet tubes may be not formed with umbrella portions. The through holes are formed in the peripheral walls on the inner side in the vehicle width direction of the outlet tubes in the present embodiment, but the through holes may also be formed in the peripheral walls on the outer side in the vehicle width direction of the outlet tubes when the intake air temperature sensor is located on the outer side in the vehicle width direction of the outlet tubes. In the present embodiment, the intake air temperature sensor is attached to the upper wall of the air cleaner case, but the intake air temperature sensor may also be attached to the bottom wall of the air cleaner case. In the present embodiment, the through holes of the pair of outlet tubes face each other, but the through holes of the pair of outlet tubes may also not face each other. In addition, in the present embodiment, the pair of outlet tubes is formed with different lengths, but the pair of outlet tubes may also be formed with the same length. In addition, the air cleaner may be applied not only to the straddle-type vehicle shown in the drawings but also to other types of straddle-type vehicles. The straddle-type vehicle is not limited to general vehicles on which a rider rides in a posture of straddling a seat, and. includes a small-sized scooter-type vehicle on which a rider rides without straddling a seat, As described above, the air cleaner (50) according to the present embodiment is an air cleaner configured to be disposed inside a vehicle body frame (10), and including: an air cleaner case (51) in which an intake chamber (56) is formed; an intake air temperature sensor (95) configured to detect an intake air temperature in the intake chamber; an inlet tube (62) configured to take in air to the intake chamber; and an outlet tube (82) configured to send out air from the intake chamber. The outlet tube has an upstream portion (91) protruding into the intake chamber. The upstream portion of the outlet tube has a peripheral wall formed with a through hole (92). According to this configuration, the main air flow is formed from the inlet tube to the outlet tube. Air flows out from the through hole of the outlet tube, and air flow is also created at positions deviated from the main air flow. Even if the intake air temperature sensor is disposed at a position deviated from the main air flow, the detection accuracy of the intake air temperature sensor can be improved. In the air cleaner according to the present embodiment, the intake air temperature sensor has a detection portion (96) located downstream of a suction port (83) of the outlet tube in a top view. According to this configuration, it is possible to improve the detection accuracy of the intake air temperature sensor without the intake air temperature sensor blocking the main air flow. In the air cleaner according to the present embodiment, the detection portion of the intake air temperature sensor is located between the through hole and the suction port in the top view. According to this configuration, an air flow is created from the through hole toward the suction port, and the detection portion of the intake air temperature sensor is positioned in the middle of the flow of the intake air, thereby improving the detection accuracy. In the air cleaner of the present embodiment, the detection portion of the intake air temperature sensor is closer to the suction port than to the through hole. According to this configuration, since air is more diffused in the vehicle width direction as from the through hole toward the suction port in the top view, the degree of freedom in layout of the intake air temperature sensor is improved as approaching the suction port. In the air cleaner of the present embodiment, the outlet tube is formed with an umbrella portion (94) expanding toward the suction port. According to this configuration, the air flowing out from the through hole is easily retained by the umbrella portion, thereby improving the detection accuracy of the intake air temperature sensor. In the air cleaner of the present embodiment, among a peripheral wall on an inner side in a vehicle width direction and a peripheral wall on an outer side in the vehicle width direction of the upstream portion of the outlet tube, a peripheral wall on a side closer to the intake air temperature sensor is formed with a single through hole. According to this configuration, the air flow from the through hole is easily directed toward the detection portion of the intake air temperature sensor, thereby improving the detection accuracy of the intake air temperature sensor. In the air cleaner of the present embodiment, the intake air temperature sensor is attached to an upper wall of the air cleaner case, and the intake air temperature sensor is positioned on a lateral side of the outlet tube in a top view, and a detection portion of the intake air temperature sensor is positioned above the outlet tube. According to this configuration, since the intake air temperature sensor is provided in the upper portion of the air cleaner case, the intake air temperature sensor is protected from mud, water, or the like rolled up onto the wheel. By using the wide space on the lateral side of the outlet tube, the air flow from the through hole is easily detected by the detection portion of the intake air temperature sensor. In the air cleaner of the present embodiment, the outlet tube is a plurality of outlet tubes, and the intake air temperature sensor is positioned between the outlet tubes adjacent to each other in a top view, and the through holes of the adjacent outlet tubes face each other. According to this configuration, the air flow from the through holes of the adjacent outlet tubes is easily directed toward the intake air temperature sensor, thereby improving the detection accuracy of the intake air temperature sensor. Although the present embodiment has been described, the above-described embodiment and modifications may be combined entirely or partially as another embodiment. The technique of the present invention is not limited to the above-described embodiment, and various changes, substitutions, and modifications may be made without departing from the spirit of the technical concept of the present invention. The present invention may be implemented by other methods as long as the technical concept can be implemented by the methods through advance of the technique or other derivative techniques. Therefore, the claims cover all embodiments that may be included within the scope of the technical concept.
28,302
11857907
DETAILED DESCRIPTION I. Example Media Configurations, Generally Principles according to the present disclosure relate to interactions between filter cartridges and air cleaner systems, in advantageous manners to achieve certain, selected, desired results discussed below. The filter cartridge would generally include a filter media therein, through which air and other gases pass, during a filtering operation. The media can be of a variety of types and configurations, and can be made from using a variety of materials. For example, pleated media arrangements can be used in cartridges according to the principles of the present disclosure, as discussed below. The principles are particularly well adapted for use in situations in which the media is quite deep in extension between the inlet and outlet ends of the cartridge, but alternatives are possible. Also, the principles are often used in cartridges having relatively large cross-dimension sizes. With such arrangements, alternate media types to pleated media will often be desired. In this section, examples of some media arrangements that are usable with the techniques described herein are provided. It will be understood, however, that a variety of alternate media types can be used. The choice of media type is generally one of preference for: availability; function in a given situation of application, ease of manufacturability, etc. and the choice is not necessarily specifically related to the overall function of selected ones of various filter cartridge/air cleaner interaction features characterized herein. A. Media Pack Arrangements Using Filter Media Having Media Ridges (Flutes) Secured to Facing Media Fluted filter media (media having media ridges) can be used to provide fluid filter constructions in a variety of manners. One well known manner is characterized herein as a z-filter construction. The term “z-filter construction” as used herein, is meant to include (but not be limited) a type of filter construction in which individual ones of corrugated, folded or otherwise formed filter flutes are used to define (typically in combination with facing media) sets of longitudinal, typically parallel, inlet and outlet filter flutes for fluid flow through the media. Some examples of z-filter media are provided in U.S. Pat. Nos. 5,820,646; 5,772,883; 5,902,364; 5,792,247; 5,895,574; 6,210,469; 6,190,432; 6,350,291; 6,179,890; 6,235,195; Des. 399,944; Des. 428,128; Des. 396,098; Des. 398,046; and, Des. 437,401; each of these cited references being incorporated herein by reference. One type of z-filter media, utilizes two specific media components joined together, to form the media construction. The two components are: (1) a fluted (typically corrugated) media sheet or sheet section, and, (2) a facing media sheet or sheet section. The facing media sheet is typically non-corrugated, however it can be corrugated, for example perpendicularly to the flute direction as described in U.S. provisional 60/543,804, filed Feb. 11, 2004, and published as PCT WO 05/077487 on Aug. 25, 2005, incorporated herein by reference. The fluted media section and facing media section can comprise separate materials between one another. However, they can also be sections of the single media sheet folded to bring the facing media material into appropriate juxtaposition with the fluted media portion of the media. The fluted (typically corrugated) media sheet and the facing media sheet or sheet section together, are typically used to define media having parallel flutes. In some instances, the fluted sheet and facing sheet are separate and then secured together and are then coiled, as a media strip, to form a z-filter media construction. Such arrangements are described, for example, in U.S. Pat. Nos. 6,235,195 and 6,179,890, each of which is incorporated herein by reference. In certain other arrangements, some non-coiled sections or strips of fluted (typically corrugated) media secured to facing media, are stacked with one another, to create a filter construction. An example of this is described in FIG. 11 of U.S. Pat. No. 5,820,646, incorporated herein by reference. Herein, strips of material comprising fluted sheet (sheet of media with ridges) secured to corrugated sheet, which are then assembled into stacks to form media packs, are sometimes referred to as “single facer strips,” “single faced strips,” or as “single facer” or “single faced” media. The terms and variants thereof, are meant to refer to a fact that one face, i.e., a single face, of the fluted (typically corrugated) sheet is faced by the facing sheet, in each strip. Typically, coiling of a strip of the fluted sheet/facing sheet (i.e., single facer) combination around itself, to create a coiled media pack, is conducted with the facing sheet directed outwardly. Some techniques for coiling are described in U.S. provisional application 60/467,521, filed May 2, 2003 and PCT Application US 04/07927, filed Mar. 17, 2004, now published as WO 04/082795, each of which is incorporated herein by reference. The resulting coiled arrangement generally has, as the outer surface of the media pack, a portion of the facing sheet, as a result. The term “corrugated” used herein to refer to structure in media, is often used to refer to a flute structure resulting from passing the media between two corrugation rollers, i.e., into a nip or bite between two rollers, each of which has surface features appropriate to cause corrugations in the resulting media. The term “corrugation” is however, not meant to be limited to such flutes, unless it is stated that they result from flutes that are by techniques involving passage of media into a bite between corrugation rollers. The term “corrugated” is meant to apply even if the media is further modified or deformed after corrugation, for example by the folding techniques described in PCT WO 04/007054, and published Jan. 22, 2004, incorporated herein by reference. Corrugated media is a specific form of fluted media. Fluted media is media which has individual flutes or ridges (for example formed by corrugating or folding) extending thereacross. Serviceable filter element or filter cartridge configurations utilizing z-filter media are sometimes referred to as “straight through flow configurations” or by variants thereof. In general, in this context what is meant is that the serviceable filter elements or cartridges generally have an inlet flow end (or face) and an opposite exit flow end (or face), with flow entering and exiting the filter cartridge in generally the same straight through direction. The term “serviceable” in this context is meant to refer to a media containing filter cartridge that is periodically removed and replaced from a corresponding fluid (e.g. air) cleaner. In some instances, each of the inlet flow end (or face) and outlet flow end (or face) will be generally flat or planar, with the two parallel to one another. However, variations from this, for example non-planar faces, are possible. A straight through flow configuration (especially for a coiled or stacked media pack) is, for example, in contrast to serviceable filter cartridges such as cylindrical pleated filter cartridges of the type shown in U.S. Pat. No. 6,039,778, incorporated herein by reference, in which the flow generally makes a substantial turn as its passes into and out of the media. That is, in a 6,039,778 filter, the flow enters the cylindrical filter cartridge through a cylindrical side, and then turns to exit through an open end of the media (in forward-flow systems). In a typical reverse-flow system, the flow enters the serviceable cylindrical cartridge through an open end of the media and then turns to exit through a side of the cylindrical filter media. An example of such a reverse-flow system is shown in U.S. Pat. No. 5,613,992, incorporated by reference herein. The term “z-filter media construction” and variants thereof as used herein, without more, is meant to include, but not necessarily be limited to, any or all of: a web of corrugated or otherwise fluted media (media having media ridges) secured to (facing) media, whether the sheets are separate or part of a single web, with appropriate sealing (closure) to allow for definition of inlet and outlet flutes; and/or a media pack constructed or formed from such media into a three dimensional network of inlet and outlet flutes; and/or, a filter cartridge or construction including such a media pack. InFIG.1, an example of media1useable in z-filter media construction is shown. The media1is formed from a fluted, in this instance corrugated, sheet3and a facing sheet4. A construction such as media1is referred to herein as a single facer or single faced strip. Sometimes, the corrugated fluted or ridged sheet3,FIG.1, is of a type generally characterized herein as having a regular, curved, wave pattern of flutes, ridges or corrugations7. The term “wave pattern” in this context, is meant to refer to a flute, ridge or corrugated pattern of alternating troughs7band ridges7a. The term “regular” in this context is meant to refer to the fact that the pairs of troughs and ridges (7b,7a) alternate with generally the same repeating corrugation (flute or ridge) shape and size. (Also, typically in a regular configuration each trough7bis substantially an inverse ridge for each ridge7a.) The term “regular” is thus meant to indicate that the corrugation (or flute) pattern comprises troughs (inverted ridges) and ridges with each pair (comprising an adjacent trough and ridge) repeating, without substantial modification in size and shape of the corrugations along at least 70% of the length of the flutes. The term “substantial” in this context, refers to a modification resulting from a change in the process or form used to create the corrugated or fluted sheet, as opposed to minor variations from the fact that the media sheet3is flexible. With respect to the characterization of a repeating pattern, it is not meant that in any given filter construction, an equal number of ridges and troughs is necessarily present. The media1could be terminated, for example, between a pair comprising a ridge and a trough, or partially along a pair comprising a ridge and a trough. (For example, inFIG.1the media1depicted in fragmentary has eight complete ridges7aand seven complete troughs7b.) Also, the opposite flute ends (ends of the troughs and ridges) may vary from one another. Such variations in ends are disregarded in these definitions, unless specifically stated. That is, variations in the ends of flutes are intended to be covered by the above definitions. In the context of the characterization of a “curved” wave pattern of corrugations, in certain instances the corrugation pattern is not the result of a folded or creased shape provided to the media, but rather the apex7aof each ridge and the bottom7bof each trough is formed along a radiused curve. A typical radius for such z-filter media would be at least 0.25 mm and typically would be not more than 3 mm. An additional characteristic of the particular regular, curved, wave pattern depicted inFIG.1, for the corrugated sheet3, is that at approximately a midpoint30between each trough and each adjacent ridge, along most of the length of the flutes7, is located a transition region where the curvature inverts. For example, viewing back side or face3a,FIG.1, trough7bis a concave region, and ridge7ais a convex region. Of course when viewed toward front side or face3b, trough7bof side3aforms a ridge; and, ridge7aof face3a, forms a trough. (In some instances, region30can be a straight segment, instead of a point, with curvature inverting at ends of the segment30.) A characteristic of the particular regular, wave pattern fluted (in this instance corrugated) sheet3shown inFIG.1, is that the individual corrugations, ridges or flutes are generally straight, although alternatives are possible. By “straight” in this context, it is meant that through at least 70%, typically at least 80% of the length, the ridges7aand troughs (or inverted ridges)7bdo not change substantially in cross-section. The term “straight” in reference to corrugation pattern shown inFIG.1, in part distinguishes the pattern from the tapered flutes of corrugated media described in FIG. 1 of WO 97/40918 and PCT Publication WO 03/47722, published Jun. 12, 2003, incorporated herein by reference. The tapered flutes of FIG. 1 of WO 97/40918, for example, would be a curved wave pattern, but not a “regular” pattern, or a pattern of straight flutes, as the terms are used herein. Referring to the presentFIG.1and as referenced above, the media1has first and second opposite edges8and9. When the media1is formed into a media pack, in general edge9will form an inlet end or face for the media pack and edge8an outlet end or face, although an opposite orientation is possible. In the example depicted, the various flutes7extend completely between the opposite edges8,9, but alternatives are possible. For example, they can extend to a location adjacent or near the edges, but not completely therethrough. Also, they can be stopped and started partway through the media, as for example in the media of US 2014/0208705 A1, incorporated herein by reference. When the media is as depicted inFIG.1, adjacent edge8can provided a sealant bead10, sealing the corrugated sheet3and the facing sheet4together. Bead10will sometimes be referred to as a “single facer” or “single face” bead, or by variants, since it is a bead between the corrugated sheet3and facing sheet4, which forms the single facer (single faced) media strip1. Sealant bead10seals closed individual flutes11adjacent edge8, to passage of air therefrom (or thereto in an opposite flow). In the media depicted inFIG.1, adjacent edge9is provided seal bead14. Seal bead14generally closes flutes15to passage of unfiltered fluid therefrom (or flow therein in an opposite flow), adjacent edge9. Bead14would typically be applied as media1is configured into a media pack. If the media pack is made from a stack of strips1, bead14will form a seal between a backside17of facing sheet4, and side18of the next adjacent corrugated sheet3. When the media1is cut in strips and stacked, instead of coiled, bead14is referenced as a “stacking bead.” (When bead14is used in a coiled arrangement formed from a long strip of media1, it may be referenced as a “winding bead.”). In alternate types of through-flow media, seal material can be located differently, and added sealant or adhesive can even be avoided. For example, in some instances, the media can be folded to form an end or edge seam; or, the media can be sealed closed by alternate techniques such as ultrasound application, etc. Further, even when sealant material is used, it need not be adjacent opposite ends. Referring toFIG.1, once the filter media1is incorporated into a media pack, for example by stacking or coiling, it can be operated as follows. First, air in the direction of arrows12, would enter open flutes11adjacent end9. Due to the closure at end8, by bead10, the air would pass through the filter media1, for example as shown by arrows13. It could then exit the media or media pack, by passage through open ends15aof the flutes15, adjacent end8of the media pack. Of course operation could be conducted with air flow in the opposite direction. For the particular arrangement shown herein inFIG.1, the parallel corrugations7a,7bare generally straight completely across the media, from edge8to edge9. Straight flutes, ridges or corrugations can be deformed or folded at selected locations, especially at ends. Modifications at flute ends for closure are generally disregarded in the above definitions of “regular,” “curved” and “wave pattern.” Z-filter constructions which do not utilize straight, regular curved wave pattern corrugation shapes are known. For example in Yamada et al. U.S. Pat. No. 5,562,825 corrugation patterns which utilize somewhat semicircular (in cross section) inlet flutes adjacent narrow V-shaped (with curved sides) exit flutes are shown (see FIGS. 1 and 3, of U.S. Pat. No. 5,562,825). In Matsumoto, et al. U.S. Pat. No. 5,049,326 circular (in cross-section) or tubular flutes defined by one sheet having half tubes attached to another sheet having half tubes, with flat regions between the resulting parallel, straight, flutes are shown, see FIG. 2 of Matsumoto '326. In Ishii, et al. U.S. Pat. No. 4,925,561 (FIG. 1) flutes folded to have a rectangular cross section are shown, in which the flutes taper along their lengths. In WO 97/40918 (FIG. 1), flutes or parallel corrugations which have a curved, wave patterns (from adjacent curved convex and concave troughs) but which taper along their lengths (and thus are not straight) are shown. Also, in WO 97/40918 flutes which have curved wave patterns, but with different sized ridges and troughs, are shown. Also, flutes, which are modified in shape to include various ridges, are known. In general, the filter media is a relatively flexible material, typically a non-woven fibrous material (of cellulose fibers, synthetic fibers or both) often including a resin therein, sometimes treated with additional materials. Thus, it can be conformed or configured into the various corrugated patterns, without unacceptable media damage. Also, it can be readily coiled or otherwise configured for use, again without unacceptable media damage. Of course, it must be of a nature such that it will maintain the required corrugated configuration, during use. Typically, in the corrugation process, an inelastic deformation is caused to the media. This prevents the media from returning to its original shape. However, once the tension is released the flute or corrugations will tend to spring back, recovering only a portion of the stretch and bending that has occurred. The facing media sheet is sometimes tacked to the fluted media sheet, to inhibit this spring back in the corrugated sheet. Such tacking is shown at20. Also, typically, the media contains a resin. During the corrugation process, the media can be heated to above the glass transition point of the resin. When the resin then cools, it will help to maintain the fluted shapes. The media of the corrugated (fluted) sheet3facing sheet4or both, can be provided with a fine fiber material on one or both sides thereof, for example in accord with U.S. Pat. No. 6,673,136, incorporated herein by reference. In some instances, when such fine fiber material is used, it may be desirable to provide the fine fiber on the upstream side of the material and inside the flutes. When this occurs, air flow, during filtering, will typically be into the edge comprising the stacking bead. An issue with respect to z-filter constructions relates to closing of the individual flute ends. Although alternatives are possible, typically a sealant or adhesive is provided, to accomplish the closure. As is apparent from the discussion above, in typical z-filter media especially that which uses straight flutes as opposed to tapered flutes and sealant for flute seals, large sealant surface areas (and volume) at both the upstream end and the downstream end are needed. High quality seals at these locations are important to proper operation of the media structure that results. The high sealant volume and area, creates issues with respect to this. Attention is now directed toFIG.2, in which z-filter media; i.e., a z-filter media construction40, utilizing a regular, curved, wave pattern corrugated sheet43, and a non-corrugated flat sheet44, i.e., a single facer strip is schematically depicted. The distance D1, between points50and51, defines the extension of flat media44in region52underneath a given corrugated flute53. The length D2of the arcuate media for the corrugated flute53, over the same distance D1is of course larger than D1, due to the shape of the corrugated flute53. For a typical regular shaped media used in fluted filter applications, the linear length D2of the media53between points50and51will often be at least 1.2 times D1. Typically, D2would be within a range of 1.2-2.0 times D1, inclusive. One particularly convenient arrangement for air filters has a configuration in which D2is about 1.25-1.35×D1. Such media has, for example, been used commercially in Donaldson Powercore™ Z-filter arrangements. Another potentially convenient size would be one in which D2is about 1.4-1.6 times D1. Herein the ratio D2/D1will sometimes be characterized as the flute/flat ratio or media draw for the corrugated media. In the corrugated cardboard industry, various standard flutes have been defined. For example the standard E flute, standard X flute, standard B flute, standard C flute and standard A flute.FIG.3, attached, in combination with Table A below provides definitions of these flutes. Donaldson Company, Inc., (DCI) the assignee of the present disclosure, has used variations of the standard A and standard B flutes, in a variety of z-filter arrangements. These flutes are also defined in Table A andFIG.3. TABLE A(Flute definitions for FIG. 3)DCI A Flute: Flute/flat = 1.52:1; The Radii (R) are as follows:R1000 = .0675 inch (1.715 mm); R1001 = .0581 inch (1.476 mm);R1002 = .0575 inch (1.461 mm); R1003 = .0681 inch (1.730 mm);DCI B Flute: Flute/flat = 1.32:1; The Radii (R) are as follows:R1004 = .0600 inch (1.524 mm); R1005 = .0520 inch (1.321 mm);R1006 = .0500 inch (1.270 mm); R1007 = .0620 inch (1.575 mm);Std. E Flute: Flute/flat = 1.24:1; The Radii (R) are as follows:R1008 = .0200 inch (.508 mm); R1009 = .0300 inch (.762 mm);R1010 = .0100 inch (.254 mm); R1011 = .0400 inch (1.016 mm);Std. X Flute: Flute/flat = 1.29:1; The Radii (R) are as follows:R1012 = .0250 inch (.635 mm); R1013 = .0150 inch (.381 mm);Std. B Flute: Flute/flat = 1.29:1; The Radii (R) are as follows:R1014 = .0410 inch (1.041 mm); R1015 = .0310 inch (.7874 mm);R1016 = .0310 inch (.7874 mm);Std. C Flute: Flute/flat = 1.46:1; The Radii (R) are as follows:R1017 = .0720 inch (1.829 mm); R1018 = .0620 inch (1.575 mm);Std. A Flute: Flute/flat = 1.53:1; The Radii (R) are as follows:R1019 = .0720 inch (1.829 mm); R1020 = .0620 inch (1.575 mm). Of course other, standard, flutes definitions from the corrugated box industry are known. In general, standard flute configurations from the corrugated box industry can be used to define corrugation shapes or approximate corrugation shapes for corrugated media. Comparisons above between the DCI A flute and DCI B flute, and the corrugation industry standard A and standard B flutes, indicate some convenient variations. It is noted that alternative flute definitions such as those characterized in U.S. Ser. No. 12/215,718, filed Jun. 26, 2008; and published as US 2009/0127211; U.S. Ser. No. 12/012,785, filed Feb. 4, 2008 and published as US 2008/0282890; and/or U.S. Ser. No. 12/537,069 published as US 2010/0032365 can be used, with air cleaner features as characterized herein below. The complete disclosures of each of US 2009/0127211, US 2008/0282890 and US 2010/0032365 are incorporated herein by reference. Another media variation comprising fluted media with facing media secured thereto, can be used in arrangements according to the present disclosure, in either a stacked or coiled form, is described in US 2014/0208705 A1, owned by Baldwin Filters, Inc., published Jul. 31, 2014, and incorporated herein by reference. B. Manufacture of Media Pack Configurations Including the Media ofFIGS.1-3, SeeFIGS.4-7 InFIG.4, one example of a manufacturing process for making a media strip (single facer) corresponding to strip1,FIG.1is shown. In general, facing sheet64and the fluted (corrugated) sheet66having flutes68are brought together to form a media web69, with an adhesive bead located therebetween at70. The adhesive bead70will form a single facer bead10,FIG.1. An optional darting process occurs at station71to form center darted section72located mid-web. The z-filter media or Z-media strip74can be cut or slit at75along the bead70to create two pieces or strips76,77of z-filter media74, each of which has an edge with a strip of sealant (single facer bead) extending between the corrugating and facing sheet. Of course, if the optional darting process is used, the edge with a strip of sealant (single facer bead) would also have a set of flutes darted at this location. Techniques for conducting a process as characterized with respect toFIG.4are described in PCT WO 04/007054, published Jan. 22, 2004 incorporated herein by reference. Still in reference toFIG.4, before the z-filter media74is put through the darting station71and eventually slit at75, it must be formed. In the schematic shown inFIG.4, this is done by passing a sheet of filter media92through a pair of corrugation rollers94,95. In the schematic shown inFIG.4, the sheet of filter media92is unrolled from a roll96, wound around tension rollers98, and then passed through a nip or bite102between the corrugation rollers94,95. The corrugation rollers94,95have teeth104that will give the general desired shape of the corrugations after the flat sheet92passes through the nip102. After passing through the nip102, the sheet92becomes corrugated across the machine direction and is referenced at66as the corrugated sheet. The corrugated sheet66is then secured to facing sheet64. (The corrugation process may involve heating the media, in some instances.) Still in reference toFIG.4, the process also shows the facing sheet64being routed to the darting process station71. The facing sheet64is depicted as being stored on a roll106and then directed to the corrugated sheet66to form the Z-media74. The corrugated sheet66and the facing sheet64would typically be secured together by adhesive or by other means (for example by sonic welding). Referring toFIG.4, an adhesive line70is shown used to secure corrugated sheet66and facing sheet64together, as the sealant bead. Alternatively, the sealant bead for forming the facing bead could be applied as shown as70a. If the sealant is applied at70a, it may be desirable to put a gap in the corrugation roller95, and possibly in both corrugation rollers94,95, to accommodate the bead70a. Of course the equipment ofFIG.4can be modified to provide for the tack beads20,FIG.1, if desired. The type of corrugation provided to the corrugated media is a matter of choice, and will be dictated by the corrugation or corrugation teeth of the corrugation rollers94,95. One useful corrugation pattern will be a regular curved wave pattern corrugation, of straight flutes or ridges, as defined herein above. A typical regular curved wave pattern used, would be one in which the distance D2, as defined above, in a corrugated pattern is at least 1.2 times the distance D1as defined above. In example applications, typically D2=1.25-1.35×D1, although alternatives are possible. In some instances the techniques may be applied with curved wave patterns that are not “regular,” including, for example, ones that do not use straight flutes. Also, variations from the curved wave patterns shown, are possible. As described, the process shown inFIG.4can be used to create the center darted section72.FIG.5shows, in cross-section, one of the flutes68after darting and slitting. A fold arrangement118can be seen to form a darted flute120with four creases121a,121b,121c,121d. The fold arrangement118includes a flat first layer or portion122that is secured to the facing sheet64. A second layer or portion124is shown pressed against the first layer or portion122. The second layer or portion124is preferably formed from folding opposite outer ends126,127of the first layer or portion122. Still referring toFIG.5, two of the folds or creases121a,121bwill generally be referred to herein as “upper, inwardly directed” folds or creases. The term “upper” in this context is meant to indicate that the creases lie on an upper portion of the entire fold120, when the fold120is viewed in the orientation ofFIG.5. The term “inwardly directed” is meant to refer to the fact that the fold line or crease line of each crease121a,121b, is directed toward the other. InFIG.5, creases121c,121d, will generally be referred to herein as “lower, outwardly directed” creases. The term “lower” in this context refers to the fact that the creases121c,121dare not located on the top as are creases121a,121b, in the orientation ofFIG.5. The term “outwardly directed” is meant to indicate that the fold lines of the creases121c,121dare directed away from one another. The terms “upper” and “lower” as used in this context are meant specifically to refer to the fold120, when viewed from the orientation ofFIG.5. That is, they are not meant to be otherwise indicative of direction when the fold120is oriented in an actual product for use. Based upon these characterizations and review ofFIG.5, it can be seen that a regular fold arrangement118according toFIG.5in this disclosure is one which includes at least two “upper, inwardly directed, creases.” These inwardly directed creases are unique and help provide an overall arrangement in which the folding does not cause a significant encroachment on adjacent flutes. A third layer or portion128can also be seen pressed against the second layer or portion124. The third layer or portion128is formed by folding from opposite inner ends130,131of the third layer128. Another way of viewing the fold arrangement118is in reference to the geometry of alternating ridges and troughs of the corrugated sheet66. The first layer or portion122is formed from an inverted ridge. The second layer or portion124corresponds to a double peak (after inverting the ridge) that is folded toward, and in preferred arrangements, folded against the inverted ridge. Techniques for providing the optional dart described in connection withFIG.5, in a preferred manner, are described in PCT WO 04/007054, incorporated herein by reference. Techniques for coiling the media, with application of the winding bead, are described in PCT application US 04/07927, filed Mar. 17, 2004 and published as WO 04/082795 and incorporated herein by reference. Alternate approaches to darting the fluted ends closed are possible. Such approaches can involve, for example: darting which is not centered in each flute; and, rolling, pressing or folding over the various flutes. In general, darting involves folding or otherwise manipulating media adjacent to fluted end, to accomplish a compressed, closed, state. Techniques described herein are particularly well adapted for use in media packs that result from a step of coiling a single sheet comprising a corrugated sheet/facing sheet combination, i.e., a “single facer” strip. However, they can also be made into stacked arrangements. Coiled media or media pack arrangements can be provided with a variety of peripheral perimeter definitions. In this context the term “peripheral, perimeter definition” and variants thereof, is meant to refer to the outside perimeter shape defined, looking at either the inlet end or the outlet end of the media or media pack. Typical shapes are circular as described in PCT WO 04/007054. Other useable shapes are obround, some examples of obround being oval shape. In general oval shapes have opposite curved ends attached by a pair of opposite sides. In some oval shapes, the opposite sides are also curved. In other oval shapes, sometimes called racetrack shapes, the opposite sides are generally straight. Racetrack shapes are described for example in PCT WO 04/007054, and PCT application US 04/07927, published as WO 04/082795, each of which is incorporated herein by reference. Another way of describing the peripheral or perimeter shape is by defining the perimeter resulting from taking a cross-section through the media pack in a direction orthogonal to the winding access of the coil. Opposite flow ends or flow faces of the media or media pack can be provided with a variety of different definitions. In many arrangements, the ends or end faces are generally flat (planer) and perpendicular to one another. In other arrangements, one or both of the end faces include tapered, for example, stepped, portions which can either be defined to project axially outwardly from an axial end of the side wall of the media pack; or, to project axially inwardly from an end of the side wall of the media pack. The flute seals (for example from the single facer bead, winding bead or stacking bead) can be formed from a variety of materials. In various ones of the cited and incorporated references, hot melt or polyurethane seals are described as possible for various applications. InFIG.6, a coiled media pack (or coiled media)130constructed by coiling a single strip of single faced media is depicted, generally. The particular coiled media pack depicted is an oval media pack130a, specifically a racetrack shaped media pack131. The tail end of the media, at the outside of the media pack130is shown at131x. It will be typical to terminate that tail end along straight section of the media pack130for convenience and sealing. Typically, a hot melt seal bead or seal bead is positioned along that tail end to ensure sealing. In the media pack130, the opposite flow (end) faces are designated at132,133. One would be an inlet flow face, the other an outlet flow face. InFIG.7, there is (schematically) shown a step of forming stacked z-filter media (or media pack) from strips of z-filter media, each strip being a fluted sheet secured to a facing sheet. Referring toFIG.6, single facer strip200is being shown added to a stack201of strips202analogous to strip200. Strip200can be cut from either of strips76,77,FIG.4. At205,FIG.6, application of a stacking bead206is shown, between each layer corresponding to a strip200,202at an opposite edge from the single facer bead or seal. (Stacking can also be done with each layer being added to the bottom of the stack, as opposed to the top.) Referring toFIG.7, each strip200,202has front and rear edges207,208and opposite side edges209a,209b. Inlet and outlet flutes of the corrugated sheet/facing sheet combination comprising each strip200,202generally extend between the front and rear edges207,208, and parallel to side edges209a,209b. Still referring toFIG.7, in the media or media pack201being formed, opposite flow faces are indicated at210,211. The selection of which one of faces210,211is the inlet end face and which is the outlet end face, during filtering, is a matter of choice. In some instances the stacking bead206is positioned adjacent the upstream or inlet face211; in others the opposite is true. The flow faces210,211, extend between opposite side faces220,221. The stacked media configuration or pack201shown being formed inFIG.7, is sometimes referred to herein as a “blocked” stacked media pack. The term “blocked” in this context, is an indication that the arrangement is formed to a rectangular block in which all faces are 90° relative to all adjoining wall faces. For example, in some instances the stack can be created with each strip200being slightly offset from alignment with an adjacent strip, to create a parallelogram or slanted block shape, with the inlet face and outlet face parallel to one another, but not perpendicular to upper and bottom surfaces. In some instances, the media or media pack will be referenced as having a parallelogram shape in any cross-section, meaning that any two opposite side faces extend generally parallel to one another. It is noted that a blocked, stacked arrangement corresponding toFIG.7is described in the prior art of U.S. Pat. No. 5,820,646, incorporated herein by reference. It is also noted that stacked arrangements are described in U.S. Pat. Nos. 5,772,883; 5,792,247; U.S. Provisional 60/457,255 filed Mar. 25, 2003; and U.S. Ser. No. 10/731,564 filed Dec. 8, 2003 and published as 2004/0187689. Each of these latter references is incorporated herein by reference. It is noted that a stacked arrangement shown in U.S. Ser. No. 10/731,504, published as 2005/0130508 is a slanted stacked arrangement. It is also noted that, in some instances, more than one stack can be incorporated into a single media pack. Also, in some instances, the stack can be generated with one or more flow faces that have a recess therein, for example, as shown in U.S. Pat. No. 7,625,419 incorporated herein by reference. C. Selected Media or Media Pack Arrangements Comprising Multiple Spaced Coils of Fluted Media;FIGS.8-8B Alternate types of media arrangements or packs that involve flutes between opposite ends extending between can be used with selected principles according to the present disclosure. An example of such alternate media arrangement or pack is depicted inFIGS.8-8B. The media ofFIGS.8-8Bis analogous to one depicted and described in DE 20 2008 017 059 U1; and as can sometimes found in arrangements available under the mark “IQORON” from Mann & Hummel. Referring toFIG.8, the media or media pack is indicated generally at250. The media or media pack250comprises a first outer pleated (ridged) media loop251and a second, inner, pleated (ridged) media loop252, each with pleat tips (or ridges) extending between opposite flow ends. The view ofFIG.8is toward a media pack (flow) end255. The end255depicted, can be an inlet (flow) end or an outlet (flow) end, depending on selected flow direction. For many arrangements using principles characterized having the media pack250would be configured in a filter cartridge such that end255is an inlet flow end. Still referring toFIG.8, the outer pleated (ridged) media loop251is configured in an oval shape, though alternatives are possible. At260, a pleat end closure, for example molded in place, is depicted closing ends of the pleats or ridges251at media pack end255. Pleats, or ridges252(and the related pleat tips) are positioned surrounded by and spaced from loop251, and thus pleated media loop252is also depicted in a somewhat oval configuration. In this instance, ends252eof individual pleats or ridges252pin a loop252are sealed closed. Also, loop252surrounds the center252cthat is closed by a center strip253of material, typically molded-in-place. During filtering, when end255is an inlet flow end, air enters gap265between the two loops of media251,252. The air then flows either through loop251or loop252, as it moves through the media pack250, with filtering. In the example depicted, loop251is configured slanting inwardly toward loop252, in extension away from end255. Also spacers266are shown supporting a centering ring267that surrounds an end of the loop252, for structural integrity. InFIG.8A, an end256of the cartridge250, opposite end255is viewable. Here, an interior of loop252can be seen, surrounding an open gas flow region270. When air is directed through cartridge250in a general direction toward end256and away from end255, the portion of the air that passes through loop252will enter central region270and exit therefrom at end256. Of course air that has entered media loop251,FIG.8, during filtering would generally pass around (over) an outer perimeter256pof end256. InFIG.8Ba schematic cross sectional view of cartridge250is provided. Selected identified and described features are indicated by like reference numerals It will be understood from a review ofFIGS.8-8B, the above description, that the cartridge250described, is generally a cartridge which has media tips extending in a longitudinal direction between opposite flow ends255,256. In the arrangement ofFIGS.8-8B, the media pack250is depicted with an oval, in particular racetrack, shaped perimeter. It is depicted in this manner, since the air filter cartridges in many examples below also have an oval or racetrack shaped configuration. However, the principles can be embodied in a variety of alternate peripheral shapes. D. Other Media Variations,FIGS.9-12 Herein, inFIGS.9-12, some schematic, fragmentary, cross-sectional views are provided of still further alternate variations of media types that can be used in selected applications of the principles characterized herein. Certain examples are described in U.S. Ser. No. 62/077,749, filed Nov. 10, 2014 and owned by the Assignee of the present disclosure, Donaldson Company, Inc. In general, each of the arrangements ofFIGS.9-12represents a media type that can be stacked or coiled into an arrangement that has opposite inlet and outlet flow ends (or faces), with straight through flow. InFIG.9, an example media arrangement301from U.S. Ser. No. 62/077,749 (2658) is depicted, in which an embossed sheet302is secured to a non-embossed sheet303, then stacked and coiled into a media pack, with seals along opposite edges of the type previously described forFIG.1herein. InFIG.10, an alternate example media pack310from U.S. Ser. No. 62/077,749 is depicted, in which a first embossed sheet311is secured to a second embossed sheet312and then formed into a stacked or coiled media pack arrangement, having edge seals generally in accord withFIG.1herein. Edge seals can be conducted in either the upstream end or the downstream end, or in some instances both. Especially when the media is likely to encounter chemical material during filtering, it may be desirable to avoid a typical adhesive or sealant. InFIG.11A, a cross-section is depicted in which the fluted sheet X has various embossments on it for engagement with the facing sheet Y. Again these can be separate, or sections of the same media sheet. InFIG.11B, a schematic depiction of such an arrangement between the fluted sheet X and facing sheet Y is also shown. InFIG.11C, a still further variation of such a principle is shown between a fluted sheet X and a facing sheet Y. These are meant to help understand how a wide variety of approaches are possible. InFIG.12, still another possible variation in fluted sheet X and facing sheet Y is shown. InFIGS.12A and12B, an example media arrangement6401is depicted, in which a fluted sheet6402is secured to a facing sheet6403. The facing sheet6403may be a flat sheet. The media arrangement6401can then be stacked or coiled into a media pack, with seals along opposite edges of the type previously described forFIG.1herein. In the embodiment shown, the flutes6404of fluted sheet6402have an undulating ridgeline including a series of peaks6405and saddles6406. The peaks6405of adjacent flutes6404can be either aligned as shown inFIGS.12A and12Bor offset. Further the peak height and/or density can increase, decrease, or remain constant along the length of the flutes6404. The ratio of the peak flute height to saddle flute height can vary from about 1.5, typically from 1.1 to about 1. It is noted that there is no specific requirement that the same media be used for the fluted sheet section and the facing sheet section. A different media can be desirable in each, to obtain different effects. For example, one may be a cellulose media, while the other is a media containing some non-cellulose fiber. They may be provided with different porosity or different structural characteristics, to achieve desired results. A variety of materials can be used. For example, the fluted sheet section or the facing sheet section can include a cellulose material, synthetic material, or a mixture thereof. In some embodiments, one of the fluted sheet section and the facing sheet section includes a cellulose material and the other of the fluted sheet section and facing sheet section includes a synthetic material. Synthetic material(s) can include polymeric fibers, such as polyolefin, polyamide, polyester, polyvinyl chloride, polyvinyl alcohol (of various degrees of hydrolysis), and polyvinyl acetate fibers. Suitable synthetic fibers include, for example, polyethylene terephthalate, polyethylene, polypropylene, nylon, and rayon fibers. Other suitable synthetic fibers include those made from thermoplastic polymers, cellulosic and other fibers coated with thermoplastic polymers, and multi-component fibers in which at least one of the components includes a thermoplastic polymer. Single and multi-component fibers can be manufactured from polyester, polyethylene, polypropylene, and other conventional thermoplastic fibrous materials. The examples ofFIGS.9-12B, are meant to indicate generally that a variety alternate media packs can be used in accord with the principles herein. Attention is also directed to U.S. Ser. No. 62/077,749 incorporated herein by reference, with respect to the general principles of construction and application of some alternates media types. E. Still Further Media Types Many of the techniques characterized herein will preferably be applied when the media is oriented for filtering between opposite flow ends of the cartridge is media having flutes or pleat tips that extend in a direction between those opposite ends. However, alternatives are possible. The techniques characterized herein with respect to seal arrangement definition can be applied in filter cartridges that have opposite flow ends, with media positioned to filter fluid flow between those ends, even when the media does not include flutes or pleat tips extending in a direction between those ends. The media, for example, can be depth media, can be pleated in an alternate direction, or it can be a non-pleated material. It is indeed the case, however, that the techniques characterized herein are particularly advantageous for use with cartridges that are relatively deep in extension between flow ends, usually at least 100 mm, typically at least 150 mm, often at least 200 mm, sometimes at least 250 mm, and in some instances 300 mm or more, and are configured for large loading volume during use. These types of systems will typically be ones in which the media is configured with pleat tips or flutes extending in a direction between opposite flow ends. It is also noted that while the techniques described herein were typically developed for advantageous application and arrangements involving media packs with straight through flow configurations, the techniques can be applied to advantage in other systems. For example, the techniques can be applied when the cartridge comprises media surrounding a central interior, in which the cartridge has an open end. Such arrangements can involve “forward flow” in which air to be filtered enters the central open interior by passage through the media, and the exits through the open end; or, with reverse flow in which air to be filtered enters the open end and then turns and passes through the media. A variety of such arrangements are possible, including pleated media and alternate types of media. Configurations usable would include cylindrical and conical, among others. II. Some General Issues Relating to Air Cleaner Design and Servicing A. An Equipment System Using an Air Cleaner Assembly, Generally,FIG.13 InFIG.13, a schematic depiction of an engine equipment arrangement360is depicted. The equipment system360, in the example, comprises a vehicle or other equipment361having an internal combustion engine arrangement362with a combustion air intake363. The equipment arrangement360includes an air cleaner system365having a filter arrangement366therein, typically comprising a serviceable (i.e. removable and replaceable) filter cartridge. Intake air to the system is shown at367directed into the air cleaner assembly365before filtering of unfiltered air through media of the filter cartridge arrangement366. At368, filtered air is shown being directed into the equipment air intake363. At370, optional equipment such as turbo system is shown. Of course, alternate equipment systems can be represented by arrangements analogous to those ofFIG.13. The equipment system can be for example, an industrial air filter, an air cleaner arrangement used in association with a turbine, etc. The use in association with an internal combustion engine is typical, but not specifically required for many of the principles characterized herein. B. Ensuring that a Cartridge Installable in the Air Cleaner is an Appropriate One for the Air Cleaner of Concern In general, air cleaners such as used to filter equipment intake air, comprise housings having positioned therein at least a main filter cartridge, and sometimes, a safety. The main filter cartridge generally is constructed to collect particulate contaminant as it flows into the air intake stream for the equipment. This protects the equipment against damage. Such filter cartridges are generally configured to be removed and replaced, i.e. they are service parts. At various defined service intervals, and/or as increase in restriction (from dust load) becomes an issue, the cartridges are removed from the air cleaner and are refurbished or replaced. In many instances, the cartridges are specifically designed to match the equipment manufacturers' requirements for operation. It is important to ensure that the cartridge, which is replaced in the field, is a proper one for the equipment involved, and, thus fits and seals properly. In general, a primary interface between the filter cartridge and the air cleaner is along a housing seal. This interface has sometimes been used to help ensure that a cartridge that fits is also a proper one for the system of interest. Examples are provided by the descriptions of U.S. Pat. No. 8,864,866, the disclosure of which is incorporated herein by reference. In that particular reference, seal surface variations through projections and/or recesses are described, in general terms. Those general principles are applied herein, with improvements and variations for certain applications. Herein, the principles described are characterized as implemented specifically in arrangements in which a housing seal positioned on the filter cartridge, is a “radial” or “radially directed” seal. By this, reference is meant to a seal that is used to apply compressive seal forces directed either: generally toward a surrounding portion of a housing; or, alternately, with seal forces directed toward a portion of housing surrounded by the seal, for the sealing during use. With filter cartridges of the type characterized herein, a radial seal will generally be a seal that surrounds a flow passageway, with primary compressive direction (when installed) being toward or away from that flow passageway. An outwardly or radially outwardly directed seal will be one which has a seal surface on the seal arrangement (of the cartridge) that sealingly engages a surrounding structure in use. A radially inwardly directed seal, is a seal arrangement in which the seal surface of the cartridge surrounds the structure to which it sealed during use. C. Observations Concerning Issues with Installation of Cartridges in Systems in which the Housing Radial Seal of Interest is Deeply Recessed in the Housing; and/or, when Side-Load is Involved In many instances, the seal surface to be engaged by a seal on the cartridge is deeply recessed within a housing, and out of view of the service provider. In addition, it can be difficult, if not impossible, to manually reach the seal surface as the cartridge is being installed, due to the size of the housing, and a blocking effect of the cartridge. An issue with using cartridges having seals which are not merely of simple or uniform geometric shape, such as circular or oval is that it, can be difficult, depending on the design, to orient the cartridge appropriately for the sealing to properly occur during installation. Certain of the techniques characterized herein are useful to facilitate this, in application, as will be understood from the further detailed descriptions below. The problem can sometimes be exacerbated, when the cartridge is configured for side load. By side load, reference is meant to the portion of the housing through which the cartridge is installed in use. In particular, and in some instances, a straight through flow cartridge is loaded through the side of a housing and then pushed sideways into a sealing positioned. It can be difficult to manipulate and leverage the cartridge appropriately to get good sealing. Examples of advantageous side load arrangements with useful features to facilitate loading are described, for example in U.S. Pat. Nos. 7,396,375; 7,655,074; 7,905,936; 7,713,321 and 7,972,404, incorporated herein by reference. The arrangements of the references identified in the previous paragraph, generally use oval shaped seals, typically racetrack shaped ovals. (shapes with straight sides separated by semi-circular curved ends in the seal surface). When the desire is to introduce a variation in the seal surface, it can sometimes be difficult, depending on how implemented, to get good, convenient, installation in a side load application. Some principles described herein are characterized to be particularly useful in such situations, to facilitate loading. III. A First Example Assembly, FIGS.14-22 A. General Features of the Assembly,FIGS.14-15A Selected principles according to the present disclosure can be understood from reference toFIGS.14-22. The example depicted, as will be understood from the following, is an air cleaner assembly with a main filter cartridge removably installed therein. Further, the assembly is configured as “end load”, meaning that that the housing access cover is located at an opposite end of the cartridge from an air flow outlet. The principles can be applied in alternate housing configurations. Referring now toFIG.14, reference numeral400, generally indicates an air cleaner assembly in accord with selected principles according to the present disclosure. The air cleaner assembly400comprises a housing401. The housing401generally includes a main body403and an access cover404, in this instance secured in place by latches405. In the example depicted, the access cover404is fully removable from the housing body403, but the principles can be applied in alternate arrangements. The housing401generally defines an air flow inlet arrangement407and an air flow outlet arrangement408. Air to be filtered enters the housing401through inlet407passes through an internally positioned filter arrangement, with filtered air exiting through outlet arrangement408. In the example depicted, inlet flow through inlet arrangement407is generally perpendicular to air flow through a cartridge installed in the housing, and air flow through outlet arrangement408is generally in alignment with a direction of air flow through an installed filter cartridge, in use, but the principles can be practiced in alternate arrangements. InFIG.14, no specific effort is made to indicate an orientation within equipment for use. The assembly400can be oriented for use, with one of the sides, for example, the side facing the viewer inFIG.14, directed upwardly, directly downwardly, or oriented laterally. The principles described herein can be applied in a variety of such arrangements and no specific orientation is required. Indeed, this can be an advantage of arrangements according to the present disclosure. InFIG.14A, a selected perspective view of the assembly400is depicted. Like features to those already identified are indicated by similar reference numerals. The housing401depicted optionally includes various mounting pads409thereon by which it can be secured to equipment. InFIG.15, an exploded elevational view of the air cleaner assembly400is depicted. Here, access cover404is shown removed from body403, for access to interior features. Optional weather gasket411is depicted. It can be secured to one or the other of the access cover404in body403if desired, or it can be a separate item. The weather gasket411is a gasket that will help provide a weather seal between the access cover404and body403when installed, for example to inhibit migration of water (for example, from rain) from entering the interior of the housing401. In the example ofFIG.15, both the inlet arrangement407and outlet arrangement405are shown depicted on the main body403; alternatives are possible. Also, as indicated previously, the inlet and outlet arrangements407/408can be alternately located or directed. Still referring toFIG.15, the air cleaner assembly400includes an interiorly received, removable and replaceable (i.e. serviceable) main filter cartridge415. The assembly400is also depicted having an optional safety filter cartridge416. In the example assembly, the safety filter cartridge416is positioned downstream of the main filter cartridge415in use. The main filter cartridge415is the cartridge responsible for collection of the majority of particulate material separated from the air flow stream, during use. The safety filter cartridge416provides a variety of functions. It can be left in place when the main filter cartridge415is removed and serviced, thus protecting the outlet for clean air from dust being knocked off inside the housing and grating thereto. The filter cartridge safety416can also collect some dust should there be a failure in the media or seal of the main filter cartridge415. These are well known uses of safety filter cartridges. The particular safety filter cartridge416depicted, is generally of a type known, see for example, U.S. Pat. No. 7,905,936 incorporated herein by reference. InFIG.15A, an exploded perspective view of the assembly400is depicted, allowing further review of general components previously discussed. Attention is directed to the safety filter cartridge416, and, in particular, to installation projection417and handle or handle arrangement418. Such features are described, for example in U.S. Pat. No. 7,905,936, referenced above, and incorporate herein by reference. During installation of the safety filer cartridge416, typically the service provider would push the safety filter cartridge416into the housing body403, engaging the projection417with a receiver appropriately positioned in body403. In this manner, the user can leverage the safety filter cartridge416into position, using the handle418. The particular safety filer cartridge416depicted uses a peripheral seal419that will engage (as a radial seal) a surrounding portion of the housing, when the safety416is properly installed. Thus, the safety416uses an outwardly directed radial seal in the terms characterized herein above. From a review ofFIGS.15and15A, it can be understood that the assembly400depicted is one in which the main filter cartridge415is installed through an end load, in accord with the characterizations of such terms above. In the example, the main cartridge415is pushed into the housing body403during installation, and toward an outlet end or outlet arrangement408. Referring toFIGS.15and15A, it can be seen that the main filter cartridge415includes a seal arrangement420on an end of the cartridge415that is recessed most deeply in the housing body403during installation. In the example depicted, this is a downstream air flow outlet end at the cartridge415. B. General Features of the Main Filter Cartridge415,FIGS.16-19 Selected features of the main filter cartridge415can be understood from reviewingFIGS.16-19. Referring first toFIG.16, the main filter cartridge415generally comprises a media pack configured for straight through flow having opposite flow ends424,425. Herein, the term “flow end” when used in characterizing the media pack427, or filter cartridge415, reference is meant to an end face or region into which (or from which) air flows during use. Typically, the flow ends are planar, but alternatives are possible. Generally, one of the ends will be an inlet flow end, and an opposite end will be an outlet flow end. For the particular filter cartridge415depicted, flow end424is an inlet flow end and flow end425is an outlet flow end. The media pack427generally comprises air filtration media that is closed to passage of inlet air entering the cartridge at inlet end424from exiting outlet flow425without filtering passage through the media. The filter cartridge415generally comprises media pack427. The media pack comprises media appropriate for the filtration operation to be conducted, generally with an air flow through the opposite ends. The media characterized above in connection withFIGS.1-12Bcan be used. The particular example media pack429depicted has a generally oval shape, with opposite curved ends427a,427b, typically approximately semi-circular, and with relatively straight (opposite) first and second side sections427c,427dextending therebetween. Such a media pack can be made from a coiled strip of corrugated media secured to facing media in accord with descriptions above, but alternatives are possible. The particular media pack427depicted would typically be constructed without a center core, for example in accord with the techniques of U.S. Pat. No. 8,226,786, but alternatives, including ones in which a center core is provided, are possible. The media pack427may include an outer sheath, shield or protective coating surrounding it. However, in many applications, the outer surface427sof the media pack427along much of the exposed length of the media pack will comprise facing media with no outer protective coating other than, perhaps, a label. In many instances, including the example ofFIGS.16-19, main filter cartridges according to the present disclosure, will include one or more optional “preforms” thereon. By the term “preform” and variants thereof in this context, reference is meant to a structural piece that is typically premade, for example molded from plastic, and is then secured to the media pack the filter cartridge using adhesive or sealant material or other material that is cured or set. Preforms, generally, are well known, see for example U.S. Pat. No. 7,905,936; U.S. 7,713,321 and U.S. Pat. No. 7,972,404. The particular cartridge415ofFIGS.16-19, includes two such optional preforms, indicated generally at430,431. The preform430is positioned adjacent end424. It includes an installation handle arrangement434, in the example depicted, in axial overlap with flow end424; and, a perimeter arrangement435that surrounds media pack427. The preform430can be positioned in place and be secured by an adhesive if desired, or with seal material. However, since preform430is positioned upstream of housing seal arrangement420, a seal between preform430and the media pack427is not critical. Referring toFIG.16, preform430also includes an optional end grid arrangement435in axial alignment with end424of the media. The end grid435can provide strength, structure and integrity to both the preform430and to the media of media pack427. Referring toFIG.17, preform431is positioned adjacent flow end425. Preform431is a seal support preform and includes an optional grid440thereon to stabilize the media end425against distortion. As a seal support preform431, preform431includes a seal support441thereon, discussed below, and positioned to support sealing pressure against seal material445of the seal arrangement420in use. A variety of seal arrangements420can be used. The particular arrangement depicted uses a seal arrangement in which seal material is molded-in-place to secure preform431in position and to also form a seal surface445aof seal material445. Techniques such as those described in U.S. Pat. Nos. 7,396,376 and 8,409,316 can be used, but alternatives are possible. Attention is directed toFIG.18, an exploded perspective view of the filter cartridge415. The various features previously identified can be readily viewed. Referring to the preform431, attention is directed to seal support flange447, which, it will be understood, projects to appropriate portions of the seal arrangement420to support the seal material445during sealing. InFIG.19, an alternate exploded perspective view is shown, taken generally toward flow end424of the cartridge415. Still referring toFIGS.16-19, it will be understood that the particular seal arrangement420is depicted with a seal surface445athat is configured to form an outwardly directed radial seal. That is, it is positioned in the cartridge415at a location to form a seal, during installation, with a surrounding portion (housing structure) of an air cleaner (typically an internal housing portion). In alternatives, the seal surface445acan be configured to surround a portion of the air cleaner (typically an internal housing portion) during installation, and thus from a radially inwardly directed seal. In addition, the radial seal depicted is a “supported seal” in that the support flange447of the preform431is positioned to support the seal material445during installation, such that the material445is, at least in part, compressed between the support flange431and a housing surface, during use. Seal supports that operate in this general manner are well known. The particular seal surface445of the example arrangement415depicted uses an optional modified oval shape. In particular, it is not simply an oval shape in which straight or oppositely arcuate seal sections are positioned between two opposite curved (for example semi-circular) ends, as would be the case with oval racetrack shaped seals of arrangements such as U.S. Pat. No. 7,905,936. It rather uses a specific arrangement of positioned variations in that surface, to achieve advantage. Such variations can be of the type related to those generally described in U.S. Pat. No. 8,864,866 incorporated herein by reference. However, specific selected configurations and variations can include features discussed herein, to advantage. In general terms, and referring toFIG.17, the advantageous non-straight sections of the seal surface are indicated generally at448as comprising alternating projection sections448pand recess sections448r, discussed further below. Referring toFIGS.18and19, it is noted that the support flange447includes similar projection/recess sections at449to provide support to the seal arrangement in the related seal sections. C. The Safety Filter,FIG.20 InFIG.20, optional safety filter416is depicted. The safety filter416comprises a preform450having media, typically pleated media451, positioned therein. The preform450has an outer perimeter rim452including projection417previously discussed. Pleat spacers are indicated in the preform at453. Handle arrangement418is shown, for managing the safety. Positioned on the preform450, and surrounding the media451, is seal member419secured in place, typically by an adhesive. Alternates are possible. D. Example Main Filter Cartridge Seal Engagement with the Housing,FIGS.21-22 As indicated above, the seal configuration of the main filter cartridge415is selected to have a configuration that can be unique to the system of concern, if desired, to prevent installation of alternate arrangements, and also to be of a type that can be safely and securely established and released. The particular arrangement depicted has a general oval perimeter with two opposite curved (semi-circular) ends, engaged by opposite sections of the seal arrangement that are not straight. Herein, the particular configuration depicted for the not straight section, may sometimes be referred to as a “wavy section” as discussed in more detail below. It is generally a section having a projection/recess contour as described below. Engagement of such arrangements for sealing can be understood by reference toFIGS.21,21A and22. FIG.21, a plan view of the housing401taken toward the inlet407is depicted. In this view, no cartridge is positioned in the housing.FIG.21can be seen as providing the orientation forFIG.21A. FIG.21Ais a cross-sectional view taken generally along line21A-21A,FIG.21. It is noted that there is a housing seal surface (or structure)460positioned within the housing, in this instance which will surround the cartridge seal arrangement420when installed, and against which the seal arrangement420and thus the cartridge415will seal when installed. The seal surface460and the arrangement depicted, which uses an outwardly directed radial seal, is a seal surface that surrounds the seal arrangement420in use, and against which the seal surface445ais pressed during use. The seal surface460depicted includes smooth (non-wavy) sections461and wavy or projection/recess sections462. The wavy or projection/recess sections462are sections of surface460which comprise an alternating projection/recess configuration for sealing engagement with one or more of mating wavy surfaces448,FIG.18, in the cartridge415. The particular cross-section depicted inFIG.21Ashows approximately half the overall surface460, the opposite half of surface460typically being a mirror image. As a result, one could understand there would be two wavy (or projection/recess) sections462, in the example each comprising three inwardly directed projections465with two outwardly projecting sections466therebetween. The sections can be characterized as “inwardly facing convex” for sections465; and, inwardly facing concave” for sections466, if desired. Alternatives are possible. From an examination ofFIGS.21and21A, it can be understood that housing seal surfaces460of the type usable in an arrangement involving principles described herein generally (and specifically as would be used in connection with the example cartridge415) can be features molded as a portion of a molded housing, if desired. InFIG.22, a schematic depiction is provided of the housing401with cartridge405positioned therein. E. Some Selected Variations FIGS.14-22are intended to show an example arrangement using selected principles according to the present disclosure. The features can be implemented in a wide variety of variations with respect to housing features, cartridge features, and indeed, with respect to specific seal configurations. As to seal configurations, general principles are provided herein after additional embodiments and examples are shown. It should be understood that the principles can be applied with non-straight “alternating” projections/recess versions of the seal surface that vary from these specific examples depicted in the cartridge415ofFIGS.16-19. For example, the number of alternating projections and recesses in any one of the areas can be varied. Also, the total number of areas that comprise such alternating projection/recess regions can be varied, as well as the location in the seal surface. Also, variations in shape, size, location and spacing are possible. Some principles with respect to these are characterized further below. Still referring toFIGS.14-22, it is noted that the cartridge depicted (inFIG.16) includes an installation handle434as previously characterized. It can be seen by reference to the various figures, that the handle434is positioned in overlap with an inlet flow end of the media pack, and can be used to push the cartridge into position or pull the cartridge from sealing, during servicing. This type of handle434will sometimes be referred to as an “installation handle” characterized for an axial direction of installation and removal. IV. Additional Embodiments and Variations InFIGS.23-34, a first example variation from the cartridge415is depicted. The particular depicted cartridge and cartridge components and these features, vary from the cartridge415in two primary ways: the absence of the preform at and end of the cartridge opposite the seal arrangement; and, variation in the preform arrangement at the seal end of the cartridge. It will be noted, however, that a preform such as preform430,FIG.19, could be used in arrangements in accord withFIGS.23-34, if desired. Referring toFIG.23, cartridge480generally comprises a media pack481and seal arrangement482. The media pack481may generally be constructed in accord with principles described herein above, and indeed, may be generally in accord with media pack427,FIG.16-19. The cartridge480includes opposite flow ends484,485. The seal arrangement482is positioned at flow end485. While alternatives are possible, in a typical application, it is expected that484would be an inlet flow end and485would be an outlet flow end, for the media pack481. It is noted that although there is no preform or handle arrangement at end484, there is a handle arrangement488at end485, the same end at which the seal arrangement482is depicted. The handle arrangement488may be configured as a portion of the same preform as is used in the seal arrangement482, as discussed below, although alternatives are possible. The absence of a handle arrangement adjacent flow end484is not meant to indicate that the cartridge480is not pushed in (and removed) by grasping that end. Rather, it is meant to indicate that in some instances, the cartridge480and assembly can be configured such that one can grasp and manipulate the cartridge into and out of sealing orientation without the need for a handle arrangement at an end opposite from the housing seal arrangement. It is noted, referring toFIG.23, that seal arrangement482generally comprises a seal member489molded-in-place. The seal member489includes a seal surface489s. The seal surface489sdepicted is an outwardly directed surface, configured to form an outwardly directed radial seal in accord with the principles described above. Alternatives are possible. It is noted that the seal surface489shas a shape similar, in overall feature, to the surface448s,FIGS.16and17. The configuration used in the arrangement ofFIG.23could be applied in the arrangement ofFIG.16; and, the configuration used in the arrangement ofFIG.16could be used in accord with the features ofFIG.23. InFIG.24, a plan view of the cartridge480is depicted, taken toward surface485and seal arrangement482. Cross-sectional views are indicated generally atFIGS.25and26. InFIG.27, an enlarged fragmentary view of the portion ofFIG.25is shown. From a review of these figures, it can be understood that the seal arrangement482depicted comprises a molded-in-place seal portion489and a seal support preform490. The preform490depicted includes a seal support flange491thereon. Referring toFIG.27, a cross-sectional view through seal surface490sis shown. It can be seen that the seal surface490sgenerally has a shape which tapers from a largest diameter portion489xtoward an insertion tip490t. The particular taper depicted is a stepped arrangement. However, straight chamfer arrangements are possible. This facilitates installation and is well known for a wide variety of radial seal types, see for example U.S. Pat. Nos. 7,396,376 and 8,409,316. InFIGS.28-29C, the molded seal portion489is shown separate from the cartridge and preform.FIG.28is a plan view taken from an orientation analogous toFIG.24.FIG.29is a perspective view, andFIGS.29A,29B, and,29C are cross-sectional views. InFIGS.30-34, the seal support preform490is depicted. InFIG.30, a perspective view is taken toward handle488is shown. InFIG.31, a plan view taken toward handle488is shown. InFIGS.32,33and34, cross-sectional views are shown. In the arrangements ofFIGS.23-34, some example dimensions are provided. These are intended to indicate a workable arrangement using principles according to the present disclosure. Variations in the dimensions are possible. The example dimensions are as follows: AX=16 mm radius; AY=19 mm radius; and, AZ=99 mm radius; inFIG.25, BA=200 mm; BB=182 mm; BC=198 mm; and, BD=205 mm; inFIG.26, BE=349 mm; BF=344 mm; BG=200 mm; BH=231 mm; and, BI=342 mm; inFIG.27, BJ=9 mm; and, BK=3 mm; inFIG.28, AA=349 mm; AB=16 mm radius; AC=19 mm radius; AD=44.5 mm; AE=44.5 mm; AF=34.4 mm radius; AG=5 mm radius; and, AH=205 mm; inFIG.29A, AN=313.9 mm; AO=224.6 mm; AP=336 mm; and, AQ=342 mm; inFIG.29B, AI=41.9 mm; AJ=171.4 mm; AK=145.2 mm; AL=182 mm; and, AM=198 mm; inFIG.29C; AR=31.1 mm; AS=3 mm; AT=1.5 mm; AU=2 mm; AV=4.1 mm; and, AW=14.3 mm. InFIG.31, BL=203.4 mm; BM=33 mm radius; BN=44.5 mm; BO=44.5 mm; BP=5 mm radius; BQ=60°; BR=85.4 mm radius; BS=193.9 mm; and, BT=336.9 mm; InFIG.32, BU=170 mm; and, BV=17 mm; inFIG.33, BW=314 mm; and, inFIG.34, BX=27 mm; BY=10 mm; BZ=0.3 mm; CA=127.9°; CB=1°; and, CC=2.4 mm. Typically, a maximum thickness of the molded-in-place seal section (between seal surface and support) in alignment with the seal support is at least 10 mm and usually not greater than 20 mm (often 12-16 mm) although alternatives are possible. Some analogous dimensions can be used for analogous features and the previously described embodiment ofFIGS.16-19, if desired. Positioning of a handle adjacent the seal end can provide some advantage. For example, when such a cartridge is handled, typically a service provider will handle the cartridge from the handle end and set it down with the cartridge directed upwardly. This will help keep the seal material489from being in contact with work surfaces, etc. during handling. It may be desirable to also have some form of handle arrangement, but configured so the cartridge cannot be stood on that arrangement at the opposite flow end488,FIG.23. If so, one can be added. However, if the cartridge is of a size and use that can be handled by grasping the media pack adjacent this end without a preform, one may not be desired. V. Example Arrangements in which a Wavy Seal Portion is Located Adjacent an End of a Modified Oval Shape, FIGS.35-56 A. General In the example arrangements ofFIGS.16-19and23-34, the seal surfaces were configured with two semi-circular curved ends, having opposite sections extending therebetween, defining a general oval shape, modified to include one or more wavy or projection/recess sections in what would have otherwise have been straight sections in the (respective) oval shape. It is possible to implement principles of the present disclosure in alternate arrangements including at least one wavy or projection/recess section in an otherwise end curve of the oval shape, either as an alternative, or in addition to features discussed. Some examples are described in this section and the recited figures. B. A First Example,FIGS.35-38 InFIGS.35-38, a first example filter cartridge and features therefore, are schematically depicted, having a wavy (or projection/recess) section in an arcuate “end” of the seal arrangement in accord with the principles described herein. InFIG.35, a schematic perspective view of such a cartridge is shown at500. The cartridge500would include a media pack501(shown in phantom) with opposite flow ends502,503. It is noted that the media pack501is depicted in phantom, but may be similar to the configurations of previously described media packs herein, and using media in accord with discussions above. In the particular example depicted, at flow end502, no preform is shown. However one could be positioned at this location, if desired. At end503, a seal arrangement505is depicted. The seal arrangement505includes a seal member506configured with a seal surface506s. Although alternatives are possible, the particular seal member506depicted is configured using molded-in-place material as previously discussed, and positioned with surface506sconfigured as an outwardly directed radial seal, i.e. to seal against a surrounding portion of a housing in use, alternatives are possible. InFIG.36, a plan view of cartridge500is depicted, taken towards seal arrangement505. Seal ring506comprising seal surface506sis shown depicting the perimeter shape thereof. Referring toFIG.36, surface506scan be seen as having a first end portion508, opposite side portions509,510and end portion510x, opposite portion508. The perimeter shape is generally oval, except for modifications at end510as discussed below. Thus, in the example depicted, end508is arcuate (in the example generally semi-circular) in perimeter shape, and opposite sections509,510are generally straight and parallel to one another. Alternatives are possible. Still referring toFIG.36, end510xcan be seen extending around a 180° arc, but having a surface region configured with a wavy or projection/recess shape, comprising alternating recess sections511and projection sections512. In the example depicted, there are three recess sections511and two projections512, although alternatives are possible. InFIG.37, a cross-sectional view of molded-in-place seal material505of seal arrangement505taken along line37-37,FIG.36is depicted. Regions513show where the molded-in-place portion would receive a support projection on a preform. Regions514show over molded portions to secure the seal the seal material (and preform) to the media pack. InFIG.38, a cross-sectional view taken generally along line38-38,FIG.37is shown. In the example ofFIGS.35-38, usable dimensions are indicated as follows: InFIG.37, CD=41.9 mm; CE=10.5 mm; CF=7.5 mm; CG=118.4 mm; CH=113.6 mm; CI=92.5 mm CJ=4.5 m; CK=113 mm; CL=122 mm; CJ=118.4 mm; CM=16.7 mm; and, CN=20.1 mm. InFIG.38, CO=21.2°; CP=321.7 mm; CQ=317.6 mm; CR=295.7 mm; CS=32.4°; CT=322.9 mm; CU=332 mm; CW=24.2°; and, CV=4.5°. Of course alternatives are possible using the principles according to the present disclosure. Some general variations usable are discussed further herein below. C. A Second Variation,FIGS.39-45 Principles characterized in connection with the embodiment ofFIGS.35-38can be applied in an arrangement in which a seal support preform arrangement includes a handle thereon, at the same end of the cartridge as the seal arrangement. An example is provided inFIGS.39-46as follows. InFIG.39, an example cartridge550is depicted, comprising media pack551and seal arrangement552. These may be generally in accord with the arrangement ofFIGS.35-38except for the presence of a handle arrangement553, in overlap with an end555of media551. As with the arrangement ofFIGS.35-38, the seal arrangement551comprises a molded-in-place region555of material including a region556having seal surface556s. The media pack550may generally be as previously described having opposite flow ends558,559. InFIG.40, a plan view taken toward flow end559is depicted. InFIG.41, a cross-sectional view taken along line41-41,FIG.40is shown. InFIG.42, a cross-sectional view taken along line42-42,FIG.40is shown. In these figs, preform560can be seen with seal support561 InFIG.43, the preform560is shown in perspective. InFIG.44, a plan view is shown taken toward an end opposite flange561. InFIG.45, an opposite plan view, toward flange461, is shown. InFIG.46, a cross-sectional view taken along line46-46,FIG.45is shown. In the drawings of the example ofFIGS.43-46, some dimensions are indicated. These are meant to be examples and would correspond to the following. InFIG.40, CX=23.6 mm radius; CY=26.4 mm radius; CZ=30°; and, CRC=50 mm radius; inFIG.41, DA=332 mm; DB=321.7 mm; DC=250 mm; DD=281.1 mm; and, DE=327 mm; inFIG.42, DH=118.4 mm; DF=2.4 mm; DG=122 mm; and, DI=117 mm; inFIG.44, DJ=2.4 mm DK=105 mm; and, DL=210 mm; inFIG.45, DO=112.9 mm; DP=30′; DQ=30′; DR=11.1 mm radius; and, DS=38.9 mm radius; and DT=322.9 mm; and, inFIG.46, DM=28.3 mm; and, DU=34.8 mm. Of course alternatives are possible, using principles in accord with the techniques described. D. An Example Air Cleaner Assembly,FIGS.47-56 InFIGS.47-56, an example air cleaner assembly is depicted, usable with the main filter cartridge having seal characteristics similar to those described above in the embodiments ofFIGS.35-38and/orFIGS.39-45. Referring toFIG.47, an air cleaner assembly in accord with this portion of the disclosure is indicated generally at600. The air cleaner assembly600comprises a housing601including a housing body602, and service access cover603. In the example of air cleaner assembly600depicted, as will be understood from discussion below, a variation from a previously described housing401(FIG.14) is shown in the access cover603is not removed from the housing body602, when the access cover603is opened. Rather, it remains secured to the housing body. Alternatives are possible; and, the variation can be used with the assembly400,FIG.14. Still referring toFIG.47, other features viewable include a filtered air flow outlet arrangement604, by which filtered air leaves the housing to be directed downstream equipment. Air to be filtered would generally enter the housing through an inlet at end605. At606, optional mounting pads are shown to facilitate mounting to equipment in use. The pads606can be located in a variety of locations, to facilitate securement. From the orientation depicted inFIG.47, no specific characterization is meant with respect to how the whole housing601and overall assembly600will be oriented in use. The assembly600could be positioned with the side view facing the view inFIG.47directed upwardly or downwardly. However, it could also be oriented with outlet604directed upwardly or downwardly. InFIG.48, an exploded view of air cleaner assembly600is depicted with the access cover603pivoted open. An internally received cartridge620is shown exploded from interior602iof body602. From a review ofFIG.48, it can be understood that the example air cleaner assembly600depicted is a “side load” assembly that term is used herein. That is, the cartridge620is inserted into and removed from the housing body602through a side thereof, in between inlet605and outlet604. This means, generally, that two types of movements to the cartridge620are needed during installation. In a first, see arrow609, direction generally perpendicular to air flow through the cartridge620, the cartridge620is inserted into the housing body602. In a second, see arrow610, the cartridge is pushed into a direction of flow therethrough in a sealing orientation with the housing. This type of side load is described in principle in connection with U.S. Pat. Nos. 7,396,375; 7,655,074; 7,905,936; 7,713,321 and 7,972,404, incorporated herein by reference. InFIGS.49and50, perspective views of the cartridge620are shown. The cartridge620can be seen as comprising a media pack621having opposite flow ends622,623. At flow end623, a seal arrangement625is depicted. The seal arrangement625can be generally in accord with seal arrangement552,FIGS.39-40, although variations can be used. Thus, it includes a seal member626forming a seal surface626sconfigured to form an outwardly directed radial seal; the seal surface626shaving a perimeter shape with an arcuate, semi-circular, curved end627; opposite straight side sections628,629; and, a curved end, opposite end627, at630. End630comprises a wavy or projection/recess configuration having three recess sections631and two projection sections632. At end623, a seal support preform635including a handle portion636and a support region637(FIG.53) to support the seal, is shown. The seal arrangement625can be secured in place by an over mold at638,FIG.49, of a type similar to those described above. Referring toFIGS.49and50, at flow end622, a second preform640is depicted having: a band portion641surrounding the media620; an end rim portion642extending over a portion of end622; and, an installation handle arrangement645. The particular handle arrangement625is positioned in overlap with a curved end621aof the oval media pack621. It is noted that in the particular example arrangement depicted, the handle arrangement645is aligned with the same curved end621aof the media pack621as is the wavy (projection/recess) end section630of the seal surface626sdiscussed previously. Advantages from this are discussed below, although alternatives are possible. InFIG.51, a side elevational view of filter cartridge620provided with features as described is indicated. InFIG.52, and end view taken toward end623is shown, with features discussed as indicated. InFIG.53, an exploded view is shown, with features as indicated. InFIG.54, an alternate schematic exploded perspective view analogous toFIG.53is shown. As will be understood from a review ofFIG.48, the handle arrangement645is positioned to facilitate installation when oriented adjacent the same curved end621aof the media pack621as is the wavy section630. This is because during a side installation, the end arcuate section627of the seal arrangement opposite the arcuate wavy (projection/recess) section630can be first nested, or partially nested, with the user then manipulating the handle645to fully engage the seal, and complete the installation. In this type of operation, the non-wavy arcuate section627of the seal opposite the wavy section630facilitates installation. It is noted that the handle arrangement645can also be used as a part of a projection arrangement to be engaged by the access cover603securing the cartridge in position. An example of this is shown inFIGS.55-56. The access cover603can, thus, have a variety of features that help support the cartridge620against undesired movement during installation. E. Some Useful Variations and Alternatives,FIGS.57-59 The principles described herein in connection with the various embodiments of the previous FIGS. can be applied alternatively. For example, as indicated, outwardly directed radial seals as shown can be used. Alternately, as indicated, inwardly directed radial seals can be used. Indeed, in some instances, both types of seals can be used. In the examples depicted, the seal arrangements shown are of a type that engage a surrounding portion of housing structure. The seals can be formed through installation into a trough or other receiving arrangement in a housing, in use. The above principles can be understood, for example, from the fragmentary, schematic view ofFIG.57. The housing structure arrangement700is depicted, comprising a receiving trough701for a seal arrangement during use. InFIG.57, a seal arrangement720is shown insertable into the trough701. The seal arrangement720may comprise a radially outwardly directed seal member or surface721as shown, for engagement with an outer flange7010on the trough701. Alternatively, or in addition, the seal arrangement720can comprise a radially inwardly directed seal surface722oriented and configured to engage an inner surface or flange701iof trough701in use. Thus, from a review ofFIG.57, it can be understood that either or both of an outwardly directed radial seal or an inwardly directed radial seal can be used with a trough701. It is noted that if only one is used, an opposite side of the seal arrangement can still be configured to engage a relevant surface in the trough701, but not necessarily the seal, to provide stability. InFIG.58, a seal arrangement having an inwardly directed radial seal at730is shown. InFIG.59, a seal arrangement having both an outwardly directed seal arrangement731and an inwardly directed seal arrangement732is shown. The variations discussed in this section can be implemented with any of a variety of specific features, and in any of the embodiments characterized previously. VI. Some General Principles, Comments and Observations Relating to FIGS.14-61 A. General;FIGS.60and61 The examples characterized above in connection withFIGS.41-59show that the general principles characterized herein can be applied in a variety of forms of filter cartridges and air cleaner housings. In this section some general observations of typical and preferred arrangements are characterized. FIG.60is a schematic representation of a (non-arcuate) but wavy (projection/recess) seal surface section usable in selected arrangements according to the present disclosure.FIG.60can be viewed as a schematic representation of a perimeter portion of a wavy seal surface section of the example ofFIG.24. FIG.61is of an arcuate wavy (projection/recess) surface section usable in selected arrangements according to the presented disclosure.FIG.61is generally analogous toFIG.60; and, it can be viewed as an indication of a perimeter portion of the wavy seal surface section of the example ofFIG.40. B. Selected General Features of Example Embodiments Described Thus Far and/or Shown in U.S. Provisional 62/543,090, Incorporated Herein by Reference In a typical application of the techniques characterized, with straight through flow configurations, an air filter cartridge can be provided that includes a media pack comprising filter media and having first and second, opposite flow ends. A first of the first and the second opposite flow ends can comprise an outlet flow end, with the opposite end being an inlet flow end. The media pack will be configured with the media oriented to filter air flowing into the inlet flow end prior to that air exiting the opposite outlet flow end. A variety of types of media are characterized and a variety of shapes and configurations can be used. Such cartridges (for example) are included in the cartridge depictions ofFIGS.15,16,23,39, and48. A housing seal arrangement is positioned on the media pack. The housing seal arrangement will typically be positioned on (or at) one of the two flow ends. In many instances it will be at the outlet flow end; but alternatives are possible. Examples of cartridges with the seal arrangement on a flow end are included in the depictions ofFIGS.15,16,23,39, and48. The housing seal arrangement generally comprises a radially directed seal member defining a radial seal surface oriented to releasably, sealingly, engage air cleaner structure in use. The housing seal arrangements are typically configured to define an air flow passageway in overlap with a media flow pack, and the radial seal surface extends around the air flow passageway. Examples of such cartridges are included in the depictions ofFIGS.15,16,23,39, and48. The radial seal surface may face the flow passageway, if the seal is an inwardly directed radial seal; or, it may face away from the air flow passageway if the seal is a radially outwardly directed seal, in the terms used herein. Arrangements with 2-sided seals (both radially outwardly and radially inwardly) are also possible, as described above. The radial seal surface will generally be characterized as defining a perimeter-direction in extension around the flow passageway. The term “perimeter-direction” is meant to refer to the extension of the seal surface as it goes around the inner or outer perimeter of the seal surface material and the air flow passageway, in a perimeter direction, (depending on whether the surface is inwardly or outwardly directed). In many applications, a typical seal surface includes at least a first arcuate seal section preferably configured to “radially sealingly engage non-wavy (a non-projection/recess) air cleaner structure”, although alternatives are possible. By this, and similar terms, it is meant that the seal surface is configured in this region so that if installed in an air cleaner, it will seal to a non-wavy (or non-projection/recess) surface of a corresponding housing region (structure). This does not necessarily mean that the seal surface (on the cartridge) in the first arcuate seal surface (on the cartridge) section is completely devoid of any one or all localized projections or recesses therein. Rather, it is meant that if it does have any such features, on the seal surface of the cartridge, they are preferably sufficiently small so as not to interfere with sealing, when the housing structural region seal against which sealing occurs, does not itself have wavy sections (projections and/or recesses), in the corresponding region. Example cartridges with such first arcuate sections are shown inFIG.24(see section801) and inFIG.40(see section901). Although alternatives are possible, in certain examples, the first arcuate seal surface section extends over an internal arc (between opposite arc ends) of at least 130°, usually not greater than 270°, and typically extends over an arc: within the range of 150°-210°, inclusive; often within the range of 160°-200°, inclusive, and typically an arc of 170°-190°, inclusive. Often the first arcuate seal surface will extend over an arc (between arc ends) of 180°. It is noted, however, that non-wavy (non-projection/recess) sections in arc can extend over relatively short arcs, for example arcs that extend at least 20°, typically at least 30°, often at least 40°, and often no more than 110°, in some instances, not more than 180°. Examples of these are suggested by descriptions herein below, relating to later figures. In the example ofFIG.24, arcuate ends, of the first arcuate section801, are indicated at802,803; and the first arcuate section801extends over an arc of 180°. In the example ofFIG.40, the first arcuate end901extends over an arc between the ends902,903and can be characterized as a 180° arc. It is noted that, in accord with terminology used thus far, the arcuate section901inFIG.40would not be considered to extend over an arc between end points904,905, with the arc still being characterized as 180°, but having straight sections therein. This is because, although a first arcuate section can include straight sections therein, in some instances, the arc ends will typically be considered to be the final end points where various curve sections (within the first arcuate section) end, in the overall length extension of the arc. Thus it is, the end points902,903that are at opposite ends of the first arcuate section as defined by one or more curved sections therein. In the cartridge ofFIG.24, a first wavy (projection/recess) seal section can be understood as identified by either section806, between end points803,807; or, as wavy seal (projection/recess) section808between end points802,809(the other indicated wavy seal section being a second wavy (projection/recess) seal section). In the example ofFIG.40, the first wavy (projection/recess) seal section can comprise section906extending between end points904,905. InFIG.60, a schematic representation corresponding to section806,FIG.24is shown; and, inFIG.61, a schematic representation of a wavy (projection/recess) section in accord with section906,FIG.40is shown. When the term “first arcuate seal surface” is used in this context, it is not meant to be implied or suggested that the arcuate seal surface defines a circular arc, unless it is otherwise stated, for example, by characterizing it as “circular” or as having a radius of some amount. (Even then, very minor variations from circular are intended to be included within the term unless otherwise stated). Typically, in arrangement described thus far, the seal surface includes at least a first wavy (projection/recess) seal surface section including a radially directed portion comprising an alternating radial projection/recess configuration; that is a configuration having alternating radial projections and radial recesses therein. Typically, variations are possible and some of these are characterized below. Herein, the term “radial projection/recess configuration” and variants is meant to generally characterize a “wavy” construction of alternating recesses and projections in a region. The term is not meant to indicate (in extension from an end of the section), which occurs first, a projection or recess. Thus, the term “projection/recess” configuration herein has the same meaning as “recess/projection” configuration. The term “wavy” in this context is meant to indicate alternating projections and recesses without specific additional characterization of the nature of the shape of those recesses and projections; and, is not meant to indicate whether all recesses are of the same shape (or size) and whether all projections are of the same shape (or size), unless otherwise stated. In the example ofFIG.40, a radius of the first arcuate section901is indicated generally by dimension915. Radii of the various alternating recess and projection sections of the wavy section906are indicated by916,917,918,919and920. The first arcuate seal surface, in many arrangements according to the present disclosure, is typically an arcuate seal surface section that has a non-wavy (non-projection/recess) configuration in complete perimeter-direction extension around the corresponding internal arc, see for example,FIGS.24and40. In some instances, if it does have any small projections or recesses therein, typically and preferably such recesses or projections do not cause a variant in the curve of the arc, relative to opposite sides of the variation, of more than about 2 mm, and typically no more than about 1 mm. By this, it is meant to be understood that even a non-wavy (non-projection/recess) section of seal surface can have some small projections, recesses, or projection/recess configuration to it, as long as such is sufficiently small so as not to interfere with radially sealing to a non-wavy (non-projection/recess) housing section. Herein, the term “perimeter-direction seal surface length” is mean to refer to a length dimension in the perimeter-direction, of the radial seal surface, or some identified section of the radial seal surface. That is, the reference is meant to a direction of extension to the seal surface around the air flow passageway that is surrounded by the seal member. Although alternatives are possible, and as for the arrangements depicted and described above, typically, the first arcuate seal surface section has a first total perimeter seal direction surface length of at least 5% of a total perimeter-direction seal surface length of the entire radial seal surface; often it is at least 10% of that distance, and usually at least 15% of that distance, see for example,FIG.24. Also, typically and preferably, the first arcuate seal surface has a first total perimeter-direction seal surface length of no more than 90% of a total perimeter-direction seal surface length and often is no more 80% of that length. Examples of this are provided by at least the cartridges ofFIGS.24and40. Although alternatives are possible, typically, the first wavy (projection/recess) seal section has a first total perimeter-direction seal surface length of at least 5% of a total perimeter-direction seal surface length of the radial seal surface, typically at least 10%, and often at least 15%; and, typically no more than 90%, often no more than 80% thereof, see the example ofFIG.24and the variation ofFIG.40. Typically, the first arcuate seal surface section can be characterized as having a first open perimeter-direction surface length X1. This is meant to reference a distance of extension of the seal surface, in the perimeter-direction between end points of the first arcuate seal surface section. The first wavy seal section can be characterized as having a first total perimeter-direction seal surface length of X2. In many applications according to the present disclosure, a ratio of X1to X2will be at least 0.8, often at least 1.0, and usually at least 1.50. In many instances the ratio of X1to X2will be no greater than 6.0, often no greater than 4.0, and in many instances within the range of 1.0 to 3.0, although alternatives are possible. In the example cartridge ofFIG.24, the first arcuate section perimeter-direction length X1will be the seal surface length between end points802,803of the first seal surface section801. In the same example ofFIG.24, X2would be the distance between end points803,807over the first corresponding wavy seal section806,808. In the example ofFIG.40, X1would correspond to the distance between end points902,903over the first arcuate seal surface section901; and, X2would correspond to a length between the end points905,906of the first wavy seal section906. Herein, the terms “distance”, “length”, and variants thereof, in this context, is meant to reference a seal surface distance, including contours (i.e. not necessarily a direct, shortest, line distance). Herein, it is not necessarily meant that the projections or recesses in the projection/recess configuration are curved, unless it is so stated. Also, it is not meant that they are curved to a circular definition, unless it is so stated or suggested by a definition of a radius of curvature. Thus, when the term “radius of curvature” is used, it is meant that the shape is substantially circular, and thus it may be mathematically circular or varied therefrom only slightly. Typically, for arrangements such as those previously described, at least one of a projection section and recess section, in the wavy (projection/recess) section, has a radius of curvature R2, and, the first arcuate seal surface section has a radius of curvature R1. Typically, the ratio R1/R2is at least 1.5, usually at least 2.0 and often at least 4.0. Variations are possible. This characterization can be understood, for example, by reference to the example ofFIG.24and alternatively, to the example ofFIG.40. Referring first toFIG.24, a radius of curvature R1, of the first arcuate seal surface section is indicated generally at815; and, individual radii R2of various projection sections and recess sections of the first wave seal section806(or808) are indicated by the various dimensions816,817,818,819,820(or821,822,823,824,825). What is meant by the characterizations of this paragraph, is the relationship between R1and R2, for at least a selected one of a projection section and a recess section. It is not meant to indicate that all recess sections and projection sections have the same radius as the others, etc. In the example ofFIG.24, R1would correspond to a radius815of the first arcuate seal section801; and, R2would correspond to a radius of a selected one of the various projection recess sections (816-820; or821-825) in the first wavy seal surface section (either806or808respectively). Typically, each projection section and each recess section in the curved projection/curved recess section configuration, of the first wavy (projection/recess) seal surface section has a radius of curvature R2such the ratio of R1/R2for each is at least 1.5, usually at least 2.0, and often at least 4.0. By this, it is not meant that the radius of curvature of each recess and each projection is necessarily the same. Thus R2may be different for various ones of the projections and recesses, as long as the identified ratio remains as stated. In spite of the observations in the previous paragraph, it is expected that in some typical instances, each curved recess in the first wavy (projection/recess) seal surface section when curved to a circular curvature, will have the same radius of curvature as each other recess in the same wavy (projection/recess) seal surface section; and, each curved projection section, when curved to a circular curvature, in the first wavy (projection/recess) seal surface section will have the same radius of curvature as each other curved projection in the same wavy seal surface section, seeFIGS.24and40. However, alternatives are depicted in certain figures described below. Although alternatives are possible, in some instances, each projection section in a given wavy surface section will have a larger radius of curvature than each recess section in the same wavy seal surface section, seeFIGS.24and40, as characterized by example dimensions provided herein above. In some examples, each projection section will have a radius of curvature of no more than 12 mm larger than each recess section in the same wavy (projection/recess) seal surface section; often no more than 6 mm larger, and in many instances, no more than 4 mm larger. Usually, each projection section will have a radius of curvature at least 0.4 mm larger, usually at least 0.5 mm, and in many instances at least 2 mm larger, than each recess section. Referring to withFIGS.60and61, the wavy (projection/recess) seal surface section can be characterized as having a “projection/recess depth.” In general, the term “projection/recess depth dimension” and variants thereof, is meant to refer to a radial distance between a maximum recess and maximum projection. In the schematic ofFIG.60, this projection/recess depth is represented by dimension D1. In the example ofFIG.61, it is represented by D2. Typically, the projection/recess depth D1(or D2) is such that the largest projection/recess depth within the first wavy seal (projection/recess) surface section is no greater than 70 mm, often no greater than 50 mm, and usually no greater than 30 mm. However, typically the largest projection recess depth D1(or D2) is at least 5 mm, usually at least 10 mm, and often at least 15 mm. Alternatives are possible. As indicated above, it is not required that the first arcuate seal surface section itself be a non-wavy (non-projection/recess) section. However, if it does include any projections or recesses therein, typically, each is preferably no greater than 2 mm maximum relief (usually no more than 1 mm maximum relief) from adjacent portions of the surface, if sealing to a non-wavy (non-projection/recess housing surface). In some examples depicted and described thus far, the first arcuate seal section is a non-wavy section, as shown in the examples ofFIGS.24and40. In some example and preferred arrangements, including those ofFIGS.24and40, within the first wavy (projection/recess) seal section, each recess and each projection is configured to a circular arc of a given radius (except at transitions (or inflections) where, along the perimeter dimension, each recess merges into each projection. By this, it is not meant that the circular definition (if present) of each is necessarily the same. When each projection section and each recess section, within a wavy section, is to a generally circular arc, preferably that arcuate extension is no more than semi-circular (180°), typically it is less, usually no more than 170°, and preferably no more than 150°. However, typically and preferably, each does extend over an arc of at least 45°, often at least 60°, and in many instances, at least 90°. Referring toFIG.60, a radial arc, for example, in recess section816is shown between approximate end points816aand816b. An example arc for projection section817is shown between end points816band816c. It will be understood from this, that a recess section or projection section end point is generally a point where curved transition from recess to projection (concave to convex) occurred. The reference to the arc is meant to indicate, again, that the given recess section of projection section generally does not extend over an arc that is as great as semi-circular, with preferences as indicated. This generally means that individual waves (represented by adjacent recesses and projections within a wavy section) will typically (in may applications) be relatively wide and shallow, in overall configuration. In this context, the amount of radial arc is merely meant to refer to the portion of a perimeter of a circle defined by the radius over which the arc of the projection section and recess section extends. As characterized above, the first wavy (projection/recess) seal surface section can be characterized as having first and second, opposite, end termini sections. Referring toFIG.60, the end termini sections of the wavy (projection/recess) seal surface section are identified at803and807; in the example ofFIG.61, they are identified at904and905. Typically, the wavy (projection/recess) seal sections will be configured, especially when an outwardly directed radial seal is involved, with end termini sections comprising recesses (i.e. concave shapes), such as shown inFIGS.60and61. However, in alternate applications, a wavy seal surface section can be configured with a first and second, opposite, end termini comprising projection (convex) sections, or with one terminus of each. Herein, a wavy (projection/recess) seal section may sometimes be characterized as “arcuate” or, alternatively, as “non-arcuate.” In this context, the terminology is meant to reference an extension between end points of the referenced wavy (projection/recess) seal section. For example, in the schematic ofFIG.60, the wavy (projection/recess) seal section depicted is not non-arcuate, i.e. arcuate between the end points803,807. On the other hand, in the schematic example ofFIG.61, the wavy (projection/recess) seal section is arcuate in extension between the end points804,805(in the example, extending over a 180° semi-circular arc). The terminology in this context is not meant to reference the individual waves or projection/recess definition, but merely along the perimeter of the radial seal, the perimeter-direction path directly between the two end points (i.e. as a straight or arcuate). As indicated above in connection with the examples ofFIG.24, the first wavy (projection/recess) seal surface section can be a non-arcuate wavy (projection/recess) seal surface section, i.e. be positioned in an otherwise straight portion of a seal definition. However, it can be an arcuate wavy (projection/recess) seal surface section, for example, extending over an arc between two opposite ends of the section, as shown in the example ofFIG.40. The amount of “waviness” in the seal surface section can, in some instances, be understood by comparing: a length of the wavy (projection/recess) seal surface section in the perimeter direction between end points and over the contour; to a direct length between end termini of the wavy (projection/recess) seal surface section. The length over the contour section will sometimes be characterized here as the “contoured first perimeter-direction length L1” of the first wavy (projection/recess) seal surface section. A length between end termini of the first wavy (projection/recess) seal surface section will sometimes be reference as a “non-contoured first perimeter-direction length L2.” In the example schematic ofFIG.60, the contoured first perimeter-direction length L1will be the length between end points803,807following the contour of the wavy section; the length L2would be the straight length dimension between the end points803and807, represented by a length of line L2. InFIG.61, an arcuate wavy (projection/recess) surface section is shown, and thus L1would be a length between the end points904,905, following the contour of the wavy (projection/recess) section; and, L2would be a length of an arc (non-wavy or non-projection/recess) indicated by line L2, extending between the same two end points. It is noted that, in some applications, when the wavy (projection/recess) seal section is a straight or non-arcuate seal section (FIG.60), typically a length of the contoured length L1to the non-contoured length L2will be fairly large. However, in an arcuate wavy (projection/recess) seal section, shown inFIG.61, the contoured arcuate length may be relatively close to the corresponding non-contoured arcuate length, with a ratio of L1/L2reflecting this. Often, in wavy (projection/recess) sections, a ratio of L1to L2will be no greater than 2.5, usually no greater than 2, often no greater than 1.6. However, the ratio of L1to L2will be no less than 1.0, usually no less than 1.01, and, for example, no less 1.03, and sometimes no less than 1.1. Alternatives are possible. In extension between the end termini, typically and preferably a wavy (projection/recess) seal section does not have a substantial length of extension that is straight, i.e. not curved. Indeed, in many instances, a recessed section will transition into a projection section with the curved section at each mating at a transition point, but with no significant straight (non-curved) section. However, in some instances, straight sections can be included. Typically, the first wavy (projection/recess) seal surface section, between the end termini, has no non-curved sub-section therein, (i.e. no straight section therein) of greater than 10 mm in perimeter-direction length, preferably no more than 5 mm in perimeter-direction length, usually no greater than 3 mm in length and often has no non-curved surface perimeter-direction sub-section at all. Although alternatives are possible, in many applications, the first wavy (projection/recess) seal surface section will include at least three recesses therein, and usually no more than 8 (often no more than 5) recesses therein. Also, in many instances, the first wavy (projection/recess) seal surface section will include at least 2 projections therein, and often no more than 7 projections (typically no more than 5) therein. Alternatives are possible. Examples of three recesses and two projections are shown in the wavy (projection/recess) seal sections ofFIGS.60and61. Many of the techniques characterized herein are particularly well adapted to be practiced with cartridges that have relatively large seal perimeter size. Often, the first arcuate seal surface section will have a perimeter-direction seal surface length of at least 150 mm, usually at least 200 mm, often at least 250 mm. It is noted that the first arcuate seal section surface can, in some instances, be characterized as a “single projection section” in the seal surface, in extension between end points of the arc, see the examples ofFIG.21at861and,FIG.40, at901(with example dimensions as characterized above). Consistent with typical and preferred applications in relatively large cartridges, the first wavy (projection/recess) seal surface section can be characterized as having a typically relatively large perimeter-direction seal surface length, typically at least 50 mm, often at least 80 mm, and in many instances, at least 100 mm. Examples are shown in the arrangements ofFIGS.24and40(with example dimensions as characterized above). As indicated previously, the radial seal surface can be a radially outwardly directed seal surface, a radially inwardly directed seal surface; or, the seal arrangement can be characterized as having both a radially inwardly directed radial seal surface and a radially outwardly directed radial seal surface. In many applications of the techniques described herein, the overall radial surface will be one that can be characterized as having a modified oval perimeter shape, or modified oval shape. In this context, an “oval shape” would generally comprise a shape with no wavy (projection/recess) section therein, and having two, opposite, curved ends with side sections extending therebetween. When the two curved sections are semi-circular, in the regions extending between the two arcuate curved ends are straight, the oval seal surface can be characterized as “racetrack” or, as a racetrack version of an oval shape. Herein, the term “modified” is meant to refer to at least one section of the otherwise oval (or racetrack) seal surface having a wavy (projection/recess) seal surface definition in accord with the characterizations herein. The examples ofFIGS.24and40can be characterized as “modified oval shape” seals, and in each case, the modification would be a modified racetrack oval shape. Referring toFIGS.60and61, in the examples depicted, each projection section extends to a point tangential with an unmodified, straight, or unmodified curved section of the “oval perimeter shape.” This will be typical in many applications, but is not required. Alternatives are discussed below. In an example arrangement having a modified oval perimeter shape, the seal surface has a perimeter-direction shape with: the first arcuate seal surface section extending over a semi-circular arc; the second arcuate seal surface section opposite the first arcuate seal surface section; a first side seal surface section extending between first and second arcuate seal sections; the first side seal surface section comprising the first wavy (projection/recess) seal surface section; and, a second side seal surface section extending between a first arcuate seal surface section and the second arcuate seal surface section, the second side seal surface section being opposite the first side seal surface section. The example ofFIG.24corresponds to this, with the second arcuate seal surface section being a non-wavy (non-projection/recess) section and with a second side seal section being a wavy (projection/recess) seal surface section also. In many instances, of the type of example 24, the second side seal surface section will be a mirror image of the first side seal surface section. In arrangements of the type of example 24, typically the radial seal surface has no straight perimeter-direction section therein of greater than 15 mm, usually none greater than 10 mm, and often none greater than 5 mm. Indeed, in many applications, they have no straight perimeter-direction seal surface section in there at all. However, in some applications, such as the arrangement inFIG.40, the seal surface does have straight perimeter-direction seal surface sections therein. Indeed, the arrangement ofFIG.40can be characterized as one having a modified oval perimeter shape with: a first arcuate seal surface section extending over a semi-circular arc; a second arcuate seal surface section opposite the first arcuate seal surface section and comprising a first wavy (projection/recess) seal surface section; a first side seal surface section extending between the first and second arcuate seal surface sections; and, a second side seal surface section extending between the first arcuate seal surface on the section and the second surface section; the second side surface section being opposite the first side seal surface section. In the example ofFIG.40, the first side seal surface section is a first non-wavy (non-projection/recess) side seal surface section; the second side seal surface section is a mirror image of the first side seal surface section; and, the first and second side seal surface sections are each straight and parallel to one another in perimeter direction. Alternatives are possible. In some examples characterized herein, the cartridge can include a seal support preform positioned with a seal support flange embedded in (or otherwise engaging) the seal material which defines the radial seal surface. The seal support preform can be secured in place on the media pack, for example, by molded-in-place material that also includes integral therewith, the region of seal material itself. The seal support can be continuous and solid in extension, or it can be provided with slots, slits or apertures therein. In the examples described thus far, the support flange defines a size that is sufficiently small to overlap an end of an engaged media pack. Typically, the seal support flange has a perimeter in a perimeter-direction, in radial shape alignment with a radial seal. Thus, the seal support flange has non-wavy (non-projection/recess) section(s) in overlap (alignment) with non-wavy (non-projection/recess) sections of the seal surface; and, the seal support has wavy (projection/recess) section(s) in radial overlap or alignment with wavy section(s) of the seal surface. This will help the seal support provide the desirable level of compression, in a controlled manner, to the seal in complete perimeter extension. It is noted that the seal support preform can be characterized as defining or surrounding the air flow passageway around which the radial seal extends. Often the seal support preform will include an optional media pack grid arrangement extending thereacross. This can provide rigidity in the seal support as well support to the media pack against distortion. The seal support preform can be provided with a handle bridge thereon, for example, in overlap with an end of the media pack. Examples are showing in connection withFIGS.23and39. The seal support preform will typically be positioned in an outlet flow end of the media pack, although alternatives are possible. A reason for this is that it is often desirable to separate the clean air volume from the dirty air volume at a location adjacent the outlet end of the media pack, when design parameters allow. Typically, the housing seal arrangement will include a molded-in-place portion securing the seal support preform to the media pack and surrounding the media pack, as indicated. Typically, that molded-in-place portion also includes, integral therewith, a radial seal. Typically and preferably, the molded-in-place material has an as “molded density” of no greater than 0.45 kg/cu·cm., typically no greater than 0.295 kg/cu·cm. Typically it is molded to “as molded” hardness, Shore A, of no greater than 30, typically no greater than 24, often no greater than 20, and often at least 10. Often foamed polymeric materials will be desired. Well known materials useable for such situations are foamed polyurethane, that increase in volume during use, such as for example described in such references as U.S. Pat. No. 9,457,310 incorporated herein by reference. The cartridge may include an end preform spaced from, and separate from, the seal support preform. Examples are shown inFIG.16at430; and, inFIG.49at610. This end preform can include a portion or rim surrounding the media pack, and if desired, an installation handle member. An installation handle member is a handle member oriented to be grasped to help install or remove the cartridge from a housing. If the seal support arrangement is positioned in a most deeply recessed end of the cartridge during installation, it will be understood that the preform with the installation handle member will typically be positioned at or near an opposite end of the media pack from the seal support preform. The installation handle member can be positioned in axial overlap with a flow end of the media pack (seeFIG.16); or, it can be in overlap with a side of the media pack, seeFIG.49. The term “installation handle” member and variants thereof, is meant to refer to a handle member that can be grasped and used to help either install or remove the cartridge. The features and techniques characterized herein were particularly developed for use with media packs that themselves have an oval perimeter shape, although the techniques can be applied in other applications. Typically when the media pack is an oval perimeter shape, it has a racetrack or approximately racetrack shape perimeter with: opposite curved ends and straight sides extending therebetween. With such a media pack, typically if a preform is provided that has a handle member in alignment with a curved end of the media pack, it is a handle arrangement that is in alignment with a selected curved end of the media pack that also, has in alignment therewith, an arcuate wavy seal surface section at an opposite end of the media pack. It is noted that there is no specific requirement that an air filter cartridge, component, or air cleaner assembly include all of the features characterized herein, in order to obtain some advantage according to the present disclosure. Further, features characterized with respect to each embodiment, for example, characterization to be implemented in alternate cartridges to the specific example, and without necessarily all of the other characterizations, if desired. It is noted that in the examples, media packs depicted are generally of an oval shape, for example, as might result from the various techniques characterized above for media definition. Typically such arrangements would comprise coiled arrangements of media, but alternatives are possible. The techniques can even be used in connection with arrangements of stacked media, such as shown inFIG.7. What would be typical in such instances is use of a preform that engages the media pack appropriately, which then supports the seal configuration of the type desired and characterized. It is noted that in the figures described thus far, some specific depicted examples are shown. The general features depicted, however, can be selected for aesthetic (design appearance) reasons and be consistent with the variables characterized herein for specific features in use. That is, the specific designs depicted are meant to also reflect aesthetic characteristics with variations possible in accord with the descriptions herein. C. Example Characterizations from the Disclosure of U.S. Provisional 62/543,090, Incorporated Herein by Reference 1. An air filter cartridge comprising: (a) a media pack comprising filter media and having first and second, opposite, flow ends; (i) the first one of the opposite flow ends comprising an inlet flow end; (ii) the second one of the opposite flow ends comprising an outlet flow end; and, (iii) the media pack being configured to filter air flowing into the inlet flow end prior to the air exiting the outlet flow end; and, (b) housing seal arrangement positioned on the media pack; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement comprising a radially directed seal member defining a radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the radial seal surface defining a perimeter-direction in extension around the flow passageway; and, (iv) the seal surface including: (A) a least a first arcuate seal surface section configured: to fully, radially, sealingly, engage a section of non-wavy air cleaner structure; and, extending over an internal arc of at least 130° between arc ends; and, (B) at least a first wavy seal surface section including a radially directed portion comprising an alternating radial projection/recess configuration. 2. An air filter cartridge according to the characterization of 1 wherein: (a) the first arcuate seal surface section extends over an internal arc of no greater than 270°. 3. An air filter cartridge according to any one of the characterizations of 1 and 2 wherein: (a) the first arcuate seal surface section extends over an internal arc within the range of 150°-210°, inclusive. 4. An air filter cartridge according to any one of the characterizations of 1 and 2 wherein: (a) the first arcuate seal surface section extends over an internal arc within the range of 160°-200°, inclusive. 5. An air filter cartridge according to any one of the characterizations of 1-4 wherein (a) the first arcuate seal surface section extends over an internal arc of no greater than 130°. 6. An air filter cartridge according to any one of the characterizations of 1-5 wherein: (a) the first arcuate seal surface section extends over an internal arc of 180°. 7. An air filter cartridge according to any one of the characterizations of 1-6 wherein: (a) the first arcuate seal surface section has a non-wavy configuration in complete perimeter-direction extension around the corresponding internal arc. 8. An air filter cartridge according to any one of the characterizations of 1-7 wherein: (a) the first arcuate seal surface section has a first total perimeter-direction seal surface length of at least 5% of a total perimeter-direction seal surface length of the radial seal. 9. An air filter cartridge according to any one of the characterizations of 1-8 wherein: (a) the first arcuate seal surface section has a first total perimeter-direction seal surface length of at least 10% of a total perimeter-direction seal surface length of the radial seal surface. 10. An air filter cartridge according to any one of the characterizations of 1-8 wherein: (a) the first arcuate seal surface section has a first total perimeter-direction seal surface length of at least 15% of a total perimeter-direction seal surface length of the radial seal surface. 11. An air filter cartridge according to any one of the characterizations of 1-10 wherein: (a) the first arcuate seal surface section has a first total perimeter-direction seal surface length of no more than 90% of a total perimeter-direction seal surface length of the radial seal surface. 12. An air filter cartridge according to any one of the characterizations of 1-11 wherein: (a) the first arcuate seal surface section has a first total perimeter-direction seal surface length of no more than 80% of a total perimeter-direction seal surface length of the radial seal surface. 13. An air filter cartridge according to any one of the characterizations of 1-12 wherein: (a) the first wavy seal surface section has a first total perimeter-direction seal surface length of at least 5% of a total perimeter-direction seal surface length of the radial seal surface. 14. An air filter cartridge according to any one of the characterizations of 1-13 wherein: (a) the first wavy seal surface section has a first total perimeter-direction seal surface length of at least 10% of a total perimeter-direction seal surface length of the radial seal surface. 15. An air filter cartridge according to any one of the characterizations of 1-14 wherein: (a) the first wavy seal surface section has a first total perimeter-direction seal surface length of at least 15% of a total perimeter-direction seal surface length of the radial seal surface. 16. An air filter cartridge according to any one of the characterizations of 1-15 wherein: (a) the first wavy seal surface section has a first total perimeter-direction seal surface length of no more than 90% of a total perimeter-direction seal surface length of the radial seal surface. 17. An air filter cartridge according to any one of the characterizations of 1-16 wherein: (a) the first wavy seal surface section has a first total perimeter-direction seal surface length of no more than 80% of a total perimeter-direction seal surface length of the radial seal surface. 18. An air filter cartridge according to any one of the characterizations of 1-17 wherein: (a) the first arcuate seal surface section has a first total perimeter-direction seal surface length of X1; and, (b) the first wavy seal section has a first total perimeter-direction seal surface length of X2; (i) a ratio of X1to X2being at least 0.8 19. An air filter cartridge according to the characterization of 18 wherein: (a) a ratio of X1to X2is at least 1.0. 20. An air filter cartridge according to any one of the characterizations of 18 and 19 wherein: (a) a ratio of X1to X2is at least 1.5 21. An air filter cartridge according to any one of the characterizations of 18-20 wherein: (a) a ratio of X1to X2is no greater than 6. 22. An air filter cartridge according to any one of the characterizations of 18-21 wherein: (a) a ratio of X1to X2is no greater than 4.0. 23. An air filter cartridge according to any one of the characterizations of 18-22 wherein: (a) the ratio of X1to X2is within the range of 1.0 to 3.0. 24. An air filter cartridge according to any one of the characterizations of 1-23 wherein: (a) the first arcuate seal surface section extends over an arc of 160°-200°, inclusive, and has a radius of curvature of R1; and, (b) the first wavy section comprises a curved projection/curved recess configuration having at least multiple recess sections; (i) at least a selected one of a projection section and a recess section, in the curved projection section/curved recess section configuration having a radius of curvature R2such that a ratio R1/R2is at least 1.5. 25. An air filter cartridge according to the characterization of 24 wherein: (a) the ratio R1/R2is at least 2.0 26. An air filter cartridge according to any one of the characterizations of 24 and 25 wherein: (a) the ratio R1/R2is at least 4.0 27. An air filter cartridge according to any one of the characterizations of 1-26 wherein: (a) the first arcuate seal surface sections has a radius of curvature of R1; (b) the first wavy section comprises curved projection/curved recess configuration having at least multiple recess sections and multiple projection sections; (i) each projection section and each recess section, in the curved projection section/curved recess section configuration of the first wavy seal surface section having a radius of curvature R2such that a ratio of R1/R2for each is at least 1.5. 28. An air filter cartridge according to any one of the characterizations of 1-27 wherein: (a) the first wavy section comprises a curved projection/curved recess configuration having at least multiple recess sections and multiple projection sections; (i) each projection section and each recess section, in the curved projection section/curved recess section configuration of the first wavy seal surface section having a radius of curvature R2such that a ratio of R1/R2for each is at least 2.0. 29. An air filter cartridge according to any one of the characterizations of 1-28 wherein: (a) the first wavy section comprises curved projection/curved recess configuration having at least multiple recess sections and multiple projection sections; (i) each projection section and each recess section, in the curved projection section/curved recess section configuration of the first wavy section having a radius of curvature R2such that a ratio of R1/R2for each is at least 4.0. 30. An air filter cartridge according to any one of the characterizations of 26-28 wherein: (a) each curved projection section in the first wavy seal surface section has the same radius of curvature of each other curved projection section in the first wavy seal surface section; and, (b) each curved recess section in the first wavy seal surface section has the same radius of curvature, of each other curved recess section in the first wavy seal surface section. 31. An air filter cartridge according to any one of the characterizations of 1-30 wherein: (a) each projection section in the first wavy seal surface section has a larger radius of curvature than each recess section in the first wavy seal surface section. 32. An air filter cartridge according to the characterizations of 30 wherein: (a) each projection section in the first wavy seal surface section has a radius of curvature of no more than 12 mm larger than each recess section in the first wavy seal surface section. 33. An air filter cartridge according to any one of the characterizations of 31 and 32 wherein: (a) each projection section in the first wavy seal surface section has a radius of curvature of no more than 6 mm larger than each recess section in the same first wavy seal surface section. 34. An air filter cartridge according to any one of the characterizations of 31-33 wherein: (a) each projection section in the first wavy seal surface section has a radius of curvature of no more than 4 mm larger than each recess section in the same first wavy seal surface section. 35. An air filter cartridge according to any one of the characterizations of 30-34 wherein: (a) each projection section in the first wavy seal surface section has a radius of curvature of at least 0.4 mm larger than each recess section in the same first wavy seal surface section. 36. An air filter cartridge according to any one of the characterizations of 30-35 wherein: (a) each projection section in the first wavy seal surface section has a radius of curvature of at least 0.5 mm larger than each recess section in the same first wavy seal surface section. 37. An air filter cartridge according to any one of the characterization of 30-36 wherein: (a) each projection section in the first wavy seal surface section has a radius of curvature of at least 2.0 mm larger than each recess section in the same first wavy seal surface section. 38. An air filter cartridge according to any one of the characterizations of 1-37 wherein: (a) the first wavy seal surface section has a largest projection/recess depth dimension of no greater than 70 mm. 39. An air filter cartridge according to any one of the characterizations of 1-38 wherein: (a) the first wavy seal surface section has a largest projection/recess depth dimension of no greater than 50 mm. 40. An air filter cartridge according to any one of the characterizations of 1-39 wherein: (a) the first wavy seal surface section has a largest projection/recess depth dimension of no greater than 30 mm. 41. An air filter cartridge according to any one of the characterizations of 1-40 wherein: (a) the first wavy seal surface section has a largest projection/recess depth dimension of at least 5 mm. 42. An air filter cartridge according to any one of the characterizations of 1-41 wherein: (a) the first wavy seal surface section has a largest projection/recess depth dimension of at least 10 mm. 43. An air filter cartridge according to any one of the characterizations of 1-42 wherein: (a) the first wavy seal surface section has a largest projection/recess depth dimension of at least 15 mm. 44. An air filter cartridge according to any one of the characterizations of 1-43 wherein: (a) the first arcuate seal surface section has no sub-projection therein of greater than 2 mm maximum relief. 45. An air filter cartridge according to any one of the characterizations of 1-44 wherein: (a) the first arcuate seal surface section has no sub-recess therein of greater than 2 mm maximum relief. 46. An air filter cartridge according to any one the characterizations of 1-45 wherein: (a) the first arcuate seal surface section is a non-wavy section. 47. An air filter cartridge according to any one of the characterizations of 1-46 wherein: (a) each recess section in the first wavy seal surface section, extends over a radial arc of no more than 180°. 48. An air filter cartridge according to any one of the characterizations of 1-47 wherein: (a) each recess section in the first wavy seal surface section, extends over a radial arc of no more than 170°. 49. An air filter cartridge according to any one of the characterizations of 1-48 wherein: (a) each recess section in the first wavy seal surface section, extends over a radial arc of no more than 150°. 50. An air filter cartridge according to any one of the characterizations of 1-49 wherein: (a) each recess section in the first wavy seal surface section, extends over a radial arc of at least 60°. 51. An air filter cartridge according to any one of the characterizations of 1-50 wherein: (a) each recess section in the first wavy seal surface section, extends over a radial arc of at least 90°. 52. An air filter cartridge according to any one of the characterizations of 1-51 wherein: (a) each recess section in the first wavy seal surface section, extends over a radial arc of at least 110°. 53. An air filter cartridge according to any one of the characterizations of 1-52 wherein: (a) each projection section in the first wavy seal surface section, extends over a radial arc of no more than 180°. 54. An air filter cartridge according to any one of the characterizations of 1-53 wherein: (a) each projection section in the first wavy seal surface section, extends over a radial arc of no more than 170°. 55. An air filter cartridge according to any one of the characterizations of 1-54 wherein: (a) each projection section in the first wavy seal surface section, extends over a radial arc of no more than 150°. 56. An air filter cartridge according to any one of the characterizations of 1-55 wherein: (a) each projection section in the first wavy seal surface section, extends over a radial arc of at least 60°. 57. An air filter cartridge according to any one of the characterizations of 1-56 wherein: (a) each projection section in the first wavy seal surface section, extends over a radial arc of at least 90°. 58. An air filter cartridge according to any one of the characterizations of 1-57 wherein: (a) each projection section in the first wavy seal surface section, extends over a radial arc of at least 110°. 59. An air filter cartridge according to any one of the characterizations of 1-58 wherein: (a) the first wavy seal surface section includes first and second, opposite, end terminii recess sections. 60. An air filter cartridge according to any one of the characterizations of 1-58 wherein: (a) the first wavy seal surface section includes first and second, opposite, end terminii projection sections. 61. An air filter cartridge according to any one of the characterizations of 1-60 wherein: (a) the first wavy seal surface section is a non-arcuate wavy seal surface section. 62. An air filter cartridge according to any one of the characterizations of 1-60 wherein: (a) the first wavy seal surface section is an arcuate wavy seal surface section. 63. An air filter cartridge according to any one of the characterizations of 1-62 wherein: (a) the first wavy seal surface section has contoured first perimeter-direction length L1; (b) the first wavy seal surface section has a non-contoured first perimeter-direction length dimension of L2; (i) the ratio of L1to L2being no greater than 2.5. 64. An air filter cartridge according to the characterizations of 63 wherein: (a) the ratio of L1to L2is no greater than 2.0. 65. An air filter cartridge according to any one of the characterizations of 63 and 64 wherein: (a) the ratio of L1to L2is no greater than 1.6. 66. An air filter cartridge according to any one of the characterizations of 63-65 wherein: (a) the ratio of L1to L2is no less than 1.01. 67. An air filter cartridge according to any one of the characterization of 63-66 wherein: (a) the ratio of L1to L2is no less than 1.03. 68. An air filter cartridge according to any one of the characterizations of 63-67 wherein: (a) the ratio of L1to L2is no less than 1.1. 69. An air filter cartridge according to any one of the characterizations of 1-68 wherein: (a) the first wavy seal surface section has no non-curved surface sub-section therein of greater than 5 mm in perimeter-direction length. 70. An air filter cartridge according to any one of the characterizations of 1-69 wherein: (a) the first wavy seal surface section has no non-curved surface sub-section therein of greater than 3 mm in perimeter-direction length. 71. An air filter cartridge according to any one of the characterizations of 1-70 wherein: (a) the first wavy seal surface section has no non-curved surface perimeter-direction sub-section therein. 72. An air filter cartridge according to any one of the characterizations of 1-70 wherein: (a) the first wavy seal surface section includes at least 3 recesses therein. 73. An air filter cartridge according to any one of the characterizations of 1-72 wherein: (a) the first wavy seal surface section includes no more than 8 recesses therein. 74. An air filter cartridge according to any one of the characterizations of 1-73 wherein: (a) the first wavy seal surface section includes at least 2 projections therein. 75. An air filter cartridge according to any one of the characterizations of 1-74 wherein: (a) the first wavy seal surface section includes no more than 7 projections therein. 76. An air filter cartridge according to any one of the characterizations of 1-75 wherein: (a) the first arcuate seal surface section has a projection-direction seal surface length of at least 150 mm. 77. An air filter cartridge according to any one of the characterizations of 1-76 wherein: (a) the first arcuate seal surface section has a projection-direction seal surface length of at least 200 mm. 78. An air filter cartridge according to any one of the characterizations of 1-77 wherein: (a) the first arcuate seal surface section has a projection-direction seal surface length of at least 250 mm. 79. An air filter cartridge according to any one of the characterizations of 1-78 wherein: (a) the first wavy seal surface section has a perimeter-direction seal surface length of at least 50 mm. 80. An air filter cartridge according to any one of the characterizations of 1-79 wherein: (a) the first wavy seal surface section has a perimeter-direction seal surface length of at least 80 mm. 81. An air filter cartridge according to any one of the characterizations of 1-80 wherein: (a) the first wavy seal surface section has a perimeter-direction seal surface length of at least 100 mm. 82. An air filter cartridge according to any one of the characterizations of 1-80 wherein: (a) the radial seal surface is a radially outwardly directed radial seal surface. 83. An air filter cartridge according to any one of the characterizations of 1-81 wherein: (a) the radial seal surface is a radially inwardly directed radial seal surface. 84. An air filter cartridge according to any one of the characterizations of 1-83 wherein: (a) the radial seal surface has a modified oval shape. 85. An air filter cartridge according to the characterization of 84 wherein: (a) each projection section in the first wavy seal surface section extends to a location tangential to an oval shape comprising first and second, opposite, semi-circular ends with first and second, opposite, straight sides extending therebetween. 86. An air filter cartridge according to any one of the characterizations of 1-85 wherein: (a) the seal surface has a modified oval perimeter shape with: (i) the first arcuate seal surface section extending over a semi-circular arc; (ii) a second arcuate seal surface section opposite the first arcuate seal surface section; (iii) a first side seal surface section extending between the first and second arcuate seal surface sections; the first side seal surface section comprising the first wavy seal surface section; and, (iv) a second side surface section extending between the first arcuate seal surface section and the second arcuate seal surface section; the second side seal surface section being opposite the first side seal surface section. 87. An air filter cartridge according to the characterization of 86 wherein: (a) the second side surface section is a second wavy seal surface section. 88. An air filter cartridge according to any one of the characterizations of 86 and 87 wherein: (a) the second side surface section is a mirror image of first side seal surface section. 89. An air filter cartridge according to any one of the characterizations of 86-88 wherein: (a) the radial seal surface has no straight perimeter-direction seal surface section therein of greater than 15 mm. 90. An air filter cartridge according to any one of the characterizations of 85-89 wherein: (a) the seal surface has no straight perimeter-direction seal surface section therein of greater than 10 mm. 91. An air filter cartridge according to any one of the characterizations of 85-90 wherein: (a) the seal surface has no straight perimeter-direction section therein of greater than 5 mm. 92. An air filter cartridge according to any one of the characterizations of 1-85 wherein: (a) the seal surface has a modified oval perimeter shape with: (i) the first arcuate seal surface section extending over a semi-circular arc; (ii) a second arcuate seal surface section opposite the first arcuate seal surface section and comprising the first wavy seal surface section; (iii) a first side seal surface section extending between the first and second arcuate seal surface sections; and, (iv) a second side seal surface section extending between the first arcuate seal surface section and the second arcuate seal surface section; the second side seal surface section being opposite the first side seal surface section. 93. An air filter cartridge according to claim92the characterization of: (a) the first side seal surface section is a first non-wavy side seal surface section. 94. An air filter cartridge according to any one of the characterizations of 92 and 93 wherein: (a) the second side seal surface section is a mirror image of the first side seal surface section. 95. An air filter cartridge according to any one of the characterization of 92-94 wherein: (a) the first and second side seal surface sections are each straight and parallel to one another, in perimeter-direction. 96. An air filter cartridge according to any one of the characterizations of 1-95 including: (a) a seal support preform thereon positioned to support the seal member during sealing. 97. An air filter cartridge according to the characterization of 96 wherein: (a) the seal member includes a molded-in-place portion defining the radially directed seal member; and, (b) the seal support preform includes a seal support shape embedded in the molded-in-place portion defining the radially directed seal member. 98. An air filter cartridge according to any one of the characterizations of 96 and 97 wherein: (a) the seal support flange has a perimeter shape having a perimeter-direction shape in radial-shape alignment with the radial seal. 99. An air filter cartridge according to any one of the characterizations of 96-98 wherein: (a) the seal support preform defines an air flow passageway having a media pack grid arrangement extending thereacross. 100. An air filter cartridge according to any one of the characterizations of 96-99 wherein: (a) the seal support preform includes a handle bridge thereon. 101. An air filter cartridge according to any one of the characterizations of 96-101 wherein: (a) the seal support preform is positioned at the outlet flow end of the media pack. 102. An air filter cartridge according to any one of the characterizations of 96-101 wherein: (a) the housing seal arrangement includes a molded-in-place portion securing the seal support preform to the media pack; and, surrounding the media pack. 103. An air filter cartridge according to any one of the characterizations of 96-102 including: (a) an end preform spaced from, and separate from, the seal support preform; (i) the second preform including a portion surrounding the media pack. 104. An air filter cartridge according to the characterization of 103 wherein: (a) the second preform includes a handle member in axial alignment with a flow end of the media pack. 105. An air filter cartridges according to any one of the characterization of 1-104 wherein: (a) the media pack has an oval shape with first and second, opposite, curved ends and first and second side section extending therebetween; (i) the first and second side sections having perimeter-direction shapes that mirror one another. 106. An air filter cartridge according to the characterization of 105 wherein: (a) the first and second curved ends of the media pack are semi-circular; and, (b) the first and second side sections of the media pack are straight. 107. An air filter cartridge according to any one of the characterizations of 105 and 106 wherein: (a) the first arcuate seal surface section of the radial seal surface is positioned in perimeter alignment with the first curved end of the media pack. 108. An air filter cartridge according to the characterization of 107 wherein: (a) the first wavy seal surface section is positioned in perimeter alignment with one of the first and second side sections of the media pack. 109. An air filter cartridge according to the characterization of 108 wherein: (a) the first wavy seal surface section is positioned in perimeter alignment with the second curved end of the media pack. 110. An air filter cartridge according to the characterization of 109 including: (a) an installation handle member positioned spaced from the housing seal arrangement and including a handle projection in perimeter alignment with the second curved end of the media pack. 111. An air filter cartridge according to any one of the characterizations of 1-110 wherein: (a) the seal member comprises a molded-in-place member having a hardness, Shore A, of no greater than 24. 112. An air filter cartridge according to any one of the characterizations of 1-111 wherein: (a) the seal member comprises a molded-in-place member having a hardness, Shore A, of no greater than 20. 113. An air filter cartridge according to any one of the characterizations of 1-112 wherein: (a) the seal member comprises a molded-in-place member having an as molded density of no greater than 0.45 g/cu·cm. 114. An air filter cartridge according to any one of the characterizations of 1-113 wherein: (a) the seal member comprises a molded-in-place member having an as molded density of no greater than 0.291 g/cu·cm. 115. An air filter cartridge comprising: (a) a media pack comprising filter media and having first and second, opposite, flow ends; (i) the first one of the opposite flow ends comprising an inlet flow end; (ii) the second one of the opposite flow ends comprising an outlet flow end; and, (iii) the media pack being configured to filter air flowing into the inlet flow end prior to the air exiting the outlet flow end; and, (iv) the media pack has an oval shape with first and second, opposite, curved ends and first and second side sections extending therebetween; (A) the first and second side sections having perimeter-direction shapes that mirror one another; (b) a housing seal arrangement positioned on the media pack; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement comprising a radially directed seal member defining a radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the radial seal surface defining a perimeter-direction in extension around the flow passageway; and, (iv) first and second, non-wavy, arcuate seal surface sections extending over a semi-circular arc; and, (v) first and second, opposite, side seal surface sections extending between the first and second, arcuate, seal surface sections; (A) at least the first side seal surface section being a wavy seal surface section comprising an alternating radial projection/recess configuration. 116. An air filter cartridge according to the characterization of 115 wherein: (a) the second side seal surface section is a mirror image of the first side seal surface section. 117. An air filter cartridge comprising: (a) a media pack comprising filter media and having first and second, opposite, flow ends; (i) the first one of the opposite flow ends comprising an inlet flow end; (ii) the second one of the opposite flow ends comprising an outlet flow end; and, (iii) the media pack being configured to filter air flowing into the inlet flow end prior to the air exiting the outlet flow end; and, (iv) the media pack has an oval shape with first and second, opposite, curved ends and first and second side sections extending therebetween; (A) the first and second side sections having perimeter-direction shapes that mirror one another; (b) a housing seal arrangement positioned on the media pack; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement comprising a radially directed seal member defining a radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the radial seal surface defining a perimeter-direction in extension around the flow passageway; and, (iv) a first non-wavy, semi-circular arcuate seal surface section; (v) a second, wavy arcuate seal section opposite the first, non-wavy, semi-circular seal surface section; and, (vi) first and second, opposite, side seal surface sections extending between the first and second, arcuate, seal surface sections. 118. An air filter cartridge according to the characterization of 117 wherein: (a) the first side seal section is straight. 119. An air filter cartridge according to the characterization of 118 wherein: (a) the second side seal surface section is a mirror image of the first side seal surface section. 120. An air filter cartridge comprising: (a) a media pack comprising filter media and having first and second, opposite, flow ends; (i) the first one of the opposite flow ends comprising an inlet flow end; (ii) the second one of the opposite flow ends comprising an outlet flow end; and, (iii) the media pack being configured to filter air flowing into the inlet flow end prior to the air exiting the outlet flow end; and, (b) a housing seal arrangement positioned on the media pack; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement comprising a radially directed seal member defining a radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the radial seal surface defining a perimeter-direction in extension around the flow passageway; (A) the radial seal surface having a first non-wavy arcuate seal surface section extending over an arcuate extension of at least 60°; and, (B) a first, arcuate, wavy seal surface section comprising an alternating radial projection/recess configuration and extending of an internal arc of no more than 80% of a total perimeter-direction seal surface length of the radial seal surface; (C) the first arcuate seal surface section has a radius of curvature of R1; and, (D) the first wavy section comprises a curved projection/curved recess configuration having at least three recess sections and multiple projection sections; (1) each projection section and each recess section, in the curved projection section/curved recess section configuration of the first wavy seal surface section, having a radius of curvature R2such that a ratio of R1/R2for each is at least 1.5. 121. An air cleaner assembly comprising: (a) a housing including a body and access cover; (i) the housing includes a structural seal surface including a wavy section for sealing there against of a cartridge seal; (b) an air filter cartridge is accord with any one of claims1-120positioned within the housing and releasably sealed to the structural seal surface of the housing. 122. An air cleaner assembly according to the characterization of 121 wherein: (a) the access cover is removably positioned on the housing body. 123. An air cleaner assembly according to the characterization of 121 wherein: (a) the access cover is non-removably positioned on the housing body. VII. An Issue with Certain Seal Definitions A. A Potential Issue with Certain Seals Having Seal Variations as Previously Described—the Appearance of Proper Installation and Sealing in an Incorrect Housing;FIGS.62-66 A potential issue with certain radial seal arrangements having “wavy seal” or “projection/recess” sections or patterns, in accord with the examples and descriptions above, is that a result from their use could, under certain circumstances, be a cartridge that appears to be installed in a housing when proper sealing does not occur. This issue can be understood by referring to the examples of the following discussion, andFIGS.62-66. Attention is first directed toFIG.62.FIG.62is a drawing schematically depicting the seal arrangement506ofFIG.36, with certain information added to the drawing to facilitate understanding of the issue. Referring toFIG.62, seal arrangement506, as previously indicated, includes seal surface506scomprising a radially directed seal surface. In the example, the radially directed seal surface506sis configured to show a radially outwardly directed radial seal in the terms described herein. (The issue at hand, it will be understood, can also be raised in the context of an inwardly directed seal). In particular, and referring toFIG.62, the example seal arrangement506depicted, as previously described, is oval (in particular, racetrack) and includes first and second straight, parallel, opposite side sections509,510; and, first and second (arcuate) end sections508,510x, as discussed above. In the example, end section508is semi-circular and end section510xis not. Rather, section510xhas a “projection/recess” or “wavy” shape, in terms used herein. In general terms, the opposite straight side sections509,510, can be described as being tangential with a hypothetical, standard, seal surface engagement perimeter. In the example, the hypothetical standard, seal surface engagement perimeter would be oval, and the hypothetical oval seal surface engagement definition would comprise sides co-extensive (co-linear) with the opposite straight sides509,510, and two opposite semi-circular ends. In the example, one such semi-circular end is defined co-extensive (co-linear) with the seal surface506at508, and the other semi-circular end is hypothetical and is depicted by segment line510z, extending as an arc co-linear (co-extensive) with sides509,510. Herein, such an oval shape for the hypothetical standard shape, again, will sometimes be referred to as “racetrack”, since it has two opposite parallel sides, and two semi-circular ends. It should be understood that the hypothetical, oval, seal surface engagement definition is not meant to depict the specific size of the housing component to which the sealing would occur. Indeed, typically, the seal material in the housing seal arrangement506will be compressed when installed to seal against a surrounding seal surface. (That is, the likely surrounding housing seal surface, being for a standard oval (racetrack) seal, would typically have the same shape, but be slightly smaller in perimeter size). Referring toFIG.62, it can be seen that a cartridge having the depicted seal could be installed in a housing having a housing seal surface (non-wavy or non-projection/recess) that was configured for installation of a cartridge that has an oval (racetrack) seal shape of the right size, for example, having a racetrack shape (hypothetical oval shape) corresponding to the opposite sides509,510, the end508, and the hypothetical end510z. This is facilitated, in part, by the fact the projections512in surface510xterminate tangential to the hypothetical standard shape seal line section510z. Thus, if an air cleaner had a non-projection/recess or non-wavy housing seal surface that was configured to be fully engaged by an oval (racetrack shape) in the seal, of the right size, a cartridge having the seal ofFIG.62would fit adequately such that it could appear to be properly installed even though, as a result of the recesses511, it might not be properly sealed. Herein, when it is said that a housing seal surface or housing seal surface portion of an air cleaner housing or structure, to which the cartridge is sealed, has a “non-wavy” or “non-projection/recess shape” it is meant that portion does not include any recesses or projections therein, for example over a length of extension of at least 50 mm, typically at least 100 mm. Often, there is no projection or recess in the structure or housing surface where sealing occurs, over its complete length of extension. In this context, an arcuate section of the structure in the housing, which may be an end of an oval definition, for example, should not be interpreted as a “recess” or “projection” itself. That is, what is meant to be referenced is localized projections or recesses, such as would have a length between opposite ends of no greater than about 40 mm, and usually considerably less. Of course, this issue of an appearance of sealing would not pose a problem with a seal of the type ofFIG.62, if there were no such housing in existence. It would primarily be a problem if the cartridge were otherwise sized in accord with a cartridge having a seal perimeter corresponding to the same hypothetical standard shape but not having the proper seal shape configured to sealingly engage the housing. InFIG.63, an example of a similar potential problem is shown in context of a seal arrangement482, of the type referenced above in connection with inFIG.24. In particular, seal arrangement482defines a seal perimeter489s, in this instance an outwardly directed radial seal, having two opposite, semi-circular, end sections1001,1002; and, two opposite, sides1003,1004, each having a wavy, or projection/recess seal section (1003w,1004w) therein. Here, the hypothetical standard shape (oval, racetrack) seal surface engagement definition would comprise a racetrack shaped oval with opposite curved ends1002,1001; and, opposite straight sections1006,1007; the straight sections1006,1007in the example, being tangential to the curved ends1002,1001. Again, if the resulting cartridge happened to be the same size as a cartridge that did not have the seal surface sections1003,1004, but rather had a seal surface perimeter defined in accord with hypothetical standard-geometric shape (oval) seal surface engagement perimeter (and configured to fit a housing designed for such a cartridge) the cartridge having a seal in accord withFIG.63could appear to be sealed even though it might not be, as a result of recesses1010r. This is in part, because the outward projections1010pextend tangential to the opposite straight sides1006,1007of the hypothetical standard shape (oval) seal surface engagement perimeter. Again, the appearance of sealing would primarily be an issue if there happened to exist a housing having a seal surface that was configured to properly receive, with sealing, a cartridge having such a racetrack shaped, oval, radial seal surface but with no wavy or projection/recess sections. Thus far, the example hypothetical standard shape seal perimeters referenced in this section have been ovals, in the example racetrack shaped, seeFIGS.62and63. Alternatives are possible. For example, a similar problem could arise if they hypothetical standard perimeter shape were an oval shape having a first pair of narrowly curved opposite ends, and opposite outwardly curved sides extending therebetween, an example of such a shape being elliptical. Of course, still further hypothetical, standard perimeter shapes are possible, another example being circular. InFIG.64, a hypothetical standard geometric shape seal perimeter having a perimeter shape that is generally a polygonal shape, for example, a rectangular shape (with rounded corners or vertices) is shown. The example seal surface1020is a radially outwardly directed seal surface, but similar principles can be applied with an inwardly directed seal surface. The seal surface1020can be said to define a hypothetical rectangular seal surface engagement defined by the radially outwardly directed seal surface sections1022,1023, and the opposite hypothetical side segments1024,1025. Again, the issue discussed in this section is exacerbated by tangential alignment between the hypothetical side sections1024,1025and the projections1028, in the presence of the recesses1029. Once again, a problem could arise if there were a housing in existence that was designed to be radially engaged by a seal having the hypothetical rectangular seal surface definition shown. If there was no such housing, the apparent installation without sealing issue is less likely to occur. InFIG.65, a schematic cross-sectional view depicting a portion1039of a housing seal part (structure) having a seal surface for an outwardly directed radial seal is depicted. The housing seal surface is shown at1040. Seal surface1040is meant to be understood to not include undulations or wavy sections (projection/recess sections) for proper radial engagement with a cartridge housing seal surface. Rather, it is mean to be a fairly standard shape surface that assumes a standard non-wavy (or non-projection/recess) seal surface of a cartridge radial seal meant to engage it. In the particular example, the seal surface1040is designed to surround the sealing surface of a cartridge, and thus the cartridge seal would be a radially outwardly directed seal. InFIG.66, the same housing seal surface section1040is shown (schematically) engaged by a seal1041portion of cartridge having a seal surface1045with a wavy or projection/recess seal section1045indicated in a portion where the engagement is shown occurring. It can be seen that the cartridge might appear to be installed, yet one would understand that there could be recesses in the seal surface that could prevent actual sealing from occurring. Still referring toFIG.66, attention is directed to region1046. This region indicates where seal support (for example, of the preformed plastic support) would be located on the cartridge, to radially support the seal. InFIG.66, the seal arrangement is schematically depicted, and only molded-in-place seal portions are shown. It is also noted that in the examples depicted inFIGS.62-66, the seals involved were radially outwardly directed. Similar principles/issues can be applied with radially inwardly directed seals, and with a hypothetical standard shape seal perimeter defined along the radially inside or inwardly directed surface of the seal (tangential, for example with wavy or projection/recess sections). It is noted that the issue characterized in this section is exacerbated, when the structural surface of the housing, to which seal engagement with the cartridge occurs, is positioned recessed within the housing, and out of sight of the service provider as the cartridge is installed. This is the case, however, with many air cleaner assemblies. B. Further Regarding the Concept of a “Hypothetical, Standard, Shape Seal Perimeter” By the term “hypothetical, standard shape, seal perimeter” and variants thereof, as used herein, reference is meant to a hypothetical shape which does not have projections, recesses or undulations in it, but rather corresponds to a perimeter shape that would be defined generally by non-undulating, (non-wavy or non-projection/recess) portions of a corresponding seal surface, in some instances with straight or arcuate lines extending therebetween, where “wavy”, “undulating” or projection/recess perimeter seal portions are found in the actual seal surface. As referenced above, such “hypothetical, standard shape, seal perimeters” will often be: oval, and in some examples, racetrack; polygonal (for example rectangular) or circular. However, alternatives are possible. It is not specifically required that the hypothetical line sections be tangential with projections of projection/recess sections within the cartridge. However, examples in which such a tangential relationship is found, in outwardly directed radial seals, were provided inFIGS.62-64for an understanding of the potential problem of apparent fit in a housing that was designed to take the standard seal. It is noted that the hypothetical, standard shape, seal perimeter is typically defined by lines that are co-linear or co-extensive: with portions of a seal shape that are not projection/recess portions; and, with corresponding furthest projecting portions of the seal, (in a direction that will engage a sealing surface in use). That is, the hypothetical perimeter is typically defined by a seal shape that corresponds to non-projection/recess portion(s) of the seal surface that is/are most compressed during sealing. There is no specific requirement that the non-projection/recess portions of the actual seal perimeter that defines the hypothetical standard seal perimeter be continuous throughout their extension. For example, in the arrangement depicted inFIG.63, there are two such sections (semi-circular ends) spaced from another by projection/recess sections. There is also no specific requirement that the hypothetical standard shape seal section be defined by any particular amount of co-extension. However, typically the hypothetical shape will be co-linear (co-extensive) over at least 20%, often at least 30%, usually at least 40%, of an extension of the seal surface, whether in one continuous portion or several portions added together. C. A First Solution to the Issue of Apparent Sealing: Avoid when Possible Providing Air Cleaner Housings of Appropriate Size for the Apparent Sealing to Occur Of course, as referenced above, a first solution of the type of the issue described would to avoid having any otherwise corresponding housing or other structure in existence that is of the appropriate size (but which does not have an appropriate wavy or projection/recess housing seal section) and thus cannot receive a cartridge in general accord with the issues raised in the previous section, i.e. with the appearance of installation without actual sealing. This solution can be effective whether the radial seal is radially inwardly or outwardly directed; the examples discussed previously indicating the principles in association with an outwardly directed seal, but being applicable to inwardly directed seals as discussed. In some instances, however, it may not be practical to use this approach to the issue. For example, an original equipment manufacturer may have previously defined the particular housing size, shape and location, which needs to be reproduced in the new housing products. Also, it may be desirable to provide new cartridges that are such that portions of them (or the housing) can be made with only minor modification to previously existing cartridge or housing manufacture. D. A Second Approach to the Apparent Sealing Issue: Providing the Cartridge with a Second Projection/Recess Housing Radial Seal Section in Appropriate Axial Overlap with, and Adjacent to, the Projection/Recess (Wavy) Cartridge Housing Seal Surface Section; the Second Seal Section being Sized and Positioned to Seal to a Non-Projection/Recess (Non-Wavy) Housing Seal Surface Section of a Corresponding Housing A second approach, for such a situation, especially with certain prior art air cleaner housing seal surface definitions, can be understood by consideration ofFIGS.67-70A. Referring toFIG.67, a filter cartridge1050is depicted having a seal arrangement1051positioned on a media pack1050m. Seal arrangement1051depicted, comprises a radially outwardly directed seal arrangement. The example seal arrangement1051is shown defining a hypothetical standard shape seal perimeter having an oval, and in the particular example racetrack, shape, although alternatives are possible. The actual seal surface1051has opposite straight sides1052,1053, with opposite curved ends1054,1055; each of the ends1054,1055being arcuate and having an undulating, wavy or a projection/recess configuration of projections1056and recesses1057. In the example, the seal surface defined by straight sections1051,1052, and projection/recess (wavy) sections1054,1055comprises a primary or first outwardly directed radial seal (or seal section) for engagement with an appropriate shaped (surrounding) housing surface. The issue, then, is providing the cartridge with a seal arrangement that will properly seal even when the housing has a housing seal surface that is not undulating or wavy, but rather is configured to properly seal with a standard seal of the hypothetical, standard shape seal perimeter. This solution is including by providing one or more second (or secondary) radial seal surface portions or sections in axial alignment with the undulating portions1054,1055. An example of this can be understood by non-projection/recess secondary seal portions1060,1060a,FIG.67. The secondary seal portion1060is viewable in enlargement, in the schematic depiction ofFIG.67A. It is noted that seal surface section1060of the example depicted is not projection/recess (wavy) but rather is of a more standard shape so as to facilitate sealing. It is an extension that engages side sections1052,1051at transition (radial seal) portions, see for example, transition portion1065,FIG.67A. As will be apparent from the following, it is not necessarily meant by the example ofFIG.67Athat the shape of the second seal section1060must be completely non-projection/recess. Indeed, it could have relatively small projections and/or recesses in it. It is also not necessarily meant that the hypothetical, standard, shape seal to which it would conform, would be tangential to the various projections1056. Indeed, in the example depicted, secondary or second seal section1060is specifically not tangential, but rather is recessed inwardly from projections1056. However, in the example, section1060is not recessed as far as recesses1057. What is important is that it (surface portion1060) can radially engage standard (non-wavy) seal surface structure, for example in a housing, in spite of the portion recess portion of1054, without leaking being an issue. InFIG.67B, a fragmentary, schematic, cross-sectional view taken along lines67B-67B,FIG.67Aand between two of the projections1056is depicted. A support1070for the seal, is depicted, the support1070comprising a portion of a preform. A part of the second surface section1060is viewable. InFIG.68, a schematic, partially cross-sectional view, is depicted, a showing a portion of a seal arrangement having a shape in general accord with seal arrangement1050,FIG.67, installed in a “standard” housing that has a seal surface meant to be engaged by a standard shape seal, for example, a seal arrangement that does not have an undulating surface. Referring toFIG.68, the housing seal surface, in general accord withFIG.66is shown at1040. A projection portion1056of the seal is shown in overlap, indicating where compression would occur. The secondary seal projection is shown at1060. It can be seen that an appropriate seal, completely around the cartridge seal, will occur, since surface1060is positioned where it can provide, as a secondary seal section, sealing to a portion of surface1040. It should be understood thatFIG.68is schematic to show the principles involved in the use of the secondary seal surface section1060. It is not meant to suggest the parts depicted are configured exactly to the sizes they would be, if meant to be used together. As indicated above, the secondary seal surface does not necessarily have to be provided in a completely smooth, non-undulating, (non-projection/recess or non-wavy) condition. It can include projections and/or recesses therein sufficiently small so as not to interfere with sealing to a desired (non-wavy or non-projection/recess) surface of a housing seal section. An example of this can be understood fromFIGS.69A,69B. Referring toFIG.69A, a fragmentary view of the cartridge1080is shown comprising the media pack1081with seal arrangement1082thereon. The portion depicted is generally analogous to the portion depicted inFIG.67A, with a projection/recess contour provided by projections1083and recesses1084, positioned on (around) a curved end1085of the seal arrangement1082. At1087, a secondary seal section is depicted. This secondary seal section is axially positioned relative to projections1083and recesses1084, i.e. it extends around the same curved end1085with portions1087atherein, that project slightly outwardly. Otherwise, the shape of section1087would correspond to a standard non-projection/recess shape. It is intended that the sections1087abe sufficiently shallow in projection, so that they will still compress adequately and seal to housing seal surface in a housing of appropriate shape and size, but having a non-projection/recess (non-wavy) surface definition. Thus, surface section1087comprises a portion axially positioned relative to an undulating portion of seal surface1082, so as to provide desirable sealing if the cartridge1080is installed in the wrong housing. InFIG.69B, a cross-sectional depiction taken along line69B-69B,FIG.69Ais provided, for facilitating understanding. Note seal support1088. InFIGS.69C and69D, a further example of an arrangement having a secondary seal surface section for sealing to a housing seal surface that is configured for a standard shape seal is provided. Referring toFIG.69C, a cartridge1090is depicted in schematic fragmentary view comprising media1091, with housing seal arrangement1092thereon. The housing seal arrangement1092in the example, would generally comprise a radially outwardly directed seal having a configuration generally in accord with a standard racetrack shape, oval shape, definition, except for projection/recess contour at one or both curved ends. In the example depicted, such a contour is shown at1093, comprising projections1094and recesses1095. Here, a secondary seal surface section is shown at1097, in the example generally not having any projection/recess or undulating definition therein. It is defined to axially overlap (adequately) with standard shaped portions of seal surface1092, see region1098as an example, to help ensure sealing if the cartridge1090is installed in the wrong housing. InFIG.69D, a schematic cross-sectional view taken generally along line69D-69D,FIG.69is shown. Note seal support1099. From the above, it can be understood that a wide variety of secondary seal sections can be provided. The primary issue is to ensure such a section is provided in axial overlap with a projection/recess seal section, at a location such that it can engage a standard housing seal surface if the cartridge is accidently installed in a housing having such a surface. In more general terms, then, it can be understood that an approach to the issue of having a cartridge with a wavy, undulating, or projection/recess seal section in the primary seal surface, appearing to be properly installed and sealed to a housing seal surface (structure) not having a wavy, undulating or projection/recess seal surface, is to provide the cartridge with a secondary seal surface or surface section in axial overlap with the wavy or undulating (projection/recess) portion(s) of portions of the seal. By “axial overlap”, in this context, it is not necessarily meant that it is only in axial alignment with the wavy or undulating (projection/recess) section(s) throughout its extension. It could extend completely around the cartridge. However, when the cartridge includes non-wavy seal section(s) it can merely transition into those (or align with those) as shown and described. The term “axial overlap” or “axial alignment” in this context, it is meant to refer to a location along a length dimension of the seal and cartridge in a direction generally orthogonal to a perimeter direction of the seal. In a typical arrangement such as those shown, in which the media pack comprises an arrangement having opposite flow ends or media ends, the secondary seal surface section(s) would typically be located between the first seal surface section (or primary seal surface section) at undulating wavy locations; and, the media or media pack, or at least in a direction toward an opposite (remote) end of the media or media pack. The example described in connection withFIGS.67-69B, can be characterized as creating unique radial seal configurations, in which a first seal portion (in the example, the primary seal portion, which includes the “wavy” sections therein) has a greater “largest cross-sectional dimension” thereto, than a largest cross-sectional dimension of a seal perimeter that would be defined by the second seal surface sections (i.e. the non-wavy sections). Typically, the difference in largest cross-sectional dimension for these would be at least 1 mm, usually at least 2 mm, often at least 3 mm, and in some instances, 4 mm or more. It is typical then, the first seal portion includes at least one portion that extends, in a sealing direction, at least 1 mm further, usually at least 2 mm further, often 3 mm or more further, in a sealing direction than does an axially adjacent section of a second radial seal portion. It is noted that this is unusual configuration, whether the first seal portion has a wavy section or not. Typically, a radial seal would taper downwardly in size, toward a tip remote from the media, rather than tapering downwardly in size in a direction away from the seal tip, and toward the media (or toward a remote end of the media or media pack). Herein, in this context, the reference to “first” and “second” seal sections or portions, is not meant to suggest that the entire first and second seals are separate from one another along their complete extension. As indicated in the examples, portions of the second seal can extend co-extensive with portions of the first seal, for example, in non-wavy or non-projection/recess sections. The spaced axial alignment is specifically meant to reference portions of the second seal that are associated with or adjacent wavy or projection/recess portions of the first seal. E. Configuration of a Special Housing for a Projection/Recess Contoured Seal that would not Allow for Sealing of a Standard Seal or Standard Seal Section,FIGS.70and70A In some instances, it may also be desirable to have a surface in a housing or other structure for sealing that is configured such that it cannot readily accept a standard cartridge. Principles relating to this can be understood from the above descriptions, andFIGS.70and70A. Referring toFIG.70, a schematic depiction is provided showing a housing section1100. Although not shown in detail in the figure, surface section1101, which would be a housing sealing surface section, would be configured with a (wavy) or projection/recess seal section for engagement with an appropriate (wavy) or projection/recess cartridge seal surface, such as the one discussed above in connection withFIGS.67-67B. Unlike the arrangement ofFIG.68, the particular housing section1101depicted inFIG.70, includes an outward recess at1105, which would not be sealingly engaged any secondary seal projection that is an analog to projection1060,FIG.67, or which would be found on a standard shaped seal. Referring toFIG.70A, this is exemplified by housing seal arrangement1051, installed in housing section1100, analogously toFIG.68. Here, the projection1060is shown in the recess1105, but not sealed. It is to be assumed that the seal projection arrangement1056would be engaging an associated undulating (wavy or projection/recess section of housing portion1100. F. A Third Solution—Providing the Seal Surface with an Interference Projection Arrangement Another approach to preventing the appearance of a properly installed cartridge, in a housing that can accept a cartridge corresponding to the hypothetical, standard-geometric, shape seal perimeter, would be to ensure that there is an interference projection arrangement in or on the seal. The term “interference projection arrangement” is meant to refer to a region of one or more projections in the seal surface that extend(s) sufficiently far so as to cause interference with an attempt at installation in the wrong housing. This could, for example, be one or more exaggerated projection(s) in a projection/recess seal portion, but it could also be one or more projections provided somewhere else in the seal surface. It can be provided in a supported portion of the seal surface, or a portion not specifically supported for the interference projection arrangement, as may be desirable. The amount of projection beyond any standard geometric-shaped seal perimeter (outwardly if radially directed seal is involved; inwardly if a radially inwardly directed seal is involved) that is sufficient to provide interference may be varied depending on a variety of factors including the materials of the seal arrangement and the size of the cartridge, etc. In general, all that is required is enough projection to ensure that a person attempting installation will become aware that the cartridge is not a proper one for the housing, in which an effort is being made to install the cartridge. A projection amount, in some instances, of only 1 millimeter, may be adequate. In typical instances, it may be desirable to provide an interference projection amount of at least 2 mm, and often at least 4 mm. Examples of such arrangements are discussed below. Of course the mating seal surface in a housing, for which it is intended to install the cartridge, would preferably have an appropriate receiver recess arrangement for the interference projection arrangement, in a manner that does not interfere with sealing of the cartridge to the surface. Herein above, it was indicated that the projection arrangement can be in a specifically locally supported portion of the seal surface. By this, it is meant that the seal support positioned within the seal material could include a projection thereon in specific alignment with, and corresponding to, the interference projection arrangement, if desired. On the other hand, the projection arrangement in the seal surface could be positioned in a portion in which the seal support underneath the seal material, is not modified from its configuration in order to otherwise support the seal arrangement. This latter will sometimes be referred to as a “not specifically locally supported for the interference projection” arrangement, but, of course, it is not meant to be suggested by this that there would not necessarily be any support to the seal at this location. VIII. Some Selected Seal Variations and Related Principles, FIGS.71-83 A. A First Example Type,FIGS.71-73 As indicated generally herein, it is important that a cartridge for an air cleaner housing be configured such that it can be readily, properly, installed and sealed in an intended, proper, housing. It is also particularly important, where possible, that the air cleaner system be configured so that an inappropriate, unapproved, cartridge cannot be readily installed and appear to be sealed. In general, principles described herein above, in connection with arrangements having projection/recess contour sections therein, can be used to facilitate cartridge designs that meet these issues. Some additional variations and principles can be understood from the examples ofFIG.71-73. InFIG.71, a schematic depiction is provided of a portion of a cartridge housing seal arrangement including a projection/recess contour. The sketch ofFIG.71is schematic and is meant to reference a projection/recess (wavy) seal section on a curved (arcuate) end of the cartridge having a radially outwardly directed seal surface. The cartridge can otherwise have a standard racetrack-shape hypothetical seal surface, but alternatives are possible. The principles described in connection withFIG.71can be applied with alternate shaped seals, and alternately directed seal surfaces. This will be understood from the following. Referring toFIG.71, it will be understood that the arrangement depicted includes projection/recess or wavy contour comprising, in the example, projections1201; relatively deep recesses1202between the projections1201, and relatively shallow (optional) projections1204, between end projections12010of the three projections1201, and adjacent non-wavy or non-projection/recess portions1205of a corresponding seal perimeter. In general terms used herein, line1210would comprise the hypothetical oval (racetrack) shape seal perimeter, with an undulating wavy or projection/recess portion1215extending around a curved (arcuate) perimeter section. Portion1215includes projections1201that do not extend to a location tangential to the perimeter1210, but rather extend radially (outwardly) across that perimeter1210in a sealing direction. Further, the various recesses1202,1204, extend radially inwardly from that hypothetical perimeter1210. Thus, the portion1215of the seal1210comprising the projection/recess or wavy portion, includes one or more sections that extend across (i.e. to locations on both sides of) the hypothetical standard shape (racetrack) seal perimeter line1210. Typically, and preferably in the direction extending (in a sealing direction) toward a housing seal surface to be engaged, at least selected portions of the seal extend to at least 1 mm, typically at least 2 mm; and often at least 2.5 mm, and in some instances at least 3 mm from (away from) the hypothetical standard-geometric shape seal perimeter line1210. Since the seal,FIG.71, is configured as a radially outwardly directed seal, it comprises the tips of projections1201, shown extending over (past) the line1120. The dimension corresponding to this extension, for the example depicted, is dimension EE. Typically, at least selected portions extending across the line1210in a direction opposite to that of projection1201sealing surface, would extend (opposite the sealing direction) to a location at least 1 mm, often at least 2 mm, and typically 3-8 mm from the line1210. An example is shown by dimension ED for recesses1202. In the example, relatively shallow end recesses or recess sections1204would still typically extend inwardly (or across) the hypothetical line1210by a distance of at least 0.5 mm, and usually at least 1 mm. Some example useful dimensions can be understood from the following: EA=107.4 mm diameter; EB=118.2 mm diameter; EC=at least 5 mm, for example 5-15 mm, as an example, 9.3 mm; ED=at least 2, for example, 2-8 mm, e.g. 5.4 mm; EE=3.9 mm; EF=4 mm radius; EG=11 mm radius; EH=6 mm radius; EI=10 mm radius; and, EJ=42°. Of course, these are meant to be examples only, and alternatives are possible. It is noted that the relatively shallow end recesses1204can facilitate fitting the cartridge into the intended housing. Of course, if the seal was configured to be radially inwardly directed, the seal projections1201would be directed radially in a sealing direction, inwardly, and the seal recesses1202,1204would be directed (oppositely) radially outwardly. An advantage provided by such an arrangement, is that if the housing is analogously configured for such a seal surface, it will be more difficult to position, in the housing, a cartridge that is not the appropriate one for that housing. Further, because of the extension of projections1201well beyond the hypothetical standard-geometric shape seal perimeter1210, in the direction of sealing, the projections1201would tend to interfere with installation in a housing section configured to mate with such a seal. That is, projections1201, then, comprise an interference projection arrangement of a type referenced above. The principles described in connection withFIG.71can be applied in a variety of alternate seal arrangements. InFIG.72, an example is shown in which the projection/recess portion does not extend around a curve, i.e. is not arcuate, but rather is an otherwise straight section of the seal, for example, analogous to section1024,FIG.64. Here, the hypothetical standard shape perimeter line is straight, as indicated at1230, and it can be seen that projections1231extend radially outwardly or in a sealing direction past that line1230, and recesses1232extend radially inwardly (or in opposite directions of the sealing) from that line. It is noted that end of recesses1232can be somewhat shallower by comparison to the arrangement ofFIG.71if desired. Similar dimensions to those discussed above in connection withFIG.71can be used. In the example depicted, inFIG.72, some example dimensions are provided as follows: EO=9.3 mm; EN=6.4 mm; EM=at least 2, for example 2-7 mm. InFIG.73, an analog toFIG.72is depicted, except that the radial seal is meant to be radially inwardly directed, with the hypothetical straight line segment indicated at1240; projections1241extending across that line radially inwardly in the direction of sealing; and, recesses1242extending radially outwardly away from that line. Thus, the arrangement ofFIG.73is the same asFIG.72, except flipped in reverse for an inwardly directed seal rather than outwardly directed seal. Some example dimensions provided in the example ofFIG.72are as follows: ET=3 mm; ES=6.4 mm; and, ER=at least 2, for example 2-7 mm. In general terms, arrangements in accord withFIGS.71-73can be understood to provide a general principle that, in some instances, it may be desirable to provide a projection/recess surface that extends across (i.e. to location at both sides of) a standard hypothetical seal definition, to projections and one side or recesses on the other. Typically, when such an arrangement is used, at least one (and typically selected ones) of the projections will extend at least 1 mm and usually at least 2 mm from the hypothetical seal definition. Often, the selected projections will extend at least 3 mm, and sometimes at least 4 mm (for example 3-9 mm) beyond the hypothetical seal definition line. At least one of the recesses (for example, an end recess) will often extend at least 0.5 mm. Often at least one recess will end at least 1 mm, and typically 3-8 mm beyond the line, at least the deepest recesses used. It can also be understood that, there will be in such instances, and if desired, and related instances, an “tip” amplitude of the largest projection with respect to a deepest recess on at least on one side (associated) thereof, of a total extension of at least 4 mm, often at least 5 mm, typically at least 6 mm, sometimes at least 8 mm. Such a minimum amplitude can be provided on both sides of the projection, if desired, but uneven amounts of extensions or amplitudes between the two sides are possible, as shown by end projections in the arrangement ofFIG.71. B. “Custom” Seal Definitions,FIGS.74-76 As explained generally, it is desirable to provide air cleaner arrangements, which are designed to preferably only receive a proper cartridge, authorized or approved, for the air cleaner assembly and equipment of concern. In some instances, the original equipment vehicle or equipment manufacturer will wish to have a preferred “custom” or “authorized” cartridge for an otherwise fairly standard air cleaner package. By “custom” in this context, what is meant is that the manufacturer of the vehicle or other equipment with which the air cleaner is used, may prefer a cartridge that can only be properly sealed to the installed air cleaner housing. For example, the manufacturer of the vehicle or other equipment with which the air cleaner is used, may prefer only authorized cartridges that meet certain minimum filtration performance characteristics (e.g. efficiency, pressure drop, dust loading capacity, or filter life). The techniques described herein can be applied for such custom applications in a fairly straightforward manner. Examples can be understood from the following descriptions ofFIGS.74-77. Referring first toFIG.74, a cartridge seal perimeter is schematically depicted at1260. The seal perimeter1260is a modified racetrack shaped oval, with opposite straight sides or side sections1261,1262and opposite curved (arcuate) ends (or end sections)1263,1264. End1263, in the example depicted, is shown configured with a projection/recess or wavy contour generally analogous to that depicted schematically inFIG.71. End1264, on the other hand, is configured to provide for a custom part with what could otherwise have been a more widely used standard configuration. Assume for purposes of this review, that the more widely used configuration would have comprised end1264having a semi-circular shape, with no projection or recess definition therein. The custom arrangement depicted inFIG.74includes a modification from this end at1264, and in particular, includes projection1168. The projection can be made sufficiently large to inhibit installation of the cartridge in a housing configured for the “standard” definition provided and thus be an interference projection arrangement. The customer can be provided with a housing configured with a recess to properly receive the seal1260having the definition at1268, and thus the cartridge would properly seal to that housing alone. The projection1268may include a localized corresponding seal support projecting therein, or it may be molded in overlap with a seal support having a curve generally corresponding to an end1264, without any specific support the projection1268. Either approach can be used. A variety of alternatives can be implemented using these principles. An example is shown inFIG.75at1270. Again, the example is a racetrack configuration with: opposite straight sides1271,1272; a first projection/recess end1273; and, with a contour at opposite curved end1275, in this instance comprising three projections1278. Even if the cartridge was otherwise the same as cartridge1260,FIG.74, as long as the housing is shaped to engage projections1278, and none of the projections1278is in alignment with projection1268,FIG.74, the housing would provide a custom arrangement even relative to the arrangement1260,FIG.74. Still referring to the seal perimeter1270,FIG.75, it is noted that the end of the seal perimeter at1275does correspond to a curved end having a projection/recess definition comprising the projections1278and selected recesses1279therebetween. It is noted that the recesses1279do not curve inwardly but rather have slightly outwardly (seal directed) bowed shapes, in the example, the bowed sections aligning with the hypothetical seal perimeter. It is also noted that inFIG.75, the projection/recess definition at end1273is generally analogous to that discussed above, in connection withFIG.71, although alternatives are possible. InFIG.76a variation in these principles is shown at seal surface1280. Here, again, the depiction is in connection with a racetrack shaped seal having opposite straight sides1281,1282and opposite curved ends1283,1284. Here, the opposite ends1183,1184are mirror images of one another, each comprising a projection/recess (or wavy) contour, in the example generally in accord withFIG.76. The arrangement ofFIG.76indicates further an additional manner in which custom designing of a seal surface can be provided. Although the examples and principles discussed in connection withFIGS.74-76are shown in the context of a racetrack shaped seal, they can be applied in a variety of other contexts, including, for example, polygonal (for example, rectangular) shape seals, alternate oval shape seals, circular seals or seals in which the projection/recess contour is in otherwise straight sections, as opposed to curved sections. Also, projection/recess contours can be provided in both arcuate section(s) and otherwise straight section(s) of the same seal. The principles, of course, can be applied in an radially inwardly directed seal as well as an radially outwardly directed seal. C. Variations in Projection and/or Recess Shape,FIG.77-83A In the examples depicted herein thus far, many of the “projection” and/or “recess” sections of the various seal definitions provided, are generally smooth, arcuate, curved shapes, with a single inflection point therebetween; i.e. where one arc recess switches to an arc of an adjacent projection. The term “projection/recess”, “wavy” or “undulating” and variations thereof, as used herein, in reference to a cartridge seal surface, are not meant to suggest, however, that the shape referenced is necessarily a smooth curve throughout the seal section definition. Indeed, the terms are meant to include a wide variety of possible variations from smooth curves and other variations. Some examples can be understood from the descriptions in this section concerningFIGS.77-83A. Referring first toFIG.77, the intent is to show, schematically, a seal projection which is not defined to a smoothly curved region. Referring toFIG.77, a fragmented section of seal surface is schematically depicted at1500, and is meant to depict a portion of an outwardly directed seal surface with sealing forces being the direction of double-headed arrow1501to a surrounding housing seal. Thus in the seal surface section1500depicted, there is a projection at1505, bordered on opposite sides by adjacent recesses1506. The projection1505is of a shape that is characterized herein as a “segmented” projection. That is, the projecting shape comprises a plurality of segments1505s. In the example, the segments1505sare each straight or nearly straight, but alternatives are possible. The segments could be bowed slightly outwardly or be bowed slightly inwardly, (or be different from one another) for example, and the end projection1505could still be shaped appropriately to operate as a projection in the seal surface engaging a housing seal surface of appropriate definition even including ones designed to receive a corresponding smoothly curved projection. That is, the housing seal surface section of a surrounding housing would not necessarily need to have a segmented seal engagement surface, provided the segment1505sare sized and located, and the seal material is sufficiently compressible, so as to conform to a housing seal surface of a more smoothly curved definition. In the example ofFIG.77, the recesses1506are shown not segmented. They could be segmented, however, in general accord with the principles described. Also, the principles could be applied with a projection that is a smooth arcuate curve, with only the recesses segmented. Also, it is noted that in the example ofFIG.77, the recesses1506are shown symmetrical, i.e. of the same size and shape. Alternatives are possible, including ones of the types shown above in connection withFIGS.71-73. Further, there is no specific requirement that if a projection and/or recess has a segmented shape, that: all projection/recesses in the same seal surface would necessarily have a segmented definition; or, even if that more than segmented projection and/or recess is provided, the segmented definitions will be the same. In general, all that is required so that projection/recess shape(s) used be sufficient to engage properly in housing seal surface with which it is intended to seal. An intent with respect to this portion of description, is to indicate that even when the housing seal surface is configured with smooth curves, the cartridge seal surface, configured to engage that seal surface section, may be defined with segments or other alternatives from a smooth curve, provided the variations are sufficiently small so as to allow compression to cause the conformity needed for good sealing. Thus, this section is meant to indicate that the terms “projection”, “recess”, “wavy” and variants thereof, as used herein, are not meant to suggest only smoothly curved surfaces, but rather may have a shape definition that varies therefrom. Referring still toFIG.79, it is noted that the particular truncated sections1525sdepicted, creates symmetrical sides to the corresponding projections1525. Alternatives are possible. InFIG.78, an analog toFIG.77is shown, the intent being to show similar understanding with respect to a radially inwardly directed seal. In part, seal surface1510is intended to seal in the direction of arrow1511, to a portion of a housing that the seal surface1510surrounds; i.e. surface1510is directed for radially inwardly sealing. Here, the radially inwardly directed projection1515is shown with a segmented definition generally in accord with definition1505,FIG.77, between recesses1516. The same types of variations in segments, segment shape, number of segment projections or recesses, etc. discussed above in connection withFIG.77can be applied in connection with the arrangement ofFIG.78. Another variation in projections or recess shape can be a “single” truncated definition as opposed to having multiple segments. An example is shown inFIG.79. Referring toFIG.79, the seal surface is shown at1520. In the example, it is a portion of a surface extending over an arc, such as an end of an otherwise racetrack shape seal. It is an outwardly directed seal surface1520, configured for sealing with a surrounding portion of a housing. Projections1525are shown, as well as recesses1526. Here the projections1525are truncated in the example by straight segment. That is, a smooth arcuate curvature to each of the projections1525is curtailed or truncated by segments1525s. In the example, the segments1525sare straight, although they can be provided with alternate definitions such as bowed slightly outwardly or bowed slightly inwardly, etc. In general, what is required is that the truncation1525sare sized and positioned such that they will seal even to a housing surface that is otherwise configured for a fully arcuate projection. Still referring toFIG.79, it is noted that the truncated sections are generally selected so as to create symmetry between the two sides of the projection on which they are located. Alternatives are possible, and are meant to be included within the meaning of “truncated” and variants thereof used herein. Of course, analogous principles can be applied in addition, or in the alternative, to the recesses526. A variety of specific projection shapes can be used in the same seal surface, as can be a variety of recess shapes. The principles described in connection withFIG.79can also be provided in an arrangement configured for radially inwardly directed sealing. An example of such an arrangement is shown atFIG.80at seal surface1530, which is intended to schematically depict a seal surface of a cartridge which is configured to surround a portion of a housing during seal. Inwardly directed projections1535are shown truncated, with non-truncated recesses1536therebetween. Again, variations in principles discussed above in connection with surface1520can be applied. Also, it is noted that the truncation could be in the recesses1536, as opposed to the projections1535, or in both. InFIG.81, a variation is depicted with an outwardly directed seal surface1540having truncated projection1545with recess sections1546; the recess sections1546themselves, having a slightly outwardly bowed shape. Again, such a configuration can be sealed to a housing surface that is configured to take a regular outwardly curved projection with inwardly curved recesses therebetween, provided the truncation1545recesses1546are of appropriate size and shape; and, the material of the seal is sufficiently compressible and deformable. InFIG.82, an analogous variation is shown for an inwardly directed seal by1550at inward projections1555and recesses1556having inwardly bowed shapes. InFIGS.83and83A, still further possible variations in a projection/recess or wavy seal contour are depicted. InFIG.83, a seal surface1570is shown. The seal surface is meant to be understood to be a cartridge sealing surface facing in the general direction of arrow1571; i.e. radially outwardly, and comprising spaced projections1575and recesses1576. Here the projections1575are shaped with side undercuts or indentations indicated generally at1580. In the example, each projection1575has a pair of opposite undercuts1580, although alternatives are possible. Surfaces such as surface1570can be pushed into sealing engagement with the housing seal surface that does not have an analogous shape, but rather is configured for projections without undercuts, provided the material is sufficiently compressible, and the undercuts are appropriately sized. On the other hand, projections such as projections1575can be configured to push into a housing surface having mating undercuts with the projection1575snapping around a portion of that housing surface. InFIG.83A, a variation is shown in which certain projections1590each have one side1591that does not have an undercut or recess, and one side1592that does. The example ofFIG.83Acan be otherwise analogous to the arrangement ofFIG.83. The seal variations discussed in this section above are meant to indicate a variety of general principles. A primary one is that the term “projection/recess”, variants thereof, and/or such terms as “wavy” and “undulating” are not meant to necessarily define a seal surface with smooth curves throughout, unless it is otherwise noted. The surface can comprise segments, bowed sections, undercuts, etc., and still be sized and shaped to fit an appropriate housing using principles herein. Indeed, in many instances, as long as the material is sufficiently compressible, and variations from a smooth curvature are kept relatively small, a seal surface that does not have smooth curved sections can even engage, and seal, to a housing or structural seal surface that does have smoothly curved, wavy (or projection/recess) sections. IX. Example Principles Relating to Air Leaner Assembly Configuration and its Manufacture InFIGS.84-86, schematic depictions are provided to assist in understanding typical air cleaner manufacture, and cartridge manufacture, using principles described herein. Referring first toFIG.84, a portion of an air cleaner assembly is depicted at1600. The portion1600is intended to be that portion of the air cleaner assembly which includes a housing seal surface1601for engagement by a seal surface on a cartridge, which cartridge seal surface is in accord with selected general definitions herewith. The example depicted in one in which housing section1600is an outlet section1600x, with filtered air flow leaving through outlet1605. The seal surface1601depicted is molded and generally configured to sealingly receive a cartridge outwardly directed radial seal, otherwise having a racetrack shape hypothetical seal surface with opposite straight side sections1610,1611, and opposite curved end sections1612,1613. Each of sections1612,1613includes a projection/recess, wavy or undulating contour portions comprising three outward projections1615separated by inwardly projecting sections1616. Of course, alternate shapes can be used. It is noted that in the example sections1615are smooth and arcuate in the projection outwardly, but they can still be sealed by a seal surface that does not necessarily have a matching smooth arcuate shape, but rather includes at least one projection or recess is segmented or includes bows, truncations, etc., as described, provided they are in seal material sufficiently compressible and configured to engage the surface sections1615appropriately to compress or deform into sealing engagement. In general, it will often be the case (and is typically preferred) that the housing seal arrangement comprise a “supported” seal. By this, it is meant that the seal surface compresses back against a support structure. Typically, the support structure is provided by preform part of the cartridge as indicated in certain previously described examples. InFIG.85, a fragmented depiction of a preform housing seal support arrangement is depicted (schematically) at1620. The portion, of the preform which backs up the seal, is indicated generally at1621. Curved sections1622and projection1623are shown in surface1621. When included in a cartridge having an appropriate shape, projections1623would extend into (and support) projections in the seal surface, and recesses1622would receive recesses in the seal surface. This can be understood by reference toFIG.86, which depicts a cartridge1650configured with a preform1620of the type described and shown, which has been over molded and secured in place by molding material1655, providing an outwardly directed seal surface1656sized to engage seal surface1601,FIG.84, in a sealing manner. Of course, variations as described above, can be provided in seal surface1656. It will be understood that some variations in the various projections of the seal surface1656can be provided, without changing the specific shape of the support1620. For example, truncated surfaces or segmented surfaces, etc. can be used with the same preform1620. This can be an advantage in manufacture, since it would not necessarily be required that a new preform shaped1620be made of every possible seal shape. Referring toFIG.85, it is noted that adjacent the tips, the projections1623can be characterized as having a maximum dimension adjacent a tip thereacross, or width Dx, and the various recesses1622can be characterized as having a largest dimension thereacross of Dy, with Dy/Dxbeing at least 2, (i.e Dyis at equal to at least 2×Dx) typically at least 3, and often 5 or more. That is, the projections1623are relatively narrow, and the recesses1612are relatively wide. This is in spite of the fact that in the resulting seal surface,FIG.86, the projections are relatively wide, and the recesses are relatively narrow. This, too, indicates that the support projections1623do not necessarily mimic the shape of the projections in the resulting seal, which would be a function of the mold. Rather, the projections1623need to be positioned appropriately to resist the compression of the seal surface in the projection area, a desired amount. In the example cartridge ofFIG.86, a media pack1650mis shown schematically and truncated. The media pack is configured for straight through flow, and may comprise, for example, a coiled arrangement of fluted material secured to facing materials, as previously discussed. Alternatives, of course, are possible. X. Application of the Principles in Connection with Non-Straight Through Flow Arrangements In the examples depicted thus far herein, the media packs were generally configured for straight through flow, with opposite inlet and outlet flow surfaces; aligned with an air flow direction through a region surrounded by the seal surface (whether sealing is radially inward or outward). The principles described however, can be applied in media packs, which have media surrounding an open interior. An example of this can be understood by referenced toFIG.87. InFIG.87, cartridge1700is depicted comprising media1701surrounding a cartridge interior1702. The media, for example, can be pleated, but that is not specifically required. The media1701extends between first and second end caps1705,1706. The end cap1706is an open end cap with aperture1707therethrough. The cartridge1700includes a seal surface1710, which includes a projection/recess section comprising, in the example depicted, three radially outwardly directing projections1715. In a typical arrangement, end piece1705would be closed. It is noted that the seal surface1710is generally circular in its shape, other than where the projection/recess section is shown. That is, surface1710defines a hypothetical circular shape seal surface. Alternatives are possible. It is noted that the media pack1708is shown somewhat conical, increasing in cross-dimension extension from end cap1705and end cap1706. Alternatives are possible, including cylindrical arrangements, or arrangements with an alternate taper. In more general terms, the media adjacent each end can be characterized as having a “largest cross-sectional dimension”, whether circular, oval or otherwise shaped. That largest cross-sectional dimension can be the same at both ends, or be larger at one end than the other (for example, larger at the open end than the closed; or, larger at the closed end than the open). Of course, the same principles described in connection withFIG.87can be applied with arrangements that have radially inwardly directed seals, if desired. Further, it is noted that the seal surface1710depicted is in a position, which surrounds an outer perimeter of the seal, at a location projecting radially outwardly from an adjacent end of the media1708. This variation can be used with other configurations described above. The surface1710could alternately be positioned on a projecting portion of the end piece1706backed up by seal support extending axially from the adjacent end of the media1701, if desired. In general,FIG.87is meant to indicate that the principles described herein above can be applied in arrangements of a variety of shapes and media types. The various variations and examples described then can be applied in arrangements such as those depicted and described forFIG.87. XI. Some Final Thoughts and Observations Herein, a variety of useful and advantageous features in air cleaner design and filter cartridge design are described and shown. These features can be used together, or separately, depending on the application, while still achieving some advantage according to the present disclosure. There is no specific requirement that an air cleaner assembly, filter cartridge, or component of one of these, include all of the features characterized herein. It is also noted thatFIGS.1-61and characterizations relating to them, were include previously filed U.S. Provisional U.S. Ser. No. 62/543,090, filed Aug. 9, 2017, the disclosure of which has been incorporated herein by reference. Many of the features of that provisional are also included in later describedFIGS.62-87, in various forms. In this section, some general overall observations are made. In Section A, below, some selected overall general terms and/or issues are addressed. In Section B, below, selected, example, characterizations of arrangements in accord with the present disclosure are made. A. Selected Summary of Certain Terms, Characterizations and Typical Features Many of the features characterized herein relate to specific advantageous air filter cartridges. The air filter cartridges can be of a variety of types, for a variety of uses. In many instances, they will be of a type that comprise removable and replaceable components in an air cleaner system, such as an air cleaner arrangement for filtering engine air intake for a vehicle or other equipment. Such cartridges are generally sized and configured to be readily installed in a housing. Herein, cartridges of particular concern are characterized as having a housing seal arrangement including a “radially directed” seal member or by similar terms. A radial seal member, is, generally, a seal member that seals to either surrounding structure of an air cleaner arrangement in use, or which surrounds structure of an air cleaner arrangement in use, sealing thereto. This is meant to distinguish radial arrangements from axial seal arrangements or pinch seal arrangements, as described. The “structure” reference is typically a portion of an air cleaner housing, but alternatives are possible. With a radially outwardly directed seal on the cartridge, the sealing is to surrounding structure. With a radially inwardly directed seal, the sealing is to structure that is surrounded by the seal. In many instances, the radial seal is characterized in terms of a “perimeter-direction” feature or by various related terms. “Perimeter-direction” and variants thereof, in this context, is meant to refer a direction around the seal surface as opposed to an axial direction, which would correspond to a direction between the tip of the seal surface and a direction therefrom. Herein, the term “wavy” or variants, is used in many instances to characterize one or more portions of the seal surface in the perimeter-direction. Such terms are characterized herein and are meant to be interchangeable with the term “radial projection/recess configuration” and variants thereof. There is no specific requirement that any projection/recess or wavy section comprise smooth curves. A variety of alternatives to these are characterized. It is noted that in some instances, reference is made to a first feature and a second feature as associated. “Associated” in this context will have the meaning indicated by the situation characterized, and generally is meant to refer to one of two conditions: either the second feature being a next adjacent feature of the first feature; or, the associated second feature being something engaged by the first feature during use. Herein, the term “non-wavy” and ‘non-projection/recess” is sometimes used to indicate a portion of a seal surface or other structure that does not include recesses or projections therein. The reference is meant to localized features. For example, a prior art “racetrack radial seal”, which for example, can correspond to the hypothetical shape ofFIG.62could be characterized as having a non-wavy or non-projection/recess configuration, even though the two semi-circular ends themselves, can be seen as projections. Herein, a wavy or projection/recess portion of a seal surface can sometimes be characterized as having one or more “end recesses.” In this context, the end recess is meant to refer to a recess in a selected wavy section that is at one of two opposite ends thereof, in the direction of extension of the wavy recess. Intermediate recesses would be recesses spaced from those ends by at least one projection. Herein, in connection with projections sometimes reference is meant to a “tip amplitude.” This meant to refer to a projected dimension of extension or projection between a deepest portion of the next adjacent or associated recesses, and a tip in the projection. Herein, reference is sometimes made to “sealing direction.” The term is meant to refer to the direction of engagement between the seal surface and a structure to which is sealed. With radial seals, by reference to the cartridge and seal surface, thus an outwardly directed seal has an outward sealing direction, and an inwardly directed seal has an inward sealing direction. Herein, reference is sometimes made to “first and second seals” or “seal portions” axially aligned. It is not meant to be indicated that these first and second seals (that are axially aligned) do not, at least in some portion of extension completely around the perimeter, share portions of common extension. This will be understood by reference to examples ofFIGS.67-67B. It is noted that a typical first seal surface having a projection/recess or wavy configuration in accord with the description, at least at that location, that does not correspond to or mimic a perimeter shape of a next adjacent part of a media perimeter. By not “corresponding to” or “mimicking” in this context, it is merely meant to indicate that the perimeter definition of the media and the perimeter definition of the seal in axially aligned regions are not the same general shape with respect to the seal surface, the intent is to indicate the contour definitions. With respect to the media perimeter definition, reference is meant to the overall perimeter shape adjacent the end piece having a seal thereon. This overall media definition, in the case of pleated media, is mean to refer to a definition created by the pleat tips. When the media is not pleated adjacent its perimeter, a general shape is all that is referenced. In each of the examples depicted, these type of characterizations apply. B. Characterizations of Some Example Useful Applications of the Principles Described Herein 1. An air filter cartridge comprising: (a) a media pack comprising filter media and having first and second, opposite, flow ends; (i) the first flow end comprising an inlet flow end; (ii) the second flow end comprising an outlet flow end; and, (iii) the media pack being configured to filter air flowing into the inlet flow end prior to the air exiting the outlet flow end; and, (b) a housing seal arrangement positioned on the media pack; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement comprising a first radially outwardly directed, seal member defining a first radial seal surface oriented to releasably, sealingly engage surrounding structure, in use; (iii) the first radial seal surface defining a perimeter-direction in extension around the flow passageway; and, (iv) the first radial seal surface including: (A) at least a first seal surface section including a radially directed portion comprising an alternating radial projection/recess configuration comprising at least two projections and three recesses in extension along a portion of the perimeter-direction; and, (B) at least 30% of extension of the radial seal surface, in the perimeter-direction, not comprising an alternating projection/recess configuration and having no recesses therein. 2. An air filter cartridge comprising: (a) a media pack comprising filter media; and, (b) a housing seal arrangement positioned on the media pack; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement comprising a first radially directed seal member defining a first radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the first radial seal surface defining a perimeter-direction in extension around the flow passageway; and, (iv) the first radial seal surface including: (A) a first seal surface section including a radially directed portion comprising an alternating projection/recess configuration comprising at least two projections and three recess in extension along a portion of the perimeter-direction of the radial seal surface; and, (B) a second seal surface section configured to fully, radially, sealingly engage an associated portion of surrounding structure; the associated portion of surrounding structure having no projections or recesses therein over a continuous perimeter-direction length of at least 100 mm. 3. An air filter cartridge according to characterization 2 wherein: (a) the media pack comprises filter media defining first and second, opposite, flow ends. 4. An air filter cartridge according to characterization 3 wherein: (a) the first radial seal surface section comprises first and second, opposite, side seal surface sections extending between first and second, opposite, arcuate seal surface sections. 5. An air filter cartridge comprising: (a) a media pack comprising filter media and having first and second, opposite, flow ends; (i) the first one of the opposite flow ends comprising an inlet flow end; (ii) the second one of the opposite flow ends comprising an outlet flow end; and, (iii) the media pack being configured to filter air flowing into the inlet flow end prior to the air exiting the outlet flow end; and, (b) a housing seal arrangement positioned on the media pack; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement comprising a first radially directed seal member defining a first radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the first radial seal surface defining a perimeter-direction in extension around the flow passageway; (A) the first radial seal surface having a first non-wavy arcuate seal surface section extending over an arcuate extension; and, (B) a first, arcuate, wavy seal surface section comprising an alternating radial projection/recess configuration and extending over an internal arc of no more than 80% of a total perimeter-direction seal surface length of the radial seal surface; (C) the first, arcuate, wavy seal surface section having a radius of curvature of R1; and, (D) the first, arcuate, wavy seal surface section comprises a curved projection/curved recess configuration having at least three recess sections and multiple projection sections; (1) each projection section and each recess section, in the curved projection section/curved recess section configuration of the first wavy seal surface section, having a radius of curvature R2such that a ratio of R1/R2for each is at least 1.5. 6. An air filter cartridge according to characterization 5 wherein: (a) the first non-wavy arcuate seal surface extends over an arcuate extension of at least 60°. 7. An air filter cartridge according to characterization 6 wherein: (a) the first non-wavy arcuate seal surface extends over a continuous arcuate extension of at least 60°. 8. An air filter cartridge according to characterization 6 wherein: (a) the first non-wavy arcuate seal surface includes multiple, spaced, arcuate sections therein together totaling an arcuate extension of at least 60°. 9. An air filter cartridge according to characterization 5 wherein: (a) the first non-wavy arcuate seal surface extends over an arcuate extension of at least 20°. 10. An air filter cartridge according to characterization 5 wherein: (a) the first non-wavy arcuate seal surface extends over an arcuate extension of at least 30°. 11. An air filter cartridge according to characterization 5 wherein: (a) the first non-wavy arcuate seal surface extends over an arcuate extension of at least 40°. 12. An air filter cartridge according to any one of characterizations 10 and 11 wherein: (a) the first arcuate seal surface section, of the radial seal surface, is configured to extend over an internal arc of at least 130°. 13. An air filter cartridge according to any one of characterizations 10-12 wherein: (a) the first arcuate seal surface section, of the radial seal surface, is configured to extend over a semi-circular internal arc. 14. An air filter cartridge according to any one of characterizations 2-13 wherein: (a) the housing seal arrangement comprises a first radially outwardly directed radial seal surface. 15. An air filter cartridge according to any one of characterizations 2-13 wherein: (a) the housing seal arrangement comprises a first radially inwardly directed radial seal surface. 16. An air filter cartridge according to any one of characterizations 1-15 wherein: (a) the first radial seal surface includes at least a first seal surface section and second seal surface section, in extension in the perimeter-direction, each including a radially directed portion comprising an alternating projection/recess configuration. 17. An air filter cartridge according to characterization 16 wherein: (a) the second seal surface section comprises at least three projections with recesses therebetween, in extension in the perimeter-direction. 18. An air filter cartridge according to any one of characterizations 1-17 wherein: (a) at least 40% of an extension of the first radial seal surface, in a perimeter-direction, not comprising an alternating projection/recess configuration and having no recesses therein. 19. An air filter cartridge according to any one of characterizations 1-18 wherein: (a) at least 50% of an extension of the first radial seal surface, in a perimeter-direction, not comprising an alternating projection/recess configuration and having no recesses therein. 20. An air filter cartridge according to any one of characterizations 1-19 wherein: (a) at least 50% of an extension of the first radial seal surface in the perimeter-direction is a continuous extension not comprising an alternating projection/recess configuration and having no recesses therein. 21. An air filter cartridge according to any one of characterizations 1-20 wherein: (a) the first radial seal surface includes at least two, spaced, sections together totaling at least 30% of a first seal surface extension, in the perimeter-direction, and not comprising an alternating projection/recess configuration and having no recesses therein. 22. An air filter cartridge according to any one of characterizations 1-21 wherein: (a) the first radial seal surface includes multiple spaced sections in the perimeter-direction, including at least two sections that each comprise at least 15% of perimeter-direction extension of the radial seal surface, and each not comprising an alternating projection/recess configuration and having no recesses therein. 23. An air filter cartridge according to any one of characterizations 1-22 wherein: (a) the media has an oval outer perimeter adjacent an end thereof. 24. An air filter cartridge according to any one of characterizations 1-23 wherein: (a) the media has an racetrack outer perimeter comprising two opposite straight side sections and two opposite semi-circular end sections, adjacent an end thereof. 25. An air filter cartridge according to any one of characterizations 1-24 wherein: (a) the first radial seal surface includes a perimeter direction shape having: two, opposite, straight seal surface sections and two, opposite, arcuate seal surface sections; (i) the straight seal surface sections extending between the arcuate seal surface sections. 26. An air filter cartridge according to characterization 25 wherein: (a) each one of the two, opposite, arcuate seal sections has an alternating projection/recess configuration having at least two projections and three recesses in extension along a portion of the perimeter-direction. 27. An air filter cartridge according to characterization 12 wherein: (a) each one of the two, opposite, arcuate seal sections comprises first and second end projections; and, first and second end recesses; (i) each end projection being spaced from an adjacent one of the two opposite straight sections by at least an adjacent one of the end recesses. 28. An air filter cartridge according to characterization 27 wherein: (a) each one of the two, opposite, arcuate seal sections includes an associated intermediate recess adjacent each end projection on an opposite side thereof from an adjacent one of the end recesses; (i) each associated intermediate recess having a greater depth of extension in a direction away from an outer most portion of the projection than does each next adjacent end recess. 29. An air filter cartridge according to characterization 28 wherein: (a) each end projection has a first recess/projection tip amplitude relative to an adjacent intermediate recess that is at least 3 mm larger than a second recess/projection tip amplitude relative to an adjacent one of the end recesses. 30. An air filter cartridge according to any one of characterizations 1-29 wherein: (a) the first radial seal surface comprises: (i) a portion defining a hypothetical standard shape seal surface engagement perimeter co-linear with at least one non-projection/recess seal section of the first radial seal surface; and, (ii) at least a first projection/recess seal surface section including a radially directed portion comprising a first surface definition with an installation interference projection arrangement that extends, in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter. 31. An air filter cartridge according to characterization 30 wherein: (a) the installation interference projection arrangement comprises at least one projection that extends, in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter, at least 1 mm. 32. An air filter cartridge according to any one of characterizations 30 and 31 wherein: (a) the installation interference projection arrangement comprises at least one projection that extends, in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter, at least 2 mm. 33. An air filter cartridge according to any one of characterizations 30-32 wherein: (a) the installation interference projection arrangement comprises multiple projections that extend, in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter. 34. An air filter cartridge according to any one of characterizations 1-33 wherein: (a) the first radial seal surface has a portion defining a hypothetical standard shape seal surface engagement perimeter co-linear with at least one non-projection/recess seal section of the first radial seal surface; and, (b) the first radial seal surface includes at least a first projection/recess seal surface section including a radially directed portion comprising a first surface definition with at least a first seal surface portion that extends in a direction across the hypothetical standard shape seal surface engagement perimeter. 35. An air filter cartridge according to characterization 34 wherein: (a) the first radial seal surface includes a portion that extends at least 1 mm in each direction of extension across the hypothetical standard shape seal surface engagement perimeter. 36. An air filter cartridge according to any one of characterizations 34 and 35 wherein: (a) the first radial seal surface definition includes a portion that extends at least 2 mm in each direction of extension across the hypothetical standard shape seal surface engagement perimeter. 37. An air filter cartridge according to any one of characterizations 34-36 wherein: (a) the first radial seal surface definition includes at least one projection that extends at least 3 mm in a selected direction from the hypothetical standard shape seal surface engagement perimeter. 38. An air filter cartridge according to any one of characterizations 34-37 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is oval. 39. An air filter cartridge according to any one of characterizations 34-38 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is racetrack. 40. An air filter cartridge comprising: (a) a filter media pack; and, (b) a housing seal arrangement; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement including a first radial seal member having a first radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the first radial seal surface defining a perimeter-direction in extension around the flow passageway; (iv) the first seal surface having a portion defining a hypothetical standard shape seal surface engagement perimeter co-linear with at least one non-projection/recess seal section of the first radial seal surface; and, (v) the first radial seal surface including at least a first projection/recess seal surface section including a radially directed portion comprising a first surface definition with an installation interference projection arrangement that extends, in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter. 41. An air filter cartridge according to characterization 40 wherein: (a) the interference projection arrangement comprises at least one projection that extends, in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter at least 1 mm. 42. An air filter cartridge according to any one of characterizations 40 and 41 wherein: (a) the interference projection arrangement comprises at least one projection that extends, in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter at least 2 mm. 43. An air filter cartridge according to any one of characterizations 40-42 wherein: (a) the interference projection arrangement comprises multiple projections that extend in a sealing direction, from the hypothetical standard shape seal surface engagement perimeter. 44. An air filter cartridge comprising: (a) a filter media pack; and, (b) a housing seal arrangement; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement including a first radial seal member having a first radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the first radial seal surface defining a perimeter-direction in extension around the flow passageway; (iv) the first radial seal surface having a portion defining a hypothetical standard shape seal surface engagement perimeter co-linear with at least one non-projection/recess seal section of the first radial seal surface; and, (v) the first seal surface including at least a first projection/recess seal surface section including a radially directed portion comprising a first surface definition with at least a first seal surface portion that extends in a direction across the hypothetical standard shape seal surface engagement perimeter. 45. An air filter cartridge according to characterization 44 wherein: (a) the first surface definition includes at least a first seal surface portion that extends at least 1 mm in each direction of extension across the hypothetical standard shape seal surface engagement perimeter. 46. An air filter cartridge according to any one of characterizations 44 and 45 wherein: (a) the first surface definition includes at least a first seal surface portion that extends at least 2 mm in each direction of extension across the hypothetical standard shape seal surface engagement perimeter. 47. An air filter cartridge according to any one of characterizations 6 wherein: (a) the surface definition includes at least one projection that extends at least 3 mm in a selected direction from the hypothetical standard shape seal surface engagement perimeter. 48. An air filter cartridge according to any one of characterizations 43-47 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is co-linear with at least 20% of the actual seal perimeter. 49. An air filter cartridge according to any one of characterizations 43-48 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is co-linear with at least 30% of the actual seal perimeter. 50. An air filter cartridge according to any one of characterizations 43-49 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is co-linear with at least 40% of the actual seal perimeter. 51. An air filter cartridge according to any one of characterizations 51-50 wherein: (a) the portion of the hypothetical standard shape seal surface engagement perimeter that is co-linear with the actual seal perimeter comprises a single continuous portion of the hypothetical standard shape seal surface engagement perimeter. 52. An air filter cartridge according to characterization 51 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is oval. 53. An air filter cartridge according to characterization 52 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is racetrack. 54. An air filter cartridge according to any one of characterizations 51-53 wherein: (a) the portion of the hypothetical standard shape seal surface engagement perimeter that is co-linear with the actual seal perimeter comprises spaced sections of the hypothetical standard shape seal surface engagement perimeter. 55. An air filter cartridge according to any one of characterizations 40-52 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is selected from: polygonal, and circular. 56. An air filter cartridge according to characterization 55 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is rectangular. 57. An air filter cartridge according to characterization 55 wherein: (a) the hypothetical standard shape seal surface engagement perimeter is circular. 58. An air filter cartridge comprising: (a) a filter media pack; and, (b) a housing seal arrangement; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement including a first radial seal member having a first radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the first radial seal surface defining a perimeter direction in extension around the flow passageway; and, (iv) the first seal surface including a first projection/recess seal surface section having at least one projection/recess amplitude, on at least one side thereof, of at least 5 mm; and, (v) the first seal surface including a non-projection/recess seal surface definition of at least 30% of the perimeter direction in extension around the flow passageway. 59. An air filter cartridge according to characterization 58 wherein: (a) the first seal surface includes a portion of non-projection/recess surface definition that extends continuously along at least 30% of the perimeter direction in extension around the flow passageway. 60. An air filter cartridge according to any one of characterizations 1-59 wherein: (a) the housing seal arrangement includes a second radial seal surface portion oriented to releasably, sealingly, engage on an air cleaner in use; (i) the second radial seal surface portion being in axial alignment with the first radially directed portion; and, (ii) the second radial seal surface portion being configured to sealingly engage a non-projection/recess seal surface of a housing. 61. An air filter cartridge according to characterization 60 wherein: (a) the second seal surface portion is a non-projection/recess seal surface portion. 62. An air filter cartridge comprising: (a) a filter media pack; and, (b) a housing seal arrangement; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement including a first radial seal member having a first radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the first radial seal surface defining a perimeter direction in extension around the flow passageway; and, (iv) the first radial seal surface including a first radially directed portion comprising a radial projection/recess configuration; and, (v) the housing seal arrangement including a second radial seal member having a second radial seal surface portion oriented to releasably, sealingly, engage an air cleaner in use; (A) the second radial seal surface portion being in axial alignment with the first radial seal surface portion; and, (B) the second seal surface portion being configured to sealingly engage a non-projection/recess seal surface of a housing. 63. An air filter cartridge according to any one of characterizations 1-62 wherein: (a) the media pack has an oval cross-sectional shape in extension between the first and second, opposite inlet and outlet, flow ends; (i) the oval cross-sectional shape defining first and second curved ends with sides extending in a therebetween; (b) the housing seal arrangement is positioned at the outlet flow end; and, (c) a handle arrangement is positioned on a preform adjacent the inlet flow end with a handle member in overlap with one of the first and second curved ends. 64. An air filter cartridge according to characterization 63 wherein: (a) the radial seal surface member defines a first projection/recess contour section in axial alignment with the first curved end of the media pack; and, (b) the handle arrangement is positioned in axial overlap with the second curved end of the media pack. 65. An air filter cartridge comprising: (a) a filter media pack having first and second, opposite, ends; and, (b) a housing seal arrangement positioned adjacent to the media pack first end; (i) the housing seal arrangement defining an air flow passageway; (ii) the housing seal arrangement including a first radial seal surface oriented to releasably, sealingly, engage an air cleaner in use; (iii) the first radial seal surface defining a perimeter direction in extension around the flow passageway; and, (iv) the first radial seal surface including a first radially directed seal portion having a first, largest, cross-sectional dimension; and, (v) the housing seal arrangement including a second radial seal surface portion oriented to releasably, sealingly, engage an air cleaner in use; (A) the second radial seal surface portion being in axial alignment with the first radially directed seal portion and spaced from the first radial seal portion in the direction of the media pack second end; and, (B) the second seal surface portion having a second, largest, cross-sectional dimension that is smaller than the first, largest, cross-sectional dimension. 66. An air filter cartridge according to characterization 65 wherein: (a) the first radial seal surface portion of the second radial seal surface portion are each outwardly directed radial seal sections. 67. An air filter cartridge according to any one of characterizations 65 and 66 wherein: (a) the second, largest, cross-sectional dimension is at least 2 mm smaller than the first, largest, cross-sectional dimension. 68. An air filter cartridge according to any one of characterizations 65-67 wherein: (a) the second, largest, cross-sectional dimension is at least 4 mm smaller than the first, largest, cross-sectional dimension. 69. An air filter cartridge according to any one of characterizations 1-68 wherein: (a) the media pack comprises fluted media secured to facing media. 70. An air filter cartridge according to characterization 69 wherein: (a) the media pack comprises a coiled media arrangement. 71. An air filter cartridge according to any one of characterizations 1-70 wherein: (a) the media pack comprises pleated media in extension around an open filter interior. 72. An air filter cartridge according to any one of characterizations 2, 40-62 and 65-69, wherein: (a) the filter media extends between first and second, opposite, end pieces; (i) the first end piece being an open end piece and having the housing seal arrangement thereon; (ii) the second end piece being closed; and, (iii) the media extends around an open filter interior. 73. An air filter cartridge according to characterization 72 wherein: (a) the media is pleated. 74. An air filter cartridge according to any one of characterizations 72 and 73 wherein: (a) the media defines a cylindrical outer perimeter. 75. An air filter cartridge according to any one of characterizations 72 and 73 wherein: (a) the media defines a conical outer perimeter. 76. An air filter cartridge according to any one of characterizations 72 and 73 wherein: (a) the media defines a larger outer cross-sectional dimension adjacent the first end piece than adjacent the second end piece. 77. An air filter cartridge according to any one of characterizations 72 and 73 wherein: (a) the media defines a smaller outer cross-sectional dimension adjacent the first end piece than adjacent the second end piece. 78. An air filter cartridge according to any one of characterizations 1-77 wherein: (a) the cartridge includes a seal support therein embedded within seal material of the housing seal arrangement. 79. An air filter cartridge according to characterization 78 wherein: (a) the seal support includes at least one wide recess on each side of a narrow projection tip. 80. An air filter cartridge according to characterization 79 wherein: (a) the narrow projection tip has a largest cross-dimension of Dx; and, (b) the wide recess has a largest cross-dimension of Dy; (i) Dy being at least 2×X2. 81. An air filter cartridge according to characterization 80 wherein: (a) the narrow projection tip has a largest cross-dimension of Dx; and, (b) the wide recess has a largest cross-dimension of Dy; (i) Dy being at least 4×Dx. 82. An air filter cartridge according to characterization 9 wherein: (a) the narrow projection tip has a largest cross-dimension of Dx; and, (b) the wide recess has a largest cross-dimension of Dy; (i) Dy being at least 5×Dx. 83. An air filter cartridge according to any one of characterizations 1-15 wherein: (a) at least one projection in the first radial seal surface is a segmented projection. 84. An air filter cartridge according to any one of characterizations 1-82 wherein: (a) at least one recess in the first radial seal surface is a segmented recess. 85. An air filter cartridge according to any one of characterizations 1-84 wherein: (a) at least one projection in the first radial seal surface is a truncated projection. 86. An air filter cartridge according to any one of characterizations 1-85 wherein: (a) at least one projection in the first radial seal surface includes at least one undercut side portion. 87. An air filter cartridge according to any one of characterizations 1-86 wherein: (a) at least one projection in the first radial seal surface includes at least two, opposite, undercut side portions. 88. An air filter cartridge according to any one of characterizations 1-87 wherein: (a) at least one recess in the first radial seal surface includes a portion bowed in a direction of a projection. 89. An air filter cartridge according to any one of characterizations 1-88 wherein: (a) at least one projection in the first radial seal surface includes a portion bowed in a direction of a recess. 90. An air filter cartridge according to any one of characterizations 1-89 wherein: (a) the first radial seal surface includes at least 30% of extension, in the perimeter-direction: not comprising an alternating projection/recess configuration, not having a recess therein; and, having a perimeter-direction shape corresponding to a circular arc definition. 91. An air filter cartridge according to any one of characterizations 1-89 wherein: (a) the housing seal arrangement includes a first seal surface portion having a section of wavy shape comprising an alternating projection/recess configuration with: (i) a contoured first perimeter-direction length L1; and, (ii) a corresponding non-contoured first perimeter-direction length L2; (A) wherein a ration of L1/L2is at least 1.01. 92. An air filter cartridge according to characterization 91 wherein: (a) L1/L2is at least 1.03 93. An air filter cartridge according to any one of characterizations 91 and 92 wherein: (a) L1/L2is at least 1.1. 94. An air filter cartridge according to any one of characterizations 1-93 wherein: (a) L1/L2is no greater than 2.5. 95. An air filter cartridge according to characterization 94 wherein: (a) L1/L2is no greater than 2.0. 96. An air filter cartridge according to characterization 95 wherein: (a) L1/L2is no greater than 1.6. 97. An air filter cartridge according to any one of characterizations 91-96 wherein: (a) the first seal surface includes multiple, spaced, wavy sections; and, (b) each wavy section in the seal surface, independently, has: (i) a contoured first perimeter-direction length L1; (ii) a corresponding non-contoured first perimeter-direction length L2; (A) wherein a ration of L1/L2is at least 1.01. 98. An air filter cartridge according to characterization 97 wherein: (a) L1/L2is at least 1.03 99. An air filter cartridge according to any one of characterizations 97 and 98 wherein: (a) L1/L2is at least 1.1. 100. An air filter cartridge according to any one of characterizations 97-99 wherein: (a) L1/L2is no greater than 2.5. 101. An air filter cartridge according to characterization 100 wherein: (a) L1/L2is no greater than 2.0. 102. An air filter cartridge according to characterizations 101 wherein: (a) L1/L2is no greater than 1.6. 103. An air filter cartridge according to any one of characterizations 1-102 wherein: (a) the first seal surface includes at least one perimeter-direction portion having a projection/recess definition that does not correspond to a perimeter shape of a next adjacent media perimeter. 104. An air cleaner assembly comprising: (a) a housing including a body and access cover; (i) the housing includes a structural seal surface including a wavy section for sealing there against of a cartridge seal; (b) an air filter cartridge is accord with at least one of characterizations 1-103 positioned within the housing and releasably sealed to the structural seal surface of the housing. 105. An air cleaner assembly according to characterization 104 wherein: (a) the housing includes an inlet end and an outlet end; and, (b) the housing is configured for side load of the air filter cartridge at a location between the inlet and outlet ends of the housing, see for example,FIG.47. 106. An air cleaner assembly according to characterization 105 wherein: (a) the cartridge is also in accord with at least one of characterizations 63 and 64. 107. An air cleaner assembly according to characterizations 106 wherein: (a) the cartridge is in accord with characterization 64. 108. An air cleaner assembly according to any one of characterization 104-107 wherein: (a) the housing includes a structural seal surface having at least one non-wavy section of at least 100 mm having no projection and no recess therein.
262,215
11857908
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention adds a whole new dimension to air purification by combining methods of renewable energy production with tailored air purification processes. Throughout the specification, wherever practicable, like structures will be identified by like reference numbers. In some figures, components, such as additional electrical connections or fasteners have been omitted for clarity in the drawings. Unless expressly stated otherwise, the term “or” means “either or both” such that “A or B” includes A alone, B alone, and both A and B together. For the purposes of this disclosure, unless specifically stated otherwise, “fluid,” “air,” and “water” may be used interchangeably. Referring toFIG.1, in an embodiment, the invention of the present disclosure includes a body102. The body102may have a front face104, a rear face106, a top end108, a bottom end110, a right wall112, and a left wall114. The body102may be constructed from plastic, polymer, metal, wood, or any other suitable material. In one embodiment, the material is comprised of recycled materials. The body102may be airtight and/or watertight. In such an embodiment, gaskets, rubber, or retainers may be disposed between the components of the body102. As a non-limiting example, the outer edges of the front face104may have a rubber lining that interfaces with the receiving edges of the top end108, the bottom end110, the right wall112, and the left wall114. In one embodiment, the body102is covered with a film or coating to increase the body102's durability and resistance to the elements. In an embodiment, an air intake116is disposed on the body102. In one embodiment, the air intake116is disposed on the bottom portion of the front face104. However, in alternate embodiments the air intake116may be disposed any where on the body102. The air intake116may be a hole. In one embodiment, the air intake hole is rectangular and oblong. However, the air intake hole may be any shape. A grille or a grate116A may traverse the air intake hole. As a non-limiting example, the grate116A may be a series of vertical slats running from the left end of the air intake hole to the right end of the air intake hole. In one embodiment, the grate116A is configured to prevent especially large debris or wildlife from entering the cavity302. In an embodiment, an air exhaust118is disposed on the body102. In one embodiment, the air exhaust118is disposed on the top portion of the front face104. However, in an alternate embodiment, the air exhaust118may be disposed any where on the body102. The air intake116may be configured to accept air or another fluid from outside the body102. The air exhaust118may be configured to expel air that has been purified. The air exhaust118and the air intake116may be in fluid communication. For example, air may enter the air intake116at the same rate that air leaves the air exhaust118. In an embodiment, the air exhaust118may include a grate similar to the grate116A disposed over air intake116. Referring toFIG.2, in an embodiment, the device includes a wind power assembly202. In one embodiment, the wind power assembly202includes one or more wind turbines204. Each wind turbine204may include one or more blades206. The blades206may be attached to a shaft208. In one embodiment, each wind turbine204includes five blades206. In an embodiment, each blade206may have a proximal end and a distal end. The proximal end may be the end of the blade206closest to the shaft208. The distal end of the blade206may be curved with flanges at the outer most edge of the distal end of the blade206. In such an embodiment, the blade206may be configured to capture air blowing in either direction. In a further embodiment, the stem connecting the proximal end of the blade206to the distal end of the blade206may include one or more ridges (for example, configured to better capture air). The one or more wind turbines204may be attached to the same shaft208or more that one shafts208. In an embodiment, the shaft208or shafts208may enter the body102. In one embodiment, the shaft208may be disposed through the right wall112and left wall114of the body102. In such an embodiment, a wind turbine204may be disposed on each end of the shaft208. In an embodiment, the one or more wind turbines204and/or one or more shafts208are in mechanical communication with a wind power generator. In such an embodiment, the rotation of the turbines204and/or shafts208may cause the wind power generator to generate electricity. In one embodiment, the wind power generator is in electrical communication with the computer and/or the battery216. As a non-limiting example, the wind power generator may first route electricity to the computer320and then to the battery216. In another non-limiting example, the wind power generator may route electricity directly to the battery216, but may still be in electrical communication with the computer320and receive instruction from the computer320. In an embodiment, the wind power generator is wired into a computer320, which will send excess power to the battery216. Referring toFIG.2, in an embodiment, the device includes a solar power assembly210. The solar power assembly210may include one or more solar panels212. In an embodiment, the one or more solar panels212may be monocrystalline or polycrystalline. The one or more solar panels212may be partially surrounded by a solar panel frame214(for example, surrounding the top, bottom, right side, left side, and rear face of the one or more solar panels212). The solar panel assembly210may be attached to the rear face106of the body102. In such an embodiment, a solar panel mount may be disposed between the solar panel frame214and the rear face106of the body102. In a further embodiment, the solar panel mount may be adjustable, enabling the angle between the body102and the solar panel frame214to change. In another embodiment, the solar panel mount is adjustable in multiple directions (for example, the solar panels212may be pulled further or pushed closer to the body102, the solar panels212may be turned to the right, left, up, or down). In another embodiment, the solar panel mount may be motorized or otherwise configured to adjust the solar panels212incident to the sun (for example, moving the solar panels212so that the solar panels212are perpendicular to light being emitted by the sun). In such an embodiment, the solar panel mount may be in electrical communication with the computer320. In an embodiment, the device includes a battery216. In such an embodiment, the battery216may be a lithium ion battery pack. The battery216may be disposed within the solar panel frame214or within the body102of the device. The battery216may be in electrical communication with the one or more solar panels212and/or the one or more wind turbines204. In such an embodiment, the battery216is configured to store power generated by the one or more solar panels212and/or the one or more wind turbines204. In an alternate embodiment, the battery216is located distant to the device and is tethered to the device via some length of electrical cord (for example, the cord running to the power input122). In an alternate embodiment, the device includes more than one battery216. Referring toFIG.3, in an embodiment, the body102surrounds a cavity302. In such an embodiment, the cavity302may be hollow and may serve as the housing for many of the filtration and electrical aspects of the device. In one embodiment, the cavity302includes a water reservoir304, a first chamber306, and a second chamber310. The water reservoir304may be a chamber filled with water or another fluid. The water reservoir304may be configured to remove particulates from incoming air (for example, large particles or heavy toxins). The first chamber306and/or the second chamber310may include a first air filter308and/or a second air filter312, respectively. In one embodiment, the water reservoir304, the first chamber306, and the second chamber310are arranged vertically. For example, the water reservoir304may be disposed on the bottom portion of the cavity302, the first chamber306may be disposed atop the water reservoir304, and the second chamber310may be disposed atop the first chamber306. However, in alternate embodiments, the water reservoir304, the first chamber306, and the second chamber310, may be arranged in any order. In one embodiment, the device includes just the water reservoir304and the first chamber306. The device may also function when the water reservoir304is empty (for example, if the fluid cannot be resupplied, the device may still filter air without fluid in the water reservoir304). In an alternate embodiment, the water reservoir304may also include a portion of filter media, enabling both fluid filtration and mechanical filtration. In one embodiment, the cavity302may be lined with soundproof material, in order to decrease the noise created by the device. In an embodiment, the water reservoir304contains a fluid other than water. In such an embodiment, the fluid may be configured to attach to pollution particles in the air and retain them. Effectively, such a fluid may “seek” out unwanted particles and either identify, attach, or bond with the unwanted particles. In such an embodiment, this alternate fluid would be more effective at purifying the air. As a non-limiting example, the fluid may be configured to remove organic pollutants using an electrochemical separation method. The water reservoir304may have a water reservoir air input and a water reservoir air output. The first chamber306may have a first chamber air input and a first chamber air output. The second chamber310may have a second chamber air input and a second chamber air output. The water reservoir304may also have a fluid input/output120. In one embodiment, the fluid input/output120may be a single tube, which is configured to carry fluid to the water reservoir304and/or away from the water reservoir304. In another embodiment, the fluid input/output120may be two tubes, one configured to take water from the water reservoir304and the other configured to carry water to the reservoir304. The fluid input/output120may be in fluid communication with a reservoir tank or a water pump some distance from the device. In an embodiment, the fluid input/output120may include a 90-degree joint with a threaded spout. In an embodiment, each of the water reservoir304, first chamber306, and second chamber310, are self-contained in the sense that each chamber is sealed with the exception of each chamber's various inputs and/or outputs. Each chamber is configured to contain the air and channel the air from the input of the chamber to the output of the chamber. In an embodiment, the device includes a pump314. The pump314is disposed within the cavity302(for example, above the water reservoir304or computer320). The pump314may be configured to pull air from outside the device, through the water reservoir input, through the fluid, and out the water reservoir output. As air enters the water reservoir304, the air may be cleaned as it “bubbles” through the fluid. In one embodiment, the largest pollutants and/or the heavy toxins are removed via the water reservoir304filtration. In an embodiment, the device has a power input122. In one embodiment, the power input122is configured to carry power to the device. The power input122may be in communication with a power source some distance from the device. In an embodiment, the power input122is in electrical communication with the device. An overflow port may be disposed within the water reservoir304. The overflow port may be in communication with the fluid input/output120. In an alternate embodiment, the water reservoir304may simply be drained with a standard hose. In an embodiment, a standard hose or a fluid input/output120may be used to push fresh water into the water reservoir304and the overflow may be configured to let the fouled fluid out. In an embodiment, the device may include a waste reservoir (for example, a chamber configured to receive waste fluid from the water reservoir304). In an embodiment, the water reservoir304may be continuously refreshed with clean fluid. In another embodiment, the water reservoir304is refreshed with clean fluid at pre-determined periods of time (for example, the water reservoir304is completely flushed and refilled every 12 hours). In an embodiment, the water reservoir304includes a sensor capable of determining the level of pollutant in the fluid. In such an embodiment, this sensor may be in communication with the computer320and may cause the water reservoir304to flush and replenish at certain pollution level thresholds. In an embodiment, the device includes one or more induction fans316/318. The device may include a first induction fan316and a second induction fan318. The one or more induction fans316/318may be configured to draw air into the first chamber306and/or the second chamber310. The induction fans316/318and the pump314may be in electrical communication with the battery216. The induction fans316/318and the pump314may also be in electrical communication with the power input122. In an embodiment, the pump314and induction fans316/318draw power directly from the battery216. The wind power generator and the one or more solar panels212may generate inconsistent power (for example, if there is no wind or if the sun is eclipsed by clouds). However, in an embodiment, all power inputs (wind, solar, and hardwired electricity) run directly to the battery216and then the battery216provides stable power to electrical components of the device. In an embodiment, the device includes a second induction fan318configured to propel the air from the second chamber310into the environment. In an embodiment, the first induction fan316and the second induction fan318may each be comprised of multiple fans (for example, arranged as a fan bank). In an embodiment, the first chamber306and second chamber310contain a HEPA air filter. However, in another embodiment the first chamber306and second chamber310may contain any physical filter media configured to remove unwanted particles from air. The first and second chambers306/310may contain the same type of filter media or different types of filter media. In an alternate embodiment, the first chamber306and/or second chamber310contain a fluid. In such an embodiment, the first chamber306and/or second chamber310may be arranged in the same manner as the water reservoir304. The air filter may be reusable and/or rinsable. In an embodiment, the air filters308/312may be sized to fit the first and second chambers306/310. In one embodiment, the first and second chambers306/310may each include a filter tray. The filter trays may be sized to fit within the first and second chambers306/310and may be configured to slide out from the chambers306/310. In one embodiment, the front face104of the device may be removable, enabling a user to remove the filter trays and/or the air filters308/312. In another embodiment, another part of the body102(for example, the left wall114or right wall112). In another embodiment, the front face104of the device may have one or more doors or access points that allow for the tray or filter to be removed. In such an embodiment, the doors or access points may be airtight. In an embodiment, the device includes a removable cap322. The removable cap322may be disposed between the water reservoir304and the first chamber306, such that removal of the removable cap322allows for easy maintenance within the water reservoir304, first chamber306, or between the two. In an alternate embodiment, there may be more than one removable cap322and they may be disposed on any internal component of the device. In an embodiment, the device includes a computer320. The computer320may be disposed within the cavity302. In one embodiment, the device and/or the computer320include a processor and a memory. The memory may contain a program configured to direct the flow of power within the device. As a non-limiting example, the program may instruct the solar panel212and/or wind turbine204to send a certain quantity of power to the battery216. As a further example, the program may instruct the solar panel212and/or wind turbine204to direct 70% of the generated power to the battery216and the remaining 30% to other components of the device that use power. In an embodiment, the computer320and the battery216are in communication, such that when the battery216reaches the maximum charge, the computer320directs the induction fans316/318, pump314, wind turbines204, and/or solar panels212to cease operation. In a further embodiment, the computer320may direct the induction fans316/318, pump314, wind turbines204, and/or solar panels212to resume operation when the battery216's charge level drops to a pre-determined threshold. In an embodiment, the device has a light sensor and/or a wind sensor. The light sensor and/or the wind sensor may be disposed on the outside of the body102and may be in electrical communication with the computer320. The wind sensor may be able to determine the direction and speed of the wind. The light sensor may be able to determine the intensity and direction of incident light. The light sensor may be configured to track the apparent movement of the sun through the sky, enabling the solar panels212to receive the most direct sunlight. The computer320may be configured to receive signals from the light sensor and/or the wind sensor. The light sensor and/or wind sensor may also be configured to analyze dangerous conditions. As a non-limiting example, the wind sensor and the computer320may determine if the wind speed approaches velocities that could damage the device. In a further non-limiting example, the light sensor and computer320may determine if there is a dangerous presence of light that could damage the one or more solar panels212or overload the device. In an embodiment, the wind power assembly202may include a brake that stops the wind turbines204from spinning if the wind speeds are too great. In such an embodiment, the computer320may generate a signal to the brake if the wind sensor provides the computer320with information containing dangerously high winds. In an embodiment, the computer320and/or the device include a receiver, a transmitter, and/or an antenna. In one embodiment, the device may send and receive wireless signals. As a non-limiting example, the device may receive a cell signal and output a Wi-Fi signal. In such an embodiment, the device may be configured to accept signals from major cell phone providers. If more than one device is within a certain proximity to one another, the group of devices may be configured to provide a mesh Wi-Fi system (for example, for a small town or a segment of a freeway). In another embodiment, the device may act as a node, boosting cell service or extending a Wi-Fi signal. In another embodiment, more than one devices may be configured to be in electrical communication with one another. For example, electrical wires may tether each device; enabling one device's solar and wind systems to charge the battery of another device. In an embodiment, the device is configured to operate in proximity to streetlights, traffic lights, or utility poles. The device may be especially equipped for removing pollutants from vehicle exhaust fumes. In such an embodiment, the power input122may be in electrical communication with the power source within the streetlight, traffic light, or utility pole. The tube leading to the fluid input/output120may be disposed within the streetlight, traffic light, or utility pole. The device may be attached to the traffic light or traffic light pole. In one embodiment, a standard metal clasp can be drilled into the pole in a similar fashion as to how typical lights are mounted. In one embodiment, the devices are mounted at the same height as traffic lights. In an embodiment, a device mount may be disposed between the device and the pole. In one embodiment, the device mount may have a “quick detach” feature, enabling the device to be easily removed from the device mount or the pole. In a further embodiment, the device mount may be electronically instructed to restrain or release the device. In such an embodiment, a drone may instruct the device mount and may be enabled to remove the device from the traffic light or pole. A drone may also be configured to replace air filters308/312or other components of the device. The devices may be strategically placed in order to most efficiently purify air. For example, the devices may be placed at traffic lights over intersections that are especially busy or well known for carrying high-pollution vehicles. In another embodiment, the device may be placed within commercial buildings (for example, in a building's HVAC system). In an embodiment, power may run through a step down converter, which then may route power to the battery216. The step down converter may accept up to 16V of solar power and 16V of wind power and direct power to the battery216to charge evenly and effectively. However, in various embodiments, the step down converter may accept a range of voltages from the solar and/or wind units. The battery216may then power the rest of the unit. In an embodiment, the battery216, solar panels212, and/or wind turbines204are wired to the streetlight's power input. In such an embodiment, the device may power the streetlight or other similar electronics (for example, illuminated traffic signs, neon signs, or rail road crossing barrier motors). Referring toFIG.4, a method of air purification begins by determining whether the battery contains charge sufficient to power at least the first induction fan, the second induction fan, and pump402. In an alternate embodiment, this determination may be made in reference to just the pump and first induction fan. As a non-limiting example, the computer may include information on the necessary power to operate the electrical components of the device. If402returns yes, the computer may direct power to at least the first induction fan, the second induction fan, and pump408. If402returns no, and the solar panels and/or wind generator are charging the battery404, then again a determination should be made whether the battery has sufficient power402. As a non-limiting example, the computer may track the power input to the battery by the turbines or solar panels. In such an example, the computer may be configured to anticipate when the battery will be sufficiently charged based on the rate of energy production by the turbines or solar panels. If404returns no, and the solar panels and/or wind generator are not charging the battery404, then the system may accept power from an external source406and once again determine whether the battery has sufficient power402. In accepting power from an external source406, the battery may be charged by a hardwired power source (for example, the power supply of a streetlight). In such a non-limiting example, the external source may power the battery or may power the fans and pump directly. The pump may then direct untreated air from outside the device into the water reservoir410. The water reservoir may filter large particles from the untreated air412. The pump may direct the untreated air from the water reservoir to the first chamber414. In an alternate embodiment, the first induction fan may direct the untreated air from the water reservoir to the first chamber. The first chamber may filter fine particles from the untreated air416. The first induction fan may direct the untreated air from the first chamber into the second chamber418. The second chamber may filter fine particles from the untreated air420. The second induction fan may direct, what is now, treated air from the second chamber to outside the device422. In alternate embodiments, the method may utilize any number of fans or pumps. For example, in an alternate embodiment, the method utilizes a single pump and the pump is configured to propel air through the reservoir and both chambers. In another non-limiting example, the method utilizes a single induction fan and the single induction fan is configured to propel air through the reservoir and both chambers. In further alternate embodiments, any reservoir or chamber may be configured to filter any kind of particles (for example, the reservoir may filter fine particles and the first chamber may filter heavy toxins). In an alternate embodiment, the device may be configured to receive external renewable power. As a non-limiting example, external wind turbines, hydroelectric turbines, solar panels, or other renewable sources of energy may power the device. In such a non-limiting example, these external renewable sources may be in electrical communication with the battery216and/or power input122. While certain novel features of the present invention have been shown and described, it will be understood that various omissions, substitutions and changes in the forms and details of the device illustrated and in its operation can be made by those skilled in the art without departing from the spirit of the invention.
25,232
11857909
DESCRIPTION Persons of ordinary skill in the art will realize that the following description is illustrative and not in any way limiting. Other embodiments of the claimed subject matter will readily suggest themselves to such skilled persons having the benefit of this disclosure. It shall be appreciated by those of ordinary skill in the art that the systems and methods described herein may vary as to configuration and as to details. The following detailed description of the illustrative embodiments includes reference to the accompanying drawings, which form a part of this application. The drawings show, by way of illustration, specific embodiments in which the claimed subject matter may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the claims. It is further understood that the steps described with respect to the disclosed processes may be performed in any order and are not limited to the order presented herein. As stated above, existing atmospheric water generators are frequently standalone units that operate more effectively when located outdoors. However, this requires users to be present at the atmospheric water generator, and outdoors to retrieve water from the atmospheric water generator. Alternatively, existing standalone atmospheric water generators may be located indoors to facilitate more convenient access to the collected water. However, an indoor location reduces the efficiency of atmospheric water generators because indoor air commonly has a lower dew point temperature and a lower humidity. Additionally, atmospheric water generators commonly employ a pump to operate the cooling element, which pump creates noise that is not desirable for an indoor atmospheric water generator. Therefore, there is a need for an atmospheric water generator that does not pollute an indoor location, such as a home, with the noise of the cooling element that condenses water and takes advantage of the benefit of condensing warmer, wetter outdoor air, yet still allows a user the convenience of dispensing water at an indoor location. The systems and methods disclosed herein overcome the deficiencies of existing atmospheric water generators by employing two subsystems that are separate from one another. This separation provides the benefit of allowing the collection portion of the system to be located at a remote location, such as outdoors, while dispensing water from the second portion of the system at a tap in a desired location, such as indoors. In this manner, the noise of the collection system does not disturb the user at the remote location, and the collection system is exposed to warmer and more humid outdoor air that can be more efficiently condensed by an atmospheric water generator. Existing atmospheric water generators struggle with pathogen exposure and growth in the system. The outdoor air frequently used by atmospheric water generators contains a variety of pathogens. Existing atmospheric water generators attempt to eliminate these pathogens with a combination of one or more filters, LED generated ultraviolet radiation, and exposure to ozone. However, these systems fail to completely remove pathogens from the collected water. This is especially problematic at the interior surfaces and components of atmospheric water generators, which are constantly exposed to moist climates, standing water, and/or moderate temperatures due to their location within the atmospheric water generator. Filters fail to prevent at least some pathogens from passing through, LEDs may not provide sufficiently intense ultraviolet radiation to neutralize pathogens only in certain areas of an atmospheric water generator, and ozone generators include potential fire hazards, toxicity issues, and higher operational costs, as well as requiring additional pre-treatment and post-treatment filtration. The systems and methods disclosed herein overcome the deficiencies of existing atmospheric water generators by including a titanium dioxide coating on various internal surfaces and components of an atmospheric water generator. In some conditions, titanium dioxide coatings neutralize pathogens on contact. Such an additional neutralization element may further sterilize collected water continually, without requiring the collected water to be pumped through a filter, exposed to ultraviolet radiation, or treated with ozone. In operation, collected water often sits idle within an atmospheric water generator for long periods of time between initial sterilization upon collection and storage, and later dispensation by a user. The relatively long periods of inactivity allow pathogens to proliferate on internal surfaces of an atmospheric water generator or within collected water. Thus, the passive sterilization offered from titanium dioxide coatings is beneficial because it is constantly neutralizing pathogens, even when the atmospheric water generator is not dispensing or collecting water. Existing atmospheric water generators are frequently stand alone units that operate more effectively when located outdoors. However, this requires users to be present at the atmospheric water generator, and often outdoors, to control the operation of the atmospheric water generator. Additionally, optimal water collection times may be at night, early morning, or on days having particularly beneficial water condensing conditions, such as a high dew point temperature. Therefore, it may be inconvenient and undesirable for a user to operate an atmospheric water generator efficiently that requires the user to come to the location of the atmospheric water generator to control the water collection processes of the atmospheric water generator. The systems and methods disclosed herein provide remote access and control capabilities using a downloaded smartphone application, which is also referred to as na “app.”. Thus, users may monitor and change the operating mode of one or more remotely located atmospheric water generators without the inconvenience of having to be present at the one or more atmospheric water generators. With reference toFIG.1, there is shown an illustrative system100for atmospheric water generation. The term “atmospheric water generation” can be used interchangeably with “atmospheric water generator,” and the terms are used interchangeably herein. As described herein, the system100may collect and purify atmospheric moisture to produce drinking water. The illustrative system100includes a first subsystem102and a second subsystem104. The first subsystem102may be coupled, such as by way of a pipe, tubing, water tube, conduit or other such water transmission materials106to the second subsystem104. The first subsystem102may collect and transfer atmospheric moisture to the second subsystem104for dispensation as drinking water through a water outlet or tap108. The water tube106coupling the first subsystem102to the second subsystem104allows the first subsystem102to be separate from the second subsystem104and remotely located. By way of example and not of limitation, the first subsystem102may be located outdoors and the second subsystem104may be located indoors. As a further non-limiting example, the first subsystem102may be in a basement or closet and the second subsystem104may be in a kitchen. In operation, water vapor in the air, i.e. humidity, enters the illustrative first subsystem102and the water vapor is condensed and collected from the humid air. The collected water is then held in the first subsystem102and transferred through the water tube106to the second subsystem104, which is indoors. The collected water is then stored in the second subsystem104for later dispensation at the water outlet or tap108. With reference toFIGS.2-6, there are shown various views of an illustrative first outdoor subsystem102. The illustrative first outdoor subsystem102may comprise a first housing202, a cooling element204, an air intake filter206, a plurality of light emitting diodes (LEDs)208, a water collector210, and a water storage tank212. Although the illustrative system includes a vent that receives humid air, the collected water system operates in a pressurized closed loop system that maintains an positive pressure between the first subsystem102and the second subsystem104. The closed loop system includes a pump (not shown) that maintains the positive pressure throughout the system and serves to overcome line losses due to friction and passive drops over valves, fitting and equipment. Humid air enters the first subsystem102through the air intake filter206, where an initial portion of pathogens is removed from the humid air. The humid air then contacts the cooling element204, which condenses water vapor from the air on to the cooling element204as the cooling element204suddenly lowers the temperature of the air. The condensed water then runs into the water collector210due to gravity and is fed into a water storage tank212. In the illustrative embodiment, the first subsystem102is outdoors where the air is more humid than indoors. In humid environments, indoor cooling from air conditioning systems reduces the amount of humidity in the air. Thus, it is harder to collect water vapor inside a cool room or structure than outside in a more humid environment. In various embodiments, the first housing may comprise an intake vent224. The intake vent224may include a plurality of vent holes or vent apertures that allow air to flow through the intake vent224and into the air intake filter206. The housing202may house the cooling element204, the air intake filter206, the plurality of LEDs208, the water collector210, and the water storage tank212. The housing202may be sealed during operation such that humid air is only able to enter the housing202through the air intake filter206. Thus, during operation, the air flow through the air intake filter206may be maximized, because humid air is not permitted to enter the sealed housing202through unsealed crevices in the housing202. In various embodiments, the housing202may be sealed and pressurized. The cooling element204may comprise any cooling element suitable to condense water vapor out of the atmosphere. For example, the cooling element204may comprise a typical refrigerated cooling element or coil capable of cooling air passing over its surface to condense water vapor. The typical refrigerated cooling element is operated by circulating Freon or other such common refrigerant working fluids within a closed system at various temperatures and pressures. In particular, a pump or compressor pressurizes the refrigerant in one stage, and allows the refrigerant to expand in a second stage where the refrigerant absorbs energy from matter, such as humid air. In various embodiments, the working fluid circulating in the cooling element204may be water from a natural or existing energy sink, such as a well, lake, or river, to provide an energy efficient cooling element204. The cooling element204may be carbon coated to neutralize airborne or surface pathogens, such as bacteria and other microbial organisms. Similarly, in various embodiments, the cooling element204may be coated with titanium dioxide, such as by a titanium dioxide paint, to neutralize airborne or surface pathogens. For example, carbon or titanium dioxide may be baked, painted, sprayed, sputtered, infused, or otherwise deposited on the cooling element204to form a coating. In various embodiments, it may be advantageous to bake the titanium dioxide layer onto the cooling element204and other system components as described herein, because sprayed or painted titanium dioxide may decompose, chip, flake, or otherwise degrade in the presence of liquid water. In one embodiment, the air intake filter206may fit into a removable intake vent panel207or a portion of an intake vent panel of the housing202. The intake vent panel207may include a plurality of vent holes or vent apertures that allow air to flow through the intake vent207and into the air intake filter206. In another embodiment, the intake vent panel207is removable and has no vent holes or apertures. The interior portion of the air intake filter206may abut or face the cooling element204. The intake filter206may comprise any suitable air filter and may be configured, treated, or adapted to neutralize airborne or surface pathogens. For example, and with particular reference toFIG.5, there is shown an interior (to the housing) portion of the air intake filter206. The interior portion of the filter206may include the plurality of LEDs208, which may be mounted to the air intake filter206by one or more fasteners, one or more clamps, by an adhesive, by a heat bonding technique, by bolts or screws, by an integral manufacturing or formation technique, and the like. In various embodiments, the air intake filter206may include carbon or titanium dioxide to neutralize airborne or surface pathogens. For example, carbon or titanium dioxide may be baked, painted, sprayed, sputtered, infused, or otherwise deposited on either or both of the exterior and interior portions of the intake filter206. In this manner, the air filter206may be coated with carbon or titanium dioxide. With particular reference now toFIG.6, each of the LEDs208may include an ultraviolet LED capable of eliminating airborne and surface pathogens entering the system100. In various embodiments, the system100may include a plurality of strips of LEDs mounted to the air intake filter206, and the LEDs on each strip, or the strips themselves, may be variously oriented in space. For example, the air intake filter206may comprise three strips of LEDs, and each of the three strips of LEDs may illuminate an axis (x, y, or z) of the air intake filter206. In an illustrative embodiment, each of the three strips may contain six LEDs each and may extend vertically, along a y-axis, of the air intake filter206. In various embodiments, more or fewer than one LED strip per dimensional axis may be employed to eliminate airborne and surface pathogens. The water collector210may be disposed under the cooling element204and may collect and funnel water into the water storage tank212as it condenses on the cooling element204and drips under the influence of gravity into the collector210. The water collector210may be coupled by a funnel, tray, pipe, hose, or equivalent to the water storage tank212. Again, with reference toFIG.6, there is shown a cutaway of the air intake filter206, with the cooling element204. The collector210may, like the air intake filter206, be coated with carbon or titanium dioxide to neutralize pathogens in the collecting water. Water may further be irradiated by one or more LEDs disposed over the surface of the collector210to destroy and stifle the growth of pathogens. With reference now toFIGS.7and8, illustrative cross-sectional views of the second subsystem104are shown. Accordingly, the second subsystem104may comprise a second housing214, a pathogen neutralizing module216, a water storage container218, a water inlet220, and a water outlet or tap108. The second housing214may house the pathogen neutralizing module216, the water storage container218, the water inlet220, and the water outlet or tap108. The water storage container218may comprise a tank or vessel, and as shown with reference toFIG.8, the water storage container218may contain a compressor222, such as a mechanical spring (e.g., a helical or coil spring) or a pneumatic actuator, a platform224, and a water storage bladder226. The platform may be any suitable flat surface, such as steel sheet metal, aluminum sheet metal, wood, or composite. The water storage bladder226may comprise an antimicrobial coating or material. In various embodiments, the water storage bladder226may rest on the platform224, which may, in turn, rest on the mechanical spring222. As described below, the mechanical spring222may expand and contract as water is pumped into the water storage bladder226(contraction) or released from the water storage bladder226(expansion). In other words, the mechanical spring222may be compressed to store energy as water is pumped into the bladder226and, as water is released from the bladder226into the tap108, the spring222may expand, releasing its stored energy, to squeeze the bladder226such that water is forced into the tap108. The mechanical spring222may be further tempered along its length, such that the spring222is capable of exerting a constant pressure against the inflating and deflating water storage bladder226as the spring222is compressed and decompressed. The spring222may therefore maintain the water storage bladder226at a constant pressure as the water storage bladder226is filled and emptied of water, for example at 12 PSI. However, in other embodiments, the spring222maintains the water storage bladder226at a substantially constant pressure ranging from 10 psi to 14 psi. In various embodiments, the compressor222is a pneumatic actuator containing a fixed mass of working fluid (i.e., air, hydraulic fluid). The pneumatic actuator exerts force constantly on the water storage bladder226. Similar to the mechanical spring222, the pneumatic actuator may be compressed to store energy as water is pumped into the bladder226and, as water is released from the bladder226into the tap108, the actuator may expand, releasing its stored energy, to squeeze the bladder226such that water is forced into the tap108. In another embodiment, the pneumatic actuator includes a pneumatic compressor and release valve that operate in conjunction to modulate the internal pressure of the pneumatic actuator as needed to maintain a consistent force on the water storage bladder226. In various embodiments, the pathogen neutralizing module216may comprise one or more filters, an ozone treatment module, a second plurality of LEDs, or any combination thereof. In addition, water may pass through one or more elements comprising the pathogen neutralizing module216prior to entering the water storage bladder226and/or as the water is released from the water storage bladder226, as described herein, on its way to the tap108. Further, in various embodiments, water may be treated by elements of the pathogen neutralizing module216at both stages; that is, water may be treated prior to storage in the water storage bladder226and as the water exits the water storage bladder226. By way of example and not of limitation, the pathogen neutralizing module216may include a filter that filters various particles from the water prior to entering the water storage bladder226. In another illustrative embodiment, the pathogen neutralizing module216includes an ozone generator that releases ozone into the water storage bladder226. In yet another illustrative embodiment, the pathogen neutralizing module216includes a second plurality of LEDs (not shown) that treat water as it exits the water storage bladder226. The one or more of filters may include at least one of a first sediment filter, a second sediment filter, a carbon filter, a first pathogen filter, and a second pathogen filter. The sediment filters may filter sediment and mineral content from water collected by the system100. The carbon filter may filter mineral, particulate, and other content from the water. The first and second pathogens filters filter various pathogens such as bacteria and other microbial organisms from the water. Water passes through the filter or filters. The filters may be sequentially connected to one another. For example, water may flow through the first and second sediment filters, then through the carbon filter, and finally through the first pathogen filter and the second pathogen filter. A final sediment, carbon, and/or pathogen filtration stage may be added to ensure water quality. Any one or more of the plurality of filters may be tubular or flat. Additionally, any one or more of the plurality of filters may be a membrane filter. The membrane filters may have a pore size of 0.1 microns to 10 microns. Such filters prevent bacteria, fungal spores, and other pathogenic microorganisms from passing through, thereby neutralizing such pathogens in the filter water. Bacteria typically range in size from 0.5 microns to 5 microns in length, fungal spores from 2 microns to 200 microns, and amoebas from 200 microns to 500 microns. The ozone generator may employ any one or more of the common in situ ozone generation techniques, such as corona discharge or UV photochemical generation. In operation, an air compressor or fan (not shown) may operate within the first subsystem102to draw air, through vents (not shown) in the intake vent207and into the air intake filter206. As air passes through the filter, a carbon or titanium dioxide coating on the interior portion of the air intake filter206neutralizes airborne and surface pathogens. In some embodiments, many bacteria and other microorganisms are destroyed by contact with titanium dioxide, and pathogens such as these are neutralized as they make contact with, and pass through, the air intake filter206. Thus, the system100may, during an initial purification or sterilization stage, neutralize pathogens while water vapor in the air is in a gas phase (i.e., prior to water condensation). However, in other embodiments, contact with titanium dioxide may increase pathogen content. In these embodiments, the various other elements of the pathogen neutralizing module neutralize the pathogens that are not destroyed by contact with titanium dioxide. In still other embodiments, pathogens are neutralized on contact with titanium dioxide in the presence of ultraviolet radiation. The plurality of LEDs208may irradiate humid air having water vapor as it passes through the air intake filter206to further neutralize pathogens circulating through the filter. The LEDs208may operate in the ultraviolet spectrum, such as, in an illustrative embodiment, at 254 nanometers. In various embodiments, the LEDs208may emit other spectra of UV radiation, e.g. 405 nanometers. As humid air exits the intake filter206, it may come into contact with the cooling element204. The cooling element204may be coated, like the air intake filter206, with titanium dioxide or carbon and/or illuminated by one or more ultraviolet LEDs to further reduce or neutralize pathogens in the intake air. The cooling element204may operate at a temperature that is below the dew point such that water vapor in the intake air condenses on the cooling element204and drips as it accumulates on the cooling element204into the water collector210. Thus, the system100may further neutralize pathogens during a secondary treatment, in which purification or sterilization stage—i.e., when the water vapor has condensed on the cooling element204into a liquid water phase. Referring toFIG.6, the system includes a controller having a processor and a memory having tangible, non-transitory, computer-readable instructions stored thereon that, when executed by the processor, cause the processor to adjust the operating temperature of the cooling element204to a temperature that is below the measured dew point. The dew point may be measured by one or more sensors configured to measure the dew point in the system100. The dew point may also be calculated by accessing online weather databases that include local weather conditions. In various embodiments, the processor may adjust the temperature of the cooling element204to a temperature that is between 1 to 25 degrees Fahrenheit below the measured dew point, so that the system100does not expend electrical energy beyond what is needed to reduce the cooling element204temperature to a temperature that is below the dew point. The system100may therefore improve its operating efficiency by varying the cooling element204temperature to correspond to variations in the dew point temperature. The system100may adjust the cooling element204temperature based upon the dew point temperature automatically or based upon a manual input by an operator, which may be provided to the system100by way of an application interface provided on a wireless communications device that is communicatively coupled to the system100. Moreover, the illustrative controller120may receive further system status information such as a temperature of the cooling element204, an indoor temperature, an outdoor temperature, an indoor humidity, an outdoor humidity, and the like from various sensors. The controller may use this additional information to further improve its operating efficiency when varying the cooling element204temperature. In some embodiments, the system100may improve its operating efficiency by causing the controller120to engage the cooling element204when the indoor and outdoor temperatures vary beyond a certain amount, such as 5° F., 10° F., 15° F., 20° F., or 25° F. In other embodiments, the system100may improve its operating efficiency by causing the controller120to engage when the indoor humidity and outdoor humidity vary beyond a certain percent, such as 5%, 10%, 15%, 20%, or 25%. In still other embodiments, the system100may improve its operating efficiency by causing the controller120to engage when certain combinations of outdoor temperature and humidity are favorable to water vapor condensation are measured. For example, outdoor temperatures above 75° F., 80° F., 85° F., 90° F., 95° F., or 100° F. degrees Fahrenheit and outdoor humidity of 30%, 35%, 40%, 50%, 60%, 70% or higher for condensing water vapor. The cooling system100may further power on and power off based upon a water level and/or pressure in the water storage tank212or water storage bladder226. For example, the system100may power “on” to generate water in response to a determination that the water level in either of the water storage tank212or water storage bladder226is below 100% of the total water storage capacity. Also, the system100may power off in response to a determination that the water level in either of the water storage tank212or water storage bladder226is less than 100% of the total water storage capacity. In another embodiment, the system100may power off in response to a determination that the water level in either of the water storage tank212or water storage bladder226is 100% of the total water storage capacity of either. In another embodiment, the system100may power off in response to the water pressure in either of the water storage tank212or water storage bladder226is 12 psi, 13 psi, 14 psi, or 15 psi. The water collector210, like the air intake filter206and cooling element204, may be coated with carbon or titanium dioxide and/or illuminated by ultraviolet light are associated with the first outdoor subsystem. The water collector210may funnel water into the water storage tank212, and a pump coupled to the water storage tank212may pressurize water in the tank212to a specified pressure. In a preferred embodiment, water in the water storage tank212is pressurized to a pressure in the range of 12-14 psi. In various embodiments, a pressure exceeding 12-14 psi may encourage the formation of pathogens, such as bacteria, in the plurality of filters as water is transferred from the first subsystem102to the second subsystem104. In one illustrative embodiment, a pressure exceeding 12 psi may cause one or more porous elements within at least one of the filters216may permit pathogens to enter the closed loop system second indoor subsystem. Thus, the system may limit the water pressure prior to and during filtration to pressures of approximately 12 psi, while after filtration (e.g., as water is pumped into and stored in the water storage bladder226), water pressures may also remain approximately 12 psi or water pressures may exceed 12 psi depending on engineering requirements. More specifically, water is transferred from the first subsystem102to the second subsystem104by way of the illustrative water tubing106. In various embodiments, the tubing106may comprise any suitable length, such as any length that is less than or equal to fifty feet. The tubing106may further, in certain embodiments, comprise any suitable thickness, such as one quarter of an inch, and the tubing106may, like the rest of the system, comprise an antimicrobial material or a material coated with an antimicrobial agent. As water enters the second subsystem104, it may be stored in the water storage bladder226. As water accumulates in the bladder226, the bladder may, by its increasing mass, force the compressor222, upon which it rests, to compress. Water may be maintained within the second subsystem104(e.g., within the bladder226) in a vacuum (or near vacuum), such that the water does not come into contact, after filtration and/or sterilization at the first subsystem102with secondary or unintentionally introduced airborne pathogens. In other embodiments, water may be maintained within the water bladder226in a vacuum. In further embodiments, water may be maintained within the second subsystem in a positive pressure. In still further embodiments, water may be maintained within the water bladder226in a near vacuum. The second subsystem104is therefore, in this regard, a closed or isolated system. The water storage bladder226is, in addition, may be maintained in vacuum or under positive pressure such that the bladder226is devoid of air. The illustrative second indoor subsystem104may respond to a request or an input, such as a mechanical input provided by an operator of the system100at the tap108, to dispense water by releasing energy stored in the compressed compressor222, such that the compressor222decompresses or expands, causing water to flow from the bladder226to the tap108. Thus, the water stored within the water bladder226is forced out of the water bladder226and through the tap108in response to expansion of the compressor222. In various embodiments, the compressor includes a mechanical spring, and the decompression occurs along the helical axis of the spring to squeeze the bladder226. The compressor222may be allowed to decompress, when a valve (not shown) on the tap is opened. In various embodiments, as water exits the bladder226on its way to the tap108the water passes through a series of sediment, carbon, and pathogen filters. These filters remove or neutralize sediment, minerals, various odors and discolorations, and any remaining pathogens from the water at this stage. As described above, the first subsystem102may be located outdoors and may be coupled, by way of one or more water carrying tubes106, to the second subsystem104, which may be located indoors for convenience and such that water can be dispensed indoors. Placement of the first subsystem102outdoors confers several advantages. For example, as described above, the first subsystem102may include an air compressor, which may during operation produce undesirable motor or air compressor noise if placed indoors. The first subsystem102may be separated or decoupled, by way of the water tubing106, from the second subsystem104, permitting placement of the quieter second subsystem104indoors. Generally, the humidity of outdoor air has more water vapor and is, typically, capable of producing a greater water yield than indoor air, which is often pre-filtered and dehumidified by heating and cooling systems. With reference now toFIGS.9-15, there is shown an illustrative wireless communications device display300displaying a user interface302that includes various functions, for monitoring and controlling the system100for atmospheric water generation as described herein and in accordance with various embodiments. By way of example and not of limitation, the wireless communications device may be embodied as a tablet, smartphone, or other wireless capable device. The wireless communication device may also be interchangeably referred to as mobile communication device. The user interface302may be generated by a downloaded software application executed on the wireless communications device. To this end, the mobile communications device may comprise a controller or processor280, a tangible, non-transitory, computer-readable medium or memory290, and a display. The processor280is configured to execute instructions for the software application, which may be stored on the tangible, non-transitory, computer-readable memory290of the wireless communications device300. The mobile communications device may further include a variety of communications hardware for communicating with the system100, such as a network interface card and one or more radios. The radio may be include one or more of a WiFi radio system, a BLUETOOTH radio system, a cellular radio system, and the like. The tangible, non-transitory, computer-readable memory290may have a variety of information stored thereon including a database of status information and at least one operating instruction for the system100. The status information may include data received from one or more sensors, such as indoor temperature, outdoor temperature, indoor humidity, outdoor humidity, outdoor dew point temperature, water storage tank212water level, water bladder226water level, water storage tank212pressure, and water bladder226pressure. The processor280or controller receives input from the various sensors to update the database of status information. The operating instructions for the system100may include various routines for powering on and off the fan, the cooling element204, the first and second plurality of LEDs208, and the various transfer pumps. Thus, the software application may enable remote control and monitoring of the system100. For example, an operator of the mobile communications device may interact with the user interface302to receive status information associated with the system100as well as to provide control instructions to the system100. Thus, the system100may be remotely controlled and monitored through the user interface302. For example, the processor of the wireless device may control the temperature of the cooling element204, such as to set the cooling element temperature below a dew point temperature. In various embodiments, the system100operator may receive alerts or messages indicating, as appropriate, that one or more filters, LEDs, and other system100components require replacement, cleaning, or attention. Thus, a system operator may remotely monitor a plurality of water generation systems and may, in response to detection of an alert or message, as described, dispatch a technician to perform maintenance on one or more water generation systems prior to, or in response to, system failure and in the absence of, or prior to, the placement of a service call or service inquiry to the operator by a customer or user. Accordingly, with particular reference now toFIG.9, there is shown a homepage displayed on user interface302. The homepage may include a variety of control or status icons. For example, the homepage may include a weather icon (not shown), a settings icon308, a system location and weather icon310, an outdoor temperature icon312, an outdoor humidity icon314, a system100or machine name icon (not shown), a water level icon316, an indoor temperature icon318, an indoor humidity icon320, a dew point temperature icon322, a power on/off icon324, a daily power consumption icon328, a weekly power consumption icon326, a monthly power consumption icon (not shown), and/or an annual power consumption icon (now shown). Thus, the wireless communications device may display an outside temperature, an outdoor humidity, a water level, an indoor temperature, an indoor humidity, and a dew point. In other embodiments, the wireless communications device may further display a daily power usage, a weekly power usage, a monthly power usage, and an annual power usage. In various embodiments, the weather icon (not shown) may be selected to display a temperature and/or weather for the location of the system100. In various embodiments, the weather icon (not shown) may be selected to retrieve a temperature and/or weather for the location of the system100. The software application may connect to an online weather service database or website to retrieve weather for the location of the system100in response to operator input. The user interface302may display the system100location and weather icon310in response to selection of the weather icon (not shown). As shown atFIG.10, the weather icon (not shown) may also cause the user interface302to display a city or location selection page330. The city or location selection page330may permit the operator to select a Manual Location option332to manually enter a city or location. The operator may also, from the city selection page330, select an Automatic Location option334that enables the software application to automatically determine a location of the system100. The software application may automatically determine a location of the system100by interrogating the system100. For example, the software application may communicate with the system100to request that the system100transmit its location to the software application. The location may be based upon a location record stored in the memory of the system100, a GPS signal received by a GPS receiver installed in the system100, an IP address associated with the system100or other such location determination methods. The settings icon308shown inFIG.9may enable a settings function of the software application. For example, as shown atFIG.11, an operator may select the settings icon, which may cause the user interface302to display a settings page336. From the settings page336, the operator may select a city or location338, one or more notification options340, a device management option342, an information center option344, an option to check for software updates346, or an option to contact the manufacturer348of the system100. In a second embodiment as shown atFIG.12, the settings page336may allow the operator to select an option to modify the user password350, a share option352, an option to check for software updates346, a system language option354, and an option to contact the manufacturer356of the system100. The share option352may enable the sharing function of the software application. For example, as shown atFIG.13, an operator may select the share option icon352, which may cause the application interface300to display a sharing page358. The sharing page358may permit the operator to share data associated with the system100via any suitable media sharing or social networking website or application. Where the operator selects a notification option, the user interface302may present a notification settings page360, as shown with respect toFIG.14. In various embodiments, the notification settings page360may permit the operator to select an option to display outdoor or indoor temperature or weather362. In other embodiments, where there is a plurality of systems100coupled to the software application, the notification settings page360may permit the operator to select an option to display a system with respect to which various notifications or other information should be displayed. Again, with reference toFIG.14, selection options for a system titled “water-1”364and a second system titled “water-2”366are available as illustrative operator selections. Where the operator selects a device settings option, the user interface302may present a device list page368, as shown with respect toFIG.15. In various embodiments, the device settings page368may permit the operator to name, add, or remove one or more systems100coupled to the software application. Referring toFIG.9, the outdoor temperature icon312may display the outdoor weather for the system100. For example, the outdoor temperature icon312may display the ambient temperature for the air surrounding the first subsystem102. A temperature sensor (not shown) in the first subsystem system102may measure the outdoor temperature. The outdoor humidity icon314may display the outdoor humidity for the system100. For example, the outdoor humidity icon314may display the humidity in the air surrounding the system100. A humidity sensor (not shown) in the system100may measure the humidity or the humidity may be determined from a weather station near the location of the system100. The water level icon316may display the water level in the system100. A water level sensor in the system100may measure the water level or total amount of water collected by the system100during a specified or preset period of time. More particularly, either or both of the water storage tank212(shown inFIG.6) or water storage bladder226(shown inFIG.8) may include a water level sensor, and the user interface302may be configured to display the current water level or total amount of water collected in either or both of the water storage tank212and the water storage bladder226during a specified or preset period of time. The indoor temperature icon318may display the indoor temperature for the system100. For example, the indoor temperature icon318may display the ambient temperature for the air surrounding the second subsystem104at an indoor location. A temperature sensor in the system100may measure the indoor temperature. The indoor humidity icon320may display the humidity for the air surrounding the second subsystem104at an indoor location. For example, the indoor humidity icon320may display the humidity in the air surrounding the system100. A humidity sensor in the system100may measure the indoor humidity. The dew point temperature icon322may display the dew point temperature for the air surrounding the first subsystem104at an outdoor location. For example, the dew point temperature icon322may display the current dew point temperature of the air surrounding the second subsystem104. A dew point temperature sensor in the system100may measure the dew point temperature. Where the user interface302presents a power consumption icon, the operator may calculate, based upon a cost of power and the displayed water level, a cost associated with water production. The cost associated with water production may be based upon a volume of water generated during a time period and an amount of power consumed during the time period. In various embodiments, the processor may calculate a cost associated with water production. The power consumption icon may be a daily328, weekly326, monthly, or annual power consumption icon. The displayed water level may be current or cumulative over a period of time corresponding to the power consumption icon. The cost associated with water production may be a cost per gallon or a cost per liter. The software application may further perform and display this calculation automatically or in response to an operator input requesting a cost associated with water production. It is to be understood that the detailed description of illustrative embodiments is provided for illustrative purposes. Thus, the degree of software modularity for the system and method presented above may evolve to benefit from the improved performance and lower cost of the future hardware components that meet the system and method requirements presented. Additionally, with respect to the indoor and outdoor systems described above, the systems may evolve and be improved upon based on improvements to pathogen neutralizing technologies and cooling systems for the collection of water vapor. The scope of the claims is not limited to these specific embodiments or examples. Therefore, various process limitations, elements, details, and uses can differ from those just described, or be expanded on or implemented using technologies not yet commercially viable, and yet still be within the inventive concepts of the present disclosure. The scope of the invention is determined by the following claims and their legal equivalents.
43,918
11857910
DETAILED DESCRIPTION Metal-organic frameworks for capturing one or more of SO2, CO2, and H2O are disclosed herein. Non-limiting examples of metal-organic frameworks include NbOFFIVE-1-Ni and AlFFIVE-1-Ni, among others. The metal-organic frameworks can be used in applications for removing and/or sensing one or more of SO2, CO2, and H2O from a fluid composition or an environment, either of which can proceed under dry or humid conditions and/or at room temperature. For example, the metal-organic frameworks can be used as sorbents for removing SO2from flue gas, or the metal-organic frameworks can be incorporated into QCM- or IDE-based sensors as the sensing layer for detecting and/or measuring the presence of one or more of SO2, CO2, and H2O. Such sensors can detect concentrations as low as 25 ppm to 500 ppm SO2, 400 ppm to 5000 ppm CO2, and relative humidity levels in an environment below 25% RH and/or above 65% RH, all of which is unprecedented. In either application, the sorption can be reversible such that the metal-organic frameworks may be regenerated and reused. These features and others are described elsewhere herein. Definitions The terms recited below have been defined as described below. All other terms and phrases in this disclosure shall be construed according to their ordinary meaning as understood by one of skill in the art. As used herein, “contacting” refers to the act of touching, making contact, or of bringing to close or immediate proximity, including at the cellular or molecular level, for example, to bring about a physiological reaction, a chemical reaction, or a physical change (e.g., in solution, in a reaction mixture, in vitro, or in vivo). Contacting may refer to bringing two or more components in proximity, such as physically, chemically, electrically, or some combination thereof. Mixing is an example of contacting. As used herein, “contacting” may, in addition or in the alternative, refer to, among other things, feeding, flowing, passing, injecting, introducing, and/or providing the fluid composition (e.g., a feed gas). As used herein, “detecting” refers to determining a presence and/or concentration of one or more chemical species. As used herein, “exposing” refers to subjecting to conditions of an environment. For example, conditions of an environment may include, among other things, one or more of temperature, pressure, and chemical species present in the environment. In addition or in the alternative, exposing refers to subjecting to objects present in an environment. As used herein, “sorbing” refers to one or more of absorbing and adsorbing. Sorbing may include selective sorption, such as sorption of a single species, subsequent sorption, such as sorption of a first species and then a second species (e.g., which may or may not replace the first species), or simultaneous sorption, such as sorption of two or more species at about the same time. Capturing is an example of sorbing. As used herein, “capturing” refers to the act of removing one or more chemical species from a bulk fluid composition (e.g., gas/vapor, liquid, and/or solid). For example, “capturing” may include, but is not limited to, interacting, bonding, diffusing, adsorbing, absorbing, reacting, and sieving, whether chemically, electronically, electrostatically, physically, or kinetically driven. FIG.1is a flowchart of a method of capturing chemical species, according to one or more embodiments of the present disclosure. As shown inFIG.1, the method100may comprise contacting101a metal-organic framework with a fluid composition including one or more of SO2, CO2, and H2O; sorbing102one or more of SO2, CO2, and H2O from the fluid composition on the metal-organic framework; and optionally regenerating103the metal-organic framework. The step101includes contacting a metal-organic framework with a fluid composition including at least one or more of SO2, CO2, and H2O. The contacting may include bringing the metal-organic framework and fluid composition into physical contact, or immediate or close proximity Examples of the contacting may include, but are not limited to, one or more of feeding, flowing, passing, pumping, and introducing. The contacting may proceed under any suitable conditions (e.g., temperature, pressure, etc.). For example, the contacting may proceed to or at a temperature ranging from about 0° C. to about 600° C. In many embodiments, the contacting may proceed at or to a temperature less than about 200° C. In preferred embodiments, the contacting may proceed at or to a temperature of about 25° C. (e.g., about room temperature). The metal-organic framework may include fluorinated metal-organic frameworks characterized by square grids and pillars. The metal-organic framework may include a pillar characterized by the formula MbF5(O/H2O), where Mbis Al3+or Nb5+. The pillar may include an inorganic pillar or inorganic building block. In an embodiment, the pillar may be characterized by the chemical formula: (AlF5(H2O))2−. In an embodiment, the pillar may be characterized by the chemical formula: (NbOF5)2−. The metal-organic framework may include a square grid characterized by the formula (Mb(ligand)x), where Ma is Ni and the ligand is pyrazine. In an embodiment, the square grid may be characterized by the formula (Ni(pyrazine)2). The pillar and square grid may assemble and/or associate to form a metal-organic framework characterized by one or more of the following chemical formulas: NiNbOF5(pyrazine)2·x(solv) (NbOFFIVE-1-Ni) and NiAlF5(H2O)(pyrazine)2·x(solv) (AlFFIVE-1-Ni). For example, in an embodiment, the metal-organic framework may be characterized by the chemical formula: NiNbOF5(pyrazine)2·x(solv). In an embodiment, the metal-organic framework may be characterized by the chemical formula: NiAlF5(H2O)(pyrazine)2·x(solv). The metal-organic frameworks may include a periodic array of open metal coordination sites and fluorine moieties within a contracted square-shaped one-dimensional channel. In an embodiment, the metal-organic frameworks may include AlFFIVE-1-Ni, wherein the AlFFIVE-1-Ni includes three pendant fluoride groups with a fluoride-fluoride distance of about 3.613 Å and one potential open metal site. In an embodiment, the metal-organic framework may include NbOFFIVE-1-Ni, wherein the NbOFFIVE-1-Ni includes four pendant fluoride groups with a fluoride-fluoride distance of about 3.210 and no open metal site. The fluid composition may be present in any phase. For example, the fluid composition may be present in one or more of a gas/vapor phase, liquid phase, and solid phase. In many embodiments, the fluid composition may be present in a gas/vapor phase. The fluid composition may include one or more of SO2, CO2, and water (e.g., as water vapor and/or moisture, humidity) and optionally one or more other chemical species. In some embodiments, the fluid composition includes at least SO2, optionally CO2and optionally water, and optionally one or more other chemical species. For example, in an embodiment, the fluid composition includes at least SO2. In an embodiment, the fluid composition includes at least SO2and CO2, and optionally water. In an embodiment, the fluid composition includes at least SO2, CO2, and water. In an embodiment, the fluid composition includes at least SO2, CO2, and water, and one or more other chemical species. The one or more other chemical species may include one or more of NO2and nitrogen. For example, in an embodiment, the fluid composition may be synthetic flue gas, which may include one or more of SO2, CO2, water vapor, NO2, and nitrogen. In some embodiments, the fluid composition includes CO2and optionally H2O. For example, in an embodiment, the fluid composition includes at least CO2. In some embodiments, the fluid composition includes H2O and optionally CO2. For example, in an embodiment, the fluid composition includes at least H2O. In some embodiments, the fluid composition includes CO2and H2O. In some embodiments, the fluid composition may be air (e.g., for detecting a presence of SO2at certain levels, CO2at certain levels, and/or water at certain levels). The concentration of SO2in the fluid composition may range from greater than about 0 wt % to about 99.9 wt %. In many embodiments, the concentration of SO2in the fluid composition is less than about 7 wt %. In preferred embodiments, the concentration of SO2in the fluid composition is less than about 500 ppm. In other preferred embodiments, the concentration of SO2in the fluid composition is about 25 ppm or greater. In other preferred embodiments, the concentration of SO2in the fluid composition may range from about 25 ppm to about 500 ppm. In some embodiments, the concentration of CO2in the fluid composition is in the range of about 400 ppm to about 5000 ppm. In some embodiments, the concentration of H2O in the fluid composition is equivalent to a fluid composition having a relative humidity in the range of about 0.01% RH to about 100% RH. The step102includes sorbing one or more of SO2, CO2, and H2O from the fluid composition on the metal-organic framework. The sorbing may include one or more of adsorbing, absorbing, and desorbing. In an embodiment, the sorbing may include absorbing and/or adsorbing one or more of SO2, CO2, and H2O. In an embodiment, the sorbing may include absorbing one or more of SO2, CO2, and H2O. In an embodiment, the sorbing may include adsorbing one or more of SO2, CO2, and H2O. In an embodiment, the sorbing may include absorbing one or more of SO2, CO2, and H2O. In an embodiment, the sorbing may include desorbing one or more of SO2, CO2, and H2O. The sorbing may include one or more of selective sorption (e.g., sorption of one or more select compounds), sequential sorption (e.g., sorption in a sequence of species and/or sorption in which a sorbed species is replaced by another species), and simultaneous sorption (e.g., sorption of two or more compounds, such as two or more select compounds). The sorbing may proceed under conditions that are the same as or similar to the conditions of the contacting. In some embodiments, the sorbing includes sorbing SO2. In some embodiments, the sorbing includes sorbing SO2over CO2. In some embodiments, the sorbing includes sorbing SO2and CO2about simultaneously or sequentially. In some embodiments, the sorbing includes sorbing SO2in the presence of H2O. In some embodiments, the sorbing includes sorbing SO2over CO2in the presence of H2O. In some embodiments, the sorbing includes sorbing SO2and CO2about simultaneously or sequentially in the presence of H2O. In some embodiments, the sorbing includes sorbing CO2. In some embodiments, the sorbing includes sorbing H2O. In some embodiments, the sorbing includes sorbing CO2over H2O. In some embodiments, the sorbing includes sorbing CO2in the presence of H2O. In some embodiments, the sorbing includes sorbing H2O in the presence of CO2. In some embodiments, the sorbing includes sorbing CO2and H2O about simultaneously or sequentially. In some embodiments, the fluid composition includes SO2at a concentration in the range of about 25 ppm to about 500 ppm. In some embodiments, the fluid composition includes SO2and CO2, and SO2is preferentially sorbed over CO2on the metal-organic framework. In some embodiments, the fluid composition includes SO2and CO2, and SO2and CO2are both sorbed on the metal-organic framework. In some embodiments, SO2and CO2are sorbed about simultaneously on the metal-organic framework. In some embodiments, the fluid composition includes CO2at a concentration in the range of about 400 ppm to about 5000 ppm. In some embodiments, the fluid composition includes CO2and H2O, and CO2is preferentially sorbed over H2O on the metal-organic framework. In some embodiments, the fluid composition includes CO2and H2O, and CO2and H2O are both sorbed on the metal-organic framework. In some embodiments, the CO2and H2O are sorbed about simultaneously on the metal-organic framework. In some embodiments, the sorbing proceeds at about room temperature. In some embodiments, the metal-organic frameworks may exhibit one or more of a high removal efficiency and/or high uptake, even at low concentrations of SO2. For example, the metal-organic frameworks may exhibit a removal efficiency of greater than about 70%, greater than about 80%, and/or greater than about 90%. In many embodiments, the metal-organic frameworks exhibit a removal efficiency of greater than about 90%. For example, the metal-organic frameworks may exhibit a removal efficiency of greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, and/or greater than about 99%. The metal-organic frameworks may exhibit a high uptake of SO2even at low concentrations, such as concentrations of SO2ranging from 25 ppm to 500 ppm. The metal-organic frameworks may exhibit an about equal selectivity toward SO2and CO2and/or a selectivity toward SO2over CO2. In an embodiment, the metal-organic framework includes NbOFFIVE-1-Ni. The NbOFFIVE-1-Ni may exhibit equal (e.g., about equal) selectivity toward SO2and CO2. In these embodiments, the NbOFFIVE-1-Ni may exhibit simultaneous (e.g., about simultaneous and/or substantially simultaneous) sorption of SO2and CO2, even at low concentrations of SO2and/or in a presence of water (e.g., water vapor, humidity). For example, the NbOFFIVE-1-Ni may simultaneously sorb SO2and CO2, where a concentration of SO2is less than about 500 ppm. In another embodiment, NbOFFIVE-1-Ni may exhibit a selectivity toward SO2over CO2. In an embodiment, the metal-organic framework includes AlFFIVE-1-Ni. The AlFFIVE-1-Ni may exhibit a reduced affinity for CO2(e.g., relative to NbOFFIVE-1-Ni) such that the AlFFIVE-1-Ni selectively sorbs SO2over CO2, even at low concentrations of SO2(e.g., less than about 500 ppm) and/or in a presence of water (e.g., water vapor, humidity). For example, a selectivity of SO2/CO2may be about 66. In these embodiments, the AlFFIVE-1-Ni may exhibit a selectivity towards SO2over CO2. In an embodiment, the AlFFIVE-1-Ni may sorb SO2to the substantial exclusion of CO2. In an embodiment, the AlFFIVE-1-Ni may, at first, simultaneously sorb SO2and CO2and, over time, SO2may replace the sorbed CO2, demonstrating an overall affinity for SO2. In another embodiment, the AlFFIVE-1-Ni may exhibit an about equal selectivity for SO2and CO2. The step103is optional and includes regenerating the metal-organic framework. The regenerating may include thermal treatment in a vacuum and/or inert gas environment (e.g., under nitrogen). For example, in an embodiment, the regenerating may include heating to or at a temperature of about 105° C. in a vacuum. In an embodiment, the regenerating may include heating to or at a temperature of about 105° C. in an inert gas environment. In other embodiments, the temperature of regenerating may be less than and/or greater than about 105° C. FIG.2is a flowchart of a method of a method of capturing chemical species using NiNbOF5(pyrazine)2·x(solv), according to one or more embodiments of the present disclosure. As shown inFIG.2, the method200may comprise contacting201a metal-organic framework with a fluid composition including one or more of SO2, CO2, and H2O, wherein the metal-organic framework is characterized by the chemical formula NiNbOF5(pyrazine)2·x(solv); sorbing202one or more of SO2, CO2, and H2O on the metal-organic framework; and optionally regenerating203the metal-organic framework. In an embodiment, one or more of SO2, CO2, and H2O are sorbed simultaneously (e.g., about simultaneously, substantially simultaneously, simultaneously, etc.) on the metal-organic framework. FIG.3is a flowchart of a method of capturing chemical species using NiAlF5(H2O)(pyrazine)2·x(solv), according to one or more embodiments of the present disclosure. As shown inFIG.3, the method300may comprise contacting301a metal-organic framework with a fluid composition including one or more of SO2, CO2, and H2O, wherein the metal-organic framework is characterized by the chemical formula NiAlF5(H2O)(pyrazine)2·x(solv); sorbing302one or more of SO2, CO2, and H2O on the metal-organic framework; and optionally regenerating303the metal-organic framework. In an embodiment, the metal-organic framework exhibits a selectivity towards SO2over CO2. FIG.4is a flowchart of a method of sensing, according to one or more embodiments of the present disclosure. As shown inFIG.4, the method400may comprise exposing401a sensor to an environment containing one or more of SO2, CO2, and H2O; detecting402a presence of one or more of SO2, CO2, H2O in the environment using the sensor; and optionally regenerating403the sensor. The step401includes exposing a sensor to an environment containing one or more of SO2, CO2, and H2O. The exposing may include subjecting to conditions of an environment. For example, the exposing may include subjecting the sensor to conditions and/or objects of an environment, which may include, but are not limited to, one or more of temperature and chemical species present in the environment. The environment may be an environment contaminated or potentially contaminated with SO2and/or with harmful or unsafe levels of CO2and/or with harmful or unsafe levels of humidity. The environment may be a dry and/or humid environment. For example, in an embodiment, the environment may not include any water vapor or negligible amounts of water vapor. In an embodiment, the environment may include non-negligible amounts of water vapor. The environment may be characterized by a relative humidity (RH) ranging from about 0% RH to about 100% RH. For example, in an embodiment, the environment may be characterized by a RH greater than about 60% and/or less than about 40%. The environment may be characterized by any temperature ranging from about 0° C. to about 600° C. In many embodiments, the temperature of the environment may be less than about 200° C. In preferred embodiments, the temperature of the environment may be about 25° C. (e.g., about room temperature). The metal-organic framework may be deposited as a sensing layer on a substrate to form a sensor. For example, in many embodiments, the sensor includes a layer of a metal-organic framework as the sensing layer. Any of the metal-organic frameworks of the present disclosure may be used as the sensing layer of the sensor. For example, in an embodiment, the sensor includes a layer of a metal-organic framework as the sensing layer, wherein the metal-organic framework is NbOFFIVE-1-Ni or a metal-organic framework characterized by the formula NiNbOF5(pyrazine)2·x(solv). In an embodiment, the sensor includes a layer of a metal-organic framework as the sensing layer, wherein the metal-organic framework is AlFFIVE-1-Ni or a metal-organic framework characterized by the formula NiAlF5(H2O)(pyrazine)2·x(solv). The metal-organic frameworks may be uniformly deposited (e.g., about uniformly deposited) on a substrate with low intergranular voids and/or random orientation. The layer may include crystallites ranging in size from about 150 nm to about 30 μm. The substrate may include any suitable support and/or substrate known in the art and/or commonly used in sensors. In a preferred embodiment, the substrate includes a quartz crystal microbalance (QCM) substrate. In another preferred embodiment, the substrate includes a capacitive interdigitated electrode (IDE) substrates. The sensors may further comprise any additional components known in the art and/or commonly included in sensors. The step402includes detecting a presence of one or more of SO2, CO2, and H2O in the environment using the sensor. The detecting may include measuring and/or monitoring a change in an electronic or physical property of the sensor in response to an interaction between the sensor and one or more chemical species, such as one or more of SO2, CO2, and H2O. The detecting may be used to determine a presence and/or concentration of one or more chemical species. In some embodiments, the interaction may be characterized as a change in an electronic or physical property of the sensor upon sorbing and/or desorbing one or more chemical species. The sorbing and/or desorbing may proceed as described herein. A change in capacitance may be measured in response to the sorption and/or desorption of one or more chemical species. A change in resonance frequency may be measured in response to the sorption and/or desorption of one or more chemical species. A change in electrical resistance may be measured in response to the sorption and/or desorption of one or more chemical species. The electronic properties that may be monitored and/or measured include, but are not limited to, one or more of resonance frequency, capacitance, resistance, conductance, and impedance, among others. In some embodiments, the detecting proceeds at about room temperature. In some embodiments, the detecting includes detecting SO2optionally in the presence of H2O. In some embodiments, the detecting includes detecting between 25 ppm SO2to about 500 ppm SO2in the environment. In some embodiments, the detecting includes detecting CO2optionally in the presence of H2O. In some embodiments, the detecting includes detecting between about 400 ppm of CO2and 5000 ppm of CO2in the environment. In some embodiments, the detecting includes detecting H2O optionally in the presence of CO2. In some embodiments, the detecting includes detecting relative humidity levels in the environment below about 40% RH and/or greater than about 60% RH. In some embodiments, the sensor is a capacitive sensor comprising an interdigitated electrode, wherein the sensing layer is deposited on the interdigitated electrode of the capacitive sensor, wherein the presence of one or more of SO2, CO2, and H2O is detected by measuring a change in capacitance in the sensing layer. In some embodiments, the sensor is a QCM sensor comprising an electrode, wherein the sensing layer is deposited on the electrode of the QCM, wherein the presence of one or more of SO2, CO2, and H2O is detected by measuring a change in resonance frequency in the sensing layer. The step403is optional and includes regenerating the sensor. The regenerating may include thermal treatment in a vacuum and/or inert gas environment (e.g., under nitrogen). For example, in an embodiment, the regenerating may include heating to or at a temperature of about 105° C. in a vacuum. In an embodiment, the regenerating may include heating to or at a temperature of about 105° C. in an inert gas environment. In other embodiments, the temperature of regenerating may be less than and/or greater than about 105° C. FIG.5is a flowchart of a method of sensing using a sensor based on NbOFFIVE-1-Ni, according to one or more embodiments of the present disclosure. As shown inFIG.5, the method may comprise exposing501a sensor to an environment containing one or more of SO2, CO2, and H2O, wherein the sensor includes a layer of a metal-organic framework as a sensing layer; wherein the metal-organic framework is characterized by NiNbOF5(pyrazine)2·x(solv); detecting502a presence of one or more of SO2, CO2, and H2O in the environment using the sensor; and optionally regenerating503the sensor. FIG.6is a flowchart of a method of sensing using a sensor based on AlFFIVE-1-Ni, according to one or more embodiments of the present disclosure. As shown inFIG.6, the method600may comprise exposing601a sensor to an environment containing one or more of SO2, CO2, and H2O, wherein the sensor includes a layer of a metal-organic framework as a sensing layer; wherein the metal-organic framework is characterized by NiAlF5(H2O)(pyrazine)2·x(solv); detecting602a presence of one or more of SO2, CO2, and H2O in the environment using the sensor; and optionally regenerating603the sensor. The following Examples are intended to illustrate the above invention and should not be construed as to narrow its scope. One skilled in the art will readily recognize that the Examiners suggest many other ways in which the invention could be practiced. It should be understand that numerous variations and modifications may be made while remaining within the scope of the invention. Example 1 Fluorinated MOF Platform to Address the Highly Challenging Selective Removal and Sensing of SO2from Flue Gas and Air The present Example relates to the use of isostructural fluorinated MOFs for (i) selective removal of SO2from synthetic flue gas and (ii) sensing of SO2using QCM as a transducer since the coating of MOFs on the QCM electrodes can detect the change in mass of sub nanograms upon adsorption or desorption of molecules by the MOF layer. The present Example describes an unprecedented concurrent removal of SO2/CO2from synthetic flue gas and remarkable detection capability in ppm level of SO2concentration in both dry and humid conditions. Conventional SO2scrubber agents, namely calcium oxide and zeolites, are often used to remove SO2utilizing a strong/irreversible adsorption-based process. However, adsorbents capable of sensing and selectively capturing this toxic molecule with reversibility have yet to be explored. The present Example describes novel selective removal and sensing of SO2using fluorinated metal-organic frameworks (MOFs). Single/mixed gas adsorption experiments were performed at low concentrations ranging from about 100 ppm to about 7% of SO2. Direct mixed column breakthrough and/or indirect mixed column breakthrough desorption experiments revealed an unprecedented SO2affinity for NbOFFIVE-1-Ni and AlFFIVE-1-Ni MOFs. Furthermore, MOF-coated quartz crystal microbalance (QCM) transducers were used to develop sensors with the ability to detect SO2at low concentrations ranging from about 25 to about 500 ppm. Methods and Procedures Column Breakthrough Test Set-up, Procedure, and Measurements The experimental set-up used for dynamic breakthrough measurements is shown inFIG.7. The gas manifold consisted of three lines fitted with mass flow controllers. Line “A” was used to feed an inert gas, most commonly helium, to activate the sample before each experiment. The other two lines, “B” and “C” fed pure or pre-mixed gases. Whenever required, gases flowing through lines “B” and “C” were mixed before entering a column packed with the sample using a four-way valve. In a typical experiment, about 300-500 mg of adsorbent (in the column) was treated in situ at required temperature under He flow (about 50 cm3/g) for about 8 hours. Before starting each experiment, helium reference gas was flushed through the column and then the gas flow was switched to the desired gas mixture at the same flow rate between about 10-40 cm3/g. The gas mixture downstream the column was monitored using a Hiden mass-spectrometer. After water saturation (as detected by mass spectrometer), humid He flow was allowed to continue for two more hours. At this point gas flow was changed to about 500 ppm SO2with balance N2(dry, about 23 cc/min flow rate) for about two hours. Adsorbed phase was analyzed by TPD experiment by increasing the temperature of the column under He flow (about 15 cc/min). The TPD experiment results showed that in case of NbOFFIVE-1-Ni, SO2was able to replace adsorbed water relatively more easily than AlFFIVE-1-Ni. The results were on expected line considering relative water affinity of both the compound and further support trend in sensing experiments. Fabrication of NbOFFIVE-1-Ni and AlFFIVE-1-Ni Coated QCM: The transducer was a 10 MHz AT-cut piezoelectric quartz crystal quartz microbalance (QCM) device with a thickness shear mode and placed between two gold electrodes for electrical connection. The QCM was rinsed with ethanol and dried in air. MOFs paste was then applied to the electrode of QCMs by spin-coating method (2 μm thick) no prior modification of the sensors surface was required. The QCM sensor was then fixed in a sealed chamber. Prior to measurements the fresh coated MOFs film was activated in situ for about 4 hours to have a guest free framework. The resulting coatings were ultrathin and reproducible so that the stress upon absorption of SO2inducing a change in the mass change of the thin film was effective. Apparatus: FIG.8shows the sensing set-up used in this Example for real-time measurement. All the sensor measurements were carried out at about room temperature, under a dry air total stream of about 200 sccm. MFCs (Mass flow controllers) from Alicat scientific Inc. were used to control the flow rate for gases coming from certified bottles. Stainless steel delivery lines or perfluoroalkoxy alkane, PFA tubing (in regions requiring flexibility and resistivity to VOCs) were used on the setup with Vernier metering valves (from Swagelok) as a flow regulator. To detect the change in humidity level inside the chamber a commercial humidity sensor (Honeywell HIH-4000-003) was used as a reference which has an error less than about 0.5% RH. The QCM sensor was exposed to the analyte stream until a stable response was obtained, a two-port network (Keysight E5071C ENA) circuit was used to monitor the change in resonance frequency. A LabVIEW interface was used for synchronization and data acquisition by controlling the LCR meter and the multimeter. Hence, the possibility of data loss was minimized. Results and Discussion The fluorinated MOF platforms, namely NbOFFIVE-1-Ni and AlFFIVE-1-Ni, resulted in many desirable properties. Although both of the MOFs are isostructural, the subtle differences in their chemical compositions, (NbOF5)2−instead of AlF5(H2O)2−, allowed the modulation of their properties by varying the content and intermolecular spacing of pending fluoride groups realized via different tilts of pyrazine molecules (FIGS.9A-9C). In view of the excellent stability and the modular nature of these MOF materials, their use for SO2removal and sensing in synthetic flue gas and air, respectively, was investigated. SO2Removal from Flue Gas NbOFFIVE-1-Ni was first investigated for SO2sorption. The steep, pure SO2adsorption isotherm collected at about 25° C. (FIG.10) suggested a high affinity of the NbOFFIVE-1-Ni framework for SO2. This observation was corroborated by Density Functional Theory (DFT) calculations, which revealed high SO2/NbOFFIVE-1-Ni interaction energy of about −64.8 kJ/mol. This was due to a relatively stronger interaction between the sulfur atom of SO2and the F-pillars with characteristic interatomic distances of about 2.9 Å (FIG.11A) along with a charge transfer between the guest and this region of the MOF. Interestingly, the SO2/NbOFFIVE-1-Ni interaction energy was similar to the value calculated for CO2(about −54.5 kJ/mol). This latter molecule occupied slightly different sites than SO2, implying an interaction of the guest molecule with both the F-pillars and the pyrazine groups (FIG.11B). The so-predicted energetics for a single gas behavior suggested simultaneous capture of SO2and CO2. Cyclic adsorption column breakthrough tests with SO2/N2:7/93 indicate stability and good uptake (≈2.2 mmol/g) of SO2(FIGS.12A-12D). Furthermore, adsorption column breakthrough experiments with SO2/CO2/N2: 4/4/92 gas mixture showed simultaneous and equal retention time in the column for SO2and CO2, demonstrating identical uptake of ≈1.1 mmol/g (FIG.13), which was consistent with the simulated energetics trends. Upon decreasing the SO2concentration with nitrogen in the range commonly observed in flue gas (500 ppm) (SO2/N2: 0.05/99.95 mixture), NbOFFIVE-1-Ni maintained a high SO2uptake of about 1.4 mmol/g. Interestingly, adsorption column breakthrough experiments under mimicked flue gas conditions with about 500 ppm of SO2and about 10% CO2in N2(SO2/CO2/N2: 0.05/10/89.95) resulted in equal and simultaneous retention time for both SO2and CO2, leading to uptakes of ≈0.01 mmol/g and ≈2.2 mmol/g, respectively. This direct co-adsorption experiment demonstrated that NbOFFIVE-1-Ni exhibited equal selectivity toward SO2and CO2, which is desirable for simultaneous CO2and SO2capture in flue gas (containing low SO2concentrations). Nevertheless, temperature-programmed desorption (TPD) confirmed the presence of CO2only with an undetectable amount of SO2(FIG.12D) in the adsorbed phase as the amount of SO2adsorbed was negligible owing to its low concentration. In the quest for a material with more favorable selectivity for SO2removal from flue gas than CO2(at 500 ppm of SO2), an analogue of NbOFFIVE-1-Ni with lower CO2interactions and potentially higher SO2interactions was investigated. In particular, AlFFIVE-1-Ni was explored for the structural SO2/CO2co-adsorption property. AlFFIVE-1-Ni exhibited three pendant fluoride groups with slightly higher F . . . F distance (3.613 Å) and one potential open metal site, whereas NbOFFIVE-1-Ni contained four pendants fluoride with smaller F . . . F distance (3.210(8) Å) and no open metal site. Such minute differences in structural features led to a discovery of equal selectivity for CO2and H2S over a wide range of concentrations and temperatures. Encouraged by this structure-property tuning of H2S and CO2adsorption affinity using this MOF, AlFFIVE-1-Ni was expected to be more selective toward SO2than CO2. The DFT calculations first revealed a lowering of the host/guest interaction energy of CO2for AlFFIVE-1-Ni compared to NbOFFIVE-1-Ni (−47.0 kJ/mol vs. −54.5 kJ/mol). In the case of AlFFIVE-1-Ni, the trigonal bipyramidal-like Al3+environment did not allow for further optimal interactions between a carbon atom in CO2and four F-pillars (FIG.11D), as seen in NbOFFIVE-1-Ni. Interestingly, the simulated preferential location of SO2was slightly pushed toward the pore wall, as compared to the scenario in NbOFFIVE-1-Ni, with the formation of a dual interaction between its sulfur atoms and the two nearby F-pillars as well as its oxygen atoms interacting with the pyrazine linker with shorter interacting distances (FIG.11C). The resulting geometry led to a slight enhancement of the SO2/host interaction energy (−67.3 kJ/mol) and reduced affinity toward CO2, making AlFFIVE-1-Ni a promising candidate to selectively adsorb SO2over CO2. Investigation of single SO2adsorption showed that AlFFIVE-1-Ni also exhibited a steep adsorption isotherm at about 25° C. (FIG.14). The corresponding adsorption column breakthrough experiment with SO2/N2: 7/93 mixture showed a high uptake of about 2.2 mmol/g (FIGS.15A-15D). AlFFIVE-1-Ni can be completely regenerated by heating at about 105° C. in a vacuum or inert gas environment (FIG.16). During the adsorption column breakthrough experiments carried out with low SO2(SO2/N2: 0.05/99.95) mixture, AlFFIVE-1-Ni still maintained a high uptake of SO2(about 1.6 mmol/g). Subsequent TPD analysis of the adsorbed phase confirmed the adsorption of SO2(FIG.17) at ppm level. Adsorption column breakthrough experiments with synthetic flue gas using a SO2/CO2/N2: 0.05/10/89.95 mixture showed that SO2continues to be adsorbed for long durations past the CO2breakthrough. This indicated that the adsorbed CO2was replaced by SO2from the gas mixture, which was consistent with a much higher estimated interaction energy of SO2over CO2. Subsequent TPD analysis suggested an adsorbed phase composition of about 1.5 mmol/g for CO2and about 0.5 mmol/g for SO2, which was remarkable considering the large difference in concentrations of CO2and SO2in the synthetic flue gas (FIG.15D). A selectivity of SO2/CO2≈66 showed that AlFFIVE-1-Ni was one of the most efficient materials for SO2removal at a ppm level and is promising for selectively removing SO2from flue gas. Selective SO2Detection from the Air From the adsorptive separation study above, AlFFIVE-1-Ni and NbOFFIVE-1-Ni were shown to exhibit tunable CO2/H2S selectivity, molecules that are present in environments contaminated with SO2. To benefit from the outstanding properties of this platform, the feasibility of depositing AlFFIVE-1-Ni and NbOFFIVE-1-Ni on a QCM electrode and unveiling their SO2sensing properties in the presence and absence of humidity to mimic atmospheric conditions were explored. The surface morphology of AlFFIVE-1-Ni and NbOFFIVE-1-Ni coated on QCM (see inset) was studied using scanning electron microscopy (SEM). The thin films of both MOFs were found to be compact and uniform. The densely packed MOFs crystals were uniformly deposited on the QCM substrate with low intergranular voids and random orientation. As illustrated inFIGS.18A-18B, the coating of NbOFFIVE-1-Ni led to cubic crystallites of approximately 150 nm, while for the AlFFIVE-1-Ni films, the size of the crystallites was significantly larger at ˜30 μm. Powder X-ray diffraction experiments were carried out to confirm the purity and crystallinity of the deposited MOFs (FIGS.19A-19B). The sensitivity (Δf/f)) of AlFFIVE-1-Ni and NbOFFIVE-1-Ni coated QCM devices were measured for different concentrations of SO2, ranging from 0 to 500 ppm in nitrogen. Uncoated QCM showed a negligible response to SO2. With the increase in the concentration of SO2, both MOF-coated sensors responded with a nonlinear decrease in sensitivity (FIG.20) and (FIGS.21A-21B). After each exposure cycle, the device was in situ heated at about 105° C. in ambient nitrogen for about four hours, which reactivated the MOF thin films for sensing. Humidity is present in most environments, and so it was important to understand a sensor's response in its presence. Therefore, mixed gas experiments were performed, exposing NbOFFIVE-1-Ni and AlFFIVE-1-Ni to SO2in humid conditions mimicking real-world conditions.FIG.22shows the sensor sensitivity as a function of SO2concentration in humid conditions (60% RH) at room temperature for uncoated and coated NbOFFIVE-1-Ni, AlFFIVE-1-Ni QCMs. Uncoated QCM had a near zero response to humidity and SO2. This corroborated that the sensing response to SO2under humid conditions was due to its affinity to NbOFFIVE-1-Ni and AlFFIVE-1-Ni films. The responses of two kinds of sensors were different. As seen inFIG.22and (FIGS.23A-23B), the resonance frequency of the QCMs initially decreased when the ambience was changed from dry to humid SO2conditions. The most prominent difference was the inversion in the sensor output due to the introduction of SO2at 60% RH, but not in the same manner as compared to the dry SO2case. Interestingly, when exposed to 25 ppm of SO2in the above-mentioned humid conditions, the sensor resonance frequency for SO2was reduced. Under humid conditions, the sensitivity of the two MOFs was slightly reduced when compared to dry conditions. However, NbOFFIVE-1-Ni films demonstrated a four-time higher sensitivity toward SO2in the presence of humidity compared to AlFFIVE-1-Ni. To further analyze the results obtained, it was necessary to consider the specific features of the adsorption of SO2and water on the surface of NbOFFIVE-1-Ni and AlFFIVE-1-Ni. As seen inFIG.22, the presence of humidity (60% RH) did not significantly affect the NbOFFIVE-1-Ni based sensor's response to the SO2analyte. This may be due to the affinity of SO2molecules to replace some of the adsorbed water molecules or/and coexist in the highly confined pores. In the case of AlFFIVE-1-Ni based sensor, which was isomorphic to the NbOFFIVE-1-Ni, lower sensitivity to SO2in the presence of humidity was observed. Although SO2has the affinity to replace water molecules, the reduced sensitivity was attributed to the absence of accessible ultra-microporous morphology. The number of SO2adsorbing active sites was reduced by the pre-adsorbed water, thereby limiting the available space for adsorption. This observation was supported by the fact that the water molecules strongly interacted with Al3+with higher host/guest interaction energy as compared to SO2. The TPD experiment results (FIG.24) showed that in the case of NbOFFIVE-Ni-1, the adsorbed SO2was replaced relatively easily with water molecules as compared to the co-adsorption of SO2and H2O in AlFFIVE-1-Ni or coexisted with the adsorbed water in the confined pores of NbOFFIVE-Ni-1. The most important parameters of a sensing device are its stability and reproducibility. These parameters were investigated by cyclic exposure of the sensor to different SO2concentrations after every forty-eight hours at about room temperature over a period of about twelve days (FIG.25A-25B). The three results demonstrated the stability of the sensors exposed to about 50, 100, and 157 ppm SO2gas with no significant change in the resonant frequency over time. In summary, the superior performance of two fluorinated MOFs, namely NbOFFIVE-1-Ni and AlFFIVE-1-Ni, for the capture of SO2from flue gas was successfully demonstrated. Combined single/mixed gas breakthrough experiments and molecular simulation confirmed that simultaneous capture of SO2and CO2occurred using NbOFFIVE-1-Ni, while AlFFIVE-1-Ni displayed a higher affinity for SO2with SO2/CO2selectivity ≈66. Based on this performance, QCM-based sensors were successfully fabricated for sensing SO2from air using this fluorinated MOF platform (FIG.26). Both MOF materials confirmed their potential, revealing good SO2detection capabilities above 25 ppm, the range of SO2concentrations in the air-inducing nose and eye irritation. This remarkable performance of sensing made these materials highly desirable for the fabrication of new advanced devices to improve health and environmental conditions. Example 2 Concurrent Sensing of CO2and H2O from Air Using Ultramicroporous Fluorinated Meta-Organic Frameworks Conventional materials for gas/vapor sensing are limited to a single probe detection ability for specific analytes. However, materials capable of concurrent detection of two different probes in their respective harmful levels and using two types of sensing modes have yet to be explored. In particular, the concurrent detection of uncomfortable humidity levels and CO2concentration (400-5000 ppm) in confined spaces is of extreme importance in a great variety of fields, such as submarine technology, aerospace, mining, and rescue operations. The following Example reports the deliberate construction and performance assessment of extremely sensitive sensors using an interdigitated electrode (IDE)-based capacitor and a quartz crystal microbalance (QCM) as transducing substrates. The unveiled sensors were able to simultaneously detect CO2within the 400-5000 ppm range and relative humidity levels below 40 and above 60%, using two fluorinated metal-organic frameworks-namely, NbOFFIVE-1-Ni and AlFFIVE-1-Ni-fabricated as thin films. Their subtle difference in a structure-adsorption relationship for H2O and CO2was analyzed to unveil the corresponding structure-sensing property relationships using both QCM- and IDE-based sensing modes. Metal-organic frameworks (MOFs) are a unique class of porous materials that have shown great potential for gas separation/storage, catalysis, and sensing. Recently, the use of a fluorinated MOF, namely, AlFFIVE-1-Ni, as adsorbent has offered the ability to simultaneously remove H2O and CO2from various gas streams. This property is distinctive and remarkable as the capture of both gases usually follows a competitive adsorptive mechanism. In fact, the presence of two distinct actives sites, those on open metal sites for the adsorption of H2O and those within cavities for the adsorption of CO2, explains this unique simultaneous adsorption process of the AlFFIVE-1-Ni adsorbent. In particular, this Example presents the development of the first sensing device with the ability to simultaneously detect and measure CO2and H2O. In this study, harmful levels of CO2(between 400 and 5000 ppm) and uncomfortable levels of humidity (below 40% RH and higher than 60% RH) commonly present in indoor environments were established as targets for ranges of detection. Gas sensitivity performances were analyzed using two different transduction techniques: one measuring changes in mass (using QCM) and the other measuring changes in dielectric properties (using an interdigitated electrode (IDE) capacitor). The performance of AlFFIVE-1-Ni was compared with those obtained using another fluorinated MOF, NbOFFIVE-1-Ni, which displayed a competitive adsorption process of CO2and H2O. Materials and Methods Materials All solvents and reagents were used without further purification: Ni(NO3)2·6H2O (Acros), Al(NO3)3·9H2O (Aldrich), pyrazine (Aldrich), Nb2O5(Aldrich), Ni(NO3)2·6H2O (Acros), and HF (Aldrich). AlFFIVE-1-Ni Pyrazine (384.40 mg, 4.80 mmol), Ni(NO3)2·6H2O (174.50 mg, 0.60 mmol), Al(NO3)3·9H2O (225.0 mg, 0.6 mmol), and HF (aqueous, 48%, 0.26 ml, 7.15 mmol) were mixed in a 20 Ml Teflon-lined autoclave. After dilution of the mixture with 3 mL of deionized water, the autoclave was sealed and heated to 85° C. for 24 h. After cooling the reaction mixture to room temperature, the obtained blue-violet square-shaped crystals, suitable for single-crystal X-ray structure determination, were collected by filtration, washed with ethanol, and dried in air. Elemental analysis: N %, 13.76 (theor: 14.19), C %, 21.73 (theor: 24.33), H %, 3.16 (theor: 3.57). NiAlF5(H2O)(pyr)2·2H2O (called AlFFIVE-1-Ni) was activated at 105° C. for one night under high vacuum (3 mTorr) before each adsorption measurements. NbOFFIVE-1-Ni Pyrazine (384.40 mg, 4.80 mmol), Ni(NO3)2·6H2O (174.50 mg, 0.60 mmol), Nb2O5(79.70 mg, 0.30 mmol), and HF (aqueous, 48%, 0.26 mL, 7.15 mmol) were mixed in a 20 mL Teflon-lined autoclave. The mixture was diluted with 3 mL of deionized water, and the autoclave was then sealed and heated to 130° C. for 24 h. After cooling the reaction mixture to room temperature, the obtained violet square-shaped crystals, suitable for single-crystal X-ray structure determination, were collected by filtration, washed with ethanol, and dried in air. Elemental analysis C8H12O2N4F5NiNb: N %, 11.88 (theor: 12.21), C %, 20.58 (theor: 20.54), H %, 2.54 (theor: 2.64), 0%, 11.42 (theor: 10.46). NiNbOF5(pyr)2·(H2O)2(called NbOFFIVE-1-Ni) was activated at 105° C. for 12 h under high vacuum (3 mTorr) before each adsorption experiment. QCM and IDE Electrodes. IDE-based capacitors were fabricated on a highly resistive silicon wafer using complementary metal oxide semiconductor processes. A 2 μm silicon dioxide layer was grown using wet thermal oxidation for electrical isolation. A layer of 10/300 nm Ti/Au was subsequently sputtered-deposited via physical vapor deposition in a ESC metal sputter system. Photolithography was used in the next step of the process, to define the IDEs (4 μm fingers with 5 μm spaces). The metal layer was then etched using an ion sputtering system PlasmaLab System from Oxford Instruments, with the patterned photoresist acting as the mask layer. AT-cut QCM (10 MHz) with 6 mm diameter electrodes from openQCM was used as substrate for the mass-based sensing technique. Fabrication of NbOFFIVE-1-Ni- and AlFFIVE-1-Ni-Coated IDE/QCM. Electrodes were rinsed with acetone/ethanol and dried in air. MOF paste was then deposited on one of the electrode of QCMs/IDEs by spin coating method (2 μm thick). No prior modification of the sensor surface was required for this method of deposition. The method was simple in yielding good quality and uniform films. The coated electrodes were then dried at 60° C. for 2 h under vacuum to obtain thin films of sensing materials on the electrodes. The sensors were then characterized in a custom-built sealed chamber. Before any measurements, the freshly coated MOF film on the sensors was activated in situ for 4 h to have a guest-free framework. The resulting coatings were ultrathin and reproducible so that the absorbed CO2and/or water vapor induced an effective change in the mass/dielectric properties of the thin films. Apparatus. FIG.8shows the schematic of the setup used in this study for real-time gas sensing measurements. Mass flow controllers from Alicat Scientific, Inc. were used to control the flow rate of gases from certified bottles. Stainless steel or PFA tubing (in regions requiring flexibility) along with Vernier metering valves (from Swagelok) as a flow regulator was used as delivery line in the setup. A commercial humidity sensor (Honeywell HIH-4000-003, error less than 0.5% RH) was used to monitor the humidity levels inside the test chamber. The QCM-/IDE-based sensors were exposed to the analyte stream until a stable response was attained. A two-port impedance analyzer (Keysight E5071C ENA) circuit was used for monitoring the change in resonance frequency. A LabVIEW interface was used for synchronization and data acquisition by controlling the LCR meter and the multimeter. This minimized the possibility of data loss. Results and Discussion Preparation and Characterization of Sensing Materials Recently, reticular chemistry allowed the fabrication of a series of fluorinated MOF materials with the ability to capture CO2from air or to dehydrate gas streams. The structure of these materials can be described as having a pcu underlying topology, where a square-grid Ni(pyrazine)2is pillared by inorganic building blocks, either [NbOF5]2−or [AlF5(H2O)]2−, to generate a channel-based MOF with a periodic array of fluorine moieties (FIGS.9A-9C). The structural differences between these two fluorinated MOFs resulted from the presence of an open metal site in the case of AlFFIVE-1-Ni. Markedly, gas adsorption experiments on AlFFIVE-1-Ni revealed the simultaneous adsorption of CO2and H2O molecules. In situ single-crystal X-ray diffraction and DFT calculations showed that the open metal sites were the preferred adsorption sites for H2O molecules, whereas CO2preferably adsorbed within the cavities. Desorption experiments at set temperatures conducted after adsorption of a mixture of CO2and H2O confirmed the concomitant nature of the adsorption mechanism. Similar experiments conducted with NbOFFIVE-1-Ni, an analogue with no open metal site, confirmed the competitive nature of the adsorption mechanism, with preferential adsorption of CO2to one single site located within the cavity. On the basis of these remarkable adsorptive properties, AlFFIVE-1-Ni and NbOFFIVE-1-Ni are expected to be excellent candidates for addressing challenges faced by many chemical sensors in the concurrent detection of CO2and H2O. To do so, there is a need for establishing a signal transduction process that enables the use of NbOFFIVE-1-Ni and AlFFIVE-1-Ni for chemical sensing. In recent years, QCM and IDE technologies have been proposed as new effective tools for the rapid detection of gases, volatile organic compounds, and humidity, because of their simplicity, small size, low cost, high sensitivity, shorter time of analysis, and suitability for label-free measurements. The resonant frequency of QCM substrates depends on the amount of adsorbed material. QCM can detect the change in a mass of subnanograms. The relationship between the shift in frequency and the mass loading is described by the Sauerbrey equation. Capacitive IDEs can be used to sense the change in sensing film permittivity upon gas adsorption and are seen as attractive candidates from a power consumption perspective. The key element of any chemical sensor is the sensitive layer that captures the analyte gases. MOF films are generally grown on surfaces that have been functionalized with self-assembled monolayers or by seeding with small MOF crystal. The nanostructures of these thin films have not yet been well characterized and sometimes lead to improper growth of the desired thin film. In this context, Applicants have developed, for the first time, a new synthesis method to obtain a soft homogeneous MOF solution with a paste-like consistency, making it well suited for the preparation of a wide range of homogeneous thin film. Indeed, the method can easily be adapted to the deposition or spin coating of thin films from a chemical solution. A representation of this is presented in (FIGS.27A-27B), which shows a good uniformity in the deposition of the crystals, along with an improved adhesion to the substrates. AlFFIVE-1-Ni and NbOFFIVE-1-Ni films contain close-packed crystal domains, exhibiting a good coalescence of microcrystals with small intergranular voids, leading to compact and uniform MOF films of excellent crystallinity. NbOFFIVE-1-Ni films comprised small cubic crystallites of approximately 150 nm, whereas larger crystallites of about 7 μm were found for AlFFIVE-1-Ni. The purity and crystallinity of the deposited MOF films were confirmed by powder X-ray diffraction experiments (FIGS.28A-28B). Gas Sensing Properties Concurrent Sensing of CO2and H2O The use of MOF thin films for sensing application required a critical activation step, permitting the attainment of a guest-free thin film before any sensing signal measurement was to be performed. For this reason, the MOF adsorbent was fully reactivated at 105° C., before each new cycle of analyte exposure, using in situ heating provided by a HT24S metal ceramic heater from Thorlabs. The output temperature of the heater was calibrated and monitored using a LM35DZ/NOPB commercial temperature sensor from Texas Instruments (FIG.29). This calibration was of prime importance to preserve the integrity of the MOF adsorbent and to ensure that guest-free activated NbOFFIVE-1-Ni and AlFFIVE-1-Ni were obtained before sensing experiments. The sensing characteristics and performance of NbOFFIVE-1-Ni and AlFFIVE-1-Ni were investigated at variable CO2concentration in dry and humid conditions to verify the potential application of the newly fabricated sensors. Interestingly, NbOFFIVE-1-Ni and AlFFIVE-1-Ni coated on IDE and QCM as sensors exhibited a nonlinear change in the signal over several orders of magnitude of CO2concentration (from 400 to 5000 ppm). The capacitive properties of the IDE exhibited a dielectric constant dependency of the material, because of the change in CO2concentration. The capacitance was calculated using the standard capacitance equation. The exposure of all sensors to different dry CO2concentrations led to a sharp decrease in the capacitance (FIGS.30A-30B). Additionally, the interaction of CO2with NbOFFIVE-1-Ni and AlFFIVE-1-Ni changed the local dielectric properties of the thin films, resulting in a decrease in capacitance. Remarkably, the interdigitated sensor devices coated with NbOFFIVE-1-Ni showed a significantly higher change in capacitance (about 100 times, for 400-5000 ppm of CO2) when compared to AlFFIVE-1-Ni. These observations were in agreement with the remarkably favorable selectivity of CO2obtained from calorimetric and co-adsorption tests. FIGS.30C-30Ddepict the concentration-dependent responses of NbOFFIVE-1-Ni or AlFFIVE-1-Ni coated on QCMs as sensors to different concentrations of CO2at room temperature and under dry conditions. It was observed that when the gas entered in contact with the QCM-based sensors, CO2molecules were adsorbed on the sensitive film and the mass increased in a proportional manner, producing a negative shift in resonance frequency. That is, the decrease in resonant frequency (FIGS.30C-30D) as the CO2concentration increased was seen very clearly, showing a good response of the QCM to CO2. In the case of QCM devices, the maximum shifts in frequency were −84.85 Hz for NbOFFIVE-1-Ni and −3.5 Hz for AlFFIVE-1-Ni at CO2concentrations ranging from 400 to 5000 ppm. These results were in good agreement with NbOFFIVE-1-Ni exhibiting a higher interaction with CO2at a low loading (53 kJ/mol) versus a weaker interaction (45 kJ/mol) for AlFFIVE-1-Ni. In the case of IDE sensing mode under dry CO2conditions, a high adsorptive selectivity was observed at low CO2loadings and concentrations for NbOFFIVE-1-Ni versus AlFFIVE-1-Ni. Interestingly, the MOF-coated mass-sensitive QCM devices exhibited a lower sensitivity toward CO2under dry conditions than the IDE capacitors. Part of the reason for this difference was that the IDE capacitors can detect larger effects of CO2on dielectric properties of the thin films, whereas the mass-sensitive QCM devices were only able to detect small mass changes. Effect of Synthetic Air on Concurrent Sensing of CO2and H2O. In general, the moisture from the environment had a considerable impact on the sensitivity of the gas sensor and must be taken into consideration for practical deployment of any sensor. Therefore, the concentration-dependent response of the IDE and QCM devices coated with NbOFFIVE-1-Ni or AlFFIVE-1-Ni to CO2under humid conditions was investigated. The relationship between the resonant frequencies of the QCM sensors and the RH (60%) is shown inFIGS.31A-31D. The sensitivity of NbOFFIVE-1-Ni coated on QCM as a sensor was reduced in the presence of moisture and was easily distinguishable from the response of CO2in the air. However, the sensitivity was considerably reduced with AlFFIVE-1-Ni-coated QCM, and its frequency was reduced even more, especially at low CO2concentrations. In the case of IDE-type sensing, NbOFFIVE-1-Ni- and AlFFIVE-1-Ni-coated IDE sensors were greatly affected by the presence of moisture. In fact, an often heard objection to capacitive sensor technology is that it is sensitive to humidity, yet the capacitive sensor is based on dielectric changes of the thin film upon water vapor uptake. Practically, humidity and condensable vapors are shown to have a significant effect on the IDE-based sensors because water has a dielectric constant εr of 78.3, that is, −48 times larger than CO2(εr=1.60). The presence of moisture often interferes with the IDE sensory signal of CO2and thereby can hamper its qualitative identification and quantification. Accordingly, the results presented here show that QCM-based sensors are a good alternative to compensate the loss of performance in IDE-based sensors, because of the presence of humidity. A detailed analysis of the sensitivity to H2O as a function of RH (26 to 60% RH) was performed to further delineate the water vapor adsorptive based sensing performance. After an initial activation cycle at 105° C., the sensors were cooled to room temperature and subsequently exposed to different levels of RH, using N2as a gas carrier. The RH level was varied by changing the carrier flow (0 to 200 mL/min) bubbling through the water. It should be noted that an ideal sensor swiftly senses water vapor, in the optimal range of 26-65% RH. This is the desired range of humidity levels for confined spaces, conforming to the standards set by the occupational health safety. The humidity sensing behavior of the AlFFIVE-1-Ni-/NbOFFIVE-1-Ni-coated IDE- and QCM-based sensors, as shown inFIGS.32A-32D, revealed a response in a nonlinear fashion with good sensitivity in the recommended range of humidity levels (26-65% RH). Notably, AlFFIVE-1-Ni and NbOFFIVE-1-Ni had an almost simultaneous response to change in humidity levels; however, as expected, the presence of an open metal site in highly confined pores, in the case of AlFFIVE-1-Ni thin films, offered a greater sensitivity to humidity. In fact, the exposed Al3+of the AlFFIVE-1-Ni framework served as the initial preferable adsorption site for water molecules, when exposed to different levels of RH levels. Humidity levels above 60% have a considerable impact on the sensitivity, which was related to the nature of the MOF adsorbent. AlFFIVE-1-Ni exhibited a sensitivity five times higher than NbOFFIVE-1-Ni, in the 26-60% RH range. On the other hand, a comparison of the effects of the transduction mechanisms on the sensing performance under humid conditions clearly showed that QCM-based sensors were more reluctant to changes than IDE-based devices. It is to be noted that the shift in frequency and capacitance decreased more steeply, when RH exceeded 60%, a phenomenon that can be explained by the aggregation of water molecules on thin films. To mimic the real conditions (atmospheric conditions), experiments were also performed in the presence of 500 ppm CO2, using both transduction techniques (FIGS.33A-33D). After an initial exposure to 500 ppm CO2, both samples exhibited a decrease in their sensing signals, as a function of the subsequent exposure to humidity. In the case of AlFFIVE-1-Ni, this decrease was almost two times higher than that observed for NbOFFIVE-1-Ni. Interestingly, changes in CO2levels had a lower impact (four times lower) for NbOFFIVE-1-Ni than that for AlFFIVE-1-Ni. This suggested that a partial desorption of noncoordinated water molecules occurred easily for NbOFFIVE-1-Ni, because of their relatively weak interactions occurring with the framework, compared to those of CO2with the framework. In the case of AlFFIVE-1-Ni, the water molecules coordinated to the open metal site could not be desorbed because of their stronger interaction with the open metal sites in the presence of CO2, therefore causing unchanged performances for water detection. Although both QCM and IDE responded to variable H2O and CO2concentrations, the sensitivities were not identical. Accordingly, the detection of CO2in the presence of variable humidity levels under real (atmospheric) conditions were directly observed by a shift in the resonance frequency of QCM. However, the capacitive sensor did a much better job of reflecting the changes in humidity levels in the presence of 500 ppm CO2. Stability Studies. The most important parameters for a given sensing device are its stability and reproducibility. These parameters were investigated by cyclic exposure every 48 h at room temperature for over a period of 12 days (FIGS.34A-34B). It was clearly shown that both sensor responses did not vary significantly with time, confirming their long-term stability. These results pinpointed some of the most important elements required for the choice of materials granting comfortable/healthy indoor conditions; they also shed light on the associated transduction mechanisms required for the concurrent detection of harmful levels of CO2and humidity in a condition akin to atmospheric conditions and confined environments. The response of the sensors to humidity and CO2showed that sensitivity and resolution were dependent on both the transduction mechanism and the sensing material. However, the response, stability, selectivity, detection limit, and life cycle were found to depend only on the intrinsic properties of the sensing material. In summary, the present Example reports, for the first time, the use of both IDE- and QCM-based sensors for the simultaneous detection of CO2and H2O using ultramicroporous fluorinated MOFs, exhibiting unprecedented structural CO2—H2O adsorption properties. The sensors exhibited excellent selectivity for sensing CO2at variable humidity levels; they also detected humidity levels at variable CO2concentrations. It has been shown that isostructural fluorinated MOF-based capacitance sensitive sensors possessed good CO2sensing properties under dry conditions. When working under real conditions (atmospheric conditions), the change in the dielectric constant over the change in the CO2concentrations and at a constant humidity level of 60% RH resulted in a decrease in capacitance. The detection of CO2under real conditions was directly observed on the QCM frequency shift. However, the capacitive sensor did a better job reflecting the changes in humidity in the presence of CO2. At room temperature, all the sensor's properties reported herein make the reported sensor a promising candidate for the detection of CO2and water vapor when used for indoor and confined spaces. Other embodiments of the present disclosure are possible. Although the description above contains much specificity, these should not be construed as limiting the scope of the disclosure, but as merely providing illustrations of some of the presently preferred embodiments of this disclosure. It is also contemplated that various combinations or sub-combinations of the specific features and aspects of the embodiments may be made and still fall within the scope of this disclosure. It should be understood that various features and aspects of the disclosed embodiments can be combined with or substituted for one another in order to form various embodiments. Thus, it is intended that the scope of at least some of the present disclosure should not be limited by the particular disclosed embodiments described above. Thus the scope of this disclosure should be determined by the appended claims and their legal equivalents. Therefore, it will be appreciated that the scope of the present disclosure fully encompasses other embodiments which may become obvious to those skilled in the art, and that the scope of the present disclosure is accordingly to be limited by nothing other than the appended claims, in which reference to an element in the singular is not intended to mean “one and only one” unless explicitly so stated, but rather “one or more.” All structural, chemical, and functional equivalents to the elements of the above-described preferred embodiment that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for a device or method to address each and every problem sought to be solved by the present disclosure, for it to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. The foregoing description of various preferred embodiments of the disclosure have been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure to the precise embodiments, and obviously many modifications and variations are possible in light of the above teaching. The example embodiments, as described above, were chosen and described in order to best explain the principles of the disclosure and its practical application to thereby enable others skilled in the art to best utilize the disclosure in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the disclosure be defined by the claims appended hereto. Various examples have been described. These and other examples are within the scope of the following claims.
66,657
11857911
DESCRIPTION OF THE PREFERRED EMBODIMENTS FIGS.3and4schematically illustrate the principles of the invention, for a simple case.FIG.3depicts just one module1of the cluster of 3 modules that make up one of the two adsorbers of the PSA unit. Its inlet E1, in the lower part, is connected to the common inlet manifold of axis Xe via the inlet nozzle Te1. Its outlet S1, in the upper part, is connected to the outlet manifold of axis Xs via the outlet nozzle Ts1According to the invention, the axes Xe and Xs are coincident to form the single axis6and, on the one hand, the 3 inlet nozzles and, on the other hand, the 3 outlet nozzles are geometrically identical to those depicted inFIG.3(straight length, bend, straight length). FIG.4is a view from beneath of the cluster of 3 modules (1,2,3) that make up one of the adsorbers of the PSA unit. The inlets of the modules are now identified (E1, E2, E3), and the inlet nozzles (Te1, Te2, Te3). According to the invention, the 3 inlets (E1, E2, E3) lie on the circle (7). It will be noted that, according to a preferred variant of the invention, the angles between the inlet nozzles (the angle identified (6) between the modules1and3) each measure approximately 120°. The word “substantially” used to define the alignment of the axes of the manifolds, of the position of the inlets and outlets of the modules, of the identical geometry of the nozzles, means in this instance “to within the usual production tolerances”. These tolerances cover both the construction of the various elements, their installation and connection on site, and the small modifications that may occur when the unit is in operation (under the effect of temperature, pressure, stress, etc.). The tolerances envisioned here are the normal tolerances corresponding to this type of unit. Thus, for example, the axes Xe and Xs could be not entirely vertical as depicted, but differ from the vertical by a few degrees. With respect to a “substantially” common vertical axis, the respective centers of the common inlet and outlet manifolds could be distant by, for example, one centimeter. What that means to say is that the unit is produced according to the rules of the art that are conventional for an industrial unit without the addition of additional constraints that might potentially improve the distribution of the fluids in the various modules operating in parallel but would increase the cost of embodiment and/or render same more difficult. It will be noted that the center of the generally circular orifice via which the fluids enter and leave the module is referred to here as “inlet” and “outlet” of the module. When N is greater than 4 or than 6, intermediate groupings of N/2 or N/3, etc. modules may potentially be made, and these subsets then collected together. Nevertheless, that increases the complexity of the distribution system by introducing more resistances (elbows, tees, connectors), causing more head-losses, more dead volumes and increasing the risk of poor distribution between modules. For these reasons, the installation described hereinabove is favored. As the case may be, the method according to the invention can exhibit one or more of the features below:the length of the straight inlet duct is greater than 3 times its diameter, preferably than 5 times its diameter;the length of the straight outlet duct is greater than 3 times its diameter, preferably than 5 times its diameter; this feature together with the previous one make it possible to have stream lines that are approximately uniform and parallel to the wall at the point at which streams diverge or come together so that no module is favored by, for example, the presence of an elbow or of a tee too close to this zone. If a great deal of attention is not paid to this point, major defects in the distribution between modules may result;the straight inlet duct and/or the straight outlet duct comprises within it a system for evening out the circulation of the gas mixture that is to be purified or that has been purified; this makes it possible to obtain uniform flow through the common manifolds in the collecting (separation, coming-together) zones of the nozzles. The use of this device will become essential when, by construction, it is impossible to obtain a sufficient straight length, which is to say a length equal to several times the diameter, of the common manifold, or when, because of other unavoidable spreads in other portions of the piping, there is a desire to have near-perfect distribution, for example distribution to within + or −0.5%, or even of the order of 0.25%, at this point. There are several devices available for this purpose, such as one, or preferably 2 or 3, plates extensively perforated with a number and diameter of holes suited to the operating conditions. However, other types of device will be given greater preference. Thus, the benefit of a system of the static mixer or packing type is that it is both effective and creates practically no head-losses. It will be duly noted that this is a fixed device installed inside the common manifolds rather than an adjustable system installed at the nozzles of each module. The sole purpose of the device in question is to get as close as possible, respectively upstream on the inlet side and downstream on the outlet side, to the velocity profile that characterizes a fluid flowing in steady-state along a straight length of piping.the evening-out system is a static mixer or a mixer of the cross packing type.the first circle and the second circle have substantially identical radii. This embodiment will be very widely adopted when the adsorbent is in the form of particles. It minimizes the risk of bypassing and makes it possible to obtain very uniform interfaces between adsorbents or between adsorbent and support. In the case of monoliths and more generally of contactors with parallel passages, other installations, such as a horizontal or angled arrangement, are possible and the inlets and outlets may lie on circles of different radii. It will be recalled that what is meant here by inlet and outlet is the center of the inlet and outlet orifices of the modules.the connections of the inlet nozzles Tei, where i ranges from 1 to N, of the N modules to the straight inlet duct of the common inlet manifold are spaced apart by an angle of approximately 360/N degrees.the connections of the inlet nozzles Tei, where i ranges from 1 to N, of the modules to the straight inlet duct of the common inlet manifold are spaced apart by an angle of approximately 360/N degrees. This feature, together with the previous one, once again makes it possible to encourage the symmetry of the nozzle collecting assemblies. Such a spatial distribution is not compulsory if the consequence of another arrangement can be calculated, for example using fluid mechanics, and this consequence can be incorporated into the distribution calculations. Nevertheless, a nozzle distribution like the one recommended will be preferable wherever possible because it allows the overall system to be optimized as far as possible by limiting the presence of defects in the places where defects are almost inevitable (welds, etc.).each adsorber comprises a cluster of 2 to 12 identical modules operating in parallel, preferably of 3 to 6 identical modules operating in parallel.each adsorber comprises 2 to 5 clusters of 2 to 12 modules operating in parallel, preferably of 3 to 6 modules operating in parallel, with all of the modules of the unit being identical. Note that the clusters of N modules have similar geometries. Specifically, the differences between the adsorbers will lie solely in the installation and orientation of the various modules from one adsorber to another.said unit is a unit of the O2 VSA or O2 MPSA type comprising 1 to 4 adsorbers comprising 1 to 4 clusters of 3 to 6 modules.said unit is a unit of the CO2 VSA, CO2 MPSA or CO2 PSA type comprising 1 to 12 adsorbers comprising 1 to 6 clusters of 2 to 8 modules.said unit is a unit of the CO2 VSA or CO2 MPSA type comprising 1 to 8 adsorbers comprising 1 to 4 clusters of 3 to 6 modules.the N modules each comprise a volume of adsorbent of between 50 liters and 25 m3. As explained above, according to one preferred embodiment, the unit employs a plurality M of adsorbers (M= or >1), each of these adsorbers being made up of a cluster comprising from 2 to 12, preferably from 2 to 6, identical modules operating in parallel. Upwards of 6 modules, installing them symmetrically may require more space than is available and lengthen the nozzles. It may therefore prove advantageous to replace a large-sized adsorber with several clusters of a few modules each rather than employing one cluster comprising an excessive number of modules. In that case, preference will be given to clusters comprising an identical number of modules. In the case of PSA units processing high throughputs, use will therefore be made of a variant employing a plurality M of adsorbers (M= or >1), each of these adsorbers being made up of K clusters, where K is preferably comprised between 2 and 5, each comprising N identical modules, N preferably being comprised between 3 and 6, all operating in parallel. With such a layout, it is possible to cover a broad range of throughputs. In such a configuration, namely a PSA unit comprising a plurality M of adsorbers, each of these adsorbers being made up of a plurality K of clusters of N identical modules operating in parallel, the K inlet manifolds of the clusters are connected to the main inlet manifold of the adsorber made up of these K clusters, and the K outlet manifolds of the clusters are connected to the main outlet manifold of that same adsorber. FIG.5illustrates such an installation in the event that each adsorber is formed of 4 clusters of 3 identical modules, Only the first adsorber is depicted, and is depicted incompletely, in order to avoid overloading the figure. The adsorber1is therefore made up of the clusters referenced10,20,30and40. Each cluster comprises 3 modules such as10.1,10.2,10.3in the case of the cluster10. Each cluster has its inlet manifold (12,22,32,42) and its outlet manifold (14, . . . ). The inlet nozzles of each module of the cluster10, namely the nozzles Te1, Te2and Te3, meet at the manifold12. The same is true on the outlet side with the nozzles Ts1, Ts2and Ts3, and the common manifold14. The 4 inlet manifolds of the 4 clusters are connected to the separation piece4situated at the end of the straight inlet duct of the inlet manifold2of the adsorber1. The valve3situated on this manifold allows the pressure cycle to be performed. All of the pipework downstream of this valve, including the distribution piece4, therefore forms part of the dead volumes on the supply side. The system of grouping together the outlets of the modules and of the clusters, which is depicted very partially, is similar to the system employed on the inlet side. As depicted inFIG.5, measures will be taken to ensure that the flow rates of the gas flows heading toward or coming from the K clusters via the common inlet and outlet manifolds are rendered very substantially equal by having this piping follow an equivalent geometric line. In practice, the same type of rules as for the distribution between modules of the one same cluster will be applied. The collecting piece5(not depicted) that collects together the outlet manifolds of the 4 clusters, which is equivalent to the piece4on the inlet side, will have the same axis2as this inlet piece. In order for the flow regime to be uniform, straight lengths L that are sufficiently long, namely of a length equal to at least 3 times the diameter d, preferably to 5 times the diameter d, will be provided. If necessary, use will be made in these sections of piping of a system which eliminates flow distortions associated with the presence of elbows, tees and, more generally, any obstacle encountered by the fluid. It will be appreciated that, for the sake of simplicity and symmetry, in a pressure swing adsorption unit comprising a plurality M of adsorbers (M= or >1), each of these adsorbers being made up of a plurality (K, K= or >1) of clusters each comprising N (N= or >2) modules, the M*K clusters constituting said unit have a geometric configuration that is essentially identical, although the orientation in space of these clusters may itself differ. It will be noted that, here too, there are other ways of combining the manifolds of the 4 clusters symmetrically. The manifolds of 2 clusters can be first of all connected to an intermediate manifold, and the same thing done for the 2 other clusters. The 2 intermediate manifolds are then connected to the common manifold of the adsorber, Just as with the modules, such an installation is not desirable because of the additional volumes and head-losses, but it may be rendered necessary by installation constraints, for example the width available not allowing a circular setup on this scale. The principle of the invention will now be explained in terms of its application to a unit for producing oxygen from atmospheric air using a process of the MPSA type with a high pressure of 1.55 bar abs and a low pressure of 0.47 bar abs. The 2-adsorber cycle comprises a step of producing oxygen at increasing pressure of around 1.4 to 1.55 bar abs, a co-current decompression step, a co-current decompression step with simultaneous countercurrent pumping, a countercurrent pumping step, two steps of elution with production gas and with the gas derived from decompression, a repressurization step with, simultaneously, co-current atmospheric air and gas derived from decompression, a final recompression with air and possibly with oxygen. The total cycle time is 38 seconds give or take 3 seconds according to the particular conditions on the site. The reservoirs (modules) used are all identical with a cylindrical shell ring with a diameter of 2100 mm, and a height of 1300 mm. The unit considered by way of example is a unit of medium size, each adsorber being made up of a single cluster of 3 modules. The production of oxygen ranges from around 33 to a little over 40 tonnes per day depending on the desired purity (from 90 to 93.5 mol %), the choice of machines, of adsorbents and the local conditions (temperature, humidity, altitude, etc.). The choice of machines and of adsorbent is an essentially economic choice based on the trade-off between investment and energy consumption. From the inlet to the outlet, in the direction in which air is supplied toward the oxygen outlet, each module comprises an inlet opening connected to the inlet nozzle, a flow splitter of the spherical cap type or of cylindrical shape, which is very highly perforated and acts as a deflector, a bed of inert particles of diameter 25 or 40 mm allowing the fluid to spread uniformly over the entire cross section of the adsorber, the adsorbent material, a system that makes it possible to reduce the dead volumes in the upper part and serves to maintain the bed, a second flow splitter/manifold and an outlet opening connected to the outlet nozzle. The adsorbent material consists, from the inlet toward the outlet, of one or two layers of adsorbent serving to stop most of the moisture, the CO2 and the atmospheric pollutants, a layer of zeolite serving both to capture the very last traces of impurities and contributing to the O2/N2 separation and one or two layers of lithium-exchanged zeolite suited to O2/N2 separation. Phase change materials may be added to all or some of the zeolite beds. It will be pointed out in this regard that an additional benefit connected with the use of axial adsorbers rather than radial adsorbers is the greater ease with which several layers of different adsorbents can be employed, these in this instance simply having to be superposed when packing the bed. Each of the adsorbents selected is closely specified with its supplier in order to obtain products of which the characteristics remain constant over time. This is particularly the case with particle size, density and adsorption characteristics. The modules are packed in the workshop with special tooling and detailed protocols. In this way, differences between the modules of one same unit are minimized. The manufacturing tolerances are the standard tolerances for this type of construction, namely of the order of a few millimeters. These tolerances have no impact on the performance of the modules. In practice, they are smaller than may be encountered with radial adsorbers where a lack of concentricity and longitudinal flexing of the gratings may introduce somewhat more significant effects. FIG.6is a 3-dimensional view of the 3 modules that make up the cluster. On the inlet side, in the lower part, the 3 nozzles are connected to the common inlet manifold. The latter has a straight length of the order of 5 times the diameter before heading off perpendicularly via an elbow. The diameter of the nozzle is 200 or 250 mm, depending on the model, and the diameter of the common manifold is 400 or 450 mm. The three nozzles are connected at the same level, at 120° C. from one another, and are geometrically identical. The arrangement of the nozzles on the production side, in the upper part, is identical, with nozzles of diameter 150 or 200 mm, and a 300 mm common manifold, A system G of the static mixer (or packing) type is provided in order to eliminate the effects that a nearby tee (not depicted) has on the flow. The axes of the straight parts of the manifolds are aligned and the inlets and outlets of the modules, for reasons of symmetry, are on circles of the same radius. The velocities of the flow of gases in the various pipes will range from 15 to around 50 m/s, as the case may be. It may be seen that the cluster used here follows exactly the same principle as one of the clusters ofFIG.5. FIG.7is a partial view of the unit from above, showing the 2 clusters of 3 modules with their nozzles, positioned on a standard metallic structure approximately 12 meters long by 2.5 meters wide, containing most of the piping and valves of the unit and which can be transported as-is. The machines not depicted inFIG.7, namely air compressor and vacuum pump, are positioned outside the structure, in the continuation of the major axis thereof, A support system that locally extends the metallic structure is added to the upper part in order to securely hold 2 of the support legs of the 4 modules installed in partially cantilever fashion. For each cluster, the differences between the branches that separate or bring together the fluids are minimal and essentially caused by the presence of elbows or tees on the common manifolds or by the presence of welded seams of greater or lesser thickness. Calculations using conventional pressure-drop formulae and/or using fluid mechanics simulations covering the modules with their internals (distributor, adsorbent material, retention system, etc.) show that through the precautions listed hereinabove regarding the manufacture, particularly the packing and installation, the distribution between modules can be at least as good as the distribution within the radial adsorbers used in this type of process for over a decade. It is therefore entirely possible to employ clusters of modules in place of a larger-sized adsorber without the need to install, between modules, more complex and more expensive equalizing systems which, if poorly set up as a result, for example, of a drift in the instrumentation, could act counter to the desired effect. An industrial embodiment corresponding to an 02 MPSA unit of intermediate size has been considered by way of example, but it will be appreciated that the principle of the invention can be applied to clusters comprising more modules, to adsorbers comprising for example 2 clusters of 3 modules. One possible solution in this case is to keep the configuration ofFIG.7for one adsorber, another identical element being installed in parallel, with the machines being positioned between the two structures. There is a great deal of flexibility around installation provided that symmetry is adhered to with respect to the modules and with respect to the various clusters that make up an adsorber. With just one single geometry for the modules, it is possible to cover an entire production range extending, for example in the case of O2 MPSA, from 15 to 120 tonnes of oxygen per day. It can therefore be appreciated that the mass-production effect plays a significant part in reducing costs. The invention will advantageously apply to O2 VSA and MPSA, to CO2 or CO PSA (in the broad sense), these processes generally having a low pressure close to atmospheric pressure and very often lower than the latter. It can be used more generally where there is a wish to reduce dead volumes or head-losses while at the same time ensuring good distribution of the fluids through the absorbent masses. The number of adsorbers employed will depend on the envisioned separation, and especially on the complexity of the pressure cycle involved. In the case of the above-mentioned separations, this number will preferably remain less than or equal to 4 for the production of oxygen, 6/8 for the production of CO, and 8/12 for the capture of CO2. The number of clusters and of modules per cluster will essentially depend on the throughput of charge gas and on the size adopted for the modules. In general, use will be made of 1 to 6 clusters per adsorber and of 2 to 6 modules per cluster. The dimensions of the modules will generally be limited by transportation at the upper end of the scale and by economic considerations at the bottom end (several small adsorbers to be compared with one medium-sized adsorber). Other criteria not mentioned here may favor the choice of several small adsorbers (namely clusters of N modules): evolution of unit throughput over time by adding modules, periodic module change-out if modules become contaminated. A broad range of possible dimensions for these modules is anticipated, for example a diameter of 0.4 to 2.5 meters and a height of 0.4 to 5 m, for volumes ranging from around 50 liters to 25 m3. It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above.
22,675
11857912
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The present invention will be described in more detail with the aid ofFIGS.2to4. InFIG.2B, an adsorbent mass20which retains the impurities I of the stream B has been shown. Over time, the impurity front progresses towards the outlet. The stream A for its part regenerates the adsorbent mass30by pushing the impurities back to the reservoir. It is understood that by alternating the adsorbent masses between the streams B and A, it is possible to produce a purified stream B. Such a system no longer requires that the streams A and B be simultaneous and offers a few degrees of freedom. However, it must be possible for the stream A to be able to extract all of the impurities from the stream B stopped in the adsorbent mass. Those skilled in the art know how to determine the conditions necessary for such regeneration. At constant temperature, for example, the amount of actual m3of the stream A which is passed through the adsorbent should be greater than the amount of actual m3of the stream B passed in counter-current mode. At almost equal pressure for the two gas streams (for example reservoir pressure except for pressure drops), it would thus in theory be possible to purify a gas stream B representing approximately 90% by volume of the stream A, but in practice a lower percentage will lead to a more efficient unit. It is also possible to use an absorption process40, in other words a closed loop washing, the washing liquid I of the stream B being regenerated by the stream A. The latter process may have the disadvantage of introducing into the system the constituent(s) used for washing (cf.FIG.2C). It should be noted that the proposed process is different from a conventional purification by means of which an impurity is extracted for discharge out of the system. In this case, the impurities are transferred to the reservoir feed gas, taking advantage of the fact that it is itself free of said impurities or that it contains a small amount thereof. There is thus no loss of exploitable constituents. Another advantage may be the simplicity of implementation of the invention. Example 2 in particular illustrates this aspect of the invention. It may seem paradoxical to reintroduce the impurities from the reservoir into the feed gas of this same reservoir, but in practice many applications are very well suited to this state of affairs. Here again, the examples will illustrate this point. FIG.3Aschematically represents a hydrogen production, storage, transport and distribution unit. Hydrogen of 99.99 mo. % purity is produced in the unit10. This unit10comprises, among other things, a steam reforming of natural gas which creates the H2molecules and a PSA which purifies this hydrogen to the desired purity. These are very conventional units well known to those skilled in the art. Depending on the production capacity required, the geographical location and the economic conditions, it would be possible for there to be other units for producing hydrogen molecules (reforming of propane, of methanol, electrolysis, etc.). Most of this purified hydrogen1is injected into an underground reservoir20created in a salt deposit. The stored volume corresponds to several weeks of consumption. A fraction3of the hydrogen is extracted from the reservoir and feeds a pipe4which serves several consumers located tens or even hundreds of kilometers away (4.1, 4.2, 4.3, 4.4, etc.). Some of these customers require extremely high purity (99.9999 mol %) and a secondary purification is then implanted just upstream of the place of consumption. It is then, for example, hydrogen used for the manufacture of electronic components. The secondary purification is then generally carried out by cryogenic adsorption at the temperature of liquid nitrogen. In normal operation, a small amount of pure hydrogen2, of the order of 10%, is sent directly into a local network. The purity required is in accordance with that of the production. The reservoir20essentially has 2 functions. The first is to be able to average production over a long consumption period. In fact, among the various users, the hydrogen requirements are far from constant: some processes using H2are batchwise, some operate periodically at reduced load or at high load, etc. Despite all these variations, it is therefore possible to operate the unit10on a regular basis thus optimizing production. It is also possible to have it operate for a few weeks at nominal flow rate, that is to say under the best possible conditions, and to shut it down completely for a week. It is also possible to take advantage of preferential tariffs for energy and to temporarily stop or reduce production on demand, thereby making significant energy-cost savings. The other function of the reservoir20is to have a large volume of gas in reserve to compensate for an unforeseen or programmed shutdown of the unit10while continuing to supply customers with hydrogen. The reservoir20is essentially sealed due to the local geology, but some impurities pass from the wall to the gas. They will essentially be moisture, possibly traces of HCl, H2S, CO2. Depending on the geological nature of the reservoir, traces of various hydrocarbons may be found. These additional impurities in small amounts are generally acceptable for the majority of users, the purity of the product1generally being above the specifications required for direct use of hydrogen. In the opposite case, that is to say the need for very pure hydrogen, the additional purification40, already provided for, is generally capable of removing the additional impurities. On the other hand, these impurities can be troublesome for the local network2which is usually supplied directly with purified hydrogen and which would then periodically experience additional impurities. The conventional solution is then to use an additional purification unit30to treat the gas stream5extracted directly from the reservoir. This unit (30inFIG.3A) which is only used occasionally will not be of the cryogenic type because these units, while they are very safe in terms of operation, are very expensive, require special utilities. (liquid nitrogen) and do not lend themselves well to batchwise operation. The basic solution will be an adsorption purification unit, of the TSA (Temperature Swing Adsorption) type proportioned to retain the impurities and to produce a stream of hydrogen at the required specification6. Regeneration of the adsorbent can be more or less complex depending on whether or not it is desired to limit the hydrogen losses in the purge flow7. Such a unit will comprise 2 or 3 adsorbers, an electric or steam heater, and a valve skid to allow the cycle to proceed. In the solution according to the invention (FIG.3B), just an adsorbent mass50is integrated into the path of the fluid1upstream of its entry into the reservoir. This mass swept for a long time in normal operation by hydrogen stream exiting in this case the PSA will be saturated with the residual impurities present in the purified hydrogen (traces of CO, CH4, N2) but will be completely free of water, HCl, etc. . . . . When the production unit10is stopped, the network4will be normally supplied from the reservoir. The flow used locally will also be extracted from the reservoir5and will pass in the opposite direction to the stream1through the adsorbent mass50. This mass will be proportioned according to the impurities present, the acceptable amounts and the expected duration of operation (duration of the downtime for maintenance for example, etc.). The amount of adsorbent will generally be greater than the amount required in the base solution described above, but the simplicity of operation, the absence of ancillary equipment and the fact that there is no loss of material mean that the latter solution has a much lower overall cost than the conventional solution. It is also safer since it does not require a succession of adsorption and desorption phases in order to operate. Regeneration of the adsorbent mass occurs naturally when unit10is put back into production. The stream1then passes, in counter-current mode, through the various beds of adsorbents (zeolite, activated alumina, silica gel, etc.) and entrains the impurities introduced by the stream5. As the temperature remains approximately constant and close to ambient temperature during adsorption and desorption, it is theoretically sufficient for the volume amount (actual m3) of the stream1sent to the reservoir to be greater than that of the stream5in order for it to be possible for the regeneration to be carried out. In practice, a much larger volume of gas is available and the adsorbent mass will be completely regenerated and ready for the next purification of the stream5; it will be noted that a temperature of the stream5lower than that of the stream1will promote both the stopping of the impurities and the regeneration thereof. Conversely, a lower pressure of the stream5may require a greater adsorbent mass. These points are known to those skilled in the art who will have no difficulty in determining the parameters required for good operation (type of adsorbent, useful mass, etc.) and there is no need here to go into more detail about the precise proportioning of the purification50. The second example relates to a unit for producing oxygen from atmospheric air by adsorption. More specifically, it is a VSA type unit in which the oxygen is produced at a pressure close to atmospheric pressure (1.10 bar abs) referred to as high pressure of the cycle and the regeneration is carried out by producing a vacuum of a minimum pressure, referred to as low pressure, of the order of 0.35 bar abs. There are many cycles for VSA units of this type differing by the number of adsorbers, the number of storage tanks used and by the type and/or sequence of the substeps (balancing, decompression, elution, recompression, etc.). There is no need here to go into the details regarding the unit in question. Only a few characteristics are of interest with respect to the invention. FIG.4schematically shows such an oxygen production unit. It comprises 2 adsorbers marked10and20which operate in phase shift. The air1is introduced into the system by means of the compressor30, in practice here of the fan type. The vacuum is created by means of the vacuum pump40which extracts a nitrogen-rich residue6. The oxygen produced by an adsorber, for example10, and which is not immediately used for the regeneration of the other adsorber20—stream4in the diagram—is sent (gas stream A which here corresponds to gas stream2) to the storage50after having passed through the purification unit60. The gas stream C (gas stream3in the figure), which constitutes the production of the unit, is continuously extracted at constant flow rate from the storage50. The production of oxygen leaving the adsorber is not continuous and instead takes place over only half the “adsorption” phase. In addition, as specified above, a portion of this oxygen is taken directly to participate in the regeneration of the other adsorber. A buffer tank50(storage reservoir) is therefore necessary for storing the oxygen from an adsorber in order to ensure constant production. Since the oxygen is produced at a pressure barely greater than atmospheric pressure in the example selected, a very advantageous solution for the storage reservoir50is to use a gasometer. The pressure of the gas will then remain constant, for example 1.050 bar abs and it is the volume of the reservoir that will naturally change during the course of the cycle. This type of gasometer is conventional and inexpensive. However, since the shell is made of polymer and since said polymer is slightly permeable to water, a little atmospheric moisture will pollute the very dry oxygen produced by adsorption. In almost all applications, these traces of moisture have no impact on the downstream process and are perfectly acceptable. However, in the cycle used here, it is necessary to finish recompressing the adsorber during regeneration with oxygen during a step where the other adsorber no longer produces this oxygen. A fraction of the oxygen (stream5=gas stream B) stored in the storage reservoir50should therefore be used for this purpose. It has been seen that the oxygen in the storage contained traces of moisture, of the order of 1 ppm or a few ppm. These amounts are minute but nevertheless unacceptable for the VSA. This is because this water will get trapped at the top of the adsorber on the zeolite which separates the nitrogen from the oxygen at each cycle and then after accumulation will tend to migrate toward the inlet of the adsorber following the desorption of the nitrogen. Moisture is a poison for zeolites, most particularly for the LiLSXs developed for this application, which are very efficient but also extremely sensitive to water. This risk is such that units for the production of oxygen by adsorption operating at atmospheric pressure (of the VSA type according to the current name) generally comprise more than two adsorbers in order to be able to make the production of oxygen at the outlet of the adsorbers continuous and thus to avoid low pressure storage. It became apparent that by placing a simple adsorbent mass60upstream of the storage reservoir (in the direction of production), the problem of moisture is definitely solved. The gas stream A (stream2) passes through the adsorbent mass in counter-current mode before being stored in the storage reservoir50. The gas stream B (stream5) polluted by the impurities from the storage reservoir then passes through the adsorbent mass in co-current mode. The gas entering the storage reservoir and the gas extracted for recompression are at almost the same pressure and at the same temperature. The amount of gas going to the storage reservoir is much greater than the amount of gas which is extracted for recompression. It corresponds in fact to the increased production of the volume of the recompression. The adsorbent mass is therefore regenerated at each phase without difficulty. As for the humidity, it is naturally discharged with the production3(gas stream C). In other cycles, the oxygen extracted from the tank can also be used to perform all or part of the elution of the adsorbent at the end of vacuum pumping. The problem is identical. It should be noted that an adsorbent mass placed just upstream of the reservoir according to the invention does not have the same effect at all as a mass placed at the head of each adsorber. This is because, in order for an adsorber to be able to continuously produce oxygen, the regeneration power should entrain the impurities, essentially nitrogen, toward the inlet of the adsorber. It is the role of the vacuum pump to create regenerative power from the outlet to the inlet. In other words, if the adsorbent mass were placed at the head of the adsorber, there would be no possibility of entraining all of the water in the production as is the case with the principle of the invention. It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above.
15,526
11857913
DETAILED DESCRIPTION OF THE INVENTION Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. The singular terms “a,” “an,” and “the” include plural referents unless the context clearly indicates otherwise. Similarly, the word “or” is intended to include “and” unless the context clearly indicates otherwise. The term “includes” means “comprises.” All patents and publications mentioned herein are incorporated by reference in their entirety, unless otherwise indicated. In case of conflict as to the meaning of a term or phrase, the present specification, including explanations of terms, control. Directional terms, such as “upper,” “lower,” “top,” “bottom,” “front,” “back,” “vertical,” and “horizontal,” are used herein to express and clarify the relationship between various elements. It should be understood that such terms do not denote absolute orientation (e.g., a “vertical” component can become horizontal by rotating the device). The materials, methods, and examples recited herein are illustrative only and not intended to be limiting. As used herein, “stream” refers to fluid (e.g., solids, liquid and/or gas) being conducted through various equipment. The equipment may include conduits, vessels, manifolds, units or other suitable devices. As used herein, “conduit” refers to a tubular member forming a channel through which something is conveyed. The conduit may include one or more of a pipe, a manifold, a tube or the like. The provided processes, apparatus, and systems of the present techniques may be used in swing adsorption processes that remove contaminants (CO2, H2O, and H2S) from feed streams, such as hydrocarbon containing streams. As may be appreciated and as noted above, the hydrocarbon containing feed streams may have different compositions. For example, hydrocarbon feed streams vary widely in amount of acid gas, such as from several parts per million acid gas to 90 volume percent (vol. %) acid gas. Non-limiting examples of acid gas concentrations from exemplary gas reserves sources include concentrations of approximately: (a) 4 ppm H2S, 2 vol. % CO2, 100 ppm H2O (b) 4 ppm H2S, 0.5 vol. % CO2, 200 ppm H2O (c) 1 vol. % H2S, 2 vol. % CO2, 150 ppm H2O, (d) 4 ppm H2S, 2 vol. % CO2, 500 ppm H2O, and (e) 1 vol. % H2S, 5 vol. % CO2, 500 ppm H2O. Further, in certain applications the hydrocarbon containing stream may include predominately hydrocarbons with specific amounts of CO2and/or water. The gaseous feed stream utilized in the processes herein comprises, or consists essentially of, a hydrocarbon containing stream. For example, the gaseous feed stream may have greater than 0.00005 volume percent CO2based on the total volume of the gaseous feed stream and less than 2 volume percent CO2based on the total volume of the gaseous feed stream; or less than 10 volume percent CO2based on the total volume of the gaseous feed stream. In other embodiments, the gaseous feed stream may have a CO2content from about 200 parts per million volume to about 2% volume based on the gaseous feed stream. The processing of feed streams may be more problematic when certain specifications have to be satisfied. The removal of contaminants may be performed by swing adsorption processes to prepare the stream for further downstream processing, such as NGL processing and/or LNG processing. For example, natural gas feed streams for liquefied natural gas (LNG) applications have stringent specifications on the CO2content to ensure against formation of solid CO2at cryogenic temperatures. The LNG specifications may involve the CO2content to be less than or equal to 50 ppm. Such specifications are not applied on natural gas streams in pipeline networks, which may involve the CO2content up to 2 vol. % based on the total volume of the gaseous feed stream. As such, for LNG facilities that use the pipeline gas (e.g., natural gas) as the raw feed, additional treating or processing steps are utilized to further purify the stream. Further, the present techniques may be used to lower the water content of the stream to less than 0.1 ppm. Exemplary swing adsorption processes and configurations may include U.S. Patent Application Publication Nos. US2017/0056814, US2017/0113175 and US2017/0113173, and U.S. Pat. Nos. 10,080,991, 10,124,286, 10,080,992 and 10,040,022, which are each incorporated by reference herein. The present techniques provide configurations and processes that are utilized to enhance swing adsorption processes. As noted above, rapid cycle pressure and temperature swing adsorption processes may be used to dehydrate streams and/or remove low-level CO2. To manage the temperature, compositional, and pressure pulses associated with the transition of streams within the adsorbent beds between the steps in the cycle, the present techniques may include additional steps or mechanisms. The present techniques provide a method to minimize the temperature and/or compositional fluctuations in a stream being conducted away from the rapid cycle swing adsorption process. In other configurations, a system is used to minimize the temperature and/or compositional fluctuations in one or more streams being conducted away from the rapid cycle swing adsorption process units. For example, one configuration may include using a dampening system, which is disposed downstream of the swing adsorption bed units and upstream of the downstream processing units, such as a LNG processing unit. The dampening system may be configured to dampen the respective fluctuations. By way of example, the dampening system may include a heat exchanger and/or a piping network that may be used to provide sufficient thermal mass to provide the thermal capacitance to dampen any associated temperature pulses in the product stream. In yet another example, the dampening system may include an accumulator may be used to manage the composition of the stream being conducted away from the adsorbent bed unit. The accumulator may be disposed downstream of the swing adsorption bed units and upstream of the downstream processing units, such as a LNG processing unit. As a specific example, the purge gas being conducted away from the adsorbent bed that is used in the regeneration step. The concentration of the contaminants in the purge product stream may initially be higher and then decrease during the later portion of the purge step. The accumulator may be used to mix or intermingle the purge product stream to manage the composition into a more uniform distribution of contaminants. Furthermore, the dampening system may include a heat exchanger and an accumulator. The temperature of the purge gas stream may gradually increases during the purge step. If the purge stream is to be provided to a downstream system, such as a gas turbine, the dampening system may manage the pulses to provide that the gas wobbe index is within acceptable limits. In another configuration, the swing adsorption process may include a cooling step to manage the temperature of the adsorbent bed and resulting product stream. The cooling step may adjust the temperature (e.g., cool) the adsorbent bed down after a regeneration step. As such, the product stream being conducted away from the adsorbent bed unit may be at a temperature within acceptable limits. For example, in an LNG dehydration system, a cooling step may be used after the regeneration step (e.g., a temperature swing step), which may be used to regenerate a spent adsorbent bed. By using the cooling step, the feed stream may not be relied upon to adjust the temperature of the adsorbent bed during the swing adsorption cycle because the cooling step may be used to dampen the temperature fluctuations of the resulting product stream from the adsorbent bed unit. As a result of the cooling step, the product gas temperature of the product stream may be managed within a temperature threshold that may enhance the downstream processing of the product stream. Accordingly, the product stream may be passed to the liquefaction process within acceptable temperature limits. By way of example, the acceptable temperature limits may include product streams for the swing adsorption system having temperatures within 50° F. of feed temperature for the swing adsorption system, within 25° F. of feed temperature for the swing adsorption system, or within 10° F. of feed temperature for the swing adsorption system. By way of example, conventional processes, such as molecular sieve processes, regenerate a spent molecular sieve bed by heating the bed to remove contaminants followed by cooling the molecular sieve bed to prepare the molecular sieve bed for adsorption. These steps are usually done by the same regeneration gas stream that is initially heated to heat the molecular sieve bed and later not heated to cool the molecular sieve bed. In such a configuration, the heating and cooling steps are not continuous (e.g., at least one bed is being cooled and one bed is being heated simultaneously at any instant). For LNG applications, the purge gas stream may be sourced from end-flash compression, boil-off-gas compression, directly from the feed gas or a combination thereof. The purge stream may serve as the fuel gas stream and is limited in flow rate. To use the same stream for cooling and heating, two configurations may be utilized. The first configuration may splits the available purge stream into a cool stream and a heating for different adsorbent beds. While no recycling is performed, the cooling and heating are performed continuously (e.g., at least one adsorbent bed is being cooled and one bed is being heated at any instant). If the available flow rate is not sufficient, then the stream may be recycled. However, the stream may be recycled, such that the heating stream remains contaminant free (e.g., during the cooling step contaminants from the adsorbent bed do not move into the purge stream because of the flow direction being co-current to the feed flow direction). These steps are continuous, which is beneficial for RCPSA and/or RCPSTA cycles ensuring steady flows through various streams. The recycling provides a few additional aspects, such as a method to simultaneously control the product temperature and recover heat internally (e.g., reduced overall heat required to regenerate the bed). In yet another configuration, the present techniques may utilize a cooling step in the swing adsorption process. The purge gas stream, which may be at or near ambient temperatures, may be split into two streams. The first stream may be heated and used to regenerate the adsorbent bed, while the second stream may be used to cool a recently regenerated adsorbent bed. The first and second streams may be introduced in a counter-current direction relative to the feed stream, which may performed to maintain the dryness of the product end of the adsorbent bed throughout the regeneration and cooling steps of the swing adsorption cycle. Further, in another configuration, the present techniques may utilize a different cooling step in the swing adsorption process. In this configuration, the purge stream, which may be at or near ambient temperatures, is first passed in a co-current direction relative to the direction of the feed stream to cool a recently regenerated adsorbent bed. The cooling step may lessen the temperature of the adsorbent bed, while recovering some of the heat in the adsorbent bed. The resulting gas stream is then heated and introduced to a spent adsorbent bed to regenerate the adsorbent bed. This configuration has the additional benefit of recovering some of the heat from the regeneration step of the swing adsorption cycle. In still yet another configuration, additional dampening may be achieved by operating multiple adsorbent beds out of sequence on feed. For example, a new adsorbent bed may be introduced on the feed stream, while a different adsorbent bed is already operational and producing product at nearly the feed temperature. In other configurations, the present techniques may involve temperature swing dampening. The method of managing the temperature fluctuations and/or compositional fluctuations in the purge gas stream may use a combination of heat exchangers and mixing drums. The heat exchangers may provide a method to cool the gas stream to a specific temperature range. As the purge stream may be a small flow rate in comparison the product stream, the size of the heat exchanger may be relatively small. Furthermore, in performing dehydration, the heat exchanger may be used to condense excess water in the purge stream. The mixing drum provides the proper residence time to manage the compositional pulses, such that the gas stream leaving the mixing drum is more uniform in composition. The present techniques may be a swing adsorption process, and specifically a rapid cycle adsorption process. The present techniques may include some additional equipment, such as one or more conduits and/or one or more manifolds that provide a fluid path for the cooling step and/or dampening system. In addition, other components and configurations may be utilized to provide the swing adsorption process, such as rapid cycle enabling hardware components (e.g., parallel channel adsorbent bed designs, rapid actuating valves, adsorbent bed configurations that integrate with other processes). Exemplary swing adsorption processes and configurations may include U.S. Patent Application Publication Nos. US2017/0056814, US2017/0113175 and US2017/0113173, and U.S. Pat. Nos. 10,080,991, 10,124,286, 10,080,992 and 10,040,022, which are each incorporated by reference herein. In one or more configurations, a swing adsorption process may include performing various steps. For the example, the present techniques may be used to remove contaminants from a gaseous feed stream with a swing adsorption process, which may be utilized with one or more downstream processes. The process comprising: a) performing a heating step, wherein the heating step comprises passing a heating stream through the adsorbent bed unit to remove one or more contaminants from the adsorbent bed unit (e.g., a heated purge step that comprises passing a heated purge stream through an adsorbent bed unit to remove contaminants from an adsorbent bed within a housing of the adsorbent bed unit to form a purge product stream, which may be a heated purge stream); b) performing a cooling step, wherein the cooling step may comprise passing cooling stream through an adsorbent bed unit to remove lessen the temperature of the adsorbent bed within a housing of the adsorbent bed unit to lessen the temperature of the adsorbent bed prior to the one or more adsorption steps; c) performing one or more adsorption steps, wherein each of the one or more adsorption steps comprise passing a gaseous feed stream through an adsorbent bed unit having an adsorbent bed to separate contaminants from the gaseous feed stream to form a product stream. In addition, the method may include determining whether the product stream and/or purge stream is within a temperature specification and/or composition specification; d) if the product stream and/or purge stream is within the respective specification (e.g., is below a certain threshold), passing the product stream to a downstream process; and e) if the product stream is not within the specification (e.g., above a certain threshold), passing the product stream and/or purge stream through the dampening system. In other certain embodiments, the swing adsorption process may be integrated with downstream equipment and processes. The downstream equipment and processes may include control freeze zone (CFZ) applications, niotrogen removal unit (NRU), cryogenic NGL recovery applications, LNG applications, and other such applications. Each of these different applications may include different specifications for the feed stream in the respective process. For example, a cryogenic NGL process or an LNG process and may be integrated with the respective downstream equipment. As another example, the process may involve H2O and/or CO2removal upstream of a cryogenic NGL process or the LNG process and may be integrated with respective downstream equipment. In certain configurations, the system utilizes a combined swing adsorption process, which combines TSA and PSA, for treating of pipeline quality natural gas to remove contaminants for the stream to satisfy LNG specifications. The swing adsorption process, which may be a rapid cycle process, is used to treat natural gas that is at pipeline specifications (e.g., a feed stream of predominately hydrocarbons along with less than or equal to about 2% volume CO2and/or less than or equal to 4 ppm H2S) to form a stream satisfying the LNG specifications (e.g., less than 50 ppm CO2and less than about 4 ppm H2S). The product stream, which may be the LNG feed stream, may have greater than 98 volume percent hydrocarbons based on the total volume of the product stream, while the CO2and water content are below certain thresholds. The LNG specifications and cryogenic NGL specifications may involve the CO2content to be less than or equal to 50 ppm, while the water content of the stream may be less than 0.1 ppm. Moreover, the present techniques may include a specific process flow to remove contaminants, such as CO2and/or water. For example, the process may include an adsorbent step and a regeneration step, which form the cycle. The adsorbent step may include passing a gaseous feed stream at a feed pressure and feed temperature through an adsorbent bed unit to separate one or more contaminants from the gaseous feed stream to form a product stream. The feed stream may be passed through the adsorbent bed in a forward direction (e.g., from the feed end of the adsorbent bed to the product end of the adsorbent bed). Then, the flow of the gaseous feed stream may be interrupted for a regeneration step. The regeneration step may include one or more depressurization steps, one or more heating steps, and/or one or more purge steps. The depressurization steps, which may be or include a blowdown step, may include reducing the pressure of the adsorbent bed unit by a predetermined amount for each successive depressurization step, which may be a single step and/or multiple steps. The depressurization step may be provided in a forward direction or may preferably be provided in a countercurrent direction (e.g., from the product end of the adsorbent bed to the feed end of the adsorbent bed). The heating step may include passing a heating stream into the adsorbent bed unit, which may be a recycled stream through the heating loop and is used to heat the adsorbent material. The purge step may include passing a purge stream into the adsorbent bed unit, which may be a once through purge step and the purge stream may be provided in countercurrent flow relative to the feed stream. The purge stream may be provided at a purge temperature and purge pressure, which may include the purge temperature and purge pressure being similar to the heating temperature and heating pressure used in the heating step. Then, the cycle may be repeated for additional streams. Additionally, the process may include one or more re-pressurization steps after the purge step and prior to the adsorption step. The one or more re-pressurization steps may be performed, wherein the pressure within the adsorbent bed unit is increased with each re-pressurization step by a predetermined amount with each successive re-pressurization step. The cycle duration may be for a period greater than 1 second and less than 600 seconds, for a period greater than 2 second and less than 300 seconds, for a period greater than 2 second and less than 180 seconds, for a period greater than 5 second and less than 150 seconds or for a period greater than 5 second and less than 90 seconds. In one or more embodiments, the present techniques can be used for any type of swing adsorption process. Non-limiting swing adsorption processes for which the present techniques may be used include pressure swing adsorption (PSA), vacuum pressure swing adsorption (VPSA), temperature swing adsorption (TSA), partial pressure swing adsorption (PPSA), rapid cycle pressure swing adsorption (RCPSA), rapid cycle thermal swing adsorption (RCTSA), rapid cycle partial pressure swing adsorption (RCPPSA), as well as combinations of these processes. For example, the preferred swing adsorption process may include a combined pressure swing adsorption and temperature swing adsorption, which may be performed as a rapid cycle process. Exemplary swing adsorption processes and configurations may include U.S. Patent Application Publication Nos. US2017/0056814, US2017/0113175 and US2017/0113173, and U.S. Pat. Nos. 10,080,991, 10,124,286, 10,080,992, 10,040,022, 7,959,720, 8,545,602, 8,529,663, 8,444,750, 8,529,662 and 9,358,493, which are each herein incorporated by reference in their entirety. Further still, in one or more configurations, a variety of adsorbent materials may be used to provide the mechanism for the separations. Examples include zeolite 3A, 4A, 5A, ZK4 and MOF-74. However, the process is not limited to these adsorbent materials, and others may be used as well. In one configuration, a process for removing contaminants from a gaseous feed stream with a swing adsorption process is described. The process may comprise: a) performing an adsorption step, wherein the adsorption step comprises passing a gaseous feed stream through an adsorbent bed unit to remove one or more contaminants and produce a product stream; b) interrupting the flow of the gaseous feed stream; c) performing a heating step, wherein the heating step comprises passing a heating stream through the adsorbent bed unit to remove one or more contaminants from the adsorbent bed unit; d) performing a cooling step, wherein the cooling step comprises lessening the temperature of an adsorbent material in the adsorbent bed unit by passing a cooling stream through the adsorbent bed unit; and e) repeating the steps a) to d) for at least one additional cycle in the swing adsorption process. In one or more configurations, the process may include one or more enhancements. The process may include wherein the cycle duration is for a period greater than 1 second and less than 600 seconds; wherein the gaseous feed stream is a hydrocarbon containing stream having greater than one volume percent hydrocarbons based on the total volume of the feed stream; wherein the gaseous feed stream comprises hydrocarbons and CO2, wherein the CO2content is in the range of two hundred parts per million volume and less than or equal to about 2% volume of the gaseous feed stream; wherein the swing adsorption process is configured to lower the carbon dioxide (CO2) level to less than 50 parts per million; passing the product stream to a downstream process; wherein the downstream process is a liquefied natural gas (LNG) process that comprises an LNG process unit; wherein the downstream process is a cryogenic natural gas liquefaction (NGL) process having a NGL process unit; wherein the cycle duration is greater than 2 seconds and less than 180 seconds; wherein the cooling stream is passed from the adsorbent bed unit to a conditioning unit; and the conditioned stream is passed from the conditioning unit to another adsorbent bed unit as the heating stream; wherein the heating stream is passed in a direction that is counter-current to the direction that the feed stream is passed; and the cooling stream is passed in a direction that is counter-current to the direction that the feed stream is passed; further comprising splitting a purge stream into the heating stream and the cooling stream; wherein the cooling stream is passed in a direction that is co-current to the direction that the feed stream is passed; and the heating stream is passed in a direction that is counter-current to the direction that the feed stream is passed; further comprising determining whether the product stream is within acceptable temperature limits; wherein the acceptable temperature limits include the product stream having temperatures within 50° F. of feed temperature of the gaseous feed stream; wherein the acceptable temperature limits include the product stream having temperatures within 25° F. of feed temperature of the gaseous feed stream; wherein the acceptable temperature limits include the product stream having temperatures within 10° F. of feed temperature of the gaseous feed stream; wherein the swing adsorption process is a rapid cycle temperature swing adsorption process; and/or wherein the swing adsorption process is a rapid cycle temperature swing adsorption process and a rapid cycle temperature swing adsorption process. In another configuration, a cyclical swing adsorption system is described. The system may comprise: a plurality of adsorbent bed units coupled to a plurality of manifolds, each of the adsorbent bed units is configured to pass different streams through the adsorbent bed unit between two or more steps in a swing adsorption cycle and each of the adsorbent bed units is configured to remove one or more contaminants from a feed stream to form a product stream and wherein each of the adsorbent bed units comprise: a housing; an adsorbent material disposed within the housing; a plurality of valves, wherein at least one of the plurality of valves is associated with one of the plurality of manifolds and is configured to manage fluid flow along a flow path extending between the respective manifold and the adsorbent material; and wherein the cyclical swing adsorption system is configured to dampen one or more of temperature, compositional, and pressure pulses associated with the transition of different streams through the adsorbent beds between the two or more steps in the swing adsorption cycle. In one or more configurations, the system may include one or more enhancements. The cyclical swing adsorption system may include wherein the plurality of manifolds comprise a feed manifold configured to pass the feed stream to the plurality of adsorbent bed units during an adsorption step, a product manifold configured to pass the product stream from the plurality of adsorbent bed units during the adsorption step, a purge manifold configured to pass a purge stream to the plurality of adsorbent bed units during a regeneration step, a purge product manifold configured to pass a purge product stream from the plurality of adsorbent bed units during the regeneration step, each manifold of the plurality of manifolds is associated with one swing adsorption process step of a plurality of swing adsorption process steps; wherein the plurality of manifolds comprise a cooling manifold configured to pass a cooling stream to the plurality of adsorbent bed units during a cooling step, a cooling product manifold configured to pass a cooling product stream from the plurality of adsorbent bed units during the cooling step; wherein the plurality of manifolds comprise a feed manifold configured to pass the feed stream to the plurality of adsorbent bed units during an adsorption step, a product manifold configured to pass the product stream from the plurality of adsorbent bed units during the adsorption step, a purge manifold configured to split the purge stream into a first purge stream configured to pass to the plurality of adsorbent bed units during a heating step and a second purge stream configured to pass to the plurality of adsorbent bed units during a cooling step, a first purge product manifold configured to pass a first purge product stream from the plurality of adsorbent bed units during the heating step, and a second purge product manifold configured to pass a second purge product stream from the plurality of adsorbent bed units during the cooling step; a heating unit disposed upstream of the split in the purge manifold, wherein the heating unit is configured to increase the temperature of the first purge stream prior to passing the plurality of adsorbent bed units during a heating step; wherein the plurality of manifolds comprise a feed manifold configured to pass the feed stream to the plurality of adsorbent bed units during an adsorption step, a product manifold configured to pass the product stream from the plurality of adsorbent bed units during the adsorption step, a purge manifold configured to pass a cooling stream to the plurality of adsorbent bed units during a cooling step and a cooling purge product manifold configured to pass a cooling purge product stream from the plurality of adsorbent bed units during the cooling step and configured to pass a heating stream to another of the plurality of adsorbent bed units during a heating step, and a second purge product manifold configured to pass a heating purge product stream from the plurality of adsorbent bed units during the heating step; a heating unit associated with the cooling purge product manifold and configured to heat the cooling purge product stream to form the heating stream; a liquefied natural gas (LNG) process that comprises an LNG process unit and is configured to receive the product stream; a cryogenic natural gas liquefaction (NGL) process having a NGL process unit and is configured to receive the product stream; a dampening system in fluid communication with the plurality of adsorbent bed units and configured to lessen one or more of temperature fluctuations, compositional fluctuations, and any combination thereof associated with the transition of the different streams through the adsorbent beds between the two or more steps in the swing adsorption cycle; wherein the dampening system comprises a heat exchanger configured to provide sufficient thermal capacitance to dampen temperature pulses in the product stream; wherein the dampening system comprises an accumulator configured to manage compositions of the product stream; wherein the dampening system comprises a mixing unit configured to manage compositions of the product stream; wherein the plurality of manifolds further comprise a blowdown manifold configured to pass a blowdown stream from the plurality of adsorbent bed units during a blowdown step; wherein the plurality of valves comprise one or more poppet valves; and/or wherein the plurality of adsorbent bed units are configured to operate at pressures between 0.1 bar absolute (bara) and 100 bara. The present techniques may be further understood with reference to theFIGS.1to6below. FIG.1is a three-dimensional diagram of the swing adsorption system100having six adsorbent bed units and interconnecting piping. While this configuration is a specific example, the present techniques broadly relate to adsorbent bed units that can be deployed in a symmetrical orientation, or non-symmetrical orientation and/or combination of a plurality of hardware skids. Further, this specific configuration is for exemplary purposes as other configurations may include different numbers of adsorbent bed units. In this system, the adsorbent bed units, such as adsorbent bed unit102, may be configured for a cyclical swing adsorption process for removing contaminants from feed streams (e.g., fluids, gaseous or liquids). For example, the adsorbent bed unit102may include various conduits (e.g., conduit104) for managing the flow of fluids through, to or from the adsorbent bed within the adsorbent bed unit102. These conduits from the adsorbent bed units102may be coupled to a manifold (e.g., manifold106) to distribute the flow to, from or between components. The adsorbent bed within an adsorbent bed unit may separate one or more contaminants from the feed stream to form a product stream. As may be appreciated, the adsorbent bed units may include other conduits to control other fluid steams as part of the process, such as purge streams, depressurizations streams, and the like. In particular, the adsorbent bed units may include startup mode equipment, such as one or more heating units (not shown), one or more external gas source manifolds, which may be one of the manifolds106) and one or more expanders, as noted further below, which is used as part of the startup mode for the adsorbent beds. Further, the adsorbent bed unit may also include one or more equalization vessels, such as equalization vessel108, which are dedicated to the adsorbent bed unit and may be dedicated to one or more step in the swing adsorption process. The equalization vessel108may be used to store the external stream, such as nitrogen for use in the startup mode cycle. As an example, which is discussed further below inFIG.2, the adsorbent bed unit102may include a housing, which may include a head portion and other body portions, that forms a substantially gas impermeable partition, an adsorbent bed disposed within the housing and a plurality of valves (e.g., poppet valves) providing fluid flow passages through openings in the housing between the interior region of the housing and locations external to the interior region of the housing. Each of the poppet valves may include a disk element that is seatable within the head or a disk element that is seatable within a separate valve seat inserted within the head (not shown). The configuration of the poppet valves may be any variety of valve at patterns or configuration of types of poppet valves. As an example, the adsorbent bed unit may include one or more poppet valves, each in flow communication with a different conduit associated with different streams. The poppet valves may provide fluid communication between the adsorbent bed and one of the respective conduits, manifolds or headers. The term “in direct flow communication” or “in direct fluid communication” means in direct flow communication without intervening valves or other closure means for obstructing flow. As may be appreciated, other variations may also be envisioned within the scope of the present techniques. The adsorbent bed comprises a solid adsorbent material capable of adsorbing one or more components from the feed stream. Such solid adsorbent materials are selected to be durable against the physical and chemical conditions within the adsorbent bed unit102and can include metallic, ceramic, or other materials, depending on the adsorption process. Further examples of adsorbent materials are noted further below. FIG.2is a diagram of a portion of an adsorbent bed unit200having valve assemblies and manifolds in accordance with an embodiment of the present techniques. The portion of the adsorbent bed unit200, which may be a portion of the adsorbent bed unit102ofFIG.1, includes a housing or body, which may include a cylindrical wall214and cylindrical insulation layer216along with an upper head218and a lower head220. An adsorbent bed210is disposed between an upper head218and a lower head220and the insulation layer216, resulting in an upper open zone, and lower open zone, which open zones are comprised substantially of open flow path volume. Such open flow path volume in adsorbent bed unit contains gas that has to be managed for the various steps. The housing may be configured to maintain a pressure from 0 bara (bar absolute) to 150 bara within the interior region. The upper head218and lower head220contain openings in which valve structures can be inserted, such as valve assemblies222to240, respectively (e.g., poppet valves). The upper or lower open flow path volume between the respective head218or220and adsorbent bed210can also contain distribution lines (not shown) which directly introduce fluids into the adsorbent bed210. The upper head218contains various openings (not show) to provide flow passages through the inlet manifolds242and244and the outlet manifolds248,250and252, while the lower head220contains various openings (not shown) to provide flow passages through the inlet manifold254and the outlet manifolds256,258and260. Disposed in fluid communication with the respective manifolds242to260are the valve assemblies222to240. If the valve assemblies222to240are poppet valves, each may include a disk element connected to a stem element which can be positioned within a bushing or valve guide. The stem element may be connected to an actuating means, such as actuating means (not shown), which is configured to have the respective valve impart linear motion to the respective stem. As may be appreciated, the actuating means may be operated independently for different steps in the process to activate a single valve or a single actuating means may be utilized to control two or more valves. Further, while the openings may be substantially similar in size, the openings and inlet valves for inlet manifolds may have a smaller diameter than those for outlet manifolds, given that the gas volumes passing through the inlets may tend to be lower than product volumes passing through the outlets. In swing adsorption processes, the cycle involves two or more steps that each has a certain time interval, which are summed together to be the cycle time or cycle duration. These steps include regeneration of the adsorbent bed following the adsorption step using a variety of methods including pressure swing, vacuum swing, temperature swing, purging (via any suitable type of purge fluid for the process), and combinations thereof. As an example, a PSA cycle may include the steps of adsorption, depressurization, purging, and re-pressurization. When performing the separation at high pressure, depressurization and re-pressurization (which may be referred to as equalization) may be performed in multiple steps to reduce the pressure change for each step and enhance efficiency. In some swing adsorption processes, such as rapid cycle swing adsorption processes, a substantial portion of the total cycle time is involved in the regeneration of the adsorbent bed. Accordingly, any reductions in the amount of time for regeneration results in a reduction of the total cycle time. This reduction may also reduce the overall size of the swing adsorption system. Further, one or more of the manifolds and associated valves may be utilized as a dedicated flow path for one or more streams. For example, during the adsorption or feed step, the manifold242and valve assembly222may be utilized to pass the feed gas stream to the adsorbent bed210, while the valve assembly236and manifold256may be used to conduct away the product stream from the adsorbent bed210. During the regeneration or purge step, the manifold244and valve assembly224may be utilized to pass the purge or heating stream to the adsorbent bed210, while the valve assembly236and manifold256may be used to conduct away the purge product stream from the adsorbent bed210. Further, the manifold254and valve assembly232may be utilized for a cooling stream, while the valve assembly230and manifold252may be used to conduct away the cooling product stream from the adsorbent bed210. As may be appreciated, the purge stream and/or cooling stream may be configured to flow counter current to the feed stream in certain embodiments. Alternatively, the swing adsorption process may involve sharing one or more of the manifolds and associated valves. Beneficially, this configuration may be utilized to lessen any additional valves or connections for startup mode for adsorbent bed unit configurations that are subject to space limitations on the respective heads. As noted above, the present techniques include various procedures that may be utilized for the swing adsorption process. The present techniques may include additional steps or mechanisms to manage the temperature, compositional, and pressure pulses associated with the transition of streams within the adsorbent beds between the steps in the cycle. The present techniques may include including a cooling step to minimize the temperature fluctuations in a stream being conducted away from the rapid cycle swing adsorption process. In other configurations, a system may include a dampening system that may be used to minimize the temperature fluctuations and/or compositional fluctuations in one or more streams being conducted away from the rapid cycle swing adsorption process units. As an example,FIG.3is an exemplary flow chart for performing a swing adsorption process in accordance with an embodiment of the present techniques. In this flow chart300, the swing adsorption process may remove one or more contaminants and may be used to manage the temperature fluctuations and/or compositional fluctuations in one or more streams being conducted away from the rapid cycle swing adsorption process units. For each of the adsorbent bed units, the swing adsorption process involves performing various steps, as shown in blocks302to306, which is described as being performed for a single adsorbent bed unit for simplicity. Then, the streams from the adsorbent bed units may be used with the downstream equipment, as shown in blocks308to314. The process begins by performing the swing adsorption process for the adsorbent bed units, as shown in blocks302to306. At block302, an adsorption step is performed for the adsorbent bed. The adsorption step may include passing a gaseous feed stream through the adsorbent bed to remove one or more contaminants from the gaseous feed stream and to create a product stream that is conducted away from the adsorbent bed unit. At block304, a heating step is performed for the adsorbent bed. The heating step, which may be one or more purge steps may include passing the purge stream through the adsorbent bed to create a purge product stream that is conducted away from the adsorbent bed unit. The product purge stream may include the external stream and a portion of the contaminants within the adsorbent bed. The product purge stream may be intermingled with a fuel gas stream and may be used in a turbine. Further, the purge stream may be subjected to a heating step prior to being passed to the adsorbent bed. The heating step may heat the external stream to a temperature less than 550° F., less than 500° F., less than 450° F. or less than 350° F., and may be greater than 50° F. of the gaseous feed stream temperature, greater than 100° F. of the gaseous feed stream temperature or greater than 250° F. of the gaseous feed stream temperature. For example, the purge stream used during the purge step may be a temperature in the range between 500° F. and greater than 50° F. of the gaseous feed stream temperature, in the range between 450° F. and greater than 100° F. of the gaseous feed stream temperature or 400° F. and greater than 200° F. of the gaseous feed stream temperature. The heating of the purge stream may include passing the purge stream through a heat exchanger or similar heating unit to increase the temperature of the purge stream. At block306, the cooling step may optionally be performed with the adsorbent bed. The cooling step may include passing a stream of gas to cool the adsorbent bed. The cooling step may include which may be a recycled stream that passes through heat exchangers or a refrigeration system to conduct away heat from the recycled stream. The process may repeat the step302to306for another swing adsorption cycle. After being processed, the streams from the adsorbent bed units may be used with the downstream equipment, as shown in blocks308to314. At block308, the product stream may optionally be measured. The product stream may be measured by a temperature sensor and/or a gas chromatograph or using another gas component analysis equipment. The product stream may also be measured by taking samples, using a moisture analyzer. Then, at block310, a determination may be made whether the product stream is within the respective specification. The determination may include analyzing the product stream to determine the level of one or more of the temperature, pressure, composition and any combination thereof. If the product stream is within specification (e.g., contaminants are at or below a specific threshold), the product stream may be passed to downstream process, as shown in block314. However, if the product stream is not within specifications, the product stream may be passed to the dampening system, as shown in block312. The dampening system may include a heat exchanger, conduits, an accumulator and/or a mixing unit. The downstream processes may include a CFZ process, a cryogenic NGL recovery process, or an LNG process, with the associated equipment for each. By way of example, the present techniques may include additional steps or mechanisms to manage the temperature, compositional, and pressure pulses associated with the transition of streams within the adsorbent beds between the steps in the swing adsorption cycle. In particular, the method may be used to minimize the temperature and/or compositional fluctuations in a stream through the use of cooling steps in the rapid cycle swing adsorption process, which is shown inFIGS.4to6. FIG.4is an exemplary diagram of a swing adsorption system400in accordance with an embodiment of the present techniques. In this configuration, a cooling step is used to manage the fluctuations in the streams from the swing adsorption system400. In the swing adsorption system400, a first adsorbent bed404is shown performing an adsorption step with the feed stream in a feed conduit402that is passed through the first adsorbent bed404and conducting a product stream away from the first adsorbent bed404via product conduit406. A second adsorbent bed410is shown performing a cooling step with the cooling stream in a purge conduit408that is passed through the second adsorbent bed410and conducting a cooling product stream away from the second adsorbent bed410via product conduit412. A third adsorbent bed416is shown performing a heating step or regeneration step with the purge stream in the purge conduit408that is passed through a heating unit414and then to the third adsorbent bed416and conducting a purge product stream away from the third adsorbent bed416via the product conduit412. A fourth adsorbent bed418is shown in a stand-by with no streams being passed through the fourth adsorbent bed418. In this configuration, the purge stream (which may near the ambient temperatures) is split into two different streams. The first stream is heated in the heating unit414and used to regenerate a spent third adsorbent bed416, while the second stream is used to cool a recently regenerated adsorbent bed410. These streams may be introduced in a counter-current direction to the feed stream which maintains the dryness of the product end of the adsorbent bed throughout the regeneration step and cooling step. In this configuration, the cooling stream may not be recycled back to the swing adsorbent system be used as a purge stream. To regenerate an adsorption bed, the purge stream is largely devoid of the contaminant being removed. The cooling stream may contain a significant amount contaminant. As such, it cannot be recycled as a purge stream. The cooling step may be part of the overall regeneration process, such that a larger amount of contaminant is removed, while purging in this regeneration step and a smaller (but not insignificant) amount of contaminant is removed, while purging in the cooling step. FIG.5is an exemplary diagram of a swing adsorption system500in accordance with an embodiment of the present techniques. In this configuration, a different cooling step is used to manage the fluctuations in the streams from the swing adsorption system500. In the swing adsorption system500, a first adsorbent bed504is shown performing an adsorption step with the feed stream in a feed conduit502that is passed through the first adsorbent bed504and conducting a product stream away from the first adsorbent bed504via product conduit506. A second adsorbent bed510is shown performing a cooling step with the cooling stream in a purge conduit508that is passed through the second adsorbent bed510and conducting a cooling product stream away from the second adsorbent bed510. A third adsorbent bed514is shown performing a heating step or regeneration step with the purge product stream that is passed through a heating unit512and then to the third adsorbent bed514and conducting a purge product stream away from the third adsorbent bed514via the product conduit516. A fourth adsorbent bed518is shown in a stand-by with no streams being passed through the fourth adsorbent bed518. In this configuration, the purge stream (which may be at or near ambient temperatures) is first passed in a co-current direction to the feed direction of the feed stream to cool a recently regenerated second adsorbent bed510. The cooling step lessens the temperature of the second adsorbent bed510, while recovering some of the heat in the second adsorbent bed510. The resulting gas stream is then heated and introduced to a spent third adsorbent bed514to regenerate the third adsorbent bed514. This configuration has the additional advantage of recovering some of the heat from the regeneration process. In certain configurations, the purge gas exiting the adsorbent bed after the cooling step is largely devoid of contaminant as the purge gas is flowing along the feed direction. In other configurations, the purge gas stream may be in fluid communication (e.g., tied to) with an LNG dehydration process. In such configurations, the source of the purge gas stream may be adjusted to provide enhancements. Additionally, the cooling process may be continuous (e.g., at least one adsorbent bed that is being cooled at any instant of time). FIG.6is an exemplary diagram600of product gas temperature from a swing adsorption process. In this diagram600, the temperature response606is shown along a temperature axis604in Celsius (C) and a cycle time axis602in seconds (s). An example for the second configuration, as shown inFIG.5, the temperature swing of the product end is dampened from 175° C. to 29° C. (e.g., no cooling step) from 39° C. to 29° C. The additional dampening may be achieved by operating multiple adsorbent beds out of sequence on feed. For example, a new adsorbent bed may be introduced on feed, while a different adsorbent bed is already operational and producing product at nearly the feed temperature. In one or more embodiments, the material may include an adsorbent material supported on a non-adsorbent support. The adsorbent materials may include alumina, microporous zeolites, carbons, cationic zeolites, high silica zeolites, highly siliceous ordered it) mesoporous materials, sol gel materials, aluminum phosphorous and oxygen (ALPO) materials (microporous and mesoporous materials containing predominantly aluminum phosphorous and oxygen), silicon aluminum phosphorous and oxygen (SAPO) materials (microporous and mesoporous materials containing predominantly silicon aluminum phosphorous and oxygen), metal organic framework (MOF) materials (microporous and mesoporous materials comprised of a metal organic framework) and zeolitic imidazolate frameworks (ZIF) materials (microporous and mesoporous materials comprised of zeolitic imidazolate frameworks). Other materials include microporous and mesoporous sorbents functionalized with functional groups. Examples of functional groups include primary, secondary, tertiary amines and other non protogenic basic groups such as amidines, guanidines and biguanides. In one or more embodiments, the adsorbent bed unit may be utilized to separate contaminants from a feed stream during normal operation mode. The method may include a) passing a gaseous feed stream at a feed pressure through an adsorbent bed unit having an adsorbent contactor to separate one or more contaminants from the gaseous feed stream to form a product stream, wherein the adsorbent contactor has a first portion and a second portion; b) interrupting the flow of the gaseous feed stream; performing a depressurization step, wherein the depressurization step reduces the pressure within the adsorbent bed unit; c) performing an optional heating step, wherein the heating step increases the temperature of the adsorbent bed unit to form a temperature differential between the feed end of the adsorbent bed and the product end of the adsorbent bed; and d) performing a cooling step, wherein the cooling step reduces the temperature within the adsorbent bed unit; e) performing a re-pressurization step, wherein the re-pressurization step increases the pressure within the adsorbent bed unit; and repeating the steps a) to e) for at least one additional cycle. In one or more embodiments, when using RCTSA or an integrated RCPSA and RCTSA process, the total cycle times are typically less than 600 seconds, preferably less than 400 seconds, preferably less than 300 seconds, preferably less than 250 seconds, preferably less than 180 seconds, more preferably less than 90 seconds, and even more preferably less than 60 seconds. In other embodiment, the rapid cycle configuration may be operated at lower flow rates during startup mode as compared to normal operation mode, which may result in the cycle durations being longer than the cycle durations during normal operation mode. For example, the cycle duration may be extended to 1,000 seconds for some cycles. In view of the many possible embodiments to which the principles of the disclosed invention may be applied, it should be recognized that the illustrative embodiments are only at preferred examples of the invention and should not be taken as limiting the scope of the invention.
53,677
11857914
Reference is now made in detail to the present preferred embodiments of the apparatus and method, examples of which are illustrated in the accompanying drawing figures. DETAILED DESCRIPTION Reference is now made toFIG.1which schematically illustrates the electrochemical apparatus10for removing an acid gas from a feed gas stream while also producing hydrogen gas. For purposes of this document, the terminology “acid gas” refers to any gas that forms an acid upon dissolving in water. Acid gases include, but are not necessarily limited to, carbon dioxide (CO2), sulfur dioxide (SO2), hydrogen sulfide (H2S) and nitrogen oxides (NOx). Such acid gases may participate in acid/base reactions for capture (e.g. CO2+2OH−═CO32−+H2O or SO2+OH−═HSO3−). In one particularly useful embodiment, the electrochemical apparatus10is used to remove one or more acid gases from a flue gas feed stream. The apparatus10includes an absorber12and an electrochemical regenerator14connected to the absorber. The absorber12is adapted for separating the acid gas from the feed gas stream using a lean carbon capture solvent. The gas and solvent flows are typically counter-current. The electrochemical regenerator is adapted for (a) regenerating the lean carbon capture solvent and (b) generating hydrogen gas which may be used as an energy source. More specifically, in the illustrated embodiment, an acid gas, such as carbon dioxide, from the feed gas stream, such as flue gas from a power generation station, is absorbed into a caustic solvent. Thus, the absorber12facilitates the mass transfer from the gas into a liquid and can be a packed bed tower, a hollow fiber gas-liquid contactor (e.g. Liqui-Cel by #3M) or a similar porous hydrophobic substrate. The absorber12depicted inFIG.1is similar to a shell and tube exchanger with gas flowing along the tube's inner surface while the capture solvent is on the tube's outer surface but constrained by the shell of the outer tube. The shell and the tube-side fluids may be swapped depending upon absorber design. The carbon capture solvent may be selected from a group of alkaline carbon capture solvents including, but not necessarily limited to a metal hydroxide/carbonate soluble in water, potassium hydroxide/carbonate, sodium hydroxide/carbonate, lithium hydroxide/carbonate, barium hydroxide/carbonate, ammonia hydroxide/carbonate and combinations thereof. As illustrated inFIG.1, the absorber12includes a gas inlet16, a lean carbon capture solvent inlet18, a treated gas outlet20and a rich carbon capture solvent outlet22. The electrochemical regenerator14includes: (a) a rich carbon capture solvent inlet24that is connected to the rich carbon capture solvent outlet22, (b) a lean carbon capture solvent outlet26connected to the lean carbon capture solvent inlet18, (c) a recovered acid gas or carbon dioxide outlet28and (d) a generated hydrogen gas outlet30. As illustrated inFIGS.1and3, the electrochemical regenerator14includes an outer housing32holding an electrochemical cell34having an anodic chamber36, holding an anode38, and a cathodic chamber40, holding a cathode42. The anode38and the cathode42may be made from a single material such as stainless steel plates, Monel® nickel alloy, nickel, and DSA® electrodes by De Nora Tech or stacking of layers including platinum on carbon gas diffusion electrodes, Kynol® carbon cloth and/or Monel® nickel alloy. The anodic chamber36is separated from the cathodic chamber40by an alkali metal or ion exchange membrane44that allows cation transport while retaining fluids on either side. Example membranes include Nafion® membranes, Neosepta® CMX membranes and Fumasep FKS membranes. The electrochemical regenerator14also includes a power source46, of a type known in the art, adapted for applying a voltage potential across the anode38and the cathode42whereby the acid gas is stripped from the rich carbon capture solvent in the anodic chamber36and hydrogen is generated in the cathodic chamber40. A pump48delivers the feed gas stream (in the illustrated embodiment, flue gas from the utility boiler) to the gas inlet16of the absorber12where the carbon dioxide in the feed gas stream/flue gas is absorbed by the lean carbon capture solvent/KOH creating the rich carbon capture solvent/K2CO3and KHCO3. The rich carbon capture solvent is then fed through the rich carbon capture solvent outlet22of the absorber12to the rich carbon capture inlet24of the electrochemical regenerator14. In the electrochemical regenerator14, hydrogen gas (H2) and hydroxide ion (OH−) are produced at the cathode42in the cathodic chamber40by the hydrogen evolution reaction (HER, 2H2O+2e−↔2H2+2OH−). The produced hydroxide facilitates capture of carbon dioxide in the absorber12and the hydrogen may be sold, used for energy storage or directly fed to the anode to reduce the operating voltage and energy of the apparatus. At the anode38in the anodic chamber36, hydroxide ions are consumed by the oxygen evolution reaction (OER, 4OH−↔O2+2H2O+4e−) while simultaneously shifting the CO2speciation to facilitate CO2release. Carbonate, CO32−is transformed to CO2through CO32−+H2O→HCO3−+OH−followed by HCO3−→CO2+OH−. Concurrently, to balance the negative OH−ion formed at the cathode42, the positive K+ion migrates across the cation-exchange membrane44to the cathodic chamber40, producing KOH that will be used again to capture CO2in the absorber12. The liquid effluent from the anode and cathode can be recycled to improve their utilization. Note anodic recycle line50adapted for returning rich carbon capture solvent/unreacted alkaline anolyte, KHCO3, back to the anode inlet52of the rich carbon capture solvent inlet24and cathodic recycle line54adapted for returning rich carbon capture solvent/unreacted K2CO3back to the cathode inlet56of the rich carbon capture solvent inlet24. During depolarization, the H2produced at the cathode42is fed to the anode38, changing the effective reaction from the oxygen evolution reaction (OER) to the hydrogen “oxidation” reaction (HOR, H2↔2H++2e−) which reduces the voltage and consequently energy requirement as shown inFIG.2. The electrochemical cell34illustrated inFIG.3is a sandwich-like structure of two channel configuration wherein the electrodes38,42sandwich the anode and cathode flow spaces58,60, which, in-turn, sandwich the ion-exchange membrane44. In contrast, the electrochemical cell34illustrated inFIG.4is a sandwich-like structure of three channel configuration that further includes a porous hydrophobic gas-philic membrane (flat-sheet membrane contactor)62that allows gas access while retaining the fluid. A gas channel64sandwiches the hydrophobic membrane62to the anode38. Examples of the hydrophobic membrane include Porex PM21M or teflonated gas diffusion layers typically used in fuel cell assembly. End plates (not shown) that sandwich the two or three-channel configurations are compressed to seal the cells. When using the two-channel configuration for depolarization, hydrogen is bubbled into the anode's liquid solution, and when using the three-channel configuration without depolarization, the gas channel is dead-ended. An electrochemical apparatus10, including either the two-channel cell34illustrated inFIG.3or the three-channel cell34illustrated inFIG.4is useful in a method of removing an acid gas from a feed gas stream. That method may be described as having the following steps:(a) separating the acid gas from the feed gas stream in an absorber12by contacting the feed gas stream with a lean carbon capture solvent thereby capturing carbon dioxide from the feed gas stream and generating a rich carbon capture solvent;(b) delivering the rich carbon capture solvent from the absorber12to an electrochemical regenerator14;(c) releasing the acid gas from the rich carbon capture solvent in the electrochemical regenerator14to regenerate the lean carbon capture solvent;(d) generating hydrogen gas in the electrochemical regenerator14; and(e) returning the lean carbon capture solvent to the absorber12. That method may further include the step of applying a voltage potential of at least 1.5 volts across the anode38in the anodic chamber36and the cathode42in the cathodic chamber40of the electrochemical regenerator14to release the acid gas and generate the hydrogen. The method may also include the step of selecting the carbon capture solvent from a group of alkaline carbon capture solvents consisting of a metal hydroxide/carbonate soluble in water, potassium hydroxide/carbonate, sodium hydroxide/carbonate, lithium hydroxide/carbonate, barium hydroxide/carbonate, ammonia hydroxide/carbonate and combinations thereof. The electrochemical regenerator14also has other uses or applications, including water treatment and chlorine production. In order to function for water treatment, the electrochemical regenerator14is isolated from the absorber12. In addition, a salt water supply stream is connected to the isolated electrochemical regenerator14. That salt water supply stream is then desalinated to produce a treated, clean water stream and a concentrated salt water stream. SeeFIG.5. For water treatment, porous electrodes are preferred in addition to low voltage operation (<1.3 V) to avoid the water-splitting reactions (HER, OER). In this mode, for a generic salt M+X−introduced into both cell compartments, the cation M+is electrically adsorbed onto the cathode42while the anion X−is affixed to the anode38. At the same time, leftover cation M+in the anodic chamber36is transported via the cation membrane44to the cathode42to balance the X−in the cathodic chamber40resulting in the net removal of salt from the anode to the cathode, thereby creating treated water in the anode channel58. After the electrodes38,42are saturated, their polarities can be reversed to continue desalination. Due to its capacitive nature and low voltage requirement, a depolarized operation is not possible. In order to function for chlorine gas evolution, the electrochemical regenerator14is isolated from the absorber12. In addition, a chloride solution supply (e.g. sodium chloride solution) is connected to the anodic chamber36and a water supply is connected to the cathodic chamber40. Chlorine gas is evolved in the anodic chamber36at the anode38and a metal hydroxide is generated in the cathodic chamber40at the cathode42. SeeFIG.6. Instead of oxygen evolution, the chlorine evolution reaction (2Cl−↔Cl2+2e−) occurs at >1.3 V. The leftover cation Na+in the anodic chamber36is transported via the cation membrane44to the cathodic chamber40to balance the OH−ion produced from HER. In this configuration, H2depolarization can suppress chlorine evolution, with the net result that HCl and NaOH are produced from the anode and cathode channels58,60, respectively. High purity hydrogen production with CO2emission is a redundancy. Each of the following terms: “includes”, “including”, “has”, “having”, “comprises”, and “comprising”, and, their linguistic/grammatical variants, derivatives, or/and conjugates, as used herein, means “including, but not limited to”, and is to be taken as specifying the stated component(s), feature(s), characteristic(s), parameter(s), integer(s), or step(s), and does not preclude addition of one or more additional component(s), feature(s), characteristic(s), parameter(s), integer(s), step(s), or groups thereof. Terms of approximation, such as the terms about, substantially, approximately, etc., as used herein, refers to ±10% of the stated numerical value. It is to be fully understood that certain aspects, characteristics, and features, of the apparatus and method, which are, for clarity, illustratively described and presented in the context or format of a plurality of separate embodiments, may also be illustratively described and presented in any suitable combination or sub-combination in the context or format of a single embodiment. Conversely, various aspects, characteristics, and features, of the apparatus and method which are illustratively described and presented in combination or sub-combination in the context or format of a single embodiment may also be illustratively described and presented in the context or format of a plurality of separate embodiments. Although the apparatus and method of this disclosure have been illustratively described and presented by way of specific exemplary embodiments, and examples thereof, it is evident that many alternatives, modifications, or/and variations, thereof, will be apparent to those skilled in the art. Accordingly, it is intended that all such alternatives, modifications, or/and variations, fall within the spirit of, and are encompassed by, the broad scope of the appended claims.
12,734
11857915
DESCRIPTION OF EMBODIMENTS FIG.1is a diagram illustrating a schematic structure of a gas separator2according to one embodiment of the present invention. InFIG.1, cross-hatching in the sections of some components is omitted. The gas separator2is an apparatus that separates carbon dioxide (CO2) from a mixed gas that includes carbon dioxide and other gases. For example, the mixed gas is a combustion exhaust gas emitted from a thermal power station. The gas separator2includes a separation membrane complex1, sealers21, an outer cylinder22, two seal members23, and a gas supply part26, a first gas collecting part27, a second gas collecting part28, and a cooler29. The separation membrane complex1, the sealers21, and the seal members23are placed in the internal space of the outer cylinder22. The gas supply part26, the first gas collecting part27, and the second gas collecting part28are disposed outside the outer cylinder22and connected to the outer cylinder22. In the example illustrated inFIG.1, the cooler29is disposed outside the outer cylinder22and covers the outside surface of the outer cylinder22. FIG.2is a sectional view of the separation membrane complex1.FIG.3is a sectional view illustrating part of the separation membrane complex1in enlarged dimension. The separation membrane complex1includes a porous support11and a separation membrane12formed on the support11. InFIG.2, the separation membrane12is illustrated with bold lines. InFIG.3, the separation membrane12is cross-hatched. The thickness of the separation membrane12illustrated inFIG.3is greater than the actual thickness. The support11is a porous member that is permeable to gases. In the example illustrated inFIG.2, the support11is a monolith support in which a plurality of through holes111, each extending in a longitudinal direction (i.e., an up-down direction inFIG.2), are formed in an integrally-molded columnar body. In the example illustrated inFIG.2, the support11has a generally columnar shape. Each through hole111(i.e., cell) has, for example, a generally circular shape in section perpendicular to the longitudinal direction. In the illustration inFIGS.1and2, the diameter of the through holes111is greater than the actual diameter, and the number of through holes111is smaller than the actual number. The separation membrane12is formed on the inside surfaces of the through holes111and covers approximately the entire inside surfaces of the through holes111. The support11has a length (i.e., length in the up-down direction inFIG.2) of, for example, 10 cm to 200 cm. The support11has an outer diameter of, for example, 0.5 cm to 30 cm. A distance between the central axes of adjacent through holes111is, for example, in the range of 0.3 mm to 10 mm. Surface roughness (Ra) of the support11is, for example, in the range of 0.1 μm to 5.0 μm and preferably in the range of 0.2 μm to 2.0 μm. Alternatively, the support11may have a different shape such as a honeycomb shape, a flat plate shape, a tubular shape, a cylindrical shape, a columnar shape, or a polygonal prism shape. When the support11has a tubular or cylindrical shape, the thickness of the support11is, for example, in the range of 0.1 mm to 10 mm. As the material for the support11, various substances (e.g., ceramic or metal) may be employed as long as they are chemically stable during the step of forming the zeolite membrane12on the surface of the support. In the present embodiment, the support11is formed of a ceramic sintered compact. Examples of the ceramic sintered compact that is selected as the material for the support11include alumina, silica, mullite, zirconia, titania, yttrium, silicon nitride, and silicon carbide. In the present embodiment, the support11contains at least one of alumina, silica, and mullite. The support11may contain an inorganic binder. The inorganic binder may be at least one of titania, mullite, easily sinterable alumina, silica, glass frit, clay minerals, and easily sinterable cordierite. A mean pore diameter of the support11in the vicinity of the surface where the separation membrane12is formed is preferably smaller than a mean pore diameter of the support11in the other portions. To achieve this structure, the support11has a multilayer structure. When the support11has a multilayer structure, the material for each layer may be any of the materials described above, and each layer may be formed of the same material, or may be formed of a different material. The mean pore diameter of the support11can be measured using an apparatus such as a mercury porosimeter, a perm porometer, or a nano-perm porometer. The mean pore diameter of the support11is, for example, in the range of 0.01 μm to 70 μm and preferably in the range of 0.05 μm to 25 μm. The mean pore diameter of the support11in the vicinity of the surface where the separation membrane12is formed is in the range of 0.01 μm to 1 μm and preferably in the range of 0.05 μm to 0.5 μm. In a pore size distribution of the entire support11including the surface and inside of the support11, D5 is, for example, in the range of 0.01 μm to 50 μm, D50 is, for example, in the range of 0.05 μm to 70 μm, and D95 is, for example, in the range of 0.1 μm to 2000 μm. A porosity of the support11in the vicinity of the surface where the separation membrane12is formed is, for example, in the range of 25% to 50%. The separation membrane12is a porous membrane with small pores. The separation membrane12is a gas separation membrane that separates CO2from a mixed gas of a plurality of types of gases, using a molecular sieving function. This mixed gas includes other gases that are less likely to permeate through the separation membrane12than CO2. In other words, the mixed gas includes other gases that have lower permeances than the CO2permeance of the separation membrane12. The mixed gas includes, in addition to CO2, one or more types of gases including hydrogen (H2), helium (He), nitrogen (N2), oxygen (O2), carbon monoxide (CO), nitrogen oxide, ammonia (NH3), sulfur oxide, hydrogen sulfide (H2S), sulfur fluoride, mercury (Hg), arsine (AsH3), hydrogen cyanide (HCN), carbonyl sulfide (COS), C1 to C8 hydrocarbons, organic acid, alcohol, mercaptans, ester, ether, ketone, and aldehyde. Separating CO2refers to causing at least part of CO2in the mixed gas to permeate through the separation membrane12and the support11, and the concentration of the gas will not be discussed here. In the following description, a gas that has permeated through the separation membrane12and the support11is also referred to as a “permeated gas.” Nitrogen oxide is a compound of nitrogen and oxygen. The aforementioned nitrogen oxide is, for example, a gas called NOx such as nitrogen monoxide (NO), nitrogen dioxide (NO2), nitrous oxide (also referred to as dinitrogen monoxide) (N2O), dinitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4), or dinitrogen pentoxide (N2O5). Sulfur oxide is a compound of sulfur and oxygen. The aforementioned sulfur oxide is, for example, a gas called SOXsuch as sulfur dioxide (SO2) or sulfur trioxide (SO3). Sulfur fluoride is a compound of fluorine and sulfur. The aforementioned sulfur fluoride is, for example, disulfur difluoride (F—S—S—F, S═SF2), sulfur difluoride (SF2), sulfur tetrafluoride (SF4), sulfur hexafluoride (SF6), or disulfur decafluoride (S2F10). C1 to C8 hydrocarbons are hydrocarbons containing one or more and eight or less carbon atoms. C3 to C8 hydrocarbons each may be any of a linear-chain compound, a side-chain compound, and a cyclic compound. C2 to C8 hydrocarbons each may be either a saturated hydrocarbon (i.e., the absence of a double bond and a triple bond in a molecule) or an unsaturated hydrocarbons (i.e., the presence of a double bond and/or a triple bond in a molecule). C1 to C4 may, for example, be methane (CH4), ethane (C2H6), ethylene (C2H4), propane (C3H8), propylene (C3H6), normal butane (CH3(CH2)2CH3), isobutane (CH(CH3)3), 1-butene (CH2═CHCH2CH3), 2-butene (CH3CH═CHCH3), or isobutene (CH2═C(CH3)2). The aforementioned organic acid may, for example, be carboxylic acid or sulfonic acid. The carboxylic acid may, for example, be formic acid (CH2O2), acetic acid (C2H4O2), oxalic acid (C2H2O4), acrylic acid (C3H4O2), or benzoic acid (C6H5COOH). The sulfonic acid may, for example, be ethane sulfonic acid (C2H6O3S). The organic acid may, for example, be either a chain compound or a cyclic compound. The aforementioned alcohol may, for example, be methanol (CH3OH), ethanol (C2H5OH), isopropanol (2-propanol) (CH3CH(OH)CH3), ethylene glycol (CH2(OH)CH2(OH)), or butanol (C4H9OH). The mercaptans are organic compounds with terminal sulfur hydride (SH) and are also substances called thiol or thioalcohol. The aforementioned mercaptans may, for example, be methyl mercaptans (CH3SH), ethyl mercaptans (C2H5SH), or 1-propane thiols (C3H7SH). The aforementioned ester may, for example, be formic acid ester or acetic acid ester. The aforementioned ether may, for example, be dimethyl ether ((CH3)2O), methyl ethyl ether (C2H5OCH3), or diethyl ether ((C2H5)2O). The aforementioned ketone may, for example, be acetone ((CH3)2CO), methyl ethyl ketone (C2H5COCH3), or diethyl ketone ((C2H5)2CO). The aforementioned aldehyde may, for example, be acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), or butanal (butyraldehyde) (C3H7CHO). The separation membrane12has a thickness of, for example, 0.05 μm to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.5 μm to 10 μm. Increasing the thickness of the separation membrane12improves the selectivity. Reducing the thickness of the separation membrane12increases the permeance. Surface roughness (Ra) of the separation membrane12is, for example, less than or equal to 5 μm, preferably less than or equal to 2 μm, more preferably less than or equal to 1 μm, and yet more preferably less than or equal to 0.5 μm. The separation membrane12has a mean pore diameter less than or equal to 1 nm. This improves the CO2selectivity through the separation membrane12. There are no particular limitations on the lower limit of the mean pore diameter of the separation membrane12as long as CO2can permeate through the separation membrane, but for example, the lower limit may be set greater than or equal to 0.2 nm. The mean pore diameter of the separation membrane12is preferably greater than or equal to 0.2 nm and less than or equal to 0.8 nm, more preferably greater than or equal to 0.3 nm and less than or equal to 0.6 nm, and yet more preferably greater than or equal to 0.3 nm and less than or equal to 0.5 nm. Reducing the mean pore diameter of the separation membrane12improves the selectivity. Increasing the mean pore diameter of the separation membrane12increases the permeance. The mean pore diameter of the separation membrane12is smaller than the mean pore diameter in the surface of the support11where the separation membrane12is provided. The separation membrane12is preferably an inorganic membrane, and in the present embodiment, a zeolite membrane (i.e., a zeolite in membrane form). Examples of the zeolite of the separation membrane12include a zeolite in which atoms (T atoms) located in the center of an oxygen tetrahedron (TO4) constituting the zeolite are composed of only Si or composed of Si and Al, an AlPO-type zeolite in which the T atoms are composed of Al and P, an SAPO-type zeolite in which the T atoms are composed of Si, Al, and P, an MAPSO-type zeolite in which T atoms are composed of magnesium (Mg), Si, Al, and P, and a ZnAPSO-type zeolite in which T atoms are composed of zinc (Zn), Si, Al, and P. Some of the T atoms may be replaced by other elements. When n represents a maximum number of membered rings in the zeolite of the separation membrane12, an arithmetical mean of the major and minor axes of an n-membered ring pore is assumed to be a mean pore diameter. The n-membered ring pore as used herein refers to a pore whose number of oxygen atoms that are bonded to T atoms and make a ring structure is n. When the zeolite has a plurality of n-membered ring pores where n is the same number, an arithmetical mean of the major and minor axes of all n-membered ring pores is assumed to be the mean pore diameter of the zeolite. In this way, the mean pore diameter of the zeolite membrane is uniquely determined by the framework structure of the zeolite and can be obtained from a value disclosed in “Database of Zeolite Structures” [online] by the International Zeolite Association on the Internet <URL:http://www.iza-structure.org/databases/>. There are no particular limitations on the type of the zeolite of the separation membrane12, and the zeolite may be any of the following types including AEI-type, AEN-type, AFN-type, AFV-type, AFX-type, BEA-type, CHA-type, DDR-type, ERI-type, ETL-type, FAU-type (X-type, Y-type), GIS-type, LEV-type, LTA-type, MEL-type, MFI-type, MOR-type, PAU-type, RHO-type, SAT-type, and SOD-type. From the viewpoint of increasing the CO2permeance and improving the CO2selectivity, which will be described later, the maximum number of membered rings in the zeolite is preferably less than or equal to 8 (e.g., 6 or 8). For example, the separation membrane12is a DDR-type zeolite. In other words, the separation membrane12is a zeolite membrane composed of a zeolite having a framework type code “DDR” assigned by the International Zeolite Association. In this case, the zeolite of the separation membrane12has an intrinsic pore diameter of 0.36 nm×0.44 nm and a mean pore diameter of 0.40 nm. When the separation membrane12is a zeolite membrane, the separation membrane12contains, for example, silicon (Si). For example, the separation membrane12may contain any two or more of Si, aluminum (Al), and phosphorus (P). The separation membrane12may contain alkali metal. The alkali metal is, for example, sodium (Na) or potassium (K). When the separation membrane12contains Si atoms, an Si/Al ratio in the separation membrane12is, for example, higher than or equal to 1 and lower than or equal to 100,000. The Si/Al ratio is preferably higher than or equal to 5, more preferably higher than or equal to 20, and yet more preferably higher than or equal to 100. This ratio is preferably as high as possible. The Si/Al ratio in the separation membrane12can be adjusted by, for example, adjusting the composition ratio of an Si source and an Al source in a starting material solution, which will be described later. The CO2permeance of the separation membrane12at temperatures of −50° C. to 300° C. is, for example, greater than or equal to 50 nmol/m2·s·Pa. The ratio (permeance ratio) between the CO2permeance and the CH4permeance (leakage) of the zeolite membrane12at temperatures of −50° C. to 300° C. is, for example, higher than or equal to 30. The permeance and the permeance ratio are values for the case where a difference in the partial pressure of CO2between the supply side and the permeation side of the zeolite membrane12is 1.5 MPa. The sealers21are members mounted on the opposite ends of the support11in the longitudinal direction (i.e., right-left direction inFIG.1) and covering and sealing the opposite end faces of the support11in the longitudinal direction and the outside surface of the support11in the vicinity of the opposite end faces. The sealers21prevent the inflow and outflow of gases from the opposite end faces of the support11. The sealers21are, for example, plate-like members formed of glass or resin. The material and shape of the sealers21may be appropriately changed. The sealers21has a plurality of openings that overlap with a plurality of through holes111of the support11, and therefore the opposite ends in the longitudinal direction of each through hole111of the support11are not covered with the sealers21. Accordingly, the gas can flow in and out from the opposite ends through the through holes111. The outer cylinder22is a generally cylindrical tubular member. The outer cylinder22is formed of, for example, stainless steel or carbon steel. The longitudinal direction of the outer cylinder22is approximately parallel to the longitudinal direction of the separation membrane complex1. The outer cylinder22has a gas supply port221on one end in the longitudinal direction (i.e., left end inFIG.5) and a first gas exhaust port222on the other end. The outer cylinder22also has a second exhaust port223on the side surface. The gas supply port221is connected to the gas supply part26. The first gas exhaust port222is connected to the first gas collecting part27. The second gas exhaust port223is connected to the second gas collecting part28. An internal space of the outer cylinder22is an enclosed space isolated from the space around the outer cylinder22. The two seal members23are arranged around the entire circumference between the outside surface112of the separation membrane complex1(i.e., outside surface112of the support11) and the inside surface of the outer cylinder22in the vicinity of the opposite ends of the zeolite membrane complex1in the longitudinal direction. Each seal member23is a generally ring-shaped member formed of a material that is impermeable to gases. For example, the seal members23are O-rings formed of a resin having flexibility. The seal members23are in intimate contact with the outside surface112of the separation membrane complex1and the inside surface of the outer cylinder22around the entire circumference. In the example illustrated inFIG.1, the seal members23are in tight contact with the outside surfaces of the sealers21and are indirectly in tight contact with the outside surface112of the separation membrane complex1via the sealers21. A space between the seal members23and the outside surface112of the separation membrane complex1and a space between the seal members23and the inside surface of the outer cylinder22are sealed so as to almost or completely disable the passage of gases. The gas supply part26supplies a mixed gas including CO2and other gases (e.g., nitrogen (N2)) into the internal space of the outer cylinder22through the gas supply port221. For example, the gas supply part26is a blower or pump that transmits the mixed gas toward the outer cylinder22under pressure. This blower or pump includes a pressure regulator that regulates the pressure of the mixed gas supplied to the outer cylinder22. The mixed gas supplied from the gas supply part26to the inside of the outer cylinder22is led from the left end of the separation membrane complex1in the drawing into each through hole111of the support11, as indicated by an arrow251. In the mixed gas, CO2is led out of the outside surface112of the support11while permeating through the separation membrane12provided on the inside surface of each through hole111and the support11, and is collected by the second gas collecting part28through the second gas exhaust port223as indicated by an arrow253. In other words, the gas supply part26supplies the aforementioned mixed gas to the separation membrane complex1from the side of the separation membrane12and separates CO2in the mixed gas from the mixed gas by causing CO2to permeate through the separation membrane12and the support11and to be exhausted out of a generally cylindrical area of the outside surface112of the support11that is located between the two seal members23(hereinafter, this area is referred to as a “permeation surface113”). Note that the permeation surface113does not include an area of the outside surface112of the support11that is covered with the sealers21. The second gas collecting part28may, for example, be a reservoir for storing a permeated gas such as CO2that is led out of the outer cylinder22while permeating through the separation membrane12and the support11, or may be a blower or pump that transfers the permeated gas. In the mixed gas, a gas other than the aforementioned permeated gas (hereinafter referred to as “a non-permeated gas) passes through each through hole111of the support11from the left side to the right side in the drawing, and is collected by the first gas collecting part27through the first gas discharge port222as indicated by an arrow252. For example, the first gas collecting part27may be a reservoir for storing a non-permeated gas led out of the outer cylinder22, or may be a blower or pump that transfers the non-permeated gas. The cooler29is in direct or indirect contact with the outside surface of the outer cylinder22and cools the outer cylinder22. For example, the cooler29is a generally cylindrical cooling jacket provided around the outer cylinder22. In this case, the outer cylinder22is cooled as a result of a cooling medium such as cooling water flowing continuously through the inside of the cooler29. InFIG.1, the cooling medium in the cooler29is cross-hatched. The length of the cooler29in the aforementioned longitudinal direction is, for example, approximately the same as the distance in the longitudinal direction between the two seal members23, or may be longer than this distance. In the example illustrated inFIG.1, the opposite ends of the cooler29are located at approximately the same positions in the longitudinal direction as the positions of the two seal members23. In the gas separator2, the separation membrane complex1that faces the inside surface of the outer cylinder22is also cooled as a result of the outer cylinder22being cooled by the cooler29. To be more specific, as a result of the outer cylinder22being cooled by the cooler29, the gas existing between the inside surface of the outer cylinder22and the outside surface112of the support11is cooled, and approximately the entire support11is cooled from the side of the outside surface112that is in contact with the gas. As a result, approximately the entire separation membrane12having contact with the support11is also cooled. Next, one example of the procedure for separating a mixed gas, performed by the gas separator2, will be described with reference toFIG.4. For the separation of a mixed gas, first, the separation membrane complex1is prepared by forming the separation membrane12on the support11(step S11). When step S11is described more specifically, first, seed crystals for use in the production of the separation membrane12(i.e., zeolite membrane) are prepared. For example, the seed crystals are acquired from DDR-type zeolite powder synthesized by hydrothermal synthesis. The zeolite powder may be used as-is as the seed crystals, or may be processed into the seed crystals by pulverization or other methods. Then, the porous support11is immersed in a solution in which the seed crystals are dispersed, so as to deposit the seed crystals on the support11. Alternatively, a solution in which the seed crystals are dispersed may be brought into contact with a portion of the support11on which the separation membrane12is desired to be formed, so as to deposit the seed crystals on the support11. In this way, a seed-crystal-deposited support is prepared. The seed crystals may be deposited on the support11by the other methods. The support11with the seed crystals deposited thereon is immersed in a starting material solution. The starting material solution is prepared by, for example, causing substances such as an Si source and a structure-directing agent (hereinafter, also referred to as an “SDA”) to dissolve or disperse in a solvent. The starting material solution has a composition of, for example, 1:0.15:0.12 of SiO2:SDA:(CH2)2(NH2)2. The solvent in the starting material solution may, for example, be water or alcohol such as ethanol. The SDA in the starting material solution may, for example, be an organic compound. For example, 1-adamantanamine may be used as the SDA. Then, using the seed crystals as nuclei, the DDR-type zeolite is grown by hydrothermal synthesis to form a DDR-type zeolite membrane, i.e., the separation membrane12, on the support11. The temperature of the hydrothermal synthesis is preferably in the range of 120 to 200° C., and for example, 160° C. The time of the hydrothermal synthesis is preferably in the range of 10 to 100 hours, and for example, 30 hours. When the hydrothermal synthesis has ended, the support11and the separation membrane12are rinsed with deionized water. After the rinsing, the support11and the separation membrane12are, for example, dried at 80° C. After the support11and the separation membrane12have been dried, the separation membrane12is subjected to heat treatment so as to almost completely burn and remove the SDA in the separation membrane12and cause micropores in the separation membrane12to come through the membrane. In this way, the aforementioned zeolite membrane complex1is obtained. When step S11has ended, the gas separator2illustrated inFIG.1is assembled (step S12). The separation membrane complex1is installed in the outer cylinder22. Then, the cooler29cools the separation membrane complex1via the outer cylinder22. Specifically, the cooler29cools the portion of the outer cylinder22that is located between the two seal members23, so that in the portion between the two seal members23, the gas existing between the inside surface of the outer cylinder22and the outside surface112of the support11is cooled. Moreover, the permeation surface113of the support11, which is the area having contact with the gas, is cooled, approximately the entire support11is cooled, and approximately the entire separation membrane12is also cooled (step S13). The cooling of the separation membrane complex1by the cooler29continues until the gas separator2ends the gas separation processing. Then, the gas supply part26supplies a mixed gas including CO2and other gases to the internal space of the outer cylinder22(step S14). In the present embodiment, the mixed gas is primarily composed of CO2and N2. The mixed gas may also include gases other than CO2and N2. Moisture in the mixed gas inhibits adsorption of CO2into the pores of the separation membrane12and suppresses a reduction in CO2permeance. Thus, in the internal space of the outer cylinder22, the moisture content in the mixed gas before supplied to the separation membrane complex1is preferably lower than or equal to 3000 ppm according to the volume ratio (i.e., molar ratio), more preferably lower than or equal to 1000 ppm, yet more preferably lower than or equal to 500 ppm, and in particular preferably lower than or equal to 100 ppm. If the moisture content in the mixed gas is higher than 3000 ppm, it is possible to use a mixed gas obtained by lowering the moisture content to 3000 ppm or less by a dehydrator. The pressure of the mixed gas supplied from the gas supply part26to the internal space of the outer cylinder22, i.e., initial gas pressure, is preferably higher than or equal to 0.5 MPa, more preferably higher than or equal to 1 MPa, and yet more preferably higher than or equal to 2 MPa. The initial gas pressure is also, for example, lower than or equal to 20 MPa and typically lower than or equal to 10 MPa. The temperature of the mixed gas supplied from the gas supply part26to the internal space of the outer cylinder22is, for example, in the range of −50° C. to 300° C., and in the present embodiment, approximately in the range of 10° C. to 150° C. In the internal space of the outer cylinder22, the mixed gas before supplied to the separation membrane complex1(i.e., mixed gas immediately before supplied to the separation membrane12) has approximately the same pressure and the same temperature as the pressure and temperature of the mixed gas supplied from the aforementioned gas supply part26to the internal space of the outer cylinder22. The mixed gas supplied into the outer cylinder22is led to each through hole111of the separation membrane complex1. Then, CO2in the mixed gas permeates through the separation membrane12and the support11of the separation membrane complex1, is led out from the permeation surface113of the support11, and is separated from the mixed gas (step S15). As described above, the support11is cooled by the cooler29. Thus, the temperature of the support11is lower than the temperature of the mixed gas before supplied to the separation membrane complex1(i.e., mixed gas that has flowed from the gas supply port221toward the separation membrane12and that is immediately before supplied to the separation membrane12). Specifically, the temperature of at least part of the permeation surface113of the support11is lower by 10° C. or more than the temperature of the mixed gas. Note that the temperature of the permeation surface113of the support11and the temperature of the gas immediately after having permeated through the support11are approximately the same. Thus, if it is difficult to directly measure the temperature of the permeation surface113of the support11, it can be said, from the fact that the temperature of the gas immediately after having permeated through the support11is lower by 10° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1, that the temperature of at least part of the permeation surface113of the support11is lower by 10° C. or more than the temperature of the mixed gas. When the gas separator2includes a plurality of separation membrane complexes, in at least one of the separation membrane complexes1, the temperature of at least part of the permeation surface113of the support11in the separation membrane complex1is lower by 10° C. or more than the temperature of the mixed gas immediately before supplied to the separation membrane12in the separation membrane complex1. Preferably, the temperature of the entire permeation surface113of the support11is lower by 10° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. The temperature of the entire permeation surface113does not necessarily have to be lower by 10° C. or more than the temperature of the aforementioned mixed gas, and it is also preferable that the temperature of at least part of the permeation surface113is lower by 15° C. or more than the temperature of the mixed gas. More preferably, the temperature of the entire permeation surface113of the support11is lower by 15° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. As described above, in the gas separator2, at least the temperature of part of the permeation surface113of the support11is lower by 10° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. This allows CO2to be efficiently adsorbed into the pores of the separation membrane12and thereby increases the ratio of the CO2permeance of the separation membrane12to the other permeance thereof such as the N2permeance. In other words, the CO2selectivity of the separation membrane12improves. Preferably, the concentration of CO2in the permeated gas that has permeated through the separation membrane12and the support11is made higher than the concentration of CO2in the mixed gas. The permeated gas that has permeated through the separation membrane complex1is collected by the second gas collecting part28. The pressure of the gas in the second gas collecting part28(i.e., permeation-side pressure) may be arbitrarily set, and for example, set to a pressure of approximately one atmosphere (0.101 MPa). The permeated gas collected by the second gas collecting part28may also include other gases different from CO2. A non-permeated gas (i.e., a gas not having permeated through the separation membrane12and the support11in the mixed gas) passes through each through hole111in the longitudinal direction and is exhausted out of the outer cylinder22through the first gas discharge port222. The non-permeated gas having passed through the through holes111in the separation membrane complex1is cooled by the separation membrane complex1whose temperature is lower than the temperature of the mixed gas. Therefore, the temperature of the non-permeated gas immediately after having passed through the through holes111is lower than the temperature of the mixed gas before supplied to the separation membrane complex1(i.e. mixed gas having flowed from the gas supply port221toward the separation membrane12and immediately before supplied to the separation membrane12). The non-permeated gas immediately after having passed through the through holes111is preferably higher than the temperature of the permeation surface113of the support11. The temperature of the non-permeated gas immediately after having passed through the through holes111is also preferably higher than the temperature of the permeated gas immediately after having permeated through the separation membrane complex1. Note that the temperature of the non-permeated gas immediately after having passed through the through holes111is approximately the same as the temperature of the non-permeated gas exhausted through the first gas discharge port222. The non-permeated gas exhausted out of the outer cylinder22is collected by the first gas collecting part27. For example, the pressure of the gas in the first gas collecting part27is approximately the same as the pressure of the mixed gas supplied by the gas supply part26. The non-permeated gas collected by the first gas collecting part27may include CO2that has not permeated through the separation membrane complex1. Next, the relation of a difference in temperature between the mixed gas immediately before supplied to the separation membrane12and the permeation surface113, the pressure of the mixed gas immediately before supplied to the separation membrane12, the CO2flux, and the CO2selectivity in the gas separation method illustrated as steps S11to S15described above will be described with reference to Table 1. Examples 1 to 5 and Comparative Examples 1 and 2 in Table 1 vary in temperature difference ΔT (° C.) between the mixed gas immediately before supplied to the separation membrane12and the permeation surface13and in pressure P (MPa) of the mixed gas immediately before supplied to the separation membrane12. The temperature difference ΔT(° C.) is obtained by subtracting the temperature of an area of the permeation surface113that has a lowest temperature from the temperature of the above-described mixed gas. Although not shown in Table 1, the separation membranes12according to Examples 1 to 5 and Comparative Examples 1 and 2 are DDR-type zeolite membranes. The mixed gas (except moisture) supplied from the gas supply part26to the gas separator2has a composition ratio of 50% by volume of CO2and 50% by volume of N2. The moisture content in the mixed gas is 3000 ppm. The temperature of the mixed gas immediately before supplied to the separation membrane12is 30° C. The pressure in the second gas collecting part28(i.e., permeation-side pressure) is set to a pressure of one atmosphere. In Table 1, CO2flux and CO2selectivity were obtained as follows. First, the flow rate and composition of the permeated gas that permeated through the separation membrane complex1were respectively measured using a mass flow meter and a gas chromatography. Then, the CO2permeance and the N2permeance of the separation membrane12were obtained from the measured values of the flux and composition of the permeated gas. Moreover, the permeance of CO2and N2per unit area, per unit time, and per unit pressure were obtained, respectively, and a value obtained by dividing the CO2permeance by the N2permeance was assumed to be the CO2selectivity. That is, the CO2selectivity in Table 1 corresponds to the ratio of the CO2permeance to the N2permeance. As the numerical value in Table 1 increases, the CO2selectivity improves and the ratio (vol %) of CO2in the permeated gas increases. TABLE 1Temper-Temper-Temper-Pressureatureature ofatureofofPermeationDifferenceMixedCO2CO2MixedSurfaceΔTGasFluxselec-Gas ° C.° C.° C.MPa(L/min)tivityExample 13020100.48.860.7Example 23020101.022.942.6Example 36050102.036.730.9Example 43015151.022.650.7Example 53010201.022.456.8Compar-302550.48.949.8ativeExample 1Compar-303000.49.044.3ativeExample 2 As shown in Table 1, in Examples 1 to 3 with a temperature difference ΔT of 10° C., the CO2selectivity is higher than or equal to 30.9, and the CO2flux increases as the pressure of the mixed gas increases. In Examples 2, 4, and 5 with a pressure of the mixed gas of 1.0 MPa, the CO2flux is almost the same, and the CO2selectivity improves with increasing temperature difference ΔT. In Examples 2 to 5 with a pressure of the mixed gas higher than or equal to 1.0 MPa, the CO2flux is higher than or equal to 22.4 liters (L)/min. Meanwhile, when Comparative Examples 1 and 2 with a temperature difference ΔT less than 10° C. are compared with Example 1 with the same pressure of the mixed gas, these examples show almost the same CO2flux, and differ in CO2selectivity, specifically 60.7 in Example 1, 49.8 in Comparative Example 1, and 44.3 in Comparative Example 2. In Examples 1 to 5, if the moisture content in the mixed gas was reduced to be less than 3000 ppm, the CO2permeance and the CO2selectivity became equivalent to or improved from the results shown in Table 1. In Examples 1 to 5, the temperature of the non-permeated gas (i.e., the temperature of the non-permeated gas immediately after having passed through the through holes111) was lower than the temperature of the mixed gas before supplied to the separation membrane complex1(i.e., the mixed gas immediately before supplied to the separation membrane12) and higher than the temperature of the permeation surface113of the support11. Although not shown in Table 1, if the separation membrane12was changed from the DDR type zeolite membrane to a CHA-type or Y-type (FAU-type) zeolite membrane, the CO2selectivity also improved as a result of setting the temperature difference ΔT to be greater than or equal to 10° C. as described above. The CO2selectivity further improved in the case of using a DDR-type or CHA-type zeolite membrane composed of a zeolite whose maximum number of membered rings was 8, rather than in the case of using a Y-type zeolite membrane composed of a zeolite whose maximum number of membered rings was 12. Similarly, when the separation membrane12was replaced by an inorganic membrane such as a carbon or silica membrane other than a zeolite membrane, the CO2selectivity also improved as a result of setting the temperature difference ΔT to be greater than or equal to 10° C. as described above. As described above, the gas separation method of separating CO2in a mixed gas includes the step of preparing the separation membrane complex1in which the separation membrane12with pores having a mean particle diameter less than or equal to 1 nm is formed on the porous support11(step S11), and the step of supplying a mixed gas including CO2and other gases from the side of the separation membrane12to the separation membrane complex1and obtaining a permeated gas by causing CO2in the mixed gas to permeate through the separation membrane12and the support11(step S14). Step S14is performed in a state in which the temperature of at least part of the permeation surface113of the support11, from which the permeated gas is exhausted, is lower by 10° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. This enables reducing the temperature of the separation membrane12to be lower than the temperature of the mixed gas and causing CO2to be efficiently adsorbed in the pores of the separation membrane12. As a result, it is possible to improve the CO2selectivity of the separation membrane12. According to this gas separation method, it is possible to reduce the amount of energy required for cooling more than in the case where the whole of the mixed gas is cooled before supplied to the separation membrane12. In the above-described gas separation method, the CO2concentration in the permeated gas obtained in step S14is higher than the CO2concentration in the aforementioned mixed gas. This accelerates the separation of CO2in the separation membrane12. In the above-described gas separation method, it is preferable in step S14that the temperature of the entire permeation surface113of the support11is lower by 10° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. This further improves the CO2selectivity of the separation membrane12. In the above-described gas separation method, it is preferable in step S14that the temperature of at least part of the permeation surface113of the support11is lower by 15° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. This further improves the CO2selectivity of the separation membrane12. In the above-described gas separation method, it is preferable in step S14that the pressure of the mixed gas before supplied to the separation membrane complex1is higher than or equal to 1 MPa. This increases the CO2flux in the separation membrane12. As described above, the separation membrane12is preferably an inorganic membrane. This, as described above, favorably enables increasing the CO2permeance in the separation membrane12and improving the CO2selectivity. Examples of the inorganic membrane include a zeolite membrane, a silica membrane, and a carbon membrane. More preferably, the separation membrane12is a zeolite membrane. Using a zeolite membrane having an intrinsic pore diameter as the separation membrane12in this way makes it possible to further improve the CO2selectivity of the separation membrane12. Note that the zeolite membrane as used herein refers to at least a membrane obtained by forming a zeolite in membrane form on the surface of the support11, and does not include a membrane obtained by simply dispersing zeolite particles in an organic membrane. More preferably, a maximum number of membered rings in the zeolite of the separation membrane12is less than or equal to 8. This further improves the CO2selectivity of the separation membrane12. In the above-described gas separation method, it is preferable in step S14that the moisture content in the mixed gas before supplied to the separation membrane complex1is less than or equal to 3000 ppm. This reduces a situation in which moisture in the mixed gas inhibits the adsorption of CO2in the pores of the separation membrane12. As a result, it is possible to further increase the CO2permeance in the separation membrane12and to further improve the CO2selectivity. In step S14of the above-described gas separation method, the whole of the mixed gas is not cooled before supplied to the separation membrane12, and the permeated gas is cooled by contact with the separation membrane12. Thus, according to this gas separation method, it is possible to reduce the amount of energy required for cooling more than in the case where the whole of the mixed gas is cooled before supplied to the separation membrane12. In step S14of the above-described gas separation method, the temperature of the non-permeated gas exhausted without permeating through the separation membrane12and the support11in the mixed gas is preferably higher than the temperature of the permeation surface113of the support11and lower than the temperature of the mixed gas before supplied to the separation membrane complex1. This suppresses cooling of the non-permeated gas and thereby further reduces the amount of energy required for cooling. As described above, according to the gas separation method, it is possible to improve the CO2selectivity of the separation membrane12. Accordingly, this gas separation method is particularly suitable for the case of separating CO2from a mixed gas of CO2and another gas (i.e., a gas including at least one kind of gases including hydrogen, helium, nitrogen, oxygen, carbon monoxide, nitrogen oxide, ammonia, sulfur oxide, hydrogen sulfide, sulfur fluoride, mercury, arsine, hydrogen cyanide, carbonyl sulfide, C1 to C8 hydrocarbons, organic acid, alcohol, mercaptans, ester, ether, ketone, and aldehyde). The above-described gas separator2includes the separation membrane complex1in which the separation membrane12with pores having a mean pore diameter less than or equal to 1 nm is formed on the porous support11, and the gas supply part26that supplies a mixed gas including CO2and another gas from the side of the separation membrane12to the separation membrane complex1. Then, CO2in the mixed gas is separated from the mixed gas by causing CO2to permeate through the separation membrane12and the support11in a state in which the temperature of at least part of the permeation surface113, from which the gas having permeated through the separation membrane12is exhausted, is lower by 10° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. This, as described above, allows the temperature of the separation membrane12to be lower than the temperature of the mixed gas and allows CO2to be efficiently adsorbed in the pores of the separation membrane12. As a result, it is possible to improve the CO2selectivity of the separation membrane12. According to this gas separator, it is possible to reduce the amount of energy required for cooling more than in the case where the whole of the mixed gas is cooled before supplied to the separation membrane12. The gas separator2and the gas separation method described above may be modified in various ways. For example, gases included in the mixed gas, other than CO2, may include a gas other than those given as examples in the above description, or may include only a gas other than those given as examples in the above description. The moisture content in the mixed gas before supplied to the separation membrane12may be higher than 3000 ppm. As described above, the pressure of the mixed gas may be less than 1 MPa. The temperature of the non-permeated gas immediately after having passed through the through holes111may be approximately the same as the temperature of the mixed gas before supplied to the separation membrane complex1(i.e., the mixed gas immediately before supplied to the separation membrane12). The temperature of the non-permeated gas may also be approximately the same as the temperature of the permeation surface113of the support11. When the separation membrane12is a zeolite membrane, a maximum number of membered rings in the zeolite of this zeolite membrane may be less than 8, or may be greater than 8. As described above, the separation membrane12is not limited to a zeolite membrane, and may be an inorganic membrane formed of inorganic substances other than a zeolite. The separation membrane12may also be a membrane other than inorganic membranes. While the separation membrane complex1includes the separation membrane12formed on the support11, the separation membrane complex1may further include a functional membrane or a protective membrane laminated on the separation membrane12. Such a functional membrane or a protective membrane may be an inorganic membrane such as a zeolite membrane, a silica membrane, or a carbon membrane, or may be an organic membrane such as a polyimide membrane or a silicone membrane. Moreover, a substance that can easily adsorb CO2may be added to such a functional membrane or a protective membrane laminated on the separation membrane12. The gas separator2may include a generally tubular or cylindrical single tube-type separation membrane complex, instead of the aforementioned monolith type separation membrane complex1. A mode is also possible in which the separation membrane is provided on the outside surface of a generally tubular or cylindrical support, and CO2that has permeated through the separation membrane and the support is led out to a space located radially inward of the support. There may be sealers, or there may be no sealers. In this case, the permeation surface corresponds to the inside surface of the generally tubular or cylindrical support. As a cooler, the gas separator2may include a cooling tube or the like that extends in the longitudinal direction in a central portion of the space located radially inward of the support. The shape and structure of the cooler29may be modified in various ways. For example, the cooler29may be a tube-like cooling jacket that is wound spirally on the outside surface of the outer cylinder22. A cooling medium flowing through the cooling jacket may be a liquid or slurry other than cooling water, or may be a cooled gas. A permeated gas that has permeated through the separation membrane complex1may be used as this cooled gas. Alternatively, the cooler29may be a Peltier device provided on the outside surface of the outer cylinder22. As a method of cooling the separation membrane complex1, the separation membrane complex1may be cooled by causing a low-temperature gas to flow as a sweep gas in contact with the permeation surface, or the Joule-Thomson effect by the permeation of the gas may be used for cooling. In this case, the cooler29may be omitted if it is possible to make the temperature of at least part of the permeation surface113lower by 10° C. or more than the temperature of the mixed gas before supplied to the separation membrane complex1. Even in this case, it is possible to improve the CO2selectivity of the separation membrane12in the same manner as described above. The configurations of the above-described embodiment and variations may be appropriately combined as long as there are no mutual inconsistencies. INDUSTRIAL APPLICABILITY The gas separator and the gas separation method according to the present invention are applicable for use as a device or method for separating CO2in a combustion exhaust gas emitted from a thermal power station or other such installation, and are also applicable in separating CO2in a variety of other mixed gases. REFERENCE SIGNS LIST 1Separation membrane complex2Gas separator11Support12Separation membrane26Gas supply part113Permeation surfaceS11to S15Step
49,998
11857916
DETAILED DESCRIPTION OF THE INVENTION The device of the invention comprises a gas compressor (1) and a feed line (2) for feeding a gas mixture containing methane, carbon dioxide and hydrogen sulfide to the gas compressor. Any gas compressor known to be suitable for compressing mixtures containing methane and carbon dioxide may be used, such as a turbo compressor, a piston compressor or preferably a screw compressor. The screw compressor may be a dry running compressor or a fluid-cooled compressor cooled with water or oil. When an oil cooled compressor is used, the device preferably also contains a droplet separator downstream of the compressor to prevent oil droplets from entering a membrane separation stage. The device of the invention also comprises a first membrane separation stage (3) downstream of the gas compressor (1). The first membrane separation stage comprises a gas separation membrane which has higher permeability for carbon dioxide than for methane and provides a first retentate (4) and a first permeate (5). The term permeate here refers to a gas mixture comprising the gas components of the gas mixture fed to the membrane separation stage which have passed the gas separation membrane due to the difference in partial pressure across the membrane. The term retentate refers to the gas mixture which remains after the gas components have passed the gas separation membrane. The permeate may additionally comprise a sweep gas, if a sweep gas is introduced on the side of the gas separation membrane opposite to the side where the gas mixture is fed. Since the gas separation membrane has higher permeability for carbon dioxide than for methane, the permeate will have a higher molar ratio of carbon dioxide to methane than the gas mixture fed to the first membrane separation stage, i.e. it will be enriched in carbon dioxide, and the retentate will have a higher molar ratio of methane to carbon dioxide than the gas mixture fed to the first membrane separation stage, i.e. it will be enriched in methane. Suitable membranes which have higher permeability for carbon dioxide than for methane are known from the prior art. In general, membranes containing a separation layer of a glassy polymer, i.e. a polymer having a glass transition point at a temperature above the operating temperature of the membrane separation stage, will provide higher permeability for carbon dioxide than for methane. The glassy polymer may be a polyetherimide, a polycarbonate, a polyamide, a polybenzoxazole, a polybenzimidazole, a polysulfone or a polyimide and the gas separation membrane preferably comprises at least 80% by weight of a polyimide or a mixture of polyimides. In a preferred embodiment, the gas separation membrane comprises at least 50% by weight of a polyimide prepared by reacting a dianhydride selected from 3,4,3′,4′-benzophenonetetracarboxylic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 3,4,3′,4′-biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, sulphonyldiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidenediphthalic dianhydride and mixtures thereof with a diisocyanate selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-methylenediphenyl diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-phenylene diisocyanate and mixtures thereof. The dianhydride is preferably 3,4,3′,4′-benzophenonetetracarboxylic dianhydride or a mixture of 3,4,3′,4′-benzophenonetetracarboxylic dianhydride and 1,2,4,5-benzenetetracarboxylic dianhydride. The diisocyanate is preferably a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate or a mixture of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and 4,4′-methylenediphenyl diisocyanate. Suitable polyimides of this type are commercially available from Evonik Fibres GmbH under the trade name P84® type 70, which has CAS number 9046-51-9 and is a polyimide prepared from 3,4,3′,4′-benzophenonetetracarboxylic dianhydride and a mixture of 64 mol % 2,4-tolylene diisocyanate, 16 mol % 2,6-tolylene diisocyanate and 20 mol % 4,4′-methylenediphenyl diisocyanate, and under the trade name P84® HT, which has CAS number 134119-41-8 and is a polyimide prepared from a mixture of 60 mol % 3,4,3′,4′-benzophenonetetracarboxylic dianhydride and 40 mol % 1,2,4,5-benzenetetracarboxylic dianhydride and a mixture of 80 mol % 2,4-tolylene diisocyanate and 20 mol % 2,6-tolylene diisocyanate. The gas separation membranes of this embodiment have preferably been heat treated in an inert atmosphere as described in WO 2014/202324 A1 to improve their long term stability in the process of the invention. In another preferred embodiment, the gas separation membrane comprises at least 50% by weight of a block copolyimide as described in WO 2015/091122 on page 6, line 20 to page 16, line 4. The block copolyimide preferably comprises at least 90% by weight of polyimide blocks having a block length of from 5 to 1000, preferably from 5 to 200. The gas separation membrane may be flat membrane or a hollow fiber membrane and is preferably an asymmetrical hollow fiber membrane comprising a dense polyimide layer on a porous support. The term “dense layer” here refers to a layer which comprises essentially no macropores extending through the layer and the term “porous support” here refers to a support material having macropores extending through the support. The asymmetrical hollow fiber membrane can be prepared by coating a porous hollow fiber with a polyimide to form a dense polyimide layer on the support. In a preferred embodiment, the asymmetrical hollow fiber membrane is a membrane prepared in a phase inversion process by spinning with an annular two component spinning nozzle, passing a solution of a polyimide through the annular opening and a liquid containing a non-solvent for the polyimide through the central opening. The gas separation membrane preferably comprises a dense separation layer of a glassy polymer coated with a dense layer of a rubbery polymer which rubbery polymer has higher gas permeability than the glassy polymer. The preferred gas separation membranes comprising a polyimide separation layer are preferably coated with a polydimethylsiloxane elastomer. When the gas separation membrane is a flat membrane, the first membrane separation stage preferably comprises one or several spiral wound membrane modules containing the flat membranes and when the gas separation membrane is a hollow fiber membrane the first membrane separation stage preferably comprises one or several membrane modules containing a bundle of hollow fiber membranes. The first membrane separation stage may comprise several membrane modules arranged in parallel and may also comprise several membrane modules arranged in series, wherein in a series of membrane modules the retentate provided by a membrane module is passed as feed to the membrane module subsequent in the series of membrane modules, the last membrane module of the series providing the retentate of the membrane separation stage, and the permeates of all membrane modules within a series are combined to provide the permeate of the membrane separation stage. When the first membrane separation stage comprises several membrane modules arranged in series, the membrane modules are preferably removable membrane cartridges arranged in series as a chain of cartridges in a common pressure vessel and connected to each other by a central permeate collecting tube, as described in detail in WO 2016/198450 A1. The first membrane separation stage preferably contains gas separation membranes having a pure gas selectivity of carbon dioxide over methane, determined at 20° C., of at least 20, preferably from 30 to 120 and more preferably from 40 to 100. Suitable membrane modules and membrane cartridges containing hollow fiber polyimide membranes with a pure gas selectivity of carbon dioxide over methane of more than 20 are commercially available from Evonik Fibres GmbH under the trade name SEPURAN® Green. The membrane area of the gas separation membranes in the first membrane separation stage is preferably chosen to allow for transferring from 50 to 95% of the carbon dioxide contained in the feed stream fed to the first membrane separation stage to the permeate stream provided by the first membrane separation stage. The membrane area needed for allowing this fraction of carbon dioxide to permeate in the first membrane separation stage will depend on the flow rate and composition of the feed stream, the pressures on the feed and the permeate side applied in operating the first membrane separation stage and on the gas permeance and the selectivity of the membrane at the temperature used in operating the first membrane separation stage. The device of the invention preferably also comprises a dehumidifier upstream of the first membrane separation stage to prevent water contained in the gas stream fed to the membrane separation stage from condensing in the first membrane separation stage or a subsequent membrane separation stage of the device. The dehumidifier is preferably arranged between gas compressor (1) and the first membrane separation stage, and preferably dehumidifies the compressed gas by cooling, condensing water from the cooled gas in a condenser and reheating the gas, with the reheating preferably carried out by the compressed gas in a counter current heat exchanger. The device of the invention further comprises a second membrane separation stage (6) which is connected to the first membrane separation stage (3) to receive the first retentate (4) as feed. The second membrane separation stage (6) comprises a gas separation membrane which has higher permeability for carbon dioxide than for methane and provides a second retentate (7) as a product gas enriched in methane and a second permeate (8). The second membrane separation stage may comprise the same gas separation membrane as the first membrane separation stage or may comprise a different gas separation membrane and preferably comprises the same gas separation membrane as the first membrane separation stage. The same arrangements of gas separation membranes in modules or cartridges as described above for the first membrane separation stage may be used in the second membrane separation stage. The total membrane area of the gas separation membranes in the second membrane separation stage is preferably chosen to reduce the carbon dioxide content in the second retentate below a desired limit by transferring sufficient carbon dioxide contained in the feed stream fed to the second membrane separation stage to the second permeate. The device of the invention preferably comprises an additional third membrane separation stage (9) which is connected to the first membrane separation stage (3) to receive the first permeate (5) as feed. The third membrane separation stage (9) comprises a gas separation membrane having higher permeability for carbon dioxide than for methane, providing a third retentate (10) and a third permeate (11). The third membrane separation stage may comprise the same gas separation membrane as the first membrane separation stage or may comprise a different gas separation membrane and preferably comprises the same gas separation membrane as the first membrane separation stage. The same arrangements of gas separation membranes in modules or cartridges as described above for the first membrane separation stage may be used in the third membrane separation stage. An additional third membrane separation stage (9) can provide a third permeate (11) with a low content of methane that can be discharged to the atmosphere without further treatment. When the third retentate (10) is recycled to the feed of the first membrane separation stage, the additional third membrane separation stage will also reduce methane losses and increase methane recovery with the second retentate (7). The device of the invention may additionally comprise a blower or a compressor between the first membrane separation stage and the third membrane separation stage, increasing the pressure of the first permeate (5) for feeding it to the third membrane separation stage. When such a blower or compressor is used, less membrane area is needed in the third membrane separation stage for achieving the same separation result, but additional energy is needed for the pressure increase. The device of the invention comprises a recycle conduit (12) connected to a recycle feed point (13) on the feed line (2) upstream of the gas compressor (1). If the optional third membrane separation stage (9) is not present, the recycle conduit (12) is connected to the second membrane separation stage (6) to receive the second permeate (8). If the optional third membrane separation stage (9) is present, the recycle conduit (12) is connected to the second membrane separation stage (6) to receive the second permeate (8) or is connected to the third membrane separation stage (9) to receive said third retentate (10) or is preferably connected to both said second membrane separation stage (6) and said third membrane separation stage (9) to receive said second permeate (8) and said third retentate (10). The device of the invention also comprises at least one hydrogen sulfide adsorber (14) which comprises a bed of activated carbon having catalytic activity for oxidizing hydrogen sulfide with oxygen. The hydrogen sulfide adsorber (14) is arranged between the recycle feed point (13) and the first membrane separation stage (3) and may be arranged either upstream or downstream of gas compressor (1). An activated carbon having catalytic activity for oxidizing hydrogen sulfide with oxygen is capable of catalyzing oxidation of hydrogen sulfide to elemental sulfur through intermediate stages of hydrogen disulfide and hydrogen polysulfides according to the following stochiometry: 8H2S+4O2→S8+8H2O Catalytic activity for oxidizing hydrogen sulfide with oxygen can be provided to an activated carbon by introducing iodide, iodine or a basic compound into the activated carbon. Such introducing may be through doping the activated carbon by adding iodine, an iodide salt, an iodine precursor or a non-volatile base to a carbon-containing precursor material and carbonizing the precursor material to activated carbon after this addition. Alternatively, such introducing may be by impregnating an activated carbon with an iodine, an iodide salt, hydrogen iodide, an iodine precursor or a basic compound. Suitable basic compounds are alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides and alkaline earth metal carbonates, in particular sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, calcium oxide, calcium hydroxide and calcium carbonate. Catalytic activity for oxidizing hydrogen sulfide with oxygen can also be provided by carbonizing bituminous coal to an activated carbon at specific reaction conditions. Hydrogen sulfide adsorbers which comprises a bed of activated carbon are known from the prior art and are commercially available. Activated carbon having catalytic activity for oxidizing hydrogen sulfide with oxygen is also commercially available, for example from NECATEC AG under the trade name NECA|Active® sulfo or from Donau Carbon GmbH under the trade names Desorex® K 43 J (impregnated with potassium iodide), Desorex® G 50 (impregnated with potassium hydroxide), Desorex® K 43 BG (impregnated with alkaline earth carbonate) and Desorex® G 70. An activated carbon having catalytic activity for oxidizing hydrogen sulfide with oxygen will in general also adsorb mercaptans contained in the gas mixture in addition to hydrogen sulfide by cooxidizing them with hydrogen sulfide to give alkylpolysulfides. Hydrogen sulfide adsorbers comprising a bed of activated carbon having catalytic activity for oxidizing hydrogen sulfide with oxygen have been used in the prior art for removing hydrogen sulfide from biogas prepared by anaerobic fermentation. Anaerobic fermentation is often carried out with controlled feeding of oxygen to the fermentation to reduce formation of hydrogen sulfide, which provides a biogas containing some oxygen. However, the oxygen concentration of the biogas resulting from such process is in often too low to provide effective removal of hydrogen sulfide in the adsorber. Prior art processes therefore usually add more oxygen or air to the biogas upstream of the absorber in order to achieve complete hydrogen sulfide removal and to make use of the maximum absorption capacity of the hydrogen sulfide adsorber. However, this has the disadvantage of increasing the nitrogen content of the biogas if air is added which leads to a reduced methane content of the methane enriched product gas. Furthermore, such addition of oxygen or air to the biogas carries risks, because adding too much oxygen or air may lead to explosive gas mixtures and adding too little oxygen may lead to hydrogen sulfide accumulation in the adsorber which can lead to a runaway reaction if more oxygen is added to the biogas at a later time. A further disadvantage of prior art processes is the need for drying the biogas upstream of the hydrogen sulfide adsorber, because biogas coming from anaerobic fermentation usually has a moisture content of close to 100% relative humidity, whereas a hydrogen sulfide adsorber comprising a bed of activated carbon should be operated ata relative humidity of the biogas of less than 80% to prevent pore condensation of water which lowers the rate of hydrogen sulfide adsorption. The device of the invention, having a recycle conduit (12) connected to a recycle feed point (13) on the feed line (2) upstream of the hydrogen sulfide adsorber (14), can overcome these disadvantages of the prior art. When the gas mixture fed to the device contains oxygen, the oxygen will be enriched in the second permeate (8) and the third retentate (10) compared to the original gas mixture and recycling of one or both of these streams will increase the oxygen content of the stream entering the hydrogen sulfide adsorber (14). Optimum hydrogen sulfide removal by the adsorber (14) can then be achieved without adding air or oxygen to the biogas or adding less than in prior art processes. When the device of the invention contains an additional dehumidifier between the gas compressor (1) and the first membrane separation stage (3), the second permeate (8) and the third retentate (10) will have a low water content and recycling one or both of these streams to a recycle feed point (13) upstream of the hydrogen sulfide adsorber (14) can lower the relative humidity of the gas stream entering the hydrogen sulfide adsorber (14) to a value providing optimum hydrogen sulfide removal by the adsorber (14) without drying the biogas upstream of the hydrogen sulfide adsorber. In a preferred embodiment of the device of the invention, the hydrogen sulfide adsorber (14) is arranged upstream of gas compressor (1), i.e. arranged between the recycle feed point (13) and the gas compressor (1). This prevents corrosion by hydrogen sulfide in the gas compressor. When an oil cooled gas compressor is used, this also prevents deterioration of the oil by reaction of hydrogen sulfide or mercaptans with components of the oil. In this preferred embodiment, the recycle conduit (12) preferably comprises an additional connection to an additional recycle feed point (15) located between the hydrogen sulfide adsorber (14) and the gas compressor (1). The recycle conduit (12) then also comprises at least one control valve (16) for controlling the fraction of recycled gas being passed to recycle feed point (13) and additional recycle feed point (15). Preferably, two control valves (16) are used as shown inFIG.1, one in the conduit to recycle feed point (13) and one in the conduit to additional recycle feed point (15). The additional recycle feed point (15) and control valve(s) (16) allow for adjusting the composition of the gas stream entering hydrogen sulfide adsorber (14) by changing the fraction of recycled gas which is passed to recycle feed point (13) upstream of the adsorber. In a further preferred embodiment, the device of the invention comprises an oxygen concentration measurement (17) on feed line (2) between the recycle feed point (13) and the hydrogen sulfide adsorber (14) or between the hydrogen sulfide adsorber (14) and the additional recycle feed point (15) or at both locations, and a controller which is configured to operate control valve(s) (16) to maintain the oxygen concentration within a preset range. Any device known from the prior art to be suitable for determining an oxygen concentration in a gas mixture containing methane, carbon dioxide and hydrogen sulfide may be used in this embodiment. When the oxygen concentration measurement (17) is arranged between the recycle feed point (13) and the hydrogen sulfide adsorber (14), the controller is preferably configured to maintain the oxygen concentration within a range known to provide high rates of oxidation of hydrogen sulfide on the activated carbon. Such suitable range for the oxygen concentration can be determined experimentally or can be obtained form the manufacturer of the activated carbon. When the oxygen concentration measurement (17) is arranged between the hydrogen sulfide adsorber (14) and the additional recycle feed point (15), the controller is preferably configured to maintain a minimum oxygen concentration known to prevent accumulation of non-reacted hydrogen sulfide in the hydrogen sulfide adsorber (14). Such suitable minimum concentration can be determined experimentally, for example by measuring the amounts of hydrogen sulfide and oxygen entering and leaving the adsorber and calculating the conversion of hydrogen sulfide by reaction with oxygen using the stoichiometry of the reaction equation given above. In another further preferred embodiment, the device of the invention comprises a measurement of relative humidity on feed line (2) between the recycle feed point (13) and the hydrogen sulfide adsorber (14) or between the hydrogen sulfide adsorber (14) and the additional recycle feed point (15), and a controller which is configured to operate control valve(s) (16) to maintain the relative humidity within a preset range. Any device known from the prior art to be suitable for determining relative humidity of a gas mixture containing methane, carbon dioxide and hydrogen sulfide may be used in this embodiment. The controller is preferably configured to maintain the relative humidity within a range known to provide high rates of oxidation of hydrogen sulfide on the activated carbon. A suitable range for the relative humidity can be determined experimentally or can be obtained form the manufacturer of the activated carbon. Controlling relative humidity of the gas may be combined with controlling oxygen concentration so as to maintain both parameters within the ranges providing optimum performance of the hydrogen sulfide adsorber (14). When the device of the invention comprises a hydrogen sulfide adsorber (14) upstream of gas compressor (1), it preferably comprises an additional adsorber containing activated carbon between compressor (1) and the first membrane separation stage (3) for absorbing volatile organic compounds (VOC) that could condense in one of the membrane separation stages. The activated carbon in this additional adsorber need not have catalytic activity for oxidizing hydrogen sulfide with oxygen and can be optimized for VOC removal. In another embodiment, the device of the invention comprises a carbon dioxide condensation stage as an alternative to the optional third membrane separation stage. The carbon dioxide condensation stage is then connected to the first membrane separation stage (3) to receive the first permeate (5) as feed and provide a liquid condensate enriched in carbon dioxide and a mixture of non-condensed gases. The device then comprises a further recycle conduit (19) which is connected to the carbon dioxide condensation stage to receive the mixture of non-condensed gases and which is connected to a further recycle feed point (20) arranged between the gas compressor (1) and the first membrane separation stage (3). The carbon dioxide condensation stage comprises a carbon dioxide compressor (21) compressing the first permeate (5) to a pressure higher than the triple point pressure of carbon dioxide and a carbon dioxide condenser (22) where the compressed first permeate is cooled to condense the liquid condensate (17) enriched in carbon dioxide. In this embodiment, the hydrogen sulfide adsorber (14) is preferably arranged downstream of gas compressor (1), i.e. between gas compressor (1) and the first membrane separation stage (3), and the further recycle feed point (20) is arranged between the gas compressor (1) and the hydrogen sulfide adsorber (14). When the further recycle feed point (20) is arranged between the gas compressor (1) and the hydrogen sulfide adsorber (14), the further recycle conduit (19) is preferably connected to a second additional recycle feed point (23), arranged between the hydrogen sulfide adsorber (14) and the first membrane separation stage (3), and comprises at least one additional control valve (24) for controlling the fraction of recycled gas being passed to said further recycle feed point (20) and said second additional recycle feed point (23). The second additional recycle feed point (23) and control valve(s) (24) allow for adjusting the composition of the gas stream entering hydrogen sulfide adsorber (14) by changing the fraction of recycled gas which is passed to further recycle feed point (20) upstream of the adsorber. The device may then also comprise an oxygen concentration measurement and/or a measurement of relative humidity, as described above, between the further recycle feed point (20) and the hydrogen sulfide adsorber (14) or between the hydrogen sulfide adsorber (14) and the second additional recycle feed point (23). In the process of the invention for separating methane from a gas mixture containing methane, carbon dioxide and hydrogen sulfide, the gas mixture is fed to the feed line of a device of the invention as described above and retentate is withdrawn from the second membrane separation stage as a product gas enriched in methane. The gas mixture is preferably a natural gas, a landfill gas or more preferably a biogas from an anaerobic digester. The removal of hydrogen sulfide with a hydrogen sulfide adsorber, which comprises a bed of activated carbon having catalytic activity for oxidizing hydrogen sulfide with oxygen, requires oxygen to be present in the gas mixture entering the adsorber. A high rate of hydrogen sulfide removal and a high capacity of the adsorber are only achieved at oxygen concentrations in the gas which are considerably higher than usually present in a natural gas, a landfill gas or a biogas from an anaerobic digester and therefore oxygen has to be added upstream of the hydrogen sulfide adsorber, usually by introducing air. Furthermore, at these concentrations only part of the oxygen is consumed in the hydrogen sulfide adsorber. The process of the invention allows to reuse this non-converted oxygen for hydrogen sulfide removal by recycling it to a point upstream of the hydrogen sulfide adsorber, which reduces the amount of oxygen that has to be added for hydrogen sulfide removal and, if oxygen is added as air, also reduces the amount of nitrogen introduced, leading to a product gas enriched in methane having a lower nitrogen content. When the gas mixture is a biogas from an anaerobic digester, which is operated with controlled air addition to reduce hydrogen sulfide formation in the digester, the gas mixture may comprise sufficient oxygen to oxidize all the hydrogen sulfide and recycling oxygen in the process of the invention may provide an optimum oxygen concentration in the gas fed to the hydrogen sulfide adsorber without additional addition of air. The process of the invention is preferably carried out in a device, where the recycle conduit is connected to two recycle feed points, one upstream of the hydrogen sulfide adsorber and one downstream of the hydrogen sulfide adsorber, as described above. The device then preferably comprises an oxygen concentration measurement between the recycle feed point and the hydrogen sulfide adsorber, either upstream or downstream of the hydrogen sulfide adsorber, and the fraction of recycled gas passed to the recycle feed point upstream of the hydrogen sulfide adsorber is controlled by at least one control valve and a controller to maintain the oxygen concentration in the gas fed to the hydrogen sulfide adsorber or in the gas leaving the hydrogen sulfide adsorber within a preset range. The oxygen concentration in the gas fed to the hydrogen sulfide adsorber is preferably maintained within a range of from 0.1 to 1.5% by volume, preferably from 0.3 to 1.0% by volume and most preferably 0.4 to 0.8% by volume, in order to achieve efficient removal of hydrogen sulfide and high capacity of the adsorber for hydrogen sulfide removal. The oxygen concentration in the gas fed to the hydrogen sulfide adsorber is preferably adjusted to provide at least 0.5 mol O2—for each mol hydrogen sulfide contained in the gas stream to prevent excessive accumulation of hydrogen sulfide in the hydrogen sulfide adsorber. Alternatively to an oxygen concentration measurement or in addition to it, the device may also comprise a measurement of relative humidity between the recycle feed point and the hydrogen sulfide adsorber, either upstream or downstream of the hydrogen sulfide adsorber, and the fraction of recycled gas passed to the recycle feed point upstream of the hydrogen sulfide adsorber is controlled by at least one control valve and a controller to maintain the relative humidity in the gas fed to the hydrogen sulfide adsorber or in the gas leaving the hydrogen sulfide adsorber within a preset range. The relative humidity is maintained within a range of from 25 to 95%, preferably from 30 to 90% and most preferably from 40 to 80%. This embodiment is particularly useful if the gas mixture containing methane, carbon dioxide and hydrogen sulfide is a landfill gas or a biogas having a high relative humidity of close to 100%. Such high humidity may lead to pore condensation in an activated carbon, which can decrease the efficiency of hydrogen sulfide adsorber (14) by impeding mass transport to the catalytically active sites of the activated carbon. Prior art processes therefore usually comprise a step of drying the gas mixture upstream of an adsorber containing activated carbon. With the process of the invention, it is sufficient to dry the gas mixture only after compression, where water removal by cooling and condensation is more effective and is useful to prevent condensation of water in one of the membrane separation stages. The recycle streams will then have a low water content and recycling all or a part of them upstream of the hydrogen sulfide adsorber (14) can reduce relative humidity of the gas entering the hydrogen sulfide adsorber to a value within the optimum range for efficient hydrogen sulfide removal without an extra step of dehumidifying gas upstream of the hydrogen sulfide adsorber. In another preferred embodiment, the process of the invention is carried out in a device comprising a carbon dioxide condensation stage as described above and liquefied carbon dioxide is withdrawn as an additional product from the carbon dioxide condensation stage. The first permeate (5) is then preferably compressed with carbon dioxide compressor (21) to a pressure higher than the pressure provided on the downstream side of gas compressor (1), so carbon dioxide condenser (22) provides the mixture (18) of non-condensed gases at a pressure high enough to pass them to the first membrane separation stage (3) without additional compression. This embodiment preferably uses a device where the hydrogen sulfide adsorber (14) is arranged downstream of gas compressor (1) and the further recycle conduit (19) for recycling the mixture (18) of non-condensed gases is connected to two recycle feed points, one upstream of the hydrogen sulfide adsorber and one downstream of the hydrogen sulfide adsorber, as described further above. This embodiment requires less total membrane area and provides liquefied carbon dioxide as an extra product that can be marketed, but requires additional equipment and consumes more energy for gas compression. EXAMPLES Separation of biogas was calculated with a process simulation software based on experimentally determined membrane selectivities of commercial polyimide hollow fiber membrane modules SEPURAN® Green SC 3500. Example 1 Separation of 310 Nm3/h of a biogas containing 56.3 vol-% methane, 39.0 vol-% carbon dioxide, 0.5 vol-% nitrogen, 0.5 vol-% oxygen and 3.7 vol-% water, having a relative humidity of 100%, was calculated for a three stage membrane separation in a device as shown inFIG.1, with 10 membrane modules each in the first membrane separation stage (3) and the second membrane separation stage (6) and 11 membrane modules in the third membrane separation stage (9). The feed to the first membrane separation stage (3) is compressed to 16.1 bar and dried and has a flow rate of 411.4 Nm3/h, comprising 55.3 vol-% methane, 42.8 vol-% carbon dioxide, 0.56 vol-% nitrogen and 1.09 vol-% oxygen. The first membrane separation stage (3) separates this feed into 242 Nm3/h of a first retentate (4), obtained at 16.0 bar, containing 85.5 vol-% methane, 12.7 vol-% carbon dioxide, 0.8 vol-% nitrogen and 1.0 vol-% oxygen, and a first permeate (5), obtained at 3.1 bar, containing 12.1 vol-% methane, 85.9 vol-% carbon dioxide, 0.2 vol-% nitrogen and 1.25 vol-% oxygen. The second membrane separation stage (6) separates the first retentate (4) into 176 Nm3/h of a second retentate (7), obtained at 16.0 bar, containing 98.5 vol-% methane, 0.3 vol-% carbon dioxide, 0.9 vol-% nitrogen and 0.37 vol-% oxygen, which can be fed as biomethane to a gas distribution grid, and 66 Nm3/h of a second permeate (8), obtained at 0.9 bar, containing 51.0 vol-% methane, 45.7 vol-% carbon dioxide, 0.7 vol-% nitrogen and 2.6 vol-% oxygen, which is recycled. The third membrane separation stage (9) separates the first permeate (5) into 45.9 Nm3/h of a third retentate (10), obtained at 3.0 bar, containing 41.7 vol-% methane, 55.0 vol-% carbon dioxide, 0.6 vol-% nitrogen and 2.7 vol-% oxygen, which is recycled, and a third permeate (11), obtained at 1.1 bar, containing 1.1 vol-% methane, 97.5 vol-% carbon dioxide, less than 0.1 vol-% nitrogen and 0.7 vol-% oxygen, which can be discharged. When all gas is recycled to recycle feed point (13) upstream of the hydrogen sulfide adsorber (14), the gas fed to hydrogen sulfide adsorber (14) contains 1.06% oxygen and has a relative humidity of 77%. The increase in oxygen content and reduction in relative humidity allows for operating the hydrogen sulfide adsorber (14) at high capacity and hydrogen sulfide removal without a need for drying the biogas feed stream. Example 2 Separation of 479 Nm3/h of a biogas containing 45.9 vol-% methane, 47.0 vol-% carbon dioxide, 1.5 vol-% nitrogen, 0.2 vol-% oxygen and 5.4 vol-% water, having a relative humidity of 100%, was calculated for a two stage membrane separation in a device comprising an additional carbon dioxide condensation stage as shown inFIG.2, with 12 membrane modules in the first membrane separation stage (3) and 27 membrane modules in the second membrane separation stage (6). The biogas is combined with second permeate (8) and compressed with gas compressor (1) to 17.1 bar. This compressed gas stream is combined with the mixture of non-condensed gases (18) from carbon dioxide condenser (22) to give the feed stream to the first membrane separation stage (3). The first membrane separation stage (3) separates this feed into 383 Nm3/h of a first retentate (4), obtained at 17.0 bar, containing 85.0 vol-% methane, 7.2 vol-% carbon dioxide, 3.4 vol-% nitrogen and 4.4 vol-% oxygen, and a first permeate (5), obtained at 1.05 bar, containing 6.3 vol-% methane, 88.8 vol-% carbon dioxide, 0.4 vol-% nitrogen and 4.0 vol-% oxygen. The second membrane separation stage (6) separates the first retentate (4) into 228 Nm3/h of a second retentate (7), obtained at 17.0 bar, containing 96.4 vol-% methane, less than 0.1 vol-% carbon dioxide, 3.2 vol-% nitrogen and 0.4 vol-% oxygen, which can be fed as biomethane to a gas distribution grid, and 155 Nm3/h of a second permeate (8), obtained at 0.9 bar, containing 68.1 vol-% methane, 17.8 vol-% carbon dioxide, 3.9 vol-% nitrogen and 10.3 vol-% oxygen, which is recycled. The first permeate (5) is compressed to 17.1 bar and passed to the carbon dioxide condenser (22) where liquid carbon dioxide is condensed at −20° C. 195.3 Nm3/h of a mixture of non-condensed gases (18), containing 13.6 vol-% methane, 76.8 vol-% carbon dioxide, 0.9 vol-% nitrogen and 8.7 vol-% oxygen, is recycled from the carbon dioxide condenser (22). When the mixture of non-condensed gases (18) is recycled to recycle feed point (23) downstream of the hydrogen sulfide adsorber (14), the gas fed to hydrogen sulfide adsorber (14) contains 2.7 vol-% oxygen. Therefore, an oxygen content sufficient for operating the hydrogen sulfide adsorber (14) at high capacity and hydrogen sulfide removal can already be achieved by recycling only the second permeate (8) to a recycle feed point (13) upstream of the hydrogen sulfide adsorber (14). Example 3 Separation of 8265 Nm3/h of a biogas containing 54.5 vol-% methane, 39.4 vol-% carbon dioxide, 2.5 vol-% nitrogen, 0.5 vol-% oxygen and 3.1 vol-% water, having a relative humidity of 100%, was calculated for a two stage membrane separation in a device as shown inFIG.1but without a third membrane separation stage (9) and with a blower in recycle conduit (12) providing a permeate pressure of 0.7 bar in the second membrane separation stage (6), having 91 membrane modules in the first membrane separation stage (3) and 336 membrane modules in the second membrane separation stage (6). The feed to the first membrane separation stage (3) is compressed to 11.2 bar and dried and has a flow rate of 11914 Nm3/h, comprising 44.2 vol-% methane, 52.5 vol-% carbon dioxide, 2.2 vol-% nitrogen and 0.8 vol-% oxygen. The first membrane separation stage (3) separates this feed into 8590 Nm3/h of a first retentate (4), obtained at 11.0 bar, containing 60.2 vol-% methane, 35.8 vol-% carbon dioxide, 3.0 vol-% nitrogen and 1.0 vol-% oxygen, and a first permeate (5), obtained at 1.05 bar, containing 2.8 vol-% methane, 95.7 vol-% carbon dioxide, 0.2 vol-% nitrogen and 0.5 vol-% oxygen, which can be discharged. The second membrane separation stage (6) separates the first retentate (4) into 4715 Nm3/h of a second retentate (7), obtained at 11.0 bar, containing 93.6 vol-% methane, 1.6 vol-% carbon dioxide, 4.2 vol-% nitrogen and 0.55 vol-% oxygen, which can be fed as biomethane to a gas distribution grid, and 3876 Nm3/h of a second permeate (8), obtained at 0.7 bar, containing 19.6 vol-% methane, 77.3 vol-% carbon dioxide, 1.4 vol-% nitrogen and 1.5 vol-% oxygen, which is recycled. When all gas is recycled to recycle feed point (13) upstream of the hydrogen sulfide adsorber (14), the gas fed to hydrogen sulfide adsorber (14) contains 0.8 vol-% oxygen and has a relative humidity of 69%. The increase in oxygen content and reduction in relative humidity allows for operating the hydrogen sulfide adsorber (14) at high capacity and hydrogen sulfide removal without a need for drying the biogas feed stream. Example 4 The calculation of example 3 was repeated for separation of 6600 Nm3/h of a biogas containing 51.4 vol-% methane, 43.5 vol-% carbon dioxide, 1.6 vol-% nitrogen, 0.4 vol-% oxygen and 3.1 vol-% water, having a relative humidity of 100%, in a device having 66 membrane modules in the first membrane separation stage (3) and113membrane modules in the second membrane separation stage (6). The feed to the first membrane separation stage (3) is compressed to 19.6 bar and dried and has a flow rate of 7705 Nm3/h, comprising 50.7 vol-% methane, 46.8 vol-% carbon dioxide, 1.7 vol-% nitrogen and 0.7 vol-% oxygen. The first membrane separation stage (3) separates this feed into 4675 Nm3/h of a first retentate (4), obtained at 19.6 bar, containing 80.6 vol-% methane, 16.0 vol-% carbon dioxide, 2.6 vol-% nitrogen and 0.8 vol-% oxygen, and a first permeate (5), obtained at 1.05 bar, containing 4.6 vol-% methane, 94.3 vol-% carbon dioxide, 0.2 vol-% nitrogen and 0.5 vol-% oxygen, which can be discharged. The second membrane separation stage (6) separates the first retentate (4) into 3378 Nm3/h of a second retentate (7), obtained at 19.5 bar, containing 96.4 vol-% methane, 0.4 vol-% carbon dioxide, 2.9 vol-% nitrogen and 0.3 vol-% oxygen, which can be fed as biomethane to a gas distribution grid, and 1296 Nm3/h of a second permeate (8), obtained at 0.58 bar, containing 39.5 vol-% methane, 56.7 vol-% carbon dioxide, 1.9 vol-% nitrogen and 1.9 vol-% oxygen, which is recycled. When all gas is recycled to recycle feed point (13) upstream of the hydrogen sulfide adsorber (14), the gas fed to hydrogen sulfide adsorber (14) contains 0.64 vol-% oxygen and has a relative humidity of 83%. The increase in oxygen content and reduction in relative humidity allows for operating the hydrogen sulfide adsorber (14) at high capacity and hydrogen sulfide removal without a need for drying the biogas feed stream. LIST OF REFERENCE SIGNS 1Gas compressor2Feed line3First membrane separation stage4First retentate5First permeate6Second membrane separation stage7Second retentate8Second permeate9Third membrane separation stage10Third retentate11Third permeate12Recycle conduit13Recycle feed point14Hydrogen sulfide adsorber15Additional recycle feed point16Control valve17Liquid condensate18Mixture of non-condensed gases19Further recycle conduit20Further recycle feed point21Carbon dioxide compressor22Carbon dioxide condenser23Second additional recycle feed point24Control valve
42,411
11857917
DETAILED DESCRIPTION OF THE INVENTION The drying device1schematically shown inFIG.1for the drying of compressed gas consists essentially of two vessels2filled with a moisture absorber3. This moisture absorber3is also called desiccant. It is of course possible that there are more than two vessels2. The drying device1further comprises a valve system4consisting of a first valve block5and a second valve block6. The first valve block5will connect vessels2to an inlet7for dried compressed gas, while the second valve block6will connect vessels2to an outlet8for dried compressed gas. The aforementioned valve blocks5,6are a system of different pipes and valves which can be regulated in such a way that at any one time at least one vessel2is being regenerated, while the other vessel2or the other vessels2are drying the compressed gas, wherein by regulation of the valve system4the vessels2will each in turn dry compressed gas. Furthermore, according to the invention, the drying device1is equipped with a four-way valve9, a blower10for sucking in ambient air and a gas release port11for blowing off gas, which are configured in such a way that in a first position of the four-way valve9the blower10is connected to the vessels2via the first valve block5, as shown inFIG.1, and in a second position of the four-way valve9the gas release port11is connected to the vessels2via the first valve block5. As shown inFIG.1, the drying device1is such that, in the first position of the four-way valve9, the ambient air sucked in by the blower10can enter the vessel2which is being cooled via the four-way valve9and the first valve block5. Of course, the valve block5is regulated in the appropriate way to enable the right flow path for the gas. In the example ofFIG.1, but not necessary for the invention, the drying device1is equipped with a cooling pipe12connecting the second valve block6to the inlet side13of the blower10. The figures show that a closed cooling circuit14will be formed when the four-way valve9is in the aforementioned first position, which is formed successively by the blower10, the four way-valve9, the first valve block5, a vessel2, the second valve block6and the cooling pipe12. As can be seen in the figures, the cooling pipe12contains a cooler15. For example, this cooler15can be an air-to-air cooler15. The aforementioned closed cooling circuit14will be used to cool a vessel. In addition, the drying device1is equipped with a regeneration pipe16which connects the four-way valve9to the second valve block6. In the second position of the four-way valve9, when the four-way valve9connects gas release port11to the first valve block5, the four-way valve9will connect blower10to the regeneration pipe16and thus to the second valve block6. This regeneration pipe16is equipped with a heater17, in this case an electric heater17. Thus, in the second position of the four-way valve9, a regeneration circuit18is formed comprising the blower10, the four-way valve9, the regeneration pipe16with the heater17, the second valve block6, the vessel2being regenerated, the first valve block5, the four-way valve9and the gas release port11. Regeneration circuit18will be used to regenerate a vessel. As can be seen in the figures, in this case the regeneration pipe16and the cooling pipe12partially coincide. In this case, only one pipe19will leave from the second valve block6, which also includes the aforementioned heating20. The aforementioned pipe19splits into two separate pipes19a,19b, one of which leads to the inlet side13of the blower10, in which the cooler15is included, and one to the four-way valve9. It goes without saying that, in addition to the appropriate regulation of valve blocks5,6and the four-way valve9, the aforementioned heating17and cooler15are also appropriately controlled when implementing the closed cooling circuit14and the regeneration circuit18. Finally, the drying device1in this case, but not necessary for the invention, includes a temperature sensor20to determine the inlet temperature Tinand two pressure sensors21and22to determine the inlet pressure Pin, respectively the outlet pressure Pout. It should be obvious that based on the measurements of the pressure sensors21and22, the pressure drop ΔP over the drying device1can be determined by calculating the difference between the inlet pressure Pinand the outlet pressure Pout. The operation of the drying device1and the procedure according to the invention for drying compressed gas using the drying device1is very simple and as follows. During the operation of the drying device1there will be compressed gas to be dried passing through the inlet7in the vessel2which is drying, this vessel2will hereafter be called vessel2a. When passing through this vessel2a, the desiccant3will adsorb moisture and extract it from the gas. The dried compressed gas will leave the drying device1through the outlet8. The other vessel2, which has already dried gas during a previous cycle, contains moisture and is regenerated in the meantime. This vessel2will be called vessel2bin what follows. A regeneration cycle is used, which consists of heating ambient air and passing it through the vessel2band then blowing it off. For this regeneration cycle, the aforementioned regeneration circuit18is used. For this purpose, the four-way valve9is placed in the second position and the valve blocks5,6are regulated in such a way that the regeneration circuit18is realized. The heating17is also switched on. The blower10will suck in ambient air which passes through the regeneration pipe16along the heater17where the gas is heated. Via the second valve block6the heated gas will be directed to the aforementioned vessel2b, wherein when passing through this vessel2b, it will extract moisture from the desiccant3. Via the first valve block5, the hot, moist gas will leave the drying device1through the gas release port11. After the regeneration cycle, the heating17will be switched off. When the desiccant3is regenerated, the vessel2bwill be cooled. The closed cooling circuit14is used, wherein ambient air is sent through the vessel2bthat is being cooled. The ambient air sucked in by the blower10will be circulated through the closed cooling circuit14, after passing through the vessel2bit will be cooled by the cooler15. This cooled gas will then be sent through the vessel2bagain via the blower10. After completing the cooling of the vessel2b, this vessel2bcan be used to dry compressed gas, while the other vessel2a, previously used for drying, can now be regenerated and cooled. If the vessel2bstill cools the vessel2aafter cooling, the vessel2bwill go into standby after cooling. This means that it does not dry, not regenerate or cool. The moment of switchover, i.e. the moment at which the vessel2ais started to regenerate, is determined by the procedure according to the invention. According to the invention, the time span (tads) during which a vessel2dries compressed gas is calculated on the basis of a formula: tads=A*B; where:tads=the period of time during which a vessel2dries compressed gas;A=a predetermined adsorption time;B=a product of one or more of the following factors:CΔP=a correction factor for the average pressure drop ΔPgemover the drying device1compared to a reference pressure drop ΔPrefover the drying device1;CP=a correction factor for the average inlet pressure Pgemcompared to a reference inlet pressure Pref;CT=a correction factor for the average inlet temperature Tgemcompared to a reference inlet temperature Tref;C=a fixed correction factor. In what follows it is assumed that B=CΔP*Cp*CT*C. But it is also possible that for example B=CΔP*Cpor B=CTor any other possible combination of 1 to 4 of these factors. After the calculated time span tadshas elapsed, the vessels2a,2bwill switch. This means: the vessel2awill be regenerated, while the vessel2bwill dry gas. The procedure described above will be repeated, but the function of the vessels2a,2bwill be reversed. As already mentioned, the reference pressure drop ΔPref, reference inlet pressure Prefand reference inlet temperature Trefare the values of the pressure drop ΔP over the drying device1, respectively inlet pressure Pinand inlet temperature Tinwhich are measured or determined in the drying device1when operating under reference conditions. These reference conditions are a fixed value for the temperature, e.g. 35° C., for the pressure of the compressed gas, e.g. 7 bar, and at a full flow rate of the compressed gas to be dried. When, under these reference conditions, the drying device1is operated, a pressure difference ΔP over the drying device1, an inlet pressure Pinand an inlet temperature Tinwill be determined which correspond to ΔPref, Prefand Tref. These values for the reference pressure drop ΔPref, reference inlet pressure Prefand reference inlet temperature Trefare fixed values. Preferably, the parameter A from the aforementioned formula for tadsis equal to the adsorption time during which a vessel2can adsorb when the drying device1operates under reference conditions. In other words, this parameter A is determined in the same way as the aforementioned reference values and is a fixed value. Preferably the parameter C, the fixed correction factor, is equal to a number greater than zero and less than or equal to one. In practice, C will typically have a value of 0.8 to 0.9. This is a safety factor to limit tadsso that a vessel2will never adsorb for too long but that the vessels2will be switched in time. The other parameters CΔP,6Cp, and CTare not fixed values, but are recalculated during each adsorption cycle to be able to calculate tadsfor the next adsorption cycle. Preferably the following formula is used for CΔP: CΔP=√{square root over (ΔPref/ΔPgem)}; where ΔPrefis the reference pressure drop over the drying device1and ΔPgemis the average pressure drop over the drying device1measured over a drying cycle. Alternatively, it is also possible that CΔPis determined or measured using the measured or determined flow rate. For this purpose, a flow sensor can be used, for example. It is called Cflow, where: Cflow=Flow rateref/Flow rategem; where Flow raterefis the reference flow rate through the drying device1and Flow rategem is the measured flow rate through the drying device1during a drying cycle. Another alternative is to determine or calculate CΔPbased on the rpm of a compressor to which the drying device is connected. Preferably, the following formula is used for CP: CP=Pgem/Pref; where Prefis the reference inlet pressure and Pgemis the average inlet pressure measured over a drying cycle. Preferably, the following formula is used for CT: CT=amount⁢of⁢moisture⁢per⁢m3⁢gas⁢at⁢Trefamount⁢of⁢moisture⁢per⁢m3⁢gas⁢at⁢Tgem where Trefis the reference inlet temperature and Tgemis the average inlet temperature measured over a drying cycle. The amount of moisture per m3gas at a certain temperature can be read from tables or curves known in the literature. The average pressure drop ΔPgem, the average inlet pressure Pgemand the average inlet temperature Tgemcan easily be determined from the measurements of the temperature sensor20to determine the inlet temperature Tinand the two pressure sensors21and22to determine the inlet pressure Pinand the outlet pressure Poutrespectively. Using the aforementioned formula and based on the measurements of sensors20,21and22, tadscan be calculated for the next cycle after each adsorption cycle. Preferably, the calculated time span tadsduring which a vessel2dries compressed gas is equal to the so-called minimum half cycle time. A complete cycle consists of regenerating the first vessel2and regenerating the second vessel2. So half a cycle is to regenerate one vessel2. The half cycle time is the time needed to regenerate one vessel2. The half cycle time, i.e. the time during which at least one vessel2must be regenerated, is in principle also equal to the adsorption time or the time during which a vessel2will dry gas. The calculated time span tadsis equal to the minimum half cycle time, i.e. the minimum adsorption time of a vessel2. This means that the adsorption time must be at least equal to the calculated time span tads. It is possible to let the vessel2adsorb longer if a dew point sensor is present, for example if the dew point is still high enough after the expiration of the calculated time span tads. Although the example shown and described above refers to two vessels2, it is not excluded that there may be more than two vessels2. There is always at least one vessel2that will dry compressed gas. If there are two or more vessels2drying compressed gas at the same time, tadswill be valid for both vessels. If the two vessels2do not start to dry compressed gas simultaneously, a tadswill be calculated for each of these vessels2. The current invention is by no means limited to the embodiments by way of example and shown in the figures, but such a procedure can be carried out in different variants without going beyond the scope of the invention.
13,097
11857918
DETAILED DESCRIPTIONS OF EMBODIMENTS In a first embodiment: this embodiment is a liquid water harvester based on a valve-controlled active air supply. As shown inFIGS.1to4, the harvester consists of an active air supply device1, an electric valve2, a heating film3, a moisture absorbing material4, a moisture absorbing material storage device5, an inner container6, an inner container cover7, an external hood8, and an external hood cover9and a controller. The external hood8is a structure with a top end opened and a bottom end closed. The active air supply device1is disposed at a corner of a bottom surface inside the external hood8. An air inlet of the active air supply device1penetrates through a sidewall of the external hood8to communicate with the outside. The electric valve2is disposed at the bottom surface inside the external hood8. An air outlet of the active air supply device1is communicated with an air inlet of the electric valve2. The air outlet of the active air supply device is also provided with an exit opening in a vertically upward direction. The moisture absorbing material storage device5is disposed at the center of the bottom surface inside the external hood8. The moisture absorbing material storage device5is a structure with a top opened and a bottom closed. A plurality of groups of vertically-arranged air vents5-1are disposed symmetrically at both sides of the moisture absorbing material storage device5. An air outlet of the electric valve2faces toward the air vents5-1at a side of the moisture absorbing material storage device5. The heating film3is disposed at a bottom surface in an inner cavity of the moisture absorbing material storage device5. The moisture absorbing material4is disposed on the heating film3and located inside the inner cavity of the moisture absorbing material storage device5. The top of the moisture absorbing material4is lower than the highest air vent5-1. The bottom center of the inner container6is covered on the top of the moisture absorbing material storage device5. The bottom center of the inner container6is an open structure in communication with the inner cavity of the moisture absorbing material storage device5. The interior of the inner container6is a hollow structure which is formed into a water storage cavity6-1. The inner container cover7is disposed at the top of the inner container6. A micro-nano structure condensation surface is disposed on a top of an inner wall of the inner container cover7. The micro-nano structure condensation surface is a concave-convex alternating surface, where a hydrophilic coating is disposed on a concave surface7-2and a hydrophobic coating is disposed on a convex surface7-1. The electric valve2is located below a side of the inner container6. a gap is reserved between each of an outer bottom surface and an outer sidewall of the inner container6and an inner wall of the external hood8, so as to form a ventilation area. The external hood cover9is disposed at the top of the external hood8. The external hood cover9is an open structure which has an inner diameter smaller than an inner diameter of the external hood8. The controller is disposed outside the entire harvester. A signal output end of the controller is respectively connected to a signal input end of the active air supply device1, a signal input end of the electric valve2and a signal input end of the heating film3. The use method and working principle of the liquid water harvester based on the valve-controlled active air supply in this embodiment are described below. In an adsorption state, when water in the air is to be harvested, the controller starts the active air supply device1to supply the air containing water vapor outside the harvester into the harvester; at the same time, the controller starts the electric valve2and at this time the heating film3is in an off state; a part of the air is exhausted out of the harvester upward through the ventilation area between the inner container6and the external hood8(as shown by the left arrow inFIG.1), and another part of the air enters the moisture absorbing material storage device5through the air vents5-1close to the electric valve2; after being fully contacted with the moisture absorbing material4, the air flows out of the air vents5-1away from the electric valve2and is exhausted out of the harvester upward through the ventilation area between the inner container6and the external hood8(as shown by the right arrow inFIG.1); and thus, water vapor in the air is adsorbed by the moisture absorbing material4. In a desorption stage, when the moisture absorbing material4is saturated over a period of adsorption, the controller closes the electric valve such that an air passage between the active air supply device1and the moisture absorbing material storage device5is cut off; thus, the air is all exhausted out of the harvester upward through the ventilation area between the inner container6and the external hood8(as shown by the left arrow inFIG.1); the controller starts the heating film4to start heating, and the moisture absorbing material4releases the adsorbed water vapor therein at a high temperature provided by the heating film3and exhausts it upward to the inner container6; the water vapor is condensed into water on the micro-nano structure condensation surface of the inner container cover7, and further, the water can be removed at a higher rate due to presence of the hydrophilic coating disposed on the concave surface7-2and the hydrophobic coating disposed on the convex surface7-1on the micro-nano structure condensation surface; thus, the water drops can gradually fall into the water storage cavity6-1; therefore, the desorption stage is completed, and the heating film3and the active air supply device1are turned off. After the desorption stage is completed, the adsorption and desorption cycle can be repeated. When the harvester provided by this embodiment is used, the controller may control a time of the adsorption stage and a time of the desorption stage by timing a control circuit. In other words, the working times of the active air supply device1, the electric valve2and the heating film3can be controlled respectively without human interference, leading to a high degree of automation. In this embodiment, the inner diameter of the external hood cover9is smaller than the inner diameter of the external hood8, such that the air supplied through the ventilation area between the inner container6and the external hood8can fully contact with the external surface of the inner container cover7and then flow out, thereby increasing the cooling effect. The harvester of the present embodiment has the following advantages.1. The harvester in the present embodiment can absorb water vapor from the air and produce liquid water in an environmental-friendly and energy-saving manner. Meanwhile, the harvester features small volume, ease of integration, and ease of carry.2. The liquid water harvester of the present embodiment uses the controller to control the start of the entire machine without human interference, having a high degree of automation.3. The liquid water harvester of the present embodiment uses the active air supply device1to speed up the adsorption of the moisture absorbing material for water vapor and the heat dissipation of the condensation surface of the inner container cover7, thereby entirely improving the harvesting efficiency.4. The liquid water harvester of the present embodiment, in cooperation with the electric valve2and the active air supply device1, completes the active air supply and the heat dissipation of the condensation surface by only one active air supply device1. The harvester has the advantages of simple structure, small volume, low costs, ease of integration, ease of carry, and high water harvesting efficiency.5. The condensation surface of the inner container cover7of the present embodiment adopts a special micro-nano structure surface, such that the water vapor adsorption, condensation, and harvesting efficiency can be improved by the use of the hydrophilic and hydrophobic effect of the hydrophilic concave surface and hydrophobic convex surface.6. The embodiment's liquid water harvester has good application prospects in fields such as automatic irrigation, automatic water supplementation, humidifier, individual combat supply and field survival emergency, and the like. In a second embodiment: this embodiment is the same as the first embodiment except that: the active air supply device1is a motor, an air pump, or a fan used to speed up the adsorption of the absorbing material4for water vapor and the heat dissipation of the condensation surface. In a third embodiment: this embodiment is the same as the first or second embodiment except that: the electric valve2is a ball valve or a butterfly valve, which cooperates with the active air supply device1to switch between air supply and condensation heat dissipation; and only one air supply device1can be used to complete air supply and condensation heat dissipation at the same time. In a fourth embodiment: this embodiment is the same as the first to third embodiment, except that: the moisture absorbing material4is silica gel, molecular sieve or hydrogel, which all have good adsorption for water and can release the adsorbed water under heating conditions so as to achieve desorption function; the moisture absorbing material4is placed inside the moisture absorbing material storage device5and located on the heating film3to adsorb water vapor in the air; during an adsorption process, the moisture absorbing material4adsorbs water vapor in the air; and in a desorption process (i.e. when the electric valve2is closed), the moisture absorbing material4, under the action of the heating film3, releases the high temperature water vapor upward into the inner container6along the inner cavity of the moisture absorbing material storage device5, and the high temperature water vapor is condensed on the micro-nano structure condensation surface of the inner container cover7. In a fifth embodiment: this embodiment is the same as the first embodiment except that the heating film is a PI electrothermal film, graphene, or ceramic heating sheet, which is in contact with the lower surface of the moisture absorbing material4to heat the moisture absorbing material4to enable the moisture absorbing material4to release the adsorbed moisture; At the temperature of 373K, the moisture absorbing material4can complete desorption within about 30 minutes. In a sixth embodiment: this embodiment is the same as the first embodiment except that a material of the inner container6is a high-temperature-resistant and non-toxic organic material. In a seventh embodiment: this embodiment is the same as the first embodiment except that the material of the inner container cover7is a high-temperature-resistant and non-toxic organic material. In an eighth embodiment: this embodiment is the same as the sixth or seventh embodiment except that the material of the inner container6and the inner container cover7is acrylic. In a ninth embodiment: this embodiment is the same as the first embodiment except that the hydrophilic coating is PSBMA ultra-hydrophilic coating. In a tenth embodiment: this embodiment is the same as the first embodiment except that the hydrophobic coating is PDMS ultra-hydrophobic coating. The present disclosure will be verified by the following test. Test 1: this test provides a liquid water harvester based on a valve-controlled active air supply. As shown inFIGS.1to4, the harvester consists of an active air supply device1, an electric valve2, a heating film3, a moisture absorbing material4, a moisture absorbing material storage device5, an inner container6, an inner container cover7, an external hood8, and an external hood cover9and a controller. The active air supply device1is a motor; the electric valve2is a ball valve; the moisture absorbing material4is silica gel; the heating film3is a PI electrothermal film; the material of the inner container6and the inner container cover7is acrylic. The external hood8is a structure with a top end opened and a bottom end closed. The active air supply device1is disposed at a corner of a bottom surface inside the external hood8. An air inlet of the active air supply device1penetrates through a sidewall of the external hood8to communicate with the outside. The electric valve2is disposed at the bottom surface inside the external hood8. An air outlet of the active air supply device1is communicated with an air inlet of the electric valve2. The air outlet of the active air supply device is also provided with an exit opening in a vertically upward direction. The moisture absorbing material storage device5is disposed at the center of the bottom surface inside the external hood8. The moisture absorbing material storage device5is a structure with a top opened and a bottom closed. A plurality of groups of vertically-arranged air vents5-1are disposed symmetrically at both sides of the moisture absorbing material storage device5. An air outlet of the electric valve2faces toward the air vents5-1at a side of the moisture absorbing material storage device5. The heating film3is disposed at a bottom surface in an inner cavity of the moisture absorbing material storage device5. The moisture absorbing material4is disposed on the heating film3and located inside the inner cavity of the moisture absorbing material storage device5. The top of the moisture absorbing material4is lower than the highest air vent5-1. The bottom center of the inner container6is covered on the top of the moisture absorbing material storage device5. The bottom center of the inner container6is an open structure in communication with the inner cavity of the moisture absorbing material storage device5. The interior of the inner container6is a hollow structure which is formed into a water storage cavity6-1. The inner container cover7is disposed at the top of the inner container6. A micro-nano structure condensation surface is disposed on a top of an inner wall of the inner container cover7. The micro-nano structure condensation surface is a concave-convex alternating surface, where an ultra-hydrophilic coating PSBMA is disposed on a concave surface7-2and an ultra-hydrophobic coating PDMS is disposed on a convex surface7-1; the concave surface7-2and the convex surface7-1both are strip-shaped (seeFIG.2). The electric valve2is located below a side of the inner container6. A gap is reserved between each of an outer bottom surface and an outer sidewall of the inner container6and an inner wall of the external hood8, so as to form a ventilation area. The external hood cover9is disposed at the top of the external hood8. The external hood cover9is an open structure which has an inner diameter smaller than an inner diameter of the external hood8. The controller is disposed outside the entire harvester. A signal output end of the controller is respectively connected to a signal input end of the active air supply device1, a signal input end of the electric valve2and a signal input end of the heating film3. The use method and working principle of the liquid water harvester based on the valve-controlled active air supply in this test are described below. In an adsorption state, when water in the air is to be harvested, the controller starts the active air supply device1to supply the air containing water vapor outside the harvester into the harvester; at the same time, the controller starts the electric valve2and at this time the heating film3is in an off state; a part of the air is exhausted out of the harvester upward through the ventilation area between the inner container6and the external hood8(as shown by the left arrow inFIG.1), and another part of the air enters the moisture absorbing material storage device5through the air vents5-1close to the electric valve2; after being fully contacted with the moisture absorbing material4, the air flows out of the air vents5-1away from the electric valve2and is exhausted out of the harvester upward through the ventilation area between the inner container6and the external hood8(as shown by the right arrow inFIG.1); and thus, water vapor in the air is adsorbed by the moisture absorbing material4. In a desorption stage, when the moisture absorbing material4is saturated over a period of adsorption, the controller closes the electric valve such that an air passage between the active air supply device1and the moisture absorbing material storage device5is cut off; thus, the air is all exhausted out of the harvester upward through the ventilation area between the inner container6and the external hood8(as shown by the left arrow inFIG.1); the controller starts the heating film4to start heating, and the moisture absorbing material4releases the adsorbed water vapor therein at a high temperature provided by the heating film3and exhausts it upward to the inner container6; the water vapor is condensed into water on the micro-nano structure condensation surface of the inner container cover7, and further, the water can be removed at a higher rate due to presence of the hydrophilic coating disposed on the concave surface7-2and the hydrophobic coating disposed on the convex surface7-1on the micro-nano structure condensation surface; thus, the water drops can gradually fall into the water storage cavity6-1; therefore, the desorption stage is completed, and the heating film3and the active air supply device1are turned off. After the desorption stage is completed, the adsorption and desorption cycle can be repeated. When the harvester provided by this test is used, the controller may control a time of the adsorption stage and a time of the desorption stage by timing a control circuit. In other words, the working times of the active air supply device1, the electric valve2and the heating film3can be controlled respectively without human interference, leading to a high degree of automation. In this test, the inner diameter of the external hood cover9is smaller than the inner diameter of the external hood8, such that the air supplied through the ventilation area between the inner container6and the external hood8can fully contact with the external surface of the inner container cover7and then flow out, thereby increasing the cooling effect. The harvester of the test has the following advantages.1. The harvester in the test can absorb water vapor from the air and produce liquid water in an environmental-friendly and energy-saving manner. Meanwhile, the harvester features small volume, ease of integration, and ease of carry.2. The liquid water harvester of the test uses the controller to control the start of the entire machine without human interference, having a high degree of automation.3. The liquid water harvester of the test uses the active air supply device1to speed up the adsorption of the moisture absorbing material for water vapor and the heat dissipation of the condensation surface of the inner container cover7, thereby entirely improving the harvesting efficiency.4. The liquid water harvester of the test, in cooperation with the electric valve2and the active air supply device1, completes the active air supply and the heat dissipation of the condensation surface by only one active air supply device1. The harvester has the advantages of simple structure, small volume, low costs, ease of integration, ease of carry, and high water harvesting efficiency.5. The condensation surface of the inner container cover7of the test adopts a special micro-nano structure surface, such that the water vapor adsorption, condensation, and harvesting efficiency can be improved by the use of the hydrophilic and hydrophobic effect of the hydrophilic concave surface and hydrophobic convex surface.6. The liquid water harvester of the test has good application prospects in the fields such as automatic irrigation, automatic water supplementation, humidifier, individual combat supply and field survival emergency, and the like.
20,103
11857919
DETAILED DESCRIPTION Methods, apparatuses, and systems related to electrochemical capture of Lewis acid gases from fluid mixtures are generally described. Certain embodiments are related to electrochemical methods involving selectively removing a first Lewis acid gas (e.g., sulfur dioxide) from a fluid mixture containing multiple types of Lewis acid gases (e.g., a first Lewis acid gas and a second Lewis acid gas (e.g., carbon dioxide)). Some embodiments are related to methods involving selective Lewis acid gas removal by bonding a first Lewis acid gas (e.g., sulfur dioxide) and a second Lewis acid gas (e.g., carbon dioxide) to one or more reduced electroactive species and, subsequently, selectively releasing the second Lewis acid gas (e.g., via oxidation of a second Lewis acid gas-electroactive species complex) from the resulting complexes while releasing relatively little or none of the first Lewis acid gas from the complexes. Certain embodiments are related to electrochemical systems comprising certain types of electroactive species having certain redox states in which the species is capable of binding a first Lewis acid gas but for which binding with a second Lewis acid gas is thermodynamically and/or kinetically unfavorable. The methods, apparatuses, and systems described herein may be useful in carbon capture and pollution mitigation applications. Removal and/or separation of Lewis acid gases in fluid mixtures is an important process in a number of applications, including industry and power generation. As an example, sulfur dioxide (SO2) emissions are conventionally curtailed in industrial applications via flue-gas desulfurization (FGD), which relies on large absorber contact towers (scrubbers) which have large footprints and a large balance of plant. Moreover, many other applications exist where it can be desirable to remove combustion exhaust or other industrial gas streams where Lewis acid gases such as SO2, either for avoiding complications with downstream processes or for other reasons, such as pollution mitigation. For example, the international Maritime Organization (IMO) has imposed a sulfur cap that went in effect in January 2020. Many ships are currently being retrofitted with convention scrubbers, but small vessels cannot accommodate such chemical plants on-board. Therefore, there is a need for compact and efficient Lewis acid gas capture systems. Electrochemically-mediated capture of gases may be one route toward capturing Lewis acid gases (e.g., by electrochemically generating active states of electroactive species that can bind the targeted gases). However, as a complicating factor, many fluid mixtures (e.g., gas effluents) comprise multiple Lewis acid gas species, and it can be desirable to selectively remove a first Lewis acid gas while removing essentially none or relatively little of the other Lewis acid gases. As one example, combustion products often comprise carbon dioxide and sulfur-containing gases such as SO2. It has been realized in the context of the present disclosure that certain existing electroactive species in electrochemical systems may react with both the first Lewis acid gases and the other Lewis acid gases, which can be problematic. For carbon capture systems designed to remove carbon dioxide from the gas mixture, the presence of sulfur dioxide can pose problems for efficiency and capacity because the sulfur dioxide may compete with the carbon dioxide for binding to the electroactive species. It has been discovered in the context of the present disclosure that certain methods and systems can be used to selectively bind certain Lewis acid gases over others (e.g., via judicious choice of electroactive species and/or operating conditions). In one aspect, methods are described. Some embodiments involve methods for electrochemical partial or complete removal and/or separation of Lewis acid gases in fluid. Some embodiments comprise applying a potential difference across an electrochemical cell and exposing a fluid mixture comprising a first Lewis acid gas and a second Lewis acid gas to the electrochemical cell.FIGS.1A-1Bdepict one such embodiment, where fluid mixture101comprising first Lewis acid gas102and second Lewis acid gas104is exposed to electrochemical cell100. The term “electrochemical cell” is intended to include apparatuses that meet these criteria even where the behavior of the cell could arguably be characterized as more pseudocapacitive than Faradaic and thus might otherwise be referred to as a type of capacitor. Applying a potential difference across the electrochemical cell may cause an amount of the first Lewis acid gas to be removed from the fluid mixture during and/or after application of the potential difference. For example, referring again toFIGS.1A-1B, in the absence of the potential difference, electrochemical cell100may be in electronic communication with electroactive species in an oxidized state Ox that does not bind with the first Lewis acid gas (FIG.1A). Applying a potential difference across electrochemical cell100may convert the electroactive species into a reduced state R that reacts (e.g., via binding) with first Lewis acid gas102(FIG.1B), according to some embodiments. It should be understood that whileFIGS.1A-1Bshow fluid mixture101exposed to electrochemical cell100with the electroactive species in oxidized state Ox, some embodiments comprise applying the potential difference across electrochemical cell100prior to exposing it to fluid mixture101, such that at least one reduced state (e.g., R) of the electroactive species is generated prior to exposure to fluid mixture101. In some embodiments, the method involves removing from the fluid mixture essentially none or relatively little of the second Lewis acid gas present in the fluid mixture by mole percent. For example, referring again toFIG.1B, essentially none of second Lewis acid gas104is removed from fluid mixture101upon application of the potential difference across electrochemical cell100(e.g., removed by reacting with reduced state R of the electroactive species generated by the application of the potential difference, in contrast to first Lewis acid gas102). In some instances, removing essentially none or relatively little of a second Lewis acid gas from a fluid mixture comprising a first Lewis acid gas and the second Lewis acid gas may be beneficial if it is desired to produce a fluid mixture relatively free of the first Lewis acid gas. As one non-limiting example, a fluid mixture may comprise carbon dioxide (CO2) and sulfur dioxide (SO2), but it is desired for the fluid mixture to contain only CO2(e.g., for a downstream carbon capture process). Therefore, in some embodiments, applying a potential difference to an electrochemical cell and exposing the fluid mixture to the electrochemical cell may result in removal of an amount (or all) of the SO2while removing essentially none or relatively little of the CO2. The reduced concentration of SO2in the fluid mixture after the performance of such a method may increase the efficiency and/or capacity of a downstream process involving the fluid mixture. Removing an amount of the first Lewis acid while removing essentially none or relatively little of the second Lewis acid may be accomplished according any of the variety of techniques described in the present disclosure (alone or in combination). For example, removing an amount of the first Lewis acid gas while removing essentially none or relatively little of the second Lewis acid may comprise exposing a fluid mixture comprising the first Lewis acid gas and second Lewis acid gas to conditions configured such that the first Lewis acid gas bonds with an electroactive species but the second Lewis acid gas does not bond with the electroactive species (e.g., due to thermodynamic unfavorability or kinetic reasons). In some embodiments, the conditions are configured such that both the first Lewis acid gas and second Lewis acid gas can bond with an electroactive species, but the first Lewis acid gas has a greater affinity (as measured by an equilibrium binding constant under the operative conditions) for the electroactive species than does the second Lewis acid gas. Some such configurations may result in the second Lewis acid gas (e.g., carbon dioxide) bonding to an electroactive species reversibly and the first Lewis acid gas bonding to the electroactive species irreversibly such that the first Lewis acid gas outcompetes and/or displaces the second Lewis acid gas. A net result of such reactivity is an amount of the first Lewis acid gas being removed from the fluid mixture while relatively little or none of the first Lewis acid gas is removed, despite formation of first Lewis acid gas-electroactive species complexes during at least some of the overall process. As yet another format, removal of the first Lewis acid gas may occur by bonding the first Lewis acid gas and the second Lewis acid gas (e.g., carbon dioxide) to one or more reduced electroactive species and, subsequently, selectively releasing the second Lewis acid gas (e.g., via oxidation of a second Lewis acid gas-electroactive species complex or a change in temperature) from the complexes while releasing relatively little or none of the first Lewis acid gas from the complexes. In some embodiments, the method involves removing an amount of the first Lewis acid from the fluid mixture and removing from the fluid mixture less than or equal to 10%, less than or equal to 5%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1%, less than or equal to 0.05%, less than or equal to 0.01%, less than or equal to 0.001%, and/or as little as 0.0001%, as little as 0.00001% or less of the second Lewis acid gas present in the fluid mixture by mole percent. In some embodiments, the method involves removing from the fluid mixture less than or equal to 10%, less than or equal to 5%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1%, and/or as low as 0.05%, as low as 0.01%, as low as 0.001%, and/or as little as 0.0001%, as little as 0.00001% or less of the second Lewis acid gas present in the fluid mixture by volume percent. In some embodiments, essentially none (e.g., none or a negligible amount with respect to the purpose of the fluid mixture such as carbon capture or purified gas production) of the second Lewis acid gas is removed during the performance of the method. The potential difference applied across the electrochemical cell may be performed in a charge mode. In the charge mode, a redox half reaction takes place at the negative electrode in which the electroactive species of the negative electrode is reduced. The potential difference applied across the electrochemical cell, during a charge mode, may have a particular voltage. The potential difference applied across the electrochemical cell may depend, for example, on the standard reduction potential for the generation of at least one reduced state of the electroactive species, as well as the standard reduction potential for the interconversion between a reduced state and an oxidized state of a second electroactive species, when present. In some embodiments, the potential difference is at least 0 V, at least 0.1 V, at least 0.2 V, at least 0.5 V, at least 0.8 V at least 1.0 V, at least 1.5 V, or higher. In some embodiments, the potential difference is less than or equal to 2.0 V, than or equal to 1.5 V, than or equal to 1.0 V, less than or equal to 0.5 V, or less. Combinations of these voltages are also possible. For example, in some embodiments, the potential difference applied across the electrochemical cell is at least 0.5 V and less than or equal to 2.0 V. Other values are also possible. The potential difference applied across the electrochemical cell may be performed in a discharge mode. In the discharge mode, a redox half takes place at the negative electrode in which the electroactive species of the negative electrode is oxidized. The potential difference across the electrochemical cell, during a discharge mode, may have a particular voltage. For example, in some embodiments, the potential difference may be less than 0 V, less than or equal to −0.5 V, less than or equal to −1.0 V, or less than or equal to −1.5 V. In some embodiments, the potential difference may be at least −2.0 V, at least −1.5 V, at least −1.0 V or at least −0.5 V. Combinations of these voltages are also possible, for example, at least −2.0 V and less than or equal to −0.5 V. Other values are also possible. The fluid mixture that is exposed to the electrochemical cell may come in any of a variety of forms and compositions. In some embodiments, the fluid mixture is a gas mixture. For example, fluid mixture101inFIGS.1A-1Bis a gas mixture comprising first Lewis acid gas102and second Lewis acid gas104upon exposure to electrochemical cell100, in accordance with some embodiments. In some embodiments, the fluid mixture is a liquid mixture. For example, fluid mixture101inFIGS.1A-1Bis a liquid mixture comprising a liquid (e.g., solvent) in which first Lewis acid gas102and second Lewis acid gas are present (e.g., dissolved), according to some embodiments. The liquid may be any of a variety of liquids, such as water or an organic liquid (e.g., N,N-dimethylformamide, liquid quinones), an ionic liquid, a eutectic mixture of organic material that are liquids at certain combinations, and combinations thereof. One example of liquid quinones that may be suitable for the methods and systems herein is a liquid mixture of benzoquinone and a second quinone such as a naphthoquinone as is described in Shimizu A, Takenaka K, Handa N, Nokami T, Itoh T, Yoshida J I. Liquid Quinones for Solvent-Free Redox Flow Batteries.Advanced Materials.2017 November; 29(41):1606592, which is incorporated by reference herein for all purposes. In some embodiments, the liquid of the fluid mixture comprises a carbonate ester. For example, in some embodiments, the liquid comprises dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonate, ethylene carbonate, propylene carbonate, or combinations thereof. As mentioned above, the fluid mixture may comprise a first Lewis acid gas. A Lewis acid gas generally refers to a gaseous species able to accept an electron pair from an electron pair donor (e.g., by having an empty orbital energetically accessible to the electron pair of the donor). In some instances, the pKaof a Lewis acid gas is lower than that of an electroactive species of the electrode, when present, in one or more of its reduced states. For example, in some instances the electroactive species comprises an optionally-substituted quinone having a semiquinone reduced state with a pKa, and gases having a lower pKathan that semiquinone would be considered a Lewis acid gas in those instances. In some embodiments, the first Lewis acid gas is a gas chosen from sulfur dioxide (SO2), sulfur oxides (SOx), nitrogen oxides (NOx), R2S, carbonyl sulfide (COS), R3B, boron trifluoride (BF3), or a combination thereof, wherein each R is independently H, branched or unbranched C1-C8 alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl. In some embodiments, R2S is hydrogen sulfide (H2S). In some embodiments, R3B is a borane. One example of a borane is BH3. For example, in some instances the electroactive species comprises an optionally-substituted quinone having a semiquinone reduced state with a pKa, and gases having a lower pKathan that semiquinone would be considered a Lewis acid gas in those instances. In some embodiments, the first Lewis acid gas is a gas chosen from sulfur dioxide (SO2), sulfur oxides (SOx), nitrogen oxides (NOx), R2S, carbonyl sulfide (COS), R3B, boron trifluoride (BF3), or a combination thereof, wherein each R is independently H, branched or unbranched C1-C8 alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl. In some embodiments, the first Lewis acid gas is a gas chosen from sulfur dioxide (SO2), sulfur oxides (SOx), nitrogen oxides (NOx), hydrogen sulfide (H2S), carbonyl sulfide (COS), borane (BH3), boron trifluoride (BF3), or a combination thereof. It should be understood that in this context, the first Lewis acid gas being a combination of two or more species refers to a mixture containing each of the two or more species, not a chemical product formed (e.g., addition product) by a reaction between the two or more species. One of ordinary skill in the art, with the benefit of this disclosure would understand applicable SOXand NOxLewis acid gases, and that the “x” in these formulae refer to a variable stoichiometric coefficient. In some embodiments, the first Lewis acid is a species for which removal is desirable. For example, in certain carbon capture applications, sulfur-containing gases such as SO2may be present in fluid streams (e.g., gas effluent). The sulfur-containing gases may interfere with carbon capture methods (e.g., by competing with adsorbent materials). Therefore, removing the sulfur-containing species from the fluid mixture may improve the carbon capture process. In some embodiments, the concentration of the first Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is relatively high. In some embodiments, the concentration of the first Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is greater than or equal to 0.00001 mole percent (mol %), greater than or equal to 0.0001 mol %, greater than or equal to 0.001 mol %, greater than or equal to 0.01 mole percent (mol %), greater than or equal to 0.1 mol %, greater than or equal to 0.5 mol %, greater than or equal to 1 mol %, greater than or equal to 5 mol %, greater than or equal to 10 mol %, greater than or equal to 25 mol %, greater than or equal to 50 mol %, greater than or equal to 75 mol %, greater than or equal to 90 mol %, or greater. In some embodiments, the concentration of the first Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is less than or equal to 99 mol %, less than or equal to 95 mol %, less than or equal to 90 mol %, less than or equal to 75 mol %, less than or equal to 50 mol %, less than or equal to 25 mol %, less than or equal to 10 mol %, less than or equal to 5 mol %, less than or equal to 2 mol %, less than or equal to 1 mol %, or less. Combinations (e.g., greater than or equal to 0.01 mol % and less than or equal to 99 mol %) are possible. Another possible combination is greater than or equal to 0.00001 mol % and less than or equal to 99 mol %. In some embodiments, the concentration of the first Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is greater than or equal to 0.01 volume percent (vol %), greater than or equal to 0.1 vol %, greater than or equal to 0.5 vol %, greater than or equal to 1 vol %, greater than or equal to 5 vol %, greater than or equal to 10 vol %, greater than or equal to 25 vol %, greater than or equal to 50 vol %, greater than or equal to 75 vol %, greater than or equal to 90 vol %, or greater. In some embodiments, the concentration of the first Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is less than or equal to 99 vol %, less than or equal to 95 vol %, less than or equal to 90 vol %, less than or equal to 75 vol %, less than or equal to 50 vol %, less than or equal to 25 vol %, less than or equal to 10 vol %, less than or equal to 10 vol %, less than or equal to 5 vol %, less than or equal to 2 vol %, less than or equal to 1 vol %, or less. Combinations (e.g., greater than or equal to 0.01 vol % and less than or equal to 99 vol %) are possible. In some embodiments, the fluid mixture comprises a second Lewis acid gas. In some embodiments, the second Lewis acid gas comprises one or more species chosen from carbon dioxide, nitrogen oxides, R3B, or R2S, wherein each R is independently H, branched or unbranched C1-C8 alkyl, aryl, cyclyl, heteroaryl, or heterocyclyl. In some embodiments, the second Lewis acid gas comprises one or more species chosen from carbon dioxide, nitrogen oxides, a borane, or H2S. As mentioned above, in some embodiments the second Lewis acid gas is carbon dioxide and the fluid mixture is desired to undergo a carbon capture process or a purification process (to produce substantially pure carbon dioxide, e.g., for carbon sequestration). In some embodiments, R2S is hydrogen sulfide (H2S). The methods described herein involving removing an amount of the first Lewis acid gas while removing essentially none or relatively little of any of the second Lewis acid gas (e.g., carbon dioxide) present in the fluid mixture may be beneficial for some such applications. It should be understood that in some embodiments, the fluid mixture comprises the first Lewis acid gas (e.g., SO2) and two or more other gaseous Lewis acid species (e.g., CO2and NO3), and it is desired to remove an amount of the SO2while removing essentially none or relatively little of the two or more other gaseous Lewis acid species (e.g., CO2and NO3). Another example of a Lewis acid gas that may be included in the second Lewis acid gas is NO2. In such embodiments, the second Lewis acid gas is considered to be the combination (as a mixture) of the two or more other Lewis acid gases (e.g., CO2and the NO3). A further downstream step in which an amount of the one of the two or more other Lewis acid gases (e.g., NO3) is removed (e.g., electrochemically) from the product fluid stream while removing essentially none or relatively little of the other of the two or more other Lewis acid gases (e.g., CO2) may then be performed. In some instances, the methods described herein involve removal of a sulfur-containing Lewis acid gas while removing essentially none or relatively little of a second, different sulfur-containing Lewis acid gas. For instance, in some embodiments the first Lewis acid gas is SO2and the second Lewis acid gas is H2S, and the method comprises removing an amount of the SO2while removing essentially none or relatively little H2S from the fluid mixture. As yet another example, in some instances the methods described herein involve removal of a first borane while removing essentially none or relatively little of a second, different borane. For instance, in some embodiments the first Lewis acid gas is BH3and the second Lewis acid gas is BF3, and the method comprises removing an amount of the BH3while removing essentially none or relatively little BF3from the fluid mixture. In some embodiments, the concentration of the second Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is relatively high. In some embodiments, the concentration of the second Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is greater than or equal to 0.01 mole percent (mol %), greater than or equal to 0.1 mol %, greater than or equal to 0.5 mol %, greater than or equal to 1 mol %, greater than or equal to 5 mol %, greater than or equal to 10 mol %, greater than or equal to 25 mol %, greater than or equal to 50 mol %, greater than or equal to 75 mol %, greater than or equal to 90 mol %, or greater. In some embodiments, the concentration of the second Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is less than or equal to 99 mol %, less than or equal to 95 mol %, less than or equal to 90 mol %, less than or equal to 75 mol %, less than or equal to 50 mol %, less than or equal to 25 mol %, less than or equal to 10 mol %, less than or equal to 5 mol %, less than or equal to 2 mol %, less than or equal to 1 mol %, or less. Combinations (e.g., greater than or equal to 0.01 mol % and less than or equal to 99 mol %) are possible. In some embodiments, the concentration of the second Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is greater than or equal to 0.01 volume percent (vol %), greater than or equal to 0.1 vol %, greater than or equal to 0.5 vol %, greater than or equal to 1 vol %, greater than or equal to 5 vol %, greater than or equal to 10 vol %, greater than or equal to 25 vol %, greater than or equal to 50 vol %, greater than or equal to 75 vol %, greater than or equal to 90 vol %, or greater. In some embodiments, the concentration of the second Lewis acid gas in the fluid mixture (e.g., prior to the application of the potential difference) is less than or equal to 99 vol %, less than or equal to 95 vol %, less than or equal to 90 vol %, less than or equal to 75 vol %, less than or equal to 50 vol %, less than or equal to 25 vol %, less than or equal to 10 vol %, less than or equal to 10 vol %, less than or equal to 5 vol %, less than or equal to 2 vol %, less than or equal to 1 vol %, or less. Combinations (e.g., greater than or equal to 0.01 vol % and less than or equal to 99 vol %) are possible. In some embodiments, a relatively large amount of the first Lewis acid gas is removed from the fluid mixture during the processes described herein. Removing a relatively large amount of the first Lewis acid gas may, in some cases, be beneficial for any of a variety of applications, such as capturing gases that may be deleterious if released into the atmosphere for environmental reasons, or deleterious to a downstream process for the fluid mixture (e.g., carbon capture). In some embodiments the amount of first Lewis acid gas in a treated fluid mixture (e.g., a fluid mixture from which an amount of the first Lewis acid gas is removed upon being exposed to the electrochemical cell) is less than or equal to 50%, less than or equal to 25%, less than or equal to 10%, less than or equal to 5%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1% or less of the amount (in volume percent) of the first Lewis acid gas in the original fluid mixture prior to treatment (e.g., the amount of the target in the fluid mixture prior to being exposed to electrochemical cell). In some embodiments, the amount of first Lewis acid gas in a treated fluid mixture is greater than or equal to 0.001%, greater than 0.005%, greater than or equal to 0.01%, greater than or equal to 0.05%, greater than or equal to 0.1%, greater than or equal to 0.5%, greater than or equal to 1%, greater than or equal to 2%, greater than or equal to 5%, or greater of the amount (in volume percent) of the first Lewis acid gas in the original fluid mixture prior to treatment. In some embodiments the amount of first Lewis acid gas in a treated fluid mixture (e.g., a fluid mixture from which an amount of the first Lewis acid gas is removed upon being exposed to the electrochemical cell) is less than or equal to 50%, less than or equal to 25%, less than or equal to 10%, less than or equal to 5%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1% or less of the amount (in mole percent) of the first Lewis acid gas in the original fluid mixture prior to separation (e.g., the amount of the target in the fluid mixture prior to being exposed to electrochemical cell). In some embodiments, the amount of first Lewis acid gas in a treated fluid mixture is greater than or equal to 0.001%, greater than 0.005%, greater than or equal to 0.01%, greater than or equal to 0.05%, greater than or equal to 0.1%, greater than or equal to 0.5%, greater than or equal to 1%, greater than or equal to 2%, greater than or equal to 5%, or greater of the amount (in mole percent) of the first Lewis acid gas in the original fluid mixture prior to treatment. As mentioned above, certain electroactive species may be used during the methods described herein for removing an amount of the first Lewis acid gas while removing essentially none or relatively little of the second Lewis acid gas. As used herein, an electroactive species generally refers to an agent (e.g., chemical entity) which undergoes oxidation or reduction upon exposure to an electrical potential in an electrochemical cell. It should be understood, however, that while electroactive species may undergo electrical potential-induced oxidation and reduction reactions, it may also be possible to induce changes in oxidation state chemically (e.g., via exposure to a chemical reductant or chemical oxidant in solution or at a surface). In some, but not necessarily all embodiments, an electrode comprises the electroactive species. It should be understood that when an electrode comprises an electroactive species, the electroactive species may be located at a surface of the electrode, in at least a portion of the interior of the electrode (e.g., in pores of the electrode), or both. For example, referring toFIG.2, in some embodiments, electrochemical cell100comprises negative electrode110, and negative electrode110comprises an electroactive species. The electroactive species may be on or near surface negative electrode110, the electroactive species may be in the interior of at least a portion of negative electrode110, or a combination of the both. In some embodiments, some or all of the electroactive species is not a part of an electrode. Instead, in some embodiments, the electroactive species is present in a conductive medium, such as an electrolyte (e.g., a liquid electrolyte solution). In some such embodiments, the electroactive species can freely diffuse in a conductive medium (e.g., dissolved in conductive liquid such as a liquid electrolyte solution). As used herein, a negative electrode of an electrochemical cell refers to an electrode into which electrons are injected during a charging process. For example, referring toFIG.2, when electrochemical cell100is charged (e.g., via the application of a potential by an external power source), electrons pass through an external circuit (not shown) and into negative electrode110. As such, in some cases, species in electronic communication with the negative electrode can be reduced to a reduced state (a state having an increased number of electrons) during a charging process of the electrochemical cell. The electroactive species may, in at least one conductive medium, have an oxidized state (having fewer electrons than the reduced state) and at least one reduced state (having more electrons than the oxidized state). As a non-limiting example, if the electroactive species is an optionally-substituted quinone, the neutral quinone would be considered the oxidized state, the semiquinone (product of the addition of one electron to the neutral quinone) would be considered one reduced state, and the quinone dianion (the product of the addition of one electron to neutral quinone) would be considered another reduced state. In some embodiments, the electroactive species has, in at least one conductive medium, at least one reduced state in which the species is capable of bonding with the first Lewis acid gas (e.g. SO2). A species being capable of bonding with a first Lewis acid gas generally refers to an ability for the species to undergo a bonding reaction with the first Lewis acid gas to a significant enough extent and at a rate significant enough for a useful gas capture and/or separation process to occur. For example, a species capable of bonding with a first Lewis acid gas may having a binding constant with the first Lewis acid gas of greater than or equal to 101M−1, greater than or equal to 102M−1, and/or up to 103M−1, or higher at room temperature (23° C.). A species capable of bonding with a first Lewis acid gas may be able to bond with the first Lewis acid gas on a timescale of on the order of minutes, on the order of seconds, on the order of milliseconds, or as low as on the order of microseconds or less. A species may be capable of bonding with a Lewis acid gas at at least one temperature (e.g., at least one temperature greater than or equal to 223 K and less than or equal to 573K, such as at 298 K). In some embodiments, the species is capable of bonding with a Lewis acid gas at a first temperature but bonding with the Lewis acid gas at a second temperature is thermodynamically and/or kinetically unfavorable. Such a temperature dependence may be based on a temperature dependence of a change in Gibbs free energy between the species (e.g., reduced quinone) and the Lewis acid gas (e.g., carbon dioxide). With the insight and guidance of this disclosure, one of ordinary skill in the art would be able to select an appropriate temperature for promoting bonding between the species in its at least one reduced state and the Lewis acid gas (e.g., the first Lewis acid gas). In some embodiments, the electroactive species has, in at least one conductive medium, an oxidized state in which it is capable of releasing bonded first Lewis acid gas. The electroactive species may be chosen such that in at least one reduced state it has a strong affinity for the Lewis acid gas for the particular application for which it is intended. For example, in some embodiments, where SO2is the first Lewis acid gas, the chosen electroactive species may have a binding constant with SO2of 101to 103M−1. In some embodiments, the chosen electroactive species may have a binding constant with a different first Lewis acid gas of 101to 103M−1. It has been observed that some, but not all quinones can be used as suitable electroactive species. In some embodiments, in the presence of SO2, an optionally-substituted quinone may be reduced to its semiquinone or dianion (e.g., in a single step or multiple steps), which then binds to SO2forming a complex. Other electroactive species that can form a covalent bond with the first Lewis acid gas (SO2), upon reduction may also be used. In some embodiments, the electroactive species has, in at least one conductive medium, at least one reduced state in which the species is capable of bonding with the first Lewis acid gas, but for which there is at least one temperature (e.g., 298 K) at which it is thermodynamically unfavorable for the species to react with a second Lewis acid gas. In some embodiments, the electroactive species has at least one reduced state in which the species is capable of bonding with the first Lewis acid gas, but for which it is thermodynamically unfavorable for the species to react with the second Lewis acid gas at at least one temperature in a range of greater than or equal to 223 K, greater than or equal to 248 K, greater than or equal to 273 K, greater than or equal to 298 K, and/or up to 323 K, up to 348 K, up to 373 K, up to 398 K, up to 423 K, up to 448 K, up to 473 K, up to 498 K, up to 523 K, up to 548 K, up to 573 K or higher. In some embodiments, the electroactive species has at least one reduced state in which the species is capable of bonding with the first Lewis acid gas, but for it is thermodynamically unfavorable for the species to react with the second Lewis acid gas at a temperature of 298 K. It should be understood that a reaction being thermodynamically unfavorable at a given temperature, as used herein, refers to the reaction having a positive change in Gibbs free energy (ΔGrxn) at that temperature. For example, the reaction between the species in the at least one reduced state and the second Lewis acid gas (e.g., CO2) may have a change in Gibbs free energy (ΔGrxn) of greater than 0 kcal/mol, greater than or equal to +0.1 kcal/mol, greater than or equal to +0.5 kcal/mol, greater than or equal to +1 kcal/mol, greater than or equal to +2 kcal/mol, greater than or equal to +3 kcal/mol, greater than or equal to +5 kcal/mol, and/or up to +8 kcal/mol, up to +10 kcal/mol, up to +20 kcal/mol, or more at at least one temperature in a range of greater than or equal to 223 K, greater than or equal to 248 K, greater than or equal to 273 K, greater than or equal to 298 K, and/or up to 323 K, up to 348 K, up to 373 K, up to 473 K, up to 573 K, or higher. In some embodiments, the reaction between the species in the at least one reduced state and the second Lewis acid gas (e.g., CO2) has a change in Gibbs free energy (ΔGrxn) of greater than 0 kcal/mol, greater than or equal to +0.1 kcal/mol, greater than or equal to +0.5 kcal/mol, greater than or equal to +1 kcal/mol, greater than or equal to +2 kcal/mol, greater than or equal to +3 kcal/mol, greater than or equal to +5 kcal/mol, and/or up to +8 kcal/mol, up to +10 kcal/mol, up to +20 kcal/mol, or more at a temperature of 298 K. In certain cases, the electroactive species has, in at least one conductive medium, at least one reduced state in which the species is capable of bonding with the first Lewis acid gas, but for which there is at least one temperature (e.g., 298 K) at which it is kinetically unfavorable for the species to bond with the second Lewis acid gas because a rate for the reaction is too low for a reaction to occur on a timescale commensurate with the characteristic timescale for the process/process step (e.g., gas capture), such as microseconds, milliseconds, seconds, or minutes. It has been realized that such a kinetic selectivity can be achieved in a variety of ways, including functionalizing electroactive species with certain substituents. For example, the electroactive species may be functionalized with bulky substituents (e.g., tert-butyl moieties) such that steric hindrance impedes reaction of the second Lewis acid gas with the species to a greater extent than it impedes reaction of the first Lewis acid gas with the species. In some embodiments in which the electroactive species has at least one reduced state in which the species is capable of bonding with the first Lewis acid gas, but for which there is at least one temperature (e.g., 298 K) at which it is kinetically unfavorable for the species to bond with the second Lewis acid gas, a ratio of the rate constant for the reaction of the first Lewis acid gas with the species to the rate constant for the reaction of the second Lewis acid gas is greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 50, greater than or equal to 100, and/or up to 500, up to 1000, or greater. In some embodiments in which the electroactive species has at least one reduced state in which the species is capable of bonding with the first Lewis acid gas, but for which there is at least one temperature (e.g., 298 K) at which it is kinetically unfavorable for the species to bond with the second Lewis acid gas, a ratio of the timescale of the reaction of the first Lewis acid gas with the species to the timescale of the second Lewis acid gas is greater than or equal to 2, greater than or equal to 5, greater than or equal to 10, greater than or equal to 50, greater than or equal to 100, and/or up to 500, up to 1000, or greater. A ratio of the timescales of reactions of the first Lewis acid gas with the species and the second Lewis acid gas with the species can be determined by measuring the time to 50% completion for each reaction, each reaction taking place under otherwise essentially identical conditions (same initial concentrations of gas, same temperature same concentration, same reaction medium (e.g., solvent and supporting electrolyte if present), same mixing rate, same concentration and/or accessible surface area of electroactive species, etc.). One of ordinary skill in the art, with the benefit of this disclosure, would be able to determine whether a reaction between a species and a Lewis acid gas is thermodynamically and/or kinetically favorable or unfavorable using, for example, cyclic voltammetry in the conductive medium (with the conductive medium saturated with the Lewis acid gas). It is believed that the pKaof the electroactive species in its reduced states may contribute at least in part to control of the selectivity of the species with respect to the first Lewis acid gas and the second Lewis acid gas. In some embodiments, in the at least one reduced state the electroactive species comprises a moiety having a pKathat is greater than or equal to the pKaof the first Lewis acid gas and less than the pKaof the second Lewis acid gas. As a non-limiting example, in some embodiments, in the at least one reduced state the electroactive species comprises a moiety (e.g., carbonyl group) having a pKathat is greater than or equal to SO2and less than the pKaof CO2in at least one conductive medium, or in the conductive medium of the process being performed. By judiciously choosing the pKa of the electroactive species in its reduced states (e.g., by derivatization with functional groups), selective reactivity with the first Lewis acid gas relative to the second Lewis acid gas can be achieved. One of ordinary skill in the art would be able to determine the pKaof an electroactive species (e.g., in a reduced state) by chemically or electrochemically preparing the reduced state and performing an acid base titration (e.g., colorimetrically, via cyclic voltammetry, etc.), or any other suitable technique known in the art. The relative pKavalues of species under given conditions (temperature, solvent, supporting electrolyte) can be determined using electrochemical techniques such as cyclic voltammetry or open-circuit potential techniques to determine the reduction potentials of the species, the species with the more positive reduction potential having the lower pKa. The pKamay depend on the temperature at which it is measured. In some embodiments, the pKais measured at any of the temperatures mentioned above, such as at 298 K. In some instances, the electroactive species in its at least one reduced state may be capable of reacting with both the first Lewis acid gas and the second Lewis acid gas at a first temperature, but at a second, different temperature, the electroactive species in its at least one reduced state is capable of bonding with a first Lewis acid gas, but a reaction with the second Lewis acid is thermodynamically and/or kinetically unfavorable. In some such instances, removing an amount of the first Lewis acid gas from a fluid mixture comprising the first Lewis acid gas and the second Lewis acid gas may comprise bonding both the first Lewis acid gas to one or more electroactive species in a reduced state and bonding the second Lewis acid gas to the one or more electroactive species in the reduced state at a first temperature to form first Lewis acid gas-electroactive species complexes and second Lewis acid gas-electroactive species complexes, respectively. Subsequently, the first Lewis acid gas-electroactive species complexes and second Lewis acid gas-electroactive species complexes may be exposed condition at a second, different temperature that results in release of an amount (e.g., at least 10%, at least 25%, at least 50%, at least 75%, at least 90%, at least 95%, at least 98%, at least 99%, or all by mole percent or volume percent) of the second Lewis acid gas from the complexes via reversal of the bonding reaction between the second Lewis acid gas and the electroactive species, while releasing essentially none or relatively little of the first Lewis acid gas (e.g., less than or equal to 10%, less than or equal to 5%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1%, and/or as little as 0.05%, as little as 0.01%, or less by mole percent or volume percent). Changing from the first temperature to the second temperature may cause at least partial release by shifting equilibrium constants for the respective bonding reactions toward release of the gas. For example, the complex-forming bonding reactions may each have a negative Gibbs free energy change at the first temperature, but at the second temperature the reaction involving bonding of the first Lewis acid gas may remain negative while the reaction involving bonding of the second Lewis acid may become positive (and therefore thermodynamically unfavorable). Judicious choice of electroactive species may be employed to achieve such an effect based on a variety of considerations. For example, an electroactive species may be chosen based on knowledge or measurements of changes in enthalpy and changes in entropy for the respective complex-forming reactions with the electroactive species. One non-limiting way in which the first Lewis acid gas may be removed while removing little to essentially none of the second Lewis acid gas (e.g., carbon dioxide) from the fluid mixture is by applying a certain potential across the electrochemical cell during at least a portion of the operation. For example, it is has been discovered in the context of the present disclosure that it is possible to apply a potential across the electrochemical cell (e.g., first potential) that is sufficient to reduce the electroactive species to at least one reduced state in which it is capable of bonding to the first Lewis acid gas, but the potential is insufficient to reach a state in which the species (or the electrode itself) is capable of reacting (e.g., binding) with the second Lewis acid gas. Judicious choice of electroactive species may allow for such a potential to be applied, whereas certain conventional electroactive species may not allow for such a potential to be applied. The potential applied across the electrochemical cell may be such that the electrode potential at the negative electrode is positive (e.g., by greater than or equal to 10 mV, greater than or equal to 50 mV, greater than or equal to 100 mV, greater than or equal to 200 mV, greater than or equal to 5 mV, and/or up to 1 V or more) relative to the standard reduction potential for the formation of a reduced state of the species capable of bonding to the second Lewis acid gas. While certain embodiments described above relate to selective removal of a first Lewis acid gas from a mixture comprising a first Lewis acid gas and a second Lewis acid gas via selectively reacting the first Lewis acid gas with an electroactive species to a greater extent than that of the second Lewis acid gas, other methods of selective removal of the first Lewis acid gas are contemplated as well. As one example, some embodiments are related to methods involving selective Lewis acid gas removal by bonding a first Lewis acid gas (e.g., sulfur dioxide) and a second Lewis acid gas (e.g., carbon dioxide) to one or more reduced electroactive species and, subsequently, selectively releasing the second Lewis acid gas (e.g., via oxidation of a second Lewis acid gas-electroactive species complex) from the complexes while releasing relatively little or none of the first Lewis acid gas from the complexes In some embodiments, a fluid mixture comprising a first Lewis acid gas and a second Lewis acid gas is exposed to one or more electroactive species. The electroactive species (e.g., optionally-substituted quinones) may be in a reduced state (e.g., an optionally-substituted semiquinone, an optionally substituted quinone dianion, or combinations thereof). For example, referring toFIG.3, fluid mixture101comprising first Lewis acid gas102and second Lewis acid gas104may be exposed to reduced electroactive species R. The electroactive species may initially be in an oxidized state (e.g., an optionally-substituted quinone) and then converted to a reduced state (e.g., an optionally-substituted semiquinone or quinone dianion). Such a reduction process to prepare the electroactive species in the reduced state may occur prior to the step of exposing the fluid mixture comprising a first Lewis acid gas and a second Lewis acid gas to the electroactive species, and/or during the exposure. The reduction may occur, for example, via electron transfer upon applying an electrical potential difference across an electrochemical cell comprising a negative electrode in electronic communication with the electroactive species. The electroactive species in the reduced state may be part of an electrode (e.g., immobilized on a negative electrode), freely diffusing in a liquid solution (e.g., the fluid mixture), or a combination thereof. Exposure to the one or more electroactive species in their reduced state may, for example, comprise flowing the fluid mixture to or past the electroactive species (e.g., in proximity to the electroactive species) and/or mixing the Lewis acid gases with the electroactive species in solution (e.g., via mixing separate solutions or bubbling a solution comprising the electroactive species with a gas mixture comprising the Lewis acid gases). In some embodiments, an amount of the first Lewis acid gas is bonded to a first portion the electroactive species in the reduced state to form first Lewis acid gas-electroactive species complexes. Further, in some embodiments, an amount of the second Lewis acid gas is bonded to a second portion of the electroactive species in the reduced state to form second Lewis acid gas-electroactive species complexes. The bonding of the first Lewis acid gas to the first portion of the electroactive species and the bonding of the second Lewis acid gas to the second portion of the electroactive species may occur simultaneously or sequentially. For example, in some embodiments, the second Lewis acid gas may be bonded to the reduced electroactive species (e.g., a subset or all of the electroactive species) and then, after a period of time, the first Lewis acid gas may be bonded to the reduced electroactive species (e.g., a subset or all of the electroactive species). In other embodiments, the first Lewis acid gas and the second Lewis acid gas are each bonded to the reduced electroactive species during a same period of time. It should be understood that Lewis acid gas-electroactive species complexes can be formed by any of a variety of forces, such a covalent bonds, ionic bonds, hydrogen bonds, or specific noncovalent affinity interactions. Referring again toFIG.3, first Lewis acid gas molecules102(e.g., sulfur dioxide) may bond to reduced electroactive species R to form first Lewis acid gas-electroactive species complexes107, and second Lewis acid gas molecules104(e.g., carbon dioxide) may bond to reduced electroactive species R to form second Lewis acid gas-electroactive species complexes109, according to certain embodiments. The first and second Lewis acid gases, when complexed, may be at least temporarily immobilized with respect to a structure of a device (e.g., an electrode) or with respect to a solution in which the electroactive species is present (e.g., dissolved). The first portion of the one or more electroactive species (to which the first Lewis acid gas is bonded) may, for example, be a first plurality of electroactive species molecules or polymer moieties, and the second portion of the electroactive species (to which the second Lewis acid gas is bonded) may be a second plurality of electroactive species molecules or polymer moieties. The first portion of the one or more electroactive species and the second portion of the one or more electroactive species may be the same type of species (e.g., same type of optionally-substituted quinone molecules or polymer residues)), or the first portion and second portion may include different types of species (e.g., quinones having differing substituents). In some embodiments, at least some of the second Lewis acid gas-electroactive species complexes are oxidized such that an amount (e.g., at least 10%, at least 25%, at least 50%, at least 75%, at least 90%, at least 95%, at least 98%, at least 99%, or all by mole percent or by volume percent) of the second Lewis acid gas is released from the complexes. For example, referring again toFIG.3, second Lewis acid gas-electroactive species complexes109may be oxidized during step 10 to form the electroactive species in their oxidized state Ox, thereby releasing second Lewis acid gas molecules104from the second Lewis acid gas-electroactive species complexes109. The released second Lewis acid gas molecules (e.g., carbon dioxide) may then, in some instances, be separated from the fluid mixture comprising the first Lewis acid gas-electroactive species complexes (e.g., sulfur dioxide-electroactive species complexes). Such a separation can be accomplished in some cases in which the complexes are immobilized by flowing the fluid mixture past the immobilized complexes (e.g., by flowing a gas stream or fluid stream using positive and/or negative pressure sources). In some cases in which the complexes are at least partially dissolved in solution, the second Lewis acid gas may be separated by out-gassing the second Lewis acid gas or via evaporation (e.g., via exposure to reduced pressure conditions such as exposure to vacuum). The oxidation of the second Lewis acid gas-electroactive species complexes may be performed using any of a variety of techniques such as electrochemically or chemically. For example, the oxidation step may comprise exposing the second Lewis acid gas-electroactive species complexes to an electrochemical cell while applying an electrical potential difference across the electrochemical cell. The second Lewis acid gas-electroactive species complexes may be exposed, for example to a negative electrode of the electrochemical cell either as free complexes in solution (under diffusion or forced fluid flow), or the electroactive species may be immobilized with respect to the negative electrode (e.g., via adsorption, functionalization, or inclusion in a redox-active polymer). The oxidation may, alternatively or additionally, involve the exposure to a suitable chemical oxidizing agent dissolved in solution or immobilized/deposited on a surface. In some embodiments, while at least some of the second Lewis acid gas-electroactive species complexes are oxidized (and an amount of the second Lewis acid gas is released), essentially none (e.g., a negligible amount with respect to the application being employed) of the first Lewis acid gas is released from the first Lewis acid gas-electroactive species complexes. In some embodiments, while at least some of the second Lewis acid gas-electroactive species complexes are oxidized (and an amount of the second Lewis acid gas is released), an amount of the first Lewis acid gas is released that is less than or equal to 70%, less than or equal to 50%, less than or equal to 25%, less than or equal to 10%, less than or equal to 5%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1%, less than or equal to 0.05%, and/or as low as 0.01%, as low as 0.001%, or less of the first Lewis acid gas-electroactive species complexes by mole percent. Essentially none or relatively little first Lewis acid gas may be released during oxidation of the second Lewis acid gas-electroactive species complexes for any of a variety reasons. For example, the conditions under which oxidation of the second Lewis acid gas-electroactive species complex occurs may not lead to oxidation of the first Lewis acid gas-electroactive species complex because the oxidizing power of an oxidizing agent (e.g., a chemical oxidant or an electrode at a given electrical potential) may be sufficient to oxidize the second Lewis acid gas-electroactive species complex (e.g., thermodynamically or kinetically), but insufficient to oxidize the first Lewis acid gas-electroactive species complex. Such an occurrence may happen when the different complexes have different oxidation potentials under the given conditions, which may be attributable to differing acidities of the first Lewis acid gas and the second Lewis acid gas. Another example is where the conditions under which oxidation of the second Lewis acid gas-electroactive species complexes occurs also results in oxidation of at least some of the first Lewis acid gas-electroactive species complexes, but where an affinity between the first Lewis acid gas and the electroactive species in its oxidized state is strong enough that a complex is maintained and the first Lewis acid gas is not released. Judicious choice of oxidizing agent/electrical potential and/or electroactive species (e.g., based on measured reduction potentials and/or pKavalues of the electroactive species and Lewis acid gases) may be used to employ any of the techniques described above. In some embodiments, the step of oxidizing the second Lewis acid gas-electroactive species complexes is performed multiple times. For example, the gas released during the oxidizing step (e.g., released second Lewis acid gas and a relatively small amount of first Lewis acid gas) may be separated from the fluid mixture and exposed to a second set of reduced electroactive species (e.g., at a second electrochemical cell) to form new second Lewis acid gas-electroactive species complexes and first Lewis acid gas-electroactive species, wherein a ratio of the first Lewis acid gas to second Lewis acid gas is higher than during the initial exposure step of the process. Then, the new second Lewis acid gas-electroactive species may be oxidized to release second Lewis acid gas from the complexes, while releasing essentially none or a relatively small amount of the first Lewis acid gas from the complexes. This process may be repeated, two, three, four, or more times, with each process progressively enriching a fluid mixture with the second Lewis acid gas while depleting it of the first Lewis acid gas. Such a sequential process could be performed using, for example, a distillation-type apparatus having multiple trays. In some embodiments, the first Lewis acid gas-electroactive species complexes are oxidized such that an amount (e.g., at least 10%, at least 25%, at least 50%, at least 75%, at least 90%, at least 95%, at least 98%, at least 99%, or all by mole percent or by volume percent) of the first Lewis acid gas is released. Such a release of the first Lewis acid gas (e.g., sulfur dioxide) may occur after separation from the second Lewis acid gas (e.g., carbon dioxide). In some embodiments, oxidation of the first Lewis acid gas-electroactive species complexes occurs after oxidation of the second Lewis acid gas-electroactive species complexes. As an example, in some embodiments, the oxidation of the second Lewis acid gas-electroactive species complexes is a first oxidizing step performed during a first period of time, and a second oxidizing step comprising oxidizing at least some of the first Lewis acid gas-electroactive species complexes is performed during a second (e.g., later) period of time such that an amount of the first Lewis acid gas is released. Referring again toFIG.3, first Lewis acid gas-electroactive species complex107may be oxidized during step 20 to form the electroactive species in their oxidized state Ox, thereby releasing first Lewis acid gas molecules102. The second oxidizing step may, as in the case of the first oxidizing step, be performed electrochemically or chemically. For example, the second oxidizing step may comprise exposing the second Lewis acid gas-electroactive species complexes to an electrochemical cell while applying an electrical potential difference across the electrochemical cell. In some embodiments, the electrochemical cell used for the second oxidation step is the same electrochemical cell as the first oxidation step. For example, the second Lewis acid gas-electroactive species complexes may be oxidized at a negative electrode of an electrochemical cell during a first period of time, and then the first Lewis acid gas-electroactive species complexes may be oxidized at the same negative electrode during a second period of time. The different oxidations may occur at different times by employing different electrical potentials at the different times. For example, a first electrical potential difference may be applied during the first oxidizing step, at a magnitude sufficient to oxidize the second Lewis acid gas-electroactive species complexes but insufficient (e.g., thermodynamically) to oxidize the first Lewis acid gas-electroactive species complexes. Then, during the second oxidizing step, a second electrical potential difference may be applied at a magnitude sufficient to oxidize the first Lewis acid gas-electroactive species complexes. Alternatively, the first and second oxidations may be performed at different electrochemical cells (e.g., of a gas separation system). For example, the first oxidizing step may comprise exposing the second Lewis acid gas-electroactive species complexes to a first electrochemical cell while applying an electrical potential difference across the first electrochemical cell, and the second oxidizing step may comprise exposing the first Lewis acid gas-electroactive species complexes to a second (different) electrochemical cell while applying an electrical potential difference across the second electrochemical cell. The second electrical potential difference may be different than the first electrical potential difference (e.g., resulting in a more positive electrical potential at a negative electrode). Such a process may be performed using, for example, a redox flow apparatus.FIG.4shows a schematic illustration of exemplary flow apparatus400comprising first electrochemical cell100and second electrochemical cell200. First electrochemical cell100and second electrochemical cell200may each comprise an anode110. Anodes110may each be in fluidic communication with conduit402configured to flow fluid mixtures (e.g., gaseous fluid mixtures or liquid solutions). That is, fluid in the conduit may be capable of contacting at least one surface of anodes of the first electrochemical cell and the second electrochemical cell. In the embodiment shown inFIG.4, fluid apparatus400may be configured to receive fluid mixture405(e.g., from a fluid mixture source) via an inlet, and anode110of first electrochemical cell100may be arranged with the conduit such that flow of fluid mixture405may expose fluid mixture405to anode110of first electrochemical cell100. At first electrochemical cell100, oxidizing step 10 shown inFIG.3may be performed to oxidize second Lewis acid gas-electroactive species complexes such that an amount of second Lewis acid gas is released. An intermediate outlet403may be positioned and configured to receive second Lewis acid gas407separated from fluid mixture405(e.g., via connection to a vacuum source). Flow apparatus406may be configured to transport the resulting fluid mixture406comprising first Lewis acid gas-electroactive species but at least partially (or completely) depleted of second Lewis acid gas molecules to second electrochemical cell200. Anode110of second electrochemical cell200may be arranged with conduit402such that flow of fluid mixture406may expose fluid mixture406to anode110of second electrochemical cell200. At second electrochemical cell200, oxidizing step 20 shown inFIG.3may be performed to oxidize first Lewis acid gas-electroactive species complexes such that an amount of first Lewis acid gas is released. Flow apparatus400may further be configured to expel released first Lewis acid as (e.g., as gas408from an outlet). As one non-limiting example of a process described above, sulfur dioxide and carbon dioxide may each be exposed to dissolved para-naphthoquinone dianion (p-NQ2−) in an organic liquid (e.g., via bubbling of the gases into the liquid). The para-naphthoquinone dianion may be prepared via electrochemical or chemical reduction. The exposure may result in formation of p-NQ(SO2)2and p-NQ(CO2)2complexes in solution. The solution may then be exposed to a negative electrode of an electrochemical cell during application of an oxidizing potential sufficient to oxidize the p-NQ(CO2)2to form neutral species p-NQ and CO2, but insufficient to oxidize the p-NQ(SO2)2complexes in solution. The released CO2may be removed from the solution (e.g., as part of a fluid mixture such as a gas mixture for further downstream processing such as carbon capture). The remaining solution comprising p-NQ(SO2)2may then be exposed to a negative electrode (either the same electrode or an electrode of a second electrochemical cell) during application of a more positive oxidizing potential sufficient to oxidize p-NQ(SO2)2to form p-NQ and SO2, now separated from the CO2. The electroactive species described herein may be of any suitable form, provided that it satisfies at least one of the criteria required herein. In some embodiments, the electroactive species is or comprises a molecular species. For example, the electroactive species may be or comprise an organic molecule. The electroactive species may comprise one or more functional groups capable of binding to a first Lewis acid gas in a fluid mixture (e.g., when the electroactive species is in a reduced state). The functional groups may include, for example, a carbonyl group. In some embodiments, the electroactive species is part of a polymer, such as a redox-active polymer. The electroactive species may be part of a polymeric material immobilized on the negative electrode. For example, referring toFIG.2, the electroactive species may be part of a polymeric material immobilized on negative electrode110of electrochemical cell100. As mentioned above, however, the electroactive species may be present in a conductive medium (e.g., a conductive liquid). In some embodiments, the electroactive species is or comprises an organic species. The species may be optionally-substituted (i.e., the species may comprise functional groups and/or other moieties or linkages bonded to the main structure of the species) In some embodiments, the organic species comprises one or more species chosen from optionally-substituted quinone, optionally-substituted thiolate, an optionally-substituted bipyridine, an optionally-substituted phenazine, and an optionally-substituted phenothiazine. In certain cases, the electroactive species is or comprises a redox-active polymer comprising an optionally-substituted organic species. The choice of substituent (e.g., functional groups) on the optionally-substituted species may depend on any of a variety of factors, including but not limited to its effect on the pKaand/or the standard reduction potential of the optionally-substituted species. One of ordinary skill, with the benefit of this disclosure, would understand how to determine which substituents or combinations of substituents on the optionally-substituted species (e.g., quinone) are suitable for the electroactive species based on, for example synthetic feasibility, and resulting pKaand/or standard reduction potential. As a non-limiting example, it has been discovered that substitution of certain quinones with electron-withdrawing groups can modulate the electron density of certain redox states of the quinone which may affect the species' selectivity for Lewis acid gases (e.g., by modulating the pKaof the reduced state). As one non-limiting example, it has been observed unexpectedly that functionalizing 1,4-naphthoquinone with electron withdrawing groups (e.g., nitriles to form 2,3-dicyano-1,4-napthoquinone) can impart selectivity for binding of SO2over binding CO2upon reduction. With the benefit of this insight, one or ordinary skill could screen potential electroactive species for a desired selectivity for Lewis acid gases by performing cyclic voltammetry and/or thermogravimetric analysis of the electroactive species in a desired conductive liquid at a desired temperature in the presence of the each Lewis acid gas, and determining relative reactivities. In some embodiments, the optionally-substituted quinone is or comprises an optionally-substituted naphthoquinone. In certain cases, the optionally-substituted quinone is or comprises an optionally-substituted anthraquinone. In some embodiments, the optionally substituted quinone is or comprises an optionally-substituted quinoline. In some embodiments, the optionally-substituted quinone is or comprises an optionally-substituted thiochromene-dione. In some embodiments, the optionally-substituted quinone is one of benzo[g]quinoline-5,10-dione, benzo[g]isoquinoline-5,10-dione, benzo[g]quinoxaline-5,10-dione, quinoline-5,8-dione, or 1-lamba4-thiochromene-5,8-dione. In some embodiments, the optionally-substituted quinone is or comprises an optionally-substituted phenanthrenequinone (also referred to as an optionally-substituted phenanthrenedione). The substituents (e.g., functional groups) may be any of those listed above or below. As mentioned above, the electroactive species may be part of a redox-active polymer. In some cases, any of the optionally-substituted species (e.g., organic species) described herein may be part of the redox-active polymer. In some such cases, at least a portion of the redox-active polymer comprises a backbone chain and one or more of the optionally-substituted species covalently bonded to the backbone chain. A backbone chain generally refers to the longest series of covalently bonded atoms that together create a continuous chain of the polymer molecule. In certain other cases, the optionally-substituted species described herein may be part of the backbone chain of the redox-active polymer. The electroactive species may comprise cross-linked polymeric materials. For example, in some embodiments, the electroactive species comprises or is incorporated into hydrogels, ionogels, organogels, or combinations thereof. Such cross-linked polymeric materials are generally known in the art, and may in some instances comprise electroactive species described herein as part of the three-dimensional structure (e.g., via covalent bonds). However, in some embodiments, electroactive species are incorporated into the cross-linked polymeric materials via adsorption (e.g., physisorption and/or chemisorption). In some embodiments, the electroactive species comprises an extended network. For example, the electroactive species may comprise a metal organic framework (MOF) or a covalent organic framework (COF). In some embodiments, the electroactive species comprises functionalized carbonaceous materials. For example, the electroactive species may comprise functionalized graphene, functionalized carbon nanotubes, functionalized carbon nanoribbons, edge-functionalized graphite, or combinations thereof. Exemplary functional groups with which the optionally-substituted quinone may be functionalized include, but are not limited to, halo (e.g., chloro, bromo, iodo), hydroxyl, carboxylate/carboxylic acid, sulfonate/sulfonic acid, alkylsulfonate/alkylsulfonic acid, phosphonate/phosphonic acid, alkylphosphonate/alkylphosphonic acid, acyl (e.g., acetyl, ethyl ester, etc.), amino, amido, quaternary ammonium (e.g., tetraalkylamino), branched or unbranched alkyl (e.g., C1-C18 alkyl), heteroalkyl, alkoxy, glycoxy, polyalkyleneglycoxy (e.g., polyethyleneglycoxy), imino, polyimino, branched or unbranched alkenyl, branched or unbranched alkynyl, aryl, heteroaryl, heterocyclyl, nitro, nitrile, thiyl, and/or carbonyl groups, any of which is optionally-substituted. The above-mentioned functional groups may also be employed in any of the other types of electroactive species described herein (e.g., optionally-substituted thiolate, an optionally-substituted bipyridine, an optionally-substituted phenazine, and an optionally-substituted phenothiazine, functionalized hydrogels, functionalized carbonaceous materials such as functionalized graphene, functionalized carbon nanotubes, edge-functionalized graphite, etc.). As would be understood by a person of ordinary skill in the art, a heteroaryl substitution of an aromatic species such as a quinone may be a ring fused with the aromatic species. For example, a quinone functionalized with a heteroaryl group can be a quinoline-dione (e.g., a benzoquinoline-dione). Heteroatoms in rings that are part of electroactive species, may, in some instances, affect the pKaof a reduced form of the electroactive species and/or its standard reduction potential. For example, a quinoline-dione may have a more positive standard reduction potential than a naphthoquinone, and a quinoxaline-dione may have a more positive standard reduction potential than the quinoline-dione. In certain aspects, electrochemical apparatuses are generally described.FIG.2depicts electrochemical apparatus105as one such example, according to certain embodiments. The electrochemical apparatus may, in some instances, be configured to perform the methods described herein. In some embodiments, the electrochemical apparatus comprises a chamber comprising a negative electrode. For example, in some embodiments, electrochemical apparatus105comprises chamber103and electrochemical cell100, which comprises negative electrode110. The chamber may be constructed for receiving a fluid mixture. In some instances, the chamber of the electrochemical apparatus is configured such that a fluid mixture can enter the chamber and in some instances leave the chamber. For example, in some embodiments, the chamber comprises a fluid inlet and a fluid outlet. Referring again toFIG.2, in some embodiments, electrochemical apparatus105comprises chamber103comprising fluid inlet106and fluid outlet108. As such, one or more of the methods described herein may be performed by flowing fluid mixture101(e.g., comprising a first Lewis acid gas and a second Lewis acid gas) into chamber103via fluid inlet106, thereby exposing at least a portion of the fluid mixture to the electrochemical cell (e.g., including negative electrode110). The electrochemical cell may be equipped with external circuitry and a power source (e.g., coupled to a potentiostat) to allow for application of the potential difference. The electrochemical apparatus may be configured such that at least a portion of the fluid mixture can be transported out of the chamber via a fluid outlet (e.g., fluid outlet108inFIG.2). In some embodiments, the fluid inlet is fluidically connected to a fluid mixture source (e.g., a source of a mixture comprising a first Lewis acid gas and a second Lewis acid gas). In some embodiments the fluid outlet is fluidically connected to a downstream apparatus for further processing (e.g., another electrochemical apparatus for removing another Lewis acid gas). In some embodiments, the electrochemical apparatus comprises a plurality of the chambers (e.g., each comprising a negative electrode) fluidically connected in series. In some embodiments, the electrochemical apparatus comprises the electroactive species in electronic communication with the negative electrode. For example, referring again toFIG.2, in some embodiments, the electroactive species (not pictured) is in electronic communication with negative electrode110. Electronic communication in this context generally refers to an ability to undergo electron transfer reactions, either via outer sphere (electron/hole transfer) or inner sphere (bond breaking and/or bond making) mechanisms. In some embodiments in which the electroactive species is in electronic communication with the negative electrode, the electroactive species is immobilized on the negative electrode. For example, the electroactive species may be part of a redox-active polymer immobilized on to the electrode via, in some instances, a composite layer (e.g., comprising a carbonaceous material such as carbon nanotubes). In some embodiments in which the electroactive species is in electronic communication with the negative electrode, the electroactive species is present in a conductive medium in at least a portion of the electrochemical cell, and can undergo electron transfer reactions with the electrode (directly or indirectly). For example, the electroactive species may be present (e.g., dissolved or suspended) in a conductive liquid of the electrochemical cell and be able to diffuse close enough to the negative electrode such that an electron transfer reaction can occur (e.g., to reduce the electroactive species into at least one reduced state) upon application of the potential difference across the electrochemical cell. As mentioned above, in some embodiments, the first electroactive species is immobilized on the negative electrode. Such embodiments may be distinguished from those of other embodiments, in which the electroactive species are free to be transported from one electrode to another via, for example, advection. A species immobilized on an electrode (e.g., the negative electrode) may be one that, under a given set of conditions, is not capable of freely diffusing away from or dissociating from the electrode. The electroactive species can be immobilized on an electrode in a variety of ways. For example, in some cases, an electroactive species can be immobilized on an electrode by being bound (e.g., via covalent bonds, ionic bonds, and/or intramolecular interaction such as electrostatic forces, van der Waals forces, hydrogen bonding, etc.) to a surface of the electrode or a species or material attached to the electrode. In some embodiments, the electroactive species can be immobilized on an electrode by being adsorbed onto the electrode. In some cases, the electroactive species can be immobilized on an electrode by being polymerized onto the electrode. In certain cases, the electroactive species can be immobilized on an electrode by being included in a composition (e.g., a coating, a composite layer, etc.) that is applied or deposited onto the electrode. In certain cases, the electroactive species (e.g., polymeric or molecular electroactive material) infiltrates a microfiber or, nanofiber, or carbon nanotube mat, such that the electroactive material is immobilized with respect to the mat. The mat may provide an enhanced as surface area enhancement for electrolyte and gas access, as well as expanded network for electrical conductivity. In some embodiments, the electroactive species is part of a gel composition associated with the electrode (e.g., as a layer deposited on the electrode, as a composition infiltrating pores of the electrode, or as a composition at least partially encapsulating components of the electrode such as fibers or nanotubes of the electrode). Such a gel comprising the electroactive species (e.g., a hydrogel, ionogel, organogel, etc.) may be prepared prior to association with the electrode (e.g., applied as a coating to form a layer), or the gel may be prepared in the presence of the electrode by contacting the electrode (e.g., via coating or submersion) with a gel precursor (e.g., a pre-polymer solution comprising the electroactive species) and gel formation may then be initiated (e.g., via cross-linking via introduction of a crosslinking agent, a radical initiator, heating, and/or irradiation with electromagnetic radiation (e.g., ultraviolet radiation)). In some embodiments, the electrochemical of the electrochemical apparatus further comprises a positive electrode. In some, but not necessarily all embodiments, the electrochemical cell comprises a separator between the negative electrode and the positive electrode. For example, referring toFIG.2, in some embodiments, electrochemical cell100comprises optional separator130between negative electrode110and optional positive electrode120. As used herein, a positive electrode of an electrochemical cell refers to an electrode from which electrons are removed during a charging process. For example, referring again toFIG.2, when electrochemical cell100is charged (e.g., via the application of a potential by an external power source), electrons pass from positive electrode120and into an external circuit (not shown). As such, in some cases, species associated with the positive electrode, if present, can be oxidized to an oxidized state (a state having a decreased number of electrons) during a charging process of the electrochemical cell. In some embodiments, the electroactive species in electronic communication with the negative electrode describe above is a first electroactive species and the positive electrode comprises a second electroactive species. The second electroactive species may be a different composition than the first electroactive species of the negative electrode, though it some embodiments the second electroactive species is the same as the first electroactive species. In some embodiments the positive electrode comprises an electroactive layer (sometimes referred to as a complementary electroactive layer) comprising the second electroactive species. The complementary electroactive layer may be in the form of a composite, and as such, may be a complementary electroactive composite layer. In operation, this second electroactive species may serve as a source of electrons for the reduction of the first electroactive species present in the negative electrode. Likewise, the second electroactive species may serve as a sink for electrons during the oxidation of the first electroactive species. It is in this manner that the electroactive layer of the positive electrode may be described as “complementary.” The second electroactive species may comprise, for example, a redox-active polymer. In some embodiments, the redox-active polymer is or comprises a polymer comprising ferrocene (e.g., as moieties bonded to the polymer backbone). In some embodiments, second electroactive species comprises a metallocene (e.g., ferrocene). In some such cases, the second electroactive species comprises a redox-active polymer comprising a metallocene. As one non-limiting embodiment, the redox-active polymer comprises polyvinyl ferrocene. As another example, the second electroactive species may comprise a polymer comprising a thiophene. In some such cases, the second electroactive species comprises poly(3-(4-fluorophenyl)thiophene). In some embodiments, the second electroactive species comprises phenothiazine. As another example, in some embodiments, the second electroactive species comprises (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (referred to as “TEMPO”), or derivatives thereof (e.g., comprising optional substituents). In certain cases, the second electroactive species comprises a Faradaic redox species having a standard reduction potential at least 0.5 volts (V), at least 0.6 V, at least 0.8 V, and/or up to 1.0 V, up to 1.5 V, or more positive than the first reduction potential of the first electroactive species. In some embodiments, the second electroactive species comprises an intercalation compound. For example, the second electroactive may comprise a metal ion intercalation compound. One exemplary class of intercalation compounds includes metal oxides. The intercalation compound may include intercalation compounds of alkali metal ions such as lithium ions and/or sodium ions. In some embodiments, the intercalation compound comprises an alkali metal ion transition metal oxide (e.g., a lithium cobalt oxide, a lithium manganese oxide, a lithium nickel oxide, and/or lithium oxides comprising cobalt, manganese, and/or nickel). In some embodiments, the intercalation compound comprises an alkali metal transition metal polyoxyanion, such as a lithium transition metal phosphate. One example of a suitable lithium transition metal phosphate for the positive electrode is lithium iron phosphate (LiFePO4). In some embodiments, during the charge mode, the oxidation of a second electroactive species in the form of an alkali metal ion intercalation compound (e.g., LiFePO4) provides a source of electrons for driving the reduction of the first electroactive species, while simultaneous releasing an alkali metal ion (e.g., a lithium ion) that can shuttle to through an electrolyte (e.g., on or within a separator when present) toward the negative electrode to maintain charge balance and complete an electrochemical circuit. Conversely, during a discharge mode, the reduction of a second electroactive species in the form of an alkali metal ion intercalation compound provides a sink for electrons from the oxidation of the first electroactive species, while at the same time an alkali metal ion (e.g., a lithium ion) can shuttle from the a region in proximity to the negative electrode, through an electrolyte (e.g., on or within a separator when present), and toward the positive electrode where it can be intercalated into the intercalation compound and maintain charge balance. The complementary electroactive composite layer of the positive electrode may comprise an immobilized polymeric composite of an electroactive species and of another material (e.g., a carbonaceous material). Examples of the carbonaceous material include carbon nanotube (e.g., single-walled carbon nanotube, multi-walled-carbon nanotube), carbon black, KetjenBlack, carbon black Super P, or graphene. Other materials are also possible. In certain cases, the second electroactive species can be immobilized on a positive electrode by being included in a composition (e.g., a coating, a composite layer, etc.) that is applied or deposited onto the positive electrode. In certain cases, the second electroactive species (e.g., polymeric or molecular electroactive material) infiltrates a microfiber, nanofiber, or carbon nanotube mat associated with the positive electrode, such that the second electroactive species is immobilized with respect to the mat of the positive electrode. The second electroactive species may also be part of a gel associated with the positive electrode in the same or similar manner as described above with respect to the first electroactive species. According to one or more embodiments, the electroactive composite layer of the positive electrode may have a particular ratio of weight of electroactive material to carbonaceous material. The ratio by weight may be chosen to facilitate a high electrical current per mass of electroactive material. In some embodiments, a ratio by weight of the mass of electroactive material to the mass of carbonaceous material for the complementary electroactive composite layer may be between 1 to 2 and 2 to 1. In some embodiments, it may be 1 to 1. Other ratios are also possible. The separator may serve as a protective layer that can prevent the respective electrochemical reactions at each electrode from interfering with each other. The separator may also help electronically isolate the negative and positive electrodes from one another and/or other components within the electrochemical cell to prevent short-circuiting. In some embodiments, the electrochemical cell comprises the conductive medium and the separator contains at least a portion of the conductive medium (e.g., conductive liquid). A person of ordinary skill, with the benefit of this disclosure, will be able to select a suitable separator. The separator may comprise a porous structure. In some instances, the separator is or comprises a porous solid material. In some embodiments, the separator is or comprises a membrane. The membrane of the separator may be made of suitable material. For example, the membrane of the separator may be or comprise a plastic film. Non-limiting examples of plastic films included include polyamide, polyolefin resins, polyester resins, polyurethane resin, or acrylic resin and containing lithium carbonate, or potassium hydroxide, or sodium-potassium peroxide dispersed therein. The material for the separator may comprise a cellulose membrane, a polymeric material, or a polymeric-ceramic composite material. Further examples of separators include polyvinylidene difluoride (PVDF)separators, PVDF-Alumina separators, or Celgard. In the context of this disclosure, a conductive medium is understood to be a solid or fluid medium having sufficient ionic conductivity to support the operation of an electrochemical cell (e.g., by shuttling ions between the electrodes of the electrochemical cell to maintain charge balance). As mentioned above, the conductive medium may be a liquid or a solid electrolyte. In some embodiments, the conductive medium is or comprises a non-volatile liquid. In some such instances, the conductive medium is or comprises a room temperature ionic liquid such as 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][TF2N]). It should be understood that while the conductive medium can transport ions, the conductive medium is generally not electronically conductive (e.g., a metallic conductive) capable of short-circuiting an electrochemical cell when in contact with a negative electrode and a positive electrode. In some cases, a separator contains a conductive liquid, which serves as the conductive medium. In some embodiments, the separator is at least partially (or completely) impregnated with the conductive liquid. For example, the separator may absorb an amount of the conductive liquid upon being submerged, coated, dipped, or otherwise associated with the conductive liquid. In some such cases where the separator is porous, some or all of the pores of the separator (in the interior and/or near the surface of the separator) may become at least partially filled with the conductive liquid. In some embodiments, the separator is saturated with the conductive liquid. A separator being saturated with a conductive liquid generally refers to the separator containing the maximum amount of conductive liquid capable of being contained within the volume of that separator at room temperature (23° C.) and ambient pressure. In some embodiments, the electrochemical cell may be provided without the conductive liquid present in the separator, but with the separator capable of containing the conductive liquid when it is put into operation to perform a gas separation process. One way in which the separator may be capable of containing the conductive liquid is by having a relatively high porosity and/or containing materials capable of absorbing and/or being wetted by the conductive liquid. As mentioned above, in some embodiments the conductive liquid comprises an ionic liquid, for example, a room temperature ionic liquid (“RTIL”). The RTIL electrolyte may have a low volatility (i.e., a room temperature vapor pressure of less than 10−5Pa, for example, from 10−10to 10−5Pa), thereby reducing the risk of electrodes drying, and allowing for flow of gas past the electrodes without significant loss to evaporation or entrainment. In some embodiments, the ionic liquid makes up substantially all (e.g., at least 80 vol %, at least 90 vol %, at least 95 vol %, at least 98 vol %, at least 99 vol %, at least 99.9 vol %) of the conductive liquid. The ionic liquid may comprise an anion component and a cation component. The anion of the ionic liquid may comprise, without limitation: halide, sulfate, sulfonate, carbonate, bicarbonate, phosphate, nitrate, nitrate, acetate, PF6−, BF4−, triflate, nonaflate, bis(triflyl)amide, trifluoroacetate, heptaflurorobutanoate, haloaluminate, triazolide, and amino acid derivatives (e.g. proline with the proton on the nitrogen removed). The cation of the ionic liquid may comprise, without limitation: imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium, sulfonium, thiazolium, pyrazolium, piperidinium, triazolium, pyrazolium, oxazolium, guanadinium, and dialkylmorpholinium. In some embodiments, the room temperature ionic liquid comprises an imidazolium as a cation component. As one example, in some embodiments, the room temperature ionic liquid comprises 1-butyl-3-methylimidazolium (“Bmim”) as a cation component. In some embodiments, the room temperature ionic liquid comprises bis(trifluoromethylsulfonyl)imide (“TF2N”) as an anion component. In some embodiments, the room temperature ionic liquid comprises 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][TF2N]). In some embodiments, the room temperature ionic liquid comprises 1-butyl-3-methylimidazolium tetrafluoroborate (BF4) ([Bmim][BF4]). In some embodiments, the conductive liquid comprises a low-volatility electrolyte solution. For example, the conductive liquid may comprise a liquid solvent having a relatively high boiling point and dissolved ionic species therein (e.g., dissolved supporting electrolyte ions). The liquid solvent having a relatively high boiling point may be non-aqueous. For example, the liquid solvent may comprise N,N-dimethylformamide (DMF) or the like. In some cases, one or more electrodes of the electrochemical cell comprises an electroactive composite layer. For example, in some embodiments, the negative electrode comprises an electroactive composite layer (e.g., a primary electroactive composite layer). Referring toFIG.5, negative electrode110comprises composite electroactive composite layer114facing positive electrode120of electrochemical cell500, according to certain embodiments. In certain cases, the positive electrode comprises an electroactive composite layer (e.g., a complementary electroactive composite layer). For example, inFIG.5, positive electrode120comprises electroactive composite layer124facing negative electrode110. The electroactive composite layer of the positive electrode may also be referred to as complementary electroactive composite layer, as the electroactive species within it serves as an electron sink or electron source for the electroactive material of the negative electrode. In some cases, the electroactive composite layer of an electrode (e.g., negative electrode, positive electrode) extends through the entire thickness dimension of an electrode. For example, the electroactive composite layer may intercalate through an entire thickness of an electrode. However, in some embodiments, the electroactive composite layer of an electrode does not extend through the entire thickness dimension of an electrode. In some such cases, the electroactive composite layer intercalates through some of but not the entire thickness of the electrode. In certain cases, the electroactive composite layer is a coating on the surface of another component of the electrode (e.g., a current collector, a gas permeable layer, etc.). In some embodiments, the electroactive species of an electrode (e.g., the first electroactive species of the negative electrode, the second electroactive species of the positive electrode), are part of an electroactive composite layer. For example, inFIG.5, electroactive composite layer114comprises the first electroactive species described herein, according to some embodiments. Similarly, in some embodiments, electroactive composite layer124comprises the second electroactive species (e.g., polyvinylferrocene). In addition to the electroactive species, the electroactive composite layer of the negative electrode may also comprise a carbonaceous material. Examples of suitable materials include, but are not limited to, carbon nanotube (e.g., single-walled carbon nanotube, multi-walled-carbon nanotube), carbon black, KetjenBlack, carbon black Super P, graphene, or combinations thereof. Other examples also include immobilizing and/or coating of the electroactive species (e.g., in polymeric forms, molecular forms or otherwise) into/onto a microfiber, nanofiber or carbon nanotube mat via intercalation, grafting, chemical vapor deposition (CVD), or otherwise. According to one or more embodiments, the electroactive composite layer of the negative electrode may have a particular ratio of weight of electroactive species to carbonaceous material. The ratio by weight may be chosen to facilitate a high electronic current per mass of electroactive material. In some embodiments, a ratio by weight of the mass of electroactive material to the mass of carbonaceous material may be between 1 to 1 and 1 to 10. In some embodiments, it may be 1 to 3. Other ratios are also possible. The negative electrode may further comprise a gas permeable layer. The gas permeable layer (which may also be referred to as a substrate layer) may be proximate to the electroactive composite layer, and facing outward from the electrochemical cell. In some embodiments, the gas permeable layer is in contact with the first electroactive species. In some such cases, the gas permeable layer is in direct contact with the first electroactive species, while in other such cases, the gas permeable layer is in indirect contact with the first electroactive species. It should be understood that when a portion (e.g., layer,) is “on” or “in contact with” another portion, it can be directly on the portion, or an intervening portion (e.g., layer) also may be present (in which case the portion is understood to be “indirectly on” or “in indirect contact with” the other portion). A portion that is “directly on”, “in direct contact with”, another portion means that no intervening portion is present. It should also be understood that when a portion is referred to as being “on” or “in contact with” another portion, it may cover the entire portion or a part of the portion. In some embodiments, the gas permeable layer is in contact (e.g., in direct contact with or in indirect contact with) with the electroactive composite layer of the negative electrode. A fluid mixture in the form of a gas stream (e.g., comprising the first Lewis acid gas and the second Lewis acid gas) may diffuse through the gas permeable layer to come into contact with the electroactive composite layer. The gas permeable layer may comprise a conductive solid material and act as a current collector within the cell. The gas permeable layer may comprise a porous material. In some embodiments, the gas permeable layer has a porosity, for example, of greater than or equal to 60%, greater than or equal to 70%, greater than or equal to the 75%, greater than or equal to 80%, or greater. In some embodiments, the gas permeable layer has a porosity of less than or equal to 85%, less than or equal to 90%, or more. Combinations of these ranges are possible. For example, in some embodiments, the gas permeable layer of the negative electrode has a porosity of greater than or equal to 60% and less than or equal to 90%. Other porosities are also possible. Examples of suitable materials for the gas permeable layer include, without limitation, carbon paper (treated, TEFLON-treated, or untreated), carbon cloth, and nonwoven carbon mat. Other materials may also be used. While in some embodiments the electrochemical cell comprises a single negative electrode, in other embodiments the electrochemical cell comprises more than one negative electrode. For example, in some embodiments, the negative electrode described herein is a first negative electrode, and the electrochemical cell comprises a second negative electrode. The positive electrode may be between the first negative electrode and the second negative electrode. The second negative electrode may also comprise the first electroactive species. The second negative electrode may be identical in configuration and composition to the first negative electrode. In some embodiments, the electrochemical cell comprises greater than or equal to 1 negative electrode, greater than or equal to 2 negative electrodes, greater than or equal to 3 negative electrodes, greater than or equal to 5 negative electrodes, greater than or equal to 10 negative electrodes, and/or up to 15 negative electrodes, up to 20 negative electrodes, up to 50 negative electrodes, or more. While in some embodiments the electrochemical cell comprises a single separator (e.g., between the negative electrode and the positive electrode), in other embodiments the electrochemical cell comprises more than one separator. For example, in some embodiments, the separator described herein is a first separator, and the electrochemical cell comprises a second separator. In some embodiments in which a second negative electrode is present, the second separator may be between the positive electrode and the second negative electrode. The second separator may be identical in configuration and composition to the first separator. In certain cases, the second separator is capable of comprising (e.g., being saturated with) the conductive liquid. In some embodiments, the electrochemical cell comprises greater than or equal to 1 separator, greater than or equal to 2 separators, greater than or equal to 3 separators, greater than or equal to 5 separators, greater than or equal to 10 separators, and/or up to 15 separators, up to 20 separators, up to 50 separators, or more. In some cases, each of the separators is between a respective negative electrode and positive electrode. In some embodiments of the electrochemical cell in which the positive electrode has a negative electrode on either side (e.g., a first negative electrode and a second negative electrode), the positive electrode comprises second electroactive species facing each of the negative electrodes. In some such embodiments, the positive electrode comprises two complementary electroactive composite layers, each facing one of the negative electrodes. The positive electrode may further comprise a substrate layer positioned proximate to or between the electroactive composite layer or layers. The substrate layer may be in direct contact or in indirect contact with the electroactive composite layer or layers. The substrate layer of the positive electrode may comprise the same or different material as that of the substrate layer of the negative electrode (when present). For example, the substrate layer may comprise a material such as carbon paper (treated, TEFLON-treated, or untreated), carbon cloth, or nonwoven carbon mat. The substrate may comprise, in some embodiments, a mat comprising, for example carbon nanotubes, microfibers, nanofibers, or combinations thereof. Other materials are also possible. The substrate layer of the positive electrode may comprise a conductive material and act as a current collector within the cell. In some embodiments, the substate comprises a metal and/or metal alloy. For example, the substrate may comprise a metal and/or metal alloy foil (e.g., having a relatively small thickness of less than or equal to 200 microns, less than or equal to 100 microns, less than or equal to 10 microns, and/or as low as 1 micron, or less). Examples of suitable foils could include, but are not limited to, aluminum foils, titanium foils. As a particular example, in some embodiments, the positive electrode comprises a substrate between a first complementary electroactive composite layer facing the first negative electrode and a second complementary electroactive composite layer facing the second negative electrode. In this context, an electroactive composite layer of the positive electrode can be facing a particular electrode (e.g., a negative electrode) if a line extending away from the bulk of the electroactive composite layer can intersect that electrode without passing through the substrate. An object (e.g., electroactive composite layer) can be facing another object when it is in contact with the other object, or when one or more intermediate materials are positioned between the surface and the other object. For example, two objects that are facing each other can be in contact or can include one or more intermediate materials (e.g., a separator) between them. FIG.6depicts a schematic cross-sectional diagram of an example of an electrochemical cell, according to some, but not necessarily all embodiments, and having one or more of the components described above. Electrochemical cell600comprises a positive electrode120between two negative electrodes110. Separators130separate positive and negative electrodes120and110. Each of negative electrodes110comprises an optional gas permeable layer112, which is positioned away from the center of the cell100, and an optional primary electroactive composite layer114, which faces toward the positive electrode120. In some embodiments, positive electrode120comprises substrate layer122and two complementary electroactive composite layers124thereon. The different components of the electrochemical cell100may have certain properties described throughout this disclosure, for example, comprising the electrode materials (e.g., electroactive species) described above. The configuration of two outwardly-facing negative electrodes110, as shown, for example, inFIG.2, may, in some cases, provide the advantage of doubling the gas-adsorbing area exposed to the gas compared to electrochemical cells comprising a single negative electrode and a single positive electrode. The electrochemical apparatus can be provided in any of a variety of forms, depending on a desired application and/or the nature of the fluid mixture. The electrochemical apparatus may be configured to electrochemically capture and/or separate Lewis acid gases from gas mixtures. In some such instances, the electrochemical apparatus comprises a chamber with a gaseous or vacuum headspace able to be filled at least partially with the gaseous fluid mixture. In some such embodiments, the fluid inlet of the chamber is fluidically connected to a source of the gas mixture and one or more components for causing the gas mixture to be transported, such as a pump or vacuum and associated valving. In some embodiments, the electrochemical apparatus is configured to electrochemically capture and/or separate Lewis acid gases from liquid mixtures. In some such instances, the electrochemical apparatus comprises a chamber able to be at least partially filled with a solution. In certain instances, the electrochemical apparatus, including the chamber and the electrochemical cell, is configured like that of a redox flow battery, wherein one of the flowed liquid solutions enters via the fluid inlet of the chamber and exits via the fluid outlet during operation. In certain embodiments, a portion of the chamber in fluidic contact with the negative electrode is fluidically connected to an absorbent material. As one non-limiting example, the chamber may be fluidically connected to an absorber tower. However, in some embodiments, the electrochemical apparatus is configured such that the first Lewis acid gas is captured directly at the negative electrode (e.g., by binding with the electroactive species during and/or after the application of the potential difference). In some embodiments, the electrochemical cell is configured as a solid-state electrochemical cell system. In some such instances, the electroactive species may be immobilized on at least part of the negative electrode, as described above. The electrochemical apparatus may be configured as a gas separation system. According to one or more embodiments, one or more electrochemical cells as described herein (e.g., configured for selective removal of Lewis acid gases) may be incorporated into a gas separation system. The gas separation system may comprise a plurality of electrochemical cells, according to any of the embodiments described herein, in fluid communication with a gas inlet and a gas outlet. The electrochemical cells electrically connected in parallel or in series, as described in more detail below. The gas separation system may comprise an external circuit connecting the negative electrode (or the first and second negative electrodes when both are present) and the positive electrode of each electrochemical cell to a power source configured to apply a potential difference across the negatives electrode(s) and the positive electrode of each electrochemical cell. FIG.7Ashows a schematic drawing of an exemplary system performing a gas separation process during a charge mode, according to one or more embodiments. InFIG.7A, a potential difference is applied across each of electrochemical cells700, such that each operates in a charge mode, according to certain embodiments. In the charge mode, a redox reaction (e.g., reduction) of the first electroactive species in the negative electrode710increases the affinity between the electroactive species and Lewis acid gas790, according to certain embodiments. A gas mixture775comprising the Lewis acid gas790is introduced to the system and passes in proximity to the negative electrodes710. The increased affinity causes the Lewis acid gas (e.g., SO2) to bond to the electroactive material, according to certain embodiments. In this manner, at least a portion of the Lewis acid gas is separated from the gas mixture775to produce treated gas mixture785. In some embodiments, a gas separation system comprises a plurality of electrochemical cells, and a flow field is between at least some (e.g., some or all) of the plurality of electrochemical cells. As an illustrative example,FIG.7Bshows a schematic drawing of an exemplary system comprising flow fields711separating electrochemical cells570, performing a gas separation process during a charge mode, according to one or more embodiments. It should be understood that when a first object is between a second object and a third object, it may be between an entirety of the first object and second object or between portions of the first object and second object. In some embodiments, a flow field between two neighboring electrochemical cells is directly adjacent to each of the neighboring electrochemical cells such that no intervening structures/layers are between the flow field and the electrochemical cells. However, in some embodiments, a flow field between two neighboring electrochemical cells is indirectly adjacent to one or both cells, such that there are one or more intervening structures/layers such as electrically conductive solids. A flow field generally refers to a solid structure configured to define pathways through which a fluid may flow. In some instances, a flow field comprises a solid article defining pores or channels for fluid flow while allowing the fluid to be exposed to adjacent structures. Suitable materials for the solid articles of flow fields include, but are not limited to, polymeric materials (e.g., plastics), metals/metal alloys, graphite, composite materials (e.g., a graphite-polymer composite). In some embodiments, a flow field comprises a solid article comprising one or more surfaces with patterned channels. The channel patterns may be selected to distribute fluid (e.g., gas) effectively across one or more dimensions of the flow field. Suitable channel patterns include, but are not limited to serpentine, parallel, and interdigitated.FIGS.7C,7D, and7Eshow side-view schematic drawings of faces of flows field711ahaving a serpentine pattern, flow field711bhaving a parallel pattern, and flow field711chaving an interdigitated pattern, respectively with fluid flow direction indicated as arrows, according to certain embodiments. Flow field channel patterns can be formed, for example, via etching, cutting, stamping, molding, milling, or additive manufacturing. In some embodiments, a flow field comprises a porous solid. For example, a flow field may comprise carbon fiber paper, felt, or cloth, or metal foam. InFIG.7B, Lewis acid gas790from fluid mixture775is distributed along a facial area of electrode710via flow field711(e.g., via channels not shown). It has been realized in the context of the present disclosure that flow fields may assist with distributing gas mixtures relatively uniformly across electrodes and may assist with controlling the duration of exposure of the gas to the electrodes (e.g., to promote efficient capture of target gases). Relatively uniform distribution of gas may increase efficiency by utilizing a larger percentage of electrode area (e.g., comprising electroactive species in at least one reduced state) for binding target gas. In some embodiments, during at least a portion of a charging process, a flux of the gas mixture across at least 25%, at least 50%, at least 75%, at least 90%, at least 95%, or more of a facial area of a negative electrode in the system is within 50%, within 25%, within 15%, within 10%, within 5%, within 2%, within 1% or less of an average flux across the entire facial area of the negative electrode during the charging process. As mentioned above, a gas separation system may comprise a plurality of electrochemical cells electrically connected in parallel or in series. One of ordinary skill in the art, with the benefit of this disclosure, would understand generally how to electrically connect electrochemical cells to form a circuit. Such connections can be made by establishing an electrically conductive pathway for electrons to flow between electrodes of the electrochemical cells (in other words, establishing electrical coupling between electrodes). An electrically conductive pathway may in some instances be established via one or more electrically conductive solid materials (e.g., conductive metals, alloys, polymers, composites, carbonaceous materials, or combinations thereof). For example, an electrically conductive pathway may be established via wiring electrodes of the electrochemical cells. The electrochemical cells may have any of the configurations described above. For example, in some embodiments, some or all of the electrochemical cells in the system have a single negative electrode (e.g., comprising a first electroactive species), a single positive electrode (e.g., comprising a second electroactive species), and optionally a separator between the first positive electrode and the second positive electrode.FIG.8Ashows a schematic drawing of an arrangement of electrochemical cells1100in one such system1000, where each electrochemical cell1100comprises, in order, negative electrode1010, optional separator1020, and positive electrode1030, according to certain embodiments. A gas mixture1075comprising a target gas may be introduced to the system such that gas mixture1075passes in proximity to negative electrode1010of first electrochemical cell110and positive electrode1030of neighboring second electrochemical cell1100. WhileFIG.8Ashows three electrochemical cells1100, it should be understood than any of a variety of suitable numbers of electrochemical cells may be employed in a gas separation system (e.g., electrically connected in parallel or in series), depending on the requirements of a particular application as needed. In other embodiments, some or all of the electrochemical cells in a gas separation system comprise a positive electrode (e.g., comprising a second electroactive species), a first negative electrode (e.g., comprising the first electroactive species), a second negative electrode (e.g., comprising the first electroactive species), a first separator between the first negative electrode and the positive electrode, and a second separator between the positive electrode and the second negative electrode. Examples of such electrochemical cells are shown inFIG.6andFIGS.7A-7B. FIG.8Bshows a schematic drawing of configuration in which a plurality of electrochemical cells1100in system1000are electrically connected in parallel, according to certain embodiments. In a parallel configuration, each negative electrode1010is electrically coupled to a first terminal (e.g., of a power source) and each positive electrode1030is electrically coupled to a second terminal (e.g., of a power source). For example, inFIG.8B, each negative electrode1010is electrically coupled to a first terminal of a power source via wiring115, and each positive electrode1030is electrically coupled to a second terminal of the power source via wiring116, in accordance with certain embodiments. FIG.8Cshows a schematic drawing of a configuration in which a plurality of electrochemical cells11000in system1000are electrically connected in series, according to certain embodiments. In a series configuration, a positive electrode of a first electrochemical cell is electrically connected to a negative electrode of a second electrochemical cell of the system. For example, inFIG.8B, negative electrode1010of first electrochemical cell1100ais electrically connected to positive electrode1030of second electrochemical cell1100bvia wiring1017, and negative electrode1010of second electrochemical cell1100bis electrically connected to positive electrode1030of third electrochemical cell1100cvia wiring1018, according to certain embodiments. Further, positive electrode1030of first electrochemical cell1100ais electrically coupled to a first terminal of a power source via wiring114, and negative electrode1030of third electrochemical cell1100ais electrically coupled to a second terminal of the power source via wiring119, in accordance with certain embodiments. It has been determined in the context of this disclosure that certain configurations of gas separation systems comprising a plurality of electrochemical cells electrically connected in series may promote relatively efficient charge transport/and/or gas transport. For example, in some embodiments, electrically conductive materials between electrochemical cells may establish electrically conductive pathways rather than using external wiring. For example, a gas separation system may comprise a first electrochemical cell and a second electrochemical cell electrically connected in series, where the electrical connection is established via one or more electrically conductive materials between the first electrochemical cell and the second electrochemical cell. Any of a variety of suitable electrically conductive materials may be positioned between electrochemical cells to establish electrical connection between, for example, a negative electrode of the first electrochemical cell and a positive electrode of the second electrochemical cell. For example, an electrically conductive material may be an electrically conductive solid. The electrically conductive solid may comprise, for example, a metal and/or metal alloy (e.g., steel, silver metal/alloy, copper metal/alloy, aluminum metal/alloy, titanium metal/alloy, nickel metal/alloy). In some embodiments, the electrically conductive solid comprises a carbonaceous material (e.g., graphite, single-walled carbon nanotubes, multi-walled-carbon nanotubes, carbon black, a carbon mat (e.g., carbon nanotube mat), KetjenBlack, carbon black Super P, graphene, and the like. In some embodiments, the carbonaceous material is a porous carbonaceous material as described elsewhere herein. In some embodiments, the electrically conductive solid comprises a composite of an electrically conductive solid with a binder resin. In some embodiments, an electrically conductive solid between electrochemical cells comprises an electrically conductive polymeric material. In some, but not necessarily all embodiments, an electrically conductive material between electrochemical cells comprises a bipolar plate. It should be understood that in the context of this disclosure a plate need not necessarily be flat. Bipolar plates are known to those of skill in the art and are typically used in fields other than gas separation, such as in fuel cells. A bipolar plate may be configured to separate fluid (e.g., gas) contacting the positive electrode from the fluid contacting the negative electrode. Bipolar plates may comprise electrically conductive solids such as steel, titanium, or graphite. In some embodiments, at least some of the plurality of electrochemical cells (e.g., connected in series) are separated by a flow field. As mentioned above, positioning a flow field between neighboring electrochemical cells may promote beneficial gas distribution and relatively efficient interaction between gases and the electrodes (e.g., for binding). In some embodiments, a bipolar plate as described above comprises a flow field (e.g., via etching of fluidic pathways in one or both faces of the plate), though in other embodiments a different flow field is employed as an alternative or in addition to the flow-field-containing bipolar plate. FIG.9shows a schematic diagram of exemplary gas separation system1000comprising electrochemical cells1100electrically connected in series via one or more electrically conductive materials between cells, according to certain embodiments. InFIG.9, system1000comprises electrically conductive solid materials in the form of bipolar plates1012and ribs1014. Ribs in a gas separation system may be made of any of the electrically conductive solid materials described above. In the embodiment shown inFIG.9, first electrochemical cell1100ais separated from second electrochemical cell1100bvia bipolar plate1012and rib1014. Bipolar plate1012and rib1014may be directly adjacent to negative electrode1010of first electrochemical cell1100aand positive electrode1030of second electrochemical cell1100b, thereby establishing an electrically conductive pathway for the series connection. Other electrochemical cells in the system may be electrically connected similarly. WhileFIG.9shows bipolar plates and ribs, such a depiction is non-limiting, and other configurations (e.g., without bipolar plates, without ribs, etc.) are possible.FIG.9also shows optional flow fields1011separating electrochemical cells1100, in accordance with certain embodiments. In some embodiments, one or more components (e.g., electrically conductive solids such as ribs) may establish channels between negative electrodes and positive electrodes of neighboring electrochemical cells. For example, ribs1014inFIG.9may have dimensions such that channels1013establish pathways for gas (e.g., gas mixtures) to flow between electrochemical cells1011and interact with the electrodes. For example, gas mixture1075may be passed through channel1013, through flow field1011, and between first electrochemical cell1100aand second electrochemical cell1100b, according to certain embodiments. The flow of electrical current in certain embodiments described above may encounter less electrical resistance compared to other configurations. For example, in some embodiments in which electrochemical cells are connected in series via electrically conductive materials between at least some of a stack of electrochemical cells, electrical current can flow in a direction perpendicular to the stack.FIG.9shows one such example, where electrical current can flow in direction x perpendicular to electrochemical cells1100, while gas mixture1075can flow in a direction parallel to electrochemical cells1100. InFIG.9, the path through which the current travels is relatively short and is determined by the thickness of bipolar plate1012and rib1014. In some embodiments, a thickness of the one or more electrically conductive solids between electrochemical cells is less than or equal to 10 mm, less than or equal to 5 mm, less than or equal to 2 mm, less than or equal to 1 mm, and/or as low as 0.5 mm, as low as 0.2 mm, as low as 0.1 mm, or lower. In contrast, in embodiments in which electrochemical cells are electrically connected in parallel or electrically connected in series via external wiring, electrical current must flow through up to an entire height and/or length of electrodes (e.g., current collectors of electrodes) and through electrode tabs to reach the external wiring. Such heights and/or lengths may be, for example, at least 1 cm, at least 2 cm, at least 5 cm, at least 10 cm, and/or up to 20 cm, up to 50 cm, up to 100 cm, or more. The greater distances for current travel in such embodiments generally results in greater total cell resistance, which may reduce charge transport and/or energy efficiency for methods of at least partial gas separation described herein. In some embodiments, the negative electrode or portion thereof (e.g., an electroactive composite layer of the negative electrode when present) is be able to absorb a gas (e.g., SO2, CO2) at a particular rate. For example, in some embodiments, the negative electrode or portion thereof (e.g., an electroactive composite layer of the negative electrode when present) has an absorption capacity rate of at least 0.0001 mol per m2per second, at least 0.0002 mol per m2per second, at least 0.0005 mol per m2per second, or more. In some embodiments, the negative electrode or portion thereof (e.g., an electroactive composite layer of the negative electrode when present) has an absorption capacity rate of less than or equal to 0.001 mol per m2per second, less than or equal to 0.0008 mol per m2per second, less than or equal to 0.0005 mol per m2per second, or less. In some embodiments, the electroactive composite layer has an absorption capacity rate of at least 0.0001 and less than or equal to 0.0005 mol per m2per second. Other absorption capacities rates are also possible. In some embodiments, an electroactive composite layer of a negative electrode may have a particular surface area able to be exposed to a fluid mixture (e.g., gas mixture), for example, of greater than or equal to 5 cm2, greater than or equal to 8 cm2, greater than or equal to 10 cm2, and/or up to 10 cm2, up to 20 cm2, up to 50 cm2, up to 1 m2, or more. Other values are also possible. In some embodiments, at least a portion or all of an electrode (e.g., negative electrode, positive electrode) described herein is comprises a porous material. A porous electrode may be made of any suitable material and/or may comprise any suitable shape or size. In a non-limiting embodiment, the electrode comprises a porous carbonaceous material. The term carbonaceous material is given its ordinary meaning in the art and refers to a material comprising carbon or graphite that is electrically conductive. Non-limiting example of carbonaceous materials include carbon nanotubes, carbon fibers (e.g., carbon nanofibers), carbon mat (e.g., carbon nanotube mat), and/or graphite. In some such embodiments, the electrode may be partially fabricated from the carbonaceous material or the carbonaceous material may be deposited over an underlying material. The underlying material generally comprises a conductive material, for example, a metal and/or metal alloy solid (e.g., steel, copper, aluminum, etc.). Other non-limiting examples of conductive materials are described herein. In some embodiments, an electrode (e.g., the negative electrode, the positive electrode) is porous. The porosity of an electrode may be measured as a percentage or fraction of the void spaces in the electrode. The percent porosity of an electrode may be measured using techniques known to those of ordinary skill in the art, for example, using volume/density methods, water saturation methods, water evaporation methods, mercury intrusion porosimetry methods, and nitrogen gas adsorption methods. In some embodiments, the electrode is at least 10% porous, at least 20% porous, at least 30% porous, at least 40% porous, at least 50% porous, at least 60% porous, at least 70% porous or greater. In some embodiments, the electrode is up to 90% porous, up to 85% porous, up to 80% porous, up to 70% porous, up to 50% porous, up to 30% porous, up to 20% porous, up to 10% porous or less. Combinations of these ranges are possible. For example, the electrode may be at least 10% porous and up to 90% porous. The pores may be open pores (e.g., have at least one part of the pore open to an outer surface of the electrode and/or another pore). In some cases, only a portion of the electrode is porous. For example, in some cases, only a single surface of the electrode is porous. As another example, in some cases, the outer surface of the electrode is porous and the inner core of the electrode is substantially non-porous (e.g., less than or equal to 20%, less than or equal to 10% porous, less than or equal to 5% porous, less than or equal to 1% or less). In a particular embodiment, the entire electrode is substantially porous. In some embodiments, the electrochemical cell has a particular cycle time. The cycle time of an electrochemical cell generally refers to the period of time in performance of one charge mode and one discharge mode. The cycle time may be at least 60 seconds, at least 100 seconds, at least 300 seconds, at least 500 seconds, at least 1000 seconds, or more. In some embodiments, the cycle time is less than or equal to 3600 seconds, less than or equal to 2400 seconds, less than or equal to 1800 seconds, or less. Combinations of these ranges are possible. For example, in some embodiments, the cycle time is at least 60 seconds and less than or equal to 3600 seconds, or at least 300 seconds and less than or equal to 1800 seconds. According to some embodiments, the electrochemical cell and its components have a particular thickness, depending on the desired application (e.g., gas separation of ventilator air, direct air capture, etc.). In some embodiments, the electrochemical cell has a thickness of at least 10 μm, at least 20 μm, at least 50 μm, at least 100 μm, at least 200 μm, at least 300 μm, at least 500 μm, or greater. In some embodiments, the electrochemical cell has a thickness of less than or equal to 750 μm, less than or equal to 600 μm, less than or equal to 500 μm, less than or equal to 300 μm, or less. Combinations of these ranges are possible. For example, in some embodiments, the electrochemical cell has a thickness of at least 200 μm and less than or equal to 750 μm. In some embodiments, the electrochemical cell has a thickness of at least 10 μm and less than or equal to 750 μm. In some embodiments, the negative electrode or the positive electrode has a thickness of at least 0.5 μm, at least 1 μm, at least 2 μm, at least 5 μm, at least 10 μm, at least 20 μm, at least 50 μm, at least 75 μm, at least 100 μm or more. In some embodiments, the negative electrode or the positive electrode has a thickness of less than or equal to 200 μm, less than or equal to 150 μm, less than or equal to 100 μm, or less. Combinations of these ranges are possible. For example, in some embodiments, the negative electrode or the positive electrode has a thickness of at least 50 μm and less than or equal to 200 μm. In some embodiments, in some embodiments, the negative electrode or the positive electrode has a thickness of at least 0.5 μm and less than or equal to 200 μm. In some embodiments, the electroactive composite layer of the negative electrode or the positive electrode has a thickness of at least 10 nm, at least 20 nm, at least 40 nm, at least 0.1 μm, at least 0.2 μm, at least 0.5 μm, at least 1 μm, at least 2 μm, at least 5 μm, at least 10 μm, at least 50 μm, at least 100 μm or more. In some embodiments, the electroactive composite layer of the negative electrode or the positive electrode has a thickness of less than or equal to 200 μm, less than or equal to 150 μm, less than or equal to 100 μm, less than or equal to 50 μm, less than or equal to 20 μm, less than or equal to 10 μm, less than or equal to 5 μm, less than or equal to 2 μm, less than or equal to 1 μm, less than or equal to 0.5 μm, less than or equal to 0.2 μm, less than or equal to 0.1 μm, or less. Combinations of these ranges are possible. For example, in some embodiments, the electroactive composite layer of the negative electrode or a positive electrode has a thickness of greater than or equal to 10 μm and less than or equal to 200 μm. In some embodiments, the electroactive composite layer of the negative electrode or a positive electrode has a thickness of greater than or equal to 10 nm and less than or equal to 100 nm, or greater than or equal to 50 nm and less than or equal to 500 nm. Various components of a system, such as the electrodes (e.g., negative electrode, positive electrodes), power source, electrolyte, separator, container, circuitry, insulating material, etc. can be fabricated by those of ordinary skill in the art from any of a variety of components. Components may be molded, machined, extruded, pressed, isopressed, infiltrated, coated, in green or fired states, or formed by any other suitable technique. Those of ordinary skill in the art are readily aware of techniques for forming components of system herein. The electrodes described herein (e.g., negative electrode, positive electrodes) may be of any suitable size or shape. Non-limiting examples of shapes include sheets, cubes, cylinders, hollow tubes, spheres, and the like. The electrodes may be of any suitable size, depending on the application for which they are used (e.g., separating gases from ventilated air, direct air capture, etc.). Additionally, the electrode may comprise a means to connect the electrode to another electrode, a power source, and/or another electrical device. Various electrical components of system may be in electrical communication with at least one other electrical component by a means for connecting. A means for connecting may be any material that allows the flow of electricity to occur between a first component and a second component. A non-limiting example of a means for connecting two electrical components is a wire comprising a conductive material (e.g., copper, silver, etc.). In some cases, the system may also comprise electrical connectors between two or more components (e.g., a wire and an electrode). In some cases, a wire, electrical connector, or other means for connecting may be selected such that the resistance of the material is low. In some cases, the resistances may be substantially less than the resistance of the electrodes, electrolyte, and/or other components of the system. In some embodiments, the methods and electrochemical apparatuses described herein can be performed and configured as one or more of the systems described in U.S. Patent Publication No. 2017/0113182, published on Apr. 27, 2017, filed as application Ser. No. 15/335,258 on Oct. 26, 2016, and entitled “Electrochemical Process for Gas Separation,” which is incorporated herein by reference in its entirety for all purposes. U.S. Provisional Application No. 62/892,975, filed Aug. 28, 2019, and entitled “Electrochemically Mediated Acid Gas Removal and Concentration,” and U.S. Provisional Application No. 62/988,851, filed Mar. 12, 2020, and entitled “Electrochemical Capture of Lewis Acid Gases,” are each incorporated herein by reference in its entirety for all purposes. The following examples are intended to illustrate certain embodiments of the present invention, but do not exemplify the full scope of the invention. Example 1 This Example describes the reactivity of various electroactive species with Lewis acid gases as studied by cyclic voltammetry. FIG.10Ashows cyclic voltammetry of 1,4-naphthoquinone (p-NQ) in a dry N,N-dimethylformamide solution containing 0.1 M tetra-n-butylammonium hexafluorophosphate ([nBu4][PF6]) saturated with either N2, CO2, or SO2. The cyclic voltammograms were acquired at a 100 mV/s scan rate. The cyclic voltammetry inFIG.10Ashowed expected behavior under N2and CO2, where the second (more negative) reduction wave shifted positively under CO2with respect to under N2, while the first reduction wave did not shift. However, in the presence of SO2, the first (less negative) reduction wave, along with the second reduction wave, shifted positively. This was indicative of a strong association of the semiquinone with the strong Lewis acid SO2, which caused a major shift in the Nernst potential. The dissociative oxidation peak of the complex of the reduced 1,4-napthquinone and the SO2appeared at a more positive potential than that of the CO2complex, which further confirmed the strong association of SO2with the semiquinone, as well as the quinone dianion. The differences in the cyclic voltammograms indicated different strengths of association between the reduced 1,4-naphthoquinone and SO2and CO2. These cyclic voltammetry results demonstrated that certain electroactive species such as 1,4-naphthoquinone react strongly with both SO2and CO2, such that exposure to a mixture of both Lewis acid gases would result in binding with limited to no selectivity. Such a lack of selectivity could be problematic in certain applications such as electrochemical flow systems for carbon dioxide capture where gas mixtures comprise both CO2and SO2, as SO2capture would diminish CO2capture efficiency. The difference in the strengths of association of 1,4-naphthoquinone with CO2and SO2implied that in a flow system for carbon capture from industrial exhaust, where oxides of sulfur are present at concentrations of 1,000-10,000 ppm, the “poisoning” of the quinone is quite possible. It is believed that this would mainly be due to the difference in the oxidation potential, where an electrochemical cell operating at a potential difference of around the difference between the reduction of quinone and the oxidation of its complex with CO2would not provide sufficient energy to dissociate the quinone-SO2complex. This leads to the accumulation of the complex and the subsequent decrease of the system capacity for CO2. It was realized that this lack of selectivity could be overcome by introducing an electrochemical desulfurization step which removes the oxides of sulfur from the gas mixture (e.g., flue gas) prior to the electrochemical carbon capture step. Such an electrochemical desulfurization step would involve determining electroactive species and/or conditions for selectively capturing sulfur dioxide (or other Lewis acid gases) while allowing carbon dioxide capture to be negligible. Toward that end, it was further realized that a similar flow system could be designed with an electroactive species (e.g., quinone) that has lower electron density on the oxygens upon reduction to yield a comparatively weaker base than 1,4-naphthoquinone. This was accomplished by 2,3-dicyano-1,4-naphthoquinone (DCNQ).FIG.10Bshows cyclic voltammetry of DCNQ in a dry N,N-dimethylformamide solution containing 0.1 M [nBu4][PF6] saturated with either N2, CO2, or SO2. The cyclic voltammograms were acquired at a 100 mV/s scan rate. The cyclic voltammetry inFIG.10Bshowed the behavior under CO2as being not dissimilar from that under N2, where only the dianion (formed upon the second reduction) reacted weakly with CO2. This weak interaction was demonstrated by the slight positive shift of the second reduction wave, and the emergence of a very small oxidative dissociation peak. Nevertheless, the interaction of DCNQ was very strong with SO2, a conclusion supported by the positive shift of the two reduction waves and the emergence of a very positively-shifted dissociative oxidation peak inFIG.10B. These results demonstrated that certain electroactive species (e.g., with certain substituents) have reduced states in which they are capable of reacting with a first Lewis acid gas (e.g., SO2) but for which a reaction with a second Lewis acid gas (e.g., CO2) is not thermodynamically favorable. Example 2 This Example describes the reactions of various electroactive species with Lewis acids in ionic liquids (IL). The reactions of DCNQ and p-NQ with SO2were studied by thermogravimetric analysis (TGA). DCNQ was reduced using two equivalents of cobaltocene to yield a 0.3 M solution of DCNQ2−dianion in [bmim][TF2N]. This was used, along with the p-NQ2−dianion and the NQ⋅−semiquinone ionic liquid (IL) solutions in the TGA with a flow of 30 mL min−1of 1% SO2with the balance being N2.FIG.11Ashows TGA analyses of DCNQ2−, NQ⋅−and NQ2−under 1% SO2.FIG.11Bshows TGA analyses of DCNQ2−, NQ⋅−and NQ2−in N2. It could be seen fromFIG.11AandFIG.11Bthat both NQ2−and DCNQ2−effectively and stoichiometrically reacted with SO2to form a stable diadduct which did not release under pure N2flow. The capacity of NQ⋅−for SO2was smaller than NQ2−as expected, but did not release it at the same rate it releases CO2under pure N2since the pKaof NQ⋅−is similar to that of DCNQ2−which is sufficiently high to react with a strong Lewis acid like SO2with a low pKa. This resulted in a stronger bond formation upon the sulfonation of the stronger Lewis base NQ2−which maintained a constant capacity for SO2at high temperatures (up to 150° C.) and did not release SO2under pure N2flow, as seen inFIGS.11C and11D.FIG.11Cshows TGA measurements of SO2uptake by NQ2−at different temperatures.FIG.11Dshows TGA measurements of SO2uptake release by NQ2−at different temperatures. Nevertheless, the lower basicity of DCNQ2−resulted in weaker sulfonation and subsequently a smaller capacity for SO2at higher temperatures.FIG.11Eshows TGA measurements of SO2uptake by DCNQ2−at different temperatures.FIG.11Fshows TGA measurements of SO2release by DCNQ2−at different temperatures. It is believed that the relative pKas of DCNQ2−and NQ2−explain, at least in part, their reaction extent with CO2and SO2, and are also the result of the electron density modulation on the nucleophilic oxygen (phenoxide) moieties, which are generated upon the first and second reduction of quinones. Thus, electroactive species such as quinones with finely tuned electron density can be used to selectively react with different electrophiles with varying Lewis base strengths in customized electrochemical systems where continuous separation can be performed. In addition to electron density modulation on the quinone molecule, which directly affects the thermodynamics of the electrochemical reactions, it has been realized in the context of the present disclosure that it is possible to impart further selectivity to the nucleophile generated via steric hindrance or affinity. This could be done by attaching various groups around the nucleophilic centers to accommodate the reductive addition of one target more favorably than others. FIG.12Ashows TGA measurements of capture of CO2with reduced DCNQ under 100% CO2at 30° C.FIG.12Bshows TGA measurements showing that CO2is released when the reactant is removed. Thus, reduced DCNQ reacts with CO2reversibly, but with SO2irreversibly. Example 3 This Example describes a computational analysis of DCNQ to gain insight into their electronic structure and thermodynamic properties as they related to their reactivity with Lewis Acid gases. Calculations on the neutral, singly-reduced (semiquinone) and doubly-reduced (dianion) states of DCNQ were made using density functional theory methods. All electronic structure calculations were performed with Q-Chem® version 5.1.1. Equilibrium structures were determined at the B3LYP-D3(op)/6-31++G** level of theory, with spin-unrestricted wave functions, and Grimme dispersion corrections with the optimized power approach corrections of Witte J, Mardirossian N, Neaton J B, Head-Gordon M. Assessing DFT-D3 Damping Functions Across Widely Used Density Functionals: Can We Do Better? Journal of Chemical Theory and Computation. 2017; 13(5):2043-2052, which is incorporated by reference herein in its entirety for all purposes. 1,4-naphothoquinone (Q) was treated as a neutral singlet, its semiquinone anion (Q−) and CO2-adduct anion were treated as −1 doublet (QCO2−), and the dianion Q2−, single adduct Q(CO2)2−and di-adduct Q(CO2)22−were also taken as singlets. Geometry optimizations in gas phase and solvated environments (within the SMD solvent SCRF) were performed on structures built using the Avogadro® computer program after optimization with the MMFF94 force-field. A systematic rotor search was performed to identify low lying conformers of QCO2−, QCO22−and Q(CO2)22−. Ground state binding energies were calculated by subtracting the total electronic energy of the optimized isolated species from the optimized complex, including zero point energy (ZPE) and thermal and solvation contributions. Basis set superposition error (BSSE) was accounted for by the counterpoise scheme. Frequency analysis was used to confirm ground state structures were a minimum on the potential energy surface. Natural bond orbital (NBO) partial charges and orbital characteristics were obtained with the NBO v6.0 package interfaced with Q-Chem® and second generation ALMO-EDA was performed within Q-Chem®. Reduction potentials were determined by the procedure suggested by Isse A A, Gennaro A. Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents. Journal of Physical Chemistry B. 2010; 114(23):7894-7899, which is incorporated by reference herein in its entirety for all purposes. For the reduction potential calculations, structures were optimized in the solvent SCRF (with parameters for N,N-dimethylformamide), the electron free energy was determined by Fermi-Dirac statistics with 4.28 V taken as the absolute value for the Standard Hydrogen Electrode, and junction potentials were adjusted for with data from Diggle J W, Parker A J. Liquid junction potentials in electrochemical cells involving a dissimilar solvent junction. 1974 p. 1617-1621, which is incorporated by reference herein in its entirety for all purposes. FIGS.13A-13Cshow the computed geometry changes of DCNQ upon reduction. Standard reduction potentials for the reductions of DCNQ were calculated at standard states, as follows: Δ⁢Greducti⁢o⁢n*=Gred-(Go⁢x+Ge-)⁢E0(absolute)=-Δ⁢Greducti⁢o⁢n*F⁢E0(vs⁢Ag+)=E0(absolute)+E⁡(SHE⁢vs⁢absolute)+E⁡(SCE⁢vs⁢SHE)+E(DMF/H2⁢O⁢junction)+E⁡(Ag+⁢vs⁢SCE) where SHE is the standard hydrogen electrode reference and SCE is the standard calomel reference. The calculated standard reduction potentials for DCNQ were calculated to be −0.02 and −1.52 vs. Ag+, respectively. With the same method, the reduction potentials for 1,4-napthoquinone were −1.27 V and −2.48 V vs Ag+for the first and second reductions, respectively. Electrostatic potential (ESP) maps for the different states of reduction of DCNQ and 1,4-naphthoquinone were also calculated.FIG.14Ashows ESP maps of 2,3-dicyano-1,4-naphthoquinone (top) and 1,4-naphthoquinone (bottom) in their respective neutral states.FIG.14Bshows ESP maps of 2,3-dicyano-1,4-naphthoquinone (top) and 1,4-naphthoquinone (bottom) in their respective semiquinone states.FIG.14Cshows ESP maps of 2,3-dicyano-1,4-naphthoquinone (top) and 1,4-naphthoquinone (bottom) in their respective dianion states. In the ESP maps, darker shading indicates higher charge density (more electron-rich or electron poor) and lighter shading indicates lower charge density (less electron-rich or electron poor). As can be seen inFIGS.14A-14C, the charge distributions are relatively similar between DCNQ and 1,4-naphthoquinone in the neutral (FIG.14A) and dianion (FIG.14C) states. However,FIG.14Bshows that the oxygen moieties of 1,4-naphthoquinone in its semiquinone state have a significantly higher electron density than do the oxygen moieties of DCNQ in its semiquinone state. It is believed that the electron-withdrawing effect of the nitrile substituents pull electron density from the oxygens of DCNQ. It is further believed that this shift in electron density in DCNQ renders it less thermodynamically and/or kinetically reactive toward Lewis acids (e.g., shifting the pKa) and therefore more selective for certain Lewis acids (e.g., depending on their pKa). All maps are on the same scale (imaged on van der Waals spheres). FIGS.15A-15Dshows calculated geometries and ESP maps of CO2and SO2, respectively. Example 4 This Example describes selective removal of an amount of a first Lewis acid gas from a fluid mixture comprising the first Lewis acid gas and a second, different Lewis acid gas via a reduced state of an electroactive species. In particular, a gas mixture comprising SO2and CO2was exposed to a reduced form of DCNQ, resulting in removal of the SO2from the fluid mixture to a greater extent than the CO2. The gas separation experiment employed a packed-bed bubble column apparatus comprising a borosilicate glass tube (12″ length, 0.23″ inner diameter) filled with 8.6 g of 1 mm glass beads. The bubble column apparatus was oven dried and sealed with two septa on each end. An inlet needle was inserted into the bottom of the column, and an outlet needle was inserted into the top of the column. The column was flushed with dry nitrogen gas for 10 minutes to establish an inert atmosphere inside the column. All gas streams were applied to the inlet of the column at precise flow rates using Cole-Parmer mass flow controllers. An outlet stream of the bubble column apparatus was monitored for CO2and SO2gas concentrations.FIG.16shows a schematic diagram of the gas separation experiment. The doubly reduced DCNQ species 2,3-dicyanonaphthoquinone dianion (DCNQ2−) was prepared by treating a solution of 2,3-dicyanonaphthoquinone (DCNQ) in tetrahydrofuran (THF) with sodium (Na) metal, removing residual metal via filtration, and removing the THF via evaporation. A reaction scheme for the preparation of DCNQ2−is shown below. Prior to the gas capture experiment, the column apparatus was filled with 2.4 mL solution of 12 mM 2,3-dicyanonaphthoquinone dianion (DCNQ2−) in propylene carbonate. The filling procedure was conducted under flowing nitrogen gas to maintain an inert atmosphere in the column. After filling the column with the DCNQ2−/propylene carbonate solution, a stream of dry nitrogen gas was introduced to the column inlet at a flow rate of 1 mL/minute to allow the system to equilibrate. The mass flow controller for the inlet gas was then connected to a SO2/CO2/N2gas stream (1 mole percent (mol %) SO2, 10 mol % CO2, 89 mol % N2) at 1 mL/min, and data logging was immediately started. To control for solvent physisorption of the Lewis acid gases, an identical procedure was conducted with 2.4 mL of solvent (propylene carbonate) with no DCNQ2−present. The concentration of CO2and SO2were measured versus the total volume of inlet gas introduced to the system, for the physisoprtion and DCNQ2−chemisorption experiments. It was observed that, due to the low solubility of CO2in propylene carbonate, its breakthrough in the physisoprtion experiment (i.e., in the absence of DCNQ2−) occurred at a much earlier point than that of SO2, which has a higher solubility in propylene carbonate. In the chemisorption experiment (i.e., in the presence of DCNQ2−), it was observed that CO2breakthrough occurred at a later point than in the physisorption control experiment. Integration of the concentration data showed about 70% stoichiometric capture of CO2by DCNQ2−during the chemisorption experiment. This is believed to be due to a reversible reaction of DCNQ2−with CO2to form the adduct DCNQ2−(CO2)2, as shown below. However, CO2complexed with DCNQ2−was replaced by SO2in an irreversible reaction that formed the adduct DCNQ2−(SO2)2. This DCNQ2−(SO2)2adduct formation was evident in the delayed breakthrough of SO2in the chemisorption experiment when compared to the physisorption breakthrough. The difference in reactivity was qualitatively observed. After CO2breakthrough but prior to SO2breakthrough, the entire solution in the column was observed to have a pink color (indicative of the presence of DCNQ2−and DCNQ2−(CO2)2adduct) except for a small region near the inlet of the column that was observed to have a yellow color (indicative of the presence of DCNQ2−(SO2)2). At a later point in time, after SO2breakthrough, an entirety of the column solution was observed to have the yellow color, indicating the absence of CO2in the column and presence of only DCNQ2−(SO2)2throughout the column.FIG.17Ashows a plot of a ratio of outlet gas concentration to inlet gas concentration vs. time for the physisorption and chemisorption experiments. InFIG.17A, curve A corresponds to CO2concentration in the physisorption (propylene carbonate only) experiment, curve B corresponds to CO2concentration in the chemisorption (DCNQ2−in propylene carbonate) experiment, curve C corresponds to SO2concentration in the physisorption (propylene carbonate only) experiment, and curve D corresponds to SO2concentration in the chemisorption (DCNQ2−in propylene carbonate) experiment. The results inFIG.17Ashow significantly earlier breakthrough for CO2than for SO2, and also shows a significantly delay in SO2breakthrough in the chemisorption experiment than in the physisorption experiment.FIG.17Bshows a zoomed-in view of curves A and B fromFIG.17A. The delay in SO2breakthrough accounts for a stoichiometric reaction where all the starting DCNQ2−reacted with SO2. Reaction schemes for the binding of SO2to DCNQ2−and the substitution of CO2by SO2in a DCNQ2−(CO2)2adduct are shown below. The results of the gas separation experiment demonstrated selective capture of SO2from a gas stream of 1% SO2, 10% CO2and 89% N2. The chemisorption capture of SO2by DCNQ2−is believed to be only reversible via an oxidation reaction to afford release of the SO2. Such an oxidation can occur electrochemically or by the use of an oxidative chemical reagent. While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the functions and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, and/or methods, if such features, systems, articles, materials, and/or methods are not mutually inconsistent, is included within the scope of the present invention. The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.” The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified unless clearly indicated to the contrary. Thus, as a non-limiting example, a reference to “A and/or B,” when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc. As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law. As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc. In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.
158,080
11857920
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS The following description is presented to enable a person of ordinary skill in the art to make and use embodiments described herein. Descriptions of specific devices, techniques, and applications are provided only as examples. Various modifications to the examples described herein will be readily apparent to those of ordinary skill in the art, and the general principles defined herein may be applied to other examples and applications without departing from the spirit and scope of the disclosure. Thus, the disclosure is not intended to be limited to the examples described herein and shown but is to be accorded the scope consistent with the claims. The word “exemplary” is used herein to mean “serving as an example illustration.” Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Reference will now be made in detail to aspects of the subject technology, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. The specific order or hierarchy of steps in the process disclosed herein is an example of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the processes can be rearranged while remaining within the scope of the disclosure. Any accompanying method claims present elements of the various steps in a sample order and are not meant to be limited to the specific order or hierarchy presented. The disclosed technology presented herein is relevant to the objectives and tasks of the above groups that are focused on enhanced environmental stewardship. The technology provides a new resource for terrestrial and sea applications for CO2capture and repurposing NOxabatement and SO2destruction. For example, the byproduct of the CO2capture processes described herein is sodium bicarbonate (NaHCO3), which is the compound the oceans use to maintain the chemical equilibrium necessary for life. If this product is shared with the sea, it will reverse the acidification that CO2is causing when it unavoidably transfers from the atmosphere into oceans and other bodies of water. The disclosed technology can be applied to marine and terrestrial exhaust gas sources for CO2, NOx and SO2or directly treat these compounds in the atmosphere. This integrated technology provides a combination of compatible and very green processes that capture and/or convert these gases into compounds that enhance the environment, many with commercial value. The disclosed combination of chemical processes using NaOH and NaOCl as consumable reactants has been verified through bench scale testing, to remove 99% CO2, 90% NOxand 99% SO2from combustion and chemical process exhaust gas. The ClO2obased NOx removal technology has a 99.5% removal efficiency. The results are based on testing of gas streams including but are not limited to diesel exhaust, heavy fuel oil combustion exhaust and exhaust from chemical digestion processes. The disclosed technology applies to terrestrial and ocean vessel applications. It also requires a small physical “footprint” and is carbon neutral when treating exhaust generated from the production of electricity the processes use. The technology is also carbon neutral when it uses electricity generated from solar or wind sources. All of the target gases are removed in a continuous mist, dry/wet aerosol, gas phase or liquid phase reaction(s) within vessels that can be not much larger in diameter than conventional duct for a given exhaust gas flow. The combined CO2, NOx and SO2abatement processes are collaborative. Chemical use is minimized because reaction products from one process are often reagents in another. For example, in the reaction sequence shown inFIG.1, the HOCl formed in the first capture of CO2is used to generate NaOCl in the two subsequent capture process of NOR. The primary consumable for all of these processes is sodium chloride (NaCl) or potassium chloride (KCl). The energy required to convert NaCl or KCl into other consumables used in the processes is included in the mass balance and energy study shown below. Most of the chemicals used in the CO2, NOx and SO2capturing and repurposing processes can be recycled. The entire reagent recycling only requires 70° C. that can be supplied from combustion waste heat or chilling to below 25° C. that can be supplied by seawater or other liquid of equal or lesser temperature. The electrical power required for equipment operation is also included in the provided energy study and mass balance. This process can treat the CO2, NOx and SO2made from generating the electricity required for this process if the generation source is local, for example a ship or power plant application. The process control system logic program used to collaboratively manage processes described herein has the ability to individually adjust the reaction rates of all of the processes independently as required to compensate for variations in the CO2, NOx and SO2compound ratio and overall concentrations of the compounds in exhaust gas in real time. This is done by sensing the concentration of CO2, NOx and/or SO2and then dosing only the requisite amount of reagent necessary to treat the desired amount of CO2, NOx or SO2. The disclosed methods provide for technologies that effectively sequester point source and atmospheric gases including CO2, NOxand SO2. The technology can be applied at the point source for these gases, for example, from the exhaust stack of a combustion source, or a chemical reaction that generates these gases. These gases may also be present in the liquid phase, such as when they are dissolved into an aqueous solution. This technology is also applicable for gases that have been released into the atmosphere or are present in water. This technology is also environmentally responsible because it generates non-hazardous reaction by products such as sodium bicarbonate (NaHCO3), which is also known as baking soda and has commercial value. The disclosure provides seven synergistically related chemical processes for the removal of CO2, NOx and SO2(target gases). The disclosure also describes the supporting reactions and reveals the useful aspects of the integrated chemical process methodology. The seven chemical processes and their supporting reactions share multifaceted chemical synergy that results in reduced reaction chamber volume, decreased residence time, compounds recycled with low energy and efficient production of commercially viable products. For example, the five chemical reactions described inFIG.1can occur in a single reaction chamber. The rate of reactions for all five reactions can be individually regulated by varying the concentrations and pH of solutions that contain only three chemicals. The products of some reactions are also the reactants for subsequent reactions. The process control techniques can use data from strategically placed sensors with data that is confirmed accurate through comparisons between sensors with known chemical axioms, the Process Logic Control (PLC) program employs sophisticated “if then” logic and algorithms that adroitly regulate the reaction rates of all reactions in a way that: Adjusts for changes in the ratios of the three target compounds. Adjusts for changes in concentrations of the target compounds. Determines as needed chemical dosing necessary to individually obtain a predetermined CO2and NOx and SO2removal efficiency. This approach eliminates excess chemical use. Balances the molar ratios of the two primary reactants: NaOH and Cl2/NaOCl for all seven reactions. The multi-variable if then logic of the PLC can accomplish these tasks because the seven principal reactions to treat the target compounds were deliberately chosen with CO2and —NOxreactions that use NaOH/NaOCl as their primary rate determining reagent. This ability to treat CO2or NOx or SO2with either group of compounds allows the PLC program to adjust the reaction rates of the seven equations as required to balance the chemical demand for NaOH and NaOCl. The entire group of seven processes can also act as a “polishing scrubber” that follows a less efficient CO2, NOx, SO2or other scrubber for another compound(s) where desired. The emphasis on balanced reagent usage is important because it allows a single electrochemical (E-Chem) process to generate the two major reagents for all seven processes described in this document through the conversion of NaCl into NaOH and Cl2. The Cl2is immediately converted to NaOCl and HOCl using a conventional subordinate reaction that requires a portion of the NaOH generated by the E-Chem process. This step of selecting7equations that have chemically symbiotic stoichiometry and easily managed reaction mechanics is commercially valuable because it eliminates or reduces the need for reagent storage containers. This feature is of significance when the integrated process is used aboard a vessel that chooses to generate its reactants from seawater using an electrochemical process rather than utilize ship cargo space for chemical reagents. The electrochemical process can also be used with sodium chloride brine aboard a vessel or in terrestrial applications. There is a very important justification for returning the NaHCO3to the sea, it compensates for CO2adsorbed by the sea from the atmosphere. The sea utilizes NaHCO3as its primary buffering compound to hold the ocean pH stable at approximately 8.1. The CO2enters the sea from the atmosphere as part of a natural effort to equalize the concentrations of CO2within the gas phase atmosphere and liquid phase ocean water. At this time, the world's oceans are using more NaHCO3to compensate for the adsorbed CO2than they can make through dissolving of CaCO3from shells and other materials within the sea. If this process is not balanced in some way, the oceans will lose their ability to maintain their pH. The resulting rapid change in pH will kill the algae that produce approximately 70% of the world's oxygen introduced into the atmosphere. If that happens, humans and everything else that relies on oxygen in the atmosphere will die! That would cause the world's 6thextinction process. Unfortunately, there is already so much CO2in the atmosphere from natural and anthropomorphic sources that even if we immediately stopped introducing more CO2into the atmosphere from combustion and other sources, the worlds' oceans will run out of available NaHCO3before the equilibrium between CO2in the atmosphere and oceans is reached. Therefore, intervention is required to prevent an ocean pH catastrophe. Fortunately, the CO2capture processes disclosed herein creates one mole of NaHCO3byproduct for every mole of CO2that it sequesters from any source. The processes disclosed herein are part of the solution to prevent the oceans from losing their ability to maintain the life-saving pH equilibrium. Thus, in one embodiment, the disclosure provides technology that combines processes for the removal of CO2, NOx and SO2from an exhaust gas or liquid stream using three or more sequential reaction stages within a single reactor or combination of three or more separate reaction stages. The gas/mist or gas/(wet or dry aerosol) or liquid/liquid phase reaction technology allows individual and collective scrubbing stages to treat any gas/liquid volume from less than 500 m3/minute to any size that can be built. The reaction rates can be fast enough to facilitate reaction vessel sizing that is small enough for mobile applications as well as terrestrial applications with limited space. The methodology can also be made much larger to accommodate an exceptional target gas treatment requirement. Although not commercially offered for sale or sold, the methodology has been successfully sized for a challenging marine vessel application where space is limited. The mass balance for this exercise is included in this document. The process can easily be sized for a much larger terrestrial applications. As shown inFIG.1, 1-Loop Process technology involves the initial capture of SO2. This process can occur when gas containing SO2is introduced into an aqueous mist containing sodium hypochlorite (NaOCl or NaClO, also known as “bleach”) or moving gas containing SO2through a countercurrent packed bed scrubber, bubble tray scrubber or equal that is recirculating a solution that contains NaOCl or by reacting a solution that contains SO2with a solution that contains NaOCl. In all cases the reaction forms sodium chloride (NaCl) and sulfuric acid (H2SO4). As shown below in equation [1], 1 mole of NaOCl can react with 1 mole of SO2and 1 mole of H2O to form 1 mole of NaCl and 1 mole of H2SO4: SO2+NaOCl+H2O→NaCl+H2SO4[1]. Next, as shown inFIG.1, the first capture of NOx(both NO and NO2) can occur through their reaction with NaOCl and H2O to form sodium nitrate (NaNO3) and hydrochloric acid (HCl). As shown in equation [2], 1 mole of NO and 1 mole of NO2can react with 2 moles of NaOCl and 1 mole of H2O to form 2 moles of NaNO3and 2 moles HCl: NO+NO2+2NaOCl+H2O→2NaNO3+2HCl  [2]. Next, as shown inFIG.1, the first capture of CO2can occur through its reaction with NaOCl and H2O to form hypochlorous acid (HOCl) and NaHCO3. As shown in equation [3], 1 mole of CO2can react with 1 mole of NaOCl and 1 mole of H2O to form 1 mole of HOCl and 1 mole of NaHCO3: CO2+NaOCl+H2O→HOCl+NaHCO3[3]. Next, as shown inFIG.1, the second capture of NOxcan occur through their reaction with NaOH and NaOCl to form sodium nitrite (NaNO2) and H2O. As shown in equation [4], 1 mole of NO and 1 mole of NO2can react with 2 moles of NaOH and 1 mole of NaOCl to form 2 moles NaNO2, 1 mole of NaCl and 1 mole of H2O: 4NO+4NaOCl+O2+H2O→4NaCl+4HNO3[4]. Finally, as shown inFIG.1, the second capture of CO2can occur through its reaction with NaOH to form NaHCO3. As shown in equation [5], 1 mole of CO2can react with 1 mole of NaOH to form 1 mole of NaHCO3: CO2+NaOH→NaHCO3[5]. The first forced precipitation of the products can occur upon addition of an alcohol including but not limited to methanol, ethanol, propanol, butanol including tert-butanol, and the like, or a ketone including but not limited to acetone to the reaction mixture containing products NaHCO3, Na2SO4and NaCl. Once the precipitated material has been separated from the aqueous/alcohol phase, the alcohol (methanol) can be thermally separated and recycled and the solid NaHCO3, Na2SO4and NaCl products can be stored for commercial use or returned to the sea. Alternatively, once precipitated material is removed from the aqueous/alcohol liquor, the alcohol (tert-butanol) can be separated from the aqueous phase and recycled by chilling the mixture with seawater or other cold trap of 25° C. or lower temperature plus separation of the jell or solid by any appropriate means. The solid NaHCO3, Na2SO4and NaCl products can be stored for commercial use or returned to the sea. The second forced precipitation of the products can occur upon addition of a dialkyl ketone, including but not limited to acetone, methyl ethyl ketone, diethyl ketone and the like, to the aqueous reaction mixture containing NaNO2, NaNO3. Once precipitated material is separated from the aqueous/acetone mixture, the acetone can be thermally recycled and the solid NaNO3product can be stored for use as fertilizer. In addition, as shown inFIG.1, NaOCl and NaOH and any recycled H2O can be added back into the loop sequence to maintain the reaction cycle. The reaction sequence shown inFIG.1uses a process control sequence based on multiple algorithms that effectively regulate the interrelated reaction rates of five slightly overlapping sequential reactions by varying reagent dosing parameters. The process control can integrate data from multiple sensors using multi-variable simultaneous equations that employ if-then logic and references known kinetic reaction parameters to determine the validity of the sensor data. This process control also regulates reagent injection timing into the single reaction chamber. The process control also involves regulation of the mass of reagents injected and pH of the reagent mixtures used. This multivariable process control of five reactions can be accomplished by the regulation of just three reactants: NaOCl, NaOH and HCl. The synergistic choice of reactions within the loop sequence allows the reaction products in early stages of the process to act as reagents in subsequent reactions that occur in semi-overlapping environments within the same vessel. For example, in the reaction sequence shown inFIG.1, the HOCl formed in the first capture of CO2is used to generate NaOCl in the two subsequent capture process of NOR. Precise process control is possible for the reactions shown inFIG.1because the unique and different reactions chosen for the process have uniquely different kinetic reaction rates and respond differently to the two ions formed when NaHCO3is speciated in response to the pH of its environment. Knowledge of reaction sequence and deliberately varying the pH, timing and amount of the NaOCl reagent dosed into the reaction chamber as described previously provides a predictable way to selectively capture and/or remove SO2, NOx and CO2in the process sequence. The fifth reaction in theFIG.1loop utilizes NaOH as its reagent. The rate and timing of the introduction of NaOH as specified by the PLC program in response to pre-determined sensor data regulates that process too. The process control logic used in this system requires reliable data from sensors. Non-specific sensors like Oxidation Reduction Potential (ORP) can provide unreliable process information. For example, if ORP is used to regulate the dosing of NaOCl into a reaction mixture, a change in ORP would accompany the addition of NaOCl, and that would be a valid process control variable if NaOCl was the only compound that could influence the solution ORP value. But data from an ORP probe can be unreliable because ORP is not exclusively sensing the HClO and ClO−ions in the reaction mixture. Other chemical compounds or ions in the reaction mixture can also influence the ORP value of the reaction liquid. This problem is not resolved by utilizing two or more of the same sensors. Therefore, the process control logic used for the regulation of the reactions disclosed herein does not rely on non-specific sensors where process confusion is possible. The process control described in this patent application relies on comparison between information from two uniquely different sensors in each situation where process sensor confusion is possible. For example, the dosing of NaOCl can be confirmed by data from two dissimilar sensors: the pH of process liquid and the concentration of Cl2gas in the reaction chamber. The two sensor values are compared against known speciation of NaOCl as shown inFIG.2. The combination just described is used to provide reliable process variable data for each area where the addition of NaOCl is a part of process chemistry. The concept of verifying sensor data applies to other process variables too. The FTIR data for the identity and concentrations of gases in specific sections of the reaction chamber can be compared with known relationships between gas ratios such as the presence of SO2against the pH of the process liquid mist. The monitored and regulated integration of multiple processes within a single reactor is the primary reason the reaction chambers are much smaller than would be required if the seven processes were completed in separate reaction chambers and regulated with conventional process control. The alternative methodology for removing SO2and NOx from a gas or liquid stream prior to LiOH based CO2capture is based on chlorine dioxide (ClO2o). The key to this process is generating non-ionic chlorine dioxide distinguished with a superscripted “o” as shown here: ClO2o. This can be done by several methods that are described in the previously referenced patent. Process control that meters the ClO2oaddition into a reaction chamber(s) as required to react with known quantities of nitrogen monoxide (NO) and nitrogen dioxide (NO2) provided by FTIR or other sensors capable of sensing these compounds and ClO2oin a gas or liquid stream. The ClO2oreacts with the NO and NO2 according to equations [6] and [7]: 5NO+2(ClO2)o+H2O→5NO2+2HCl  [6] 5NO2+(ClO2)o+3H2O→5HNO3+HCl  [7] The HCl and HNO3generated by equations [6] and [7] are neutralized with KOH as described in equations [8] and [9]: HCl+KOH→KCl+H2O  [8] HNO3+KOH→KNO3+H2O  [9] The KCl and KNO3products shown in equations [8] and [9] can be removed with forced precipitation using ethanol or equal. In another embodiment, the disclosure provides 2-Loop Process technology of an integrated closed two loop system, which collaboratively captures CO2and converts it to NaHCO3. During this sequence, the primary reactants include lithium hydroxide (LiOH), which can be regenerated and recycled back into the loop. The rate controlling consumable that is introduced into the loop includes sodium hydroxide (NaOH). A by-product, sodium carbonate (Na2CO3) can be generated, and can be used for further conversion of CO2into NaHCO3. This technology has many applications including use in space crafts, ships, submarines, and anesthesia. As shown inFIGS.3A and3B, Loop 1 of the 2-Loop Process involves the initial capture of CO2and a second capture of CO2. This process occurs when CO2is introduced to lithium hydroxide (LiOH) or sodium carbonate (Na2CO3). The contact and subsequent reaction between LiOH and/or Na2CO3and CO2can occur in several ways: gas containing CO2can be exposed to an aqueous mist containing LiOH and/or Na2CO3resulting in the CO2transfer through the membrane between the gas phase and the liquid droplet where it reacts with the LiOH and/or Na2CO3in the droplet. Gas containing CO2can impact a thin liquid film containing LiOH resulting in the CO2transfer through the membrane between the gas phase and the liquid film where reacts with the LiOH and/or Na2CO3in the liquid film. In another example CO2can be dissolved or suspended in an aqueous solution which is mixed with a solution containing dissolved LiOH and/or Na2CO3where it subsequently reacts with the LiOH and/or Na2CO3. In a final example, a gas containing CO2can be exposed to an aerosol conveying dry or moist LiOH granules or nano-granules that contact gas phase CO2or CO2dissolved/suspended in liquid droplets resulting in a reaction as described in equations [10A and 10B]. The reaction product and excess reactants are subsequently captured in a mist or liquid that is ultimately recirculated in this process sequence. This capture of CO2used in this methodology as described above is uniquely different from the well-known and industry practiced “dry” method that captures CO2by exposing the gas to stationary beds of granular LiOH or granular material impregnated with LiOH or other lithium materials. All of the examples of CO2capture used in this methodology, described onFIG.3A, ultimately transfer the CO2into an aqueous phase where it reacts according to the equations as shown below. As shown below in equation [10A], 2 moles of LiOH can react with 1 mole of CO2to form 1 mole of lithium carbonate (Li2CO3) and 1 mole of water (H2O). In addition, as shown in equation [10B], 2 moles of lithium hydroxide monohydrate (LiOH·H2O) can react with 1 mole of CO2to form 1 mole of Li2CO3and 3 moles of H2O: 2LiOH+CO2Li2CO3+H2O  [10A] 2LiOH·H2O+CO2Li2CO3+3H2O  [10B] That is, CO2can be captured from the atmosphere and/or from an aqueous solution and then sequestered into a solid Li salt, i.e. Li2CO3. The CO2captured described in equations [10A] and [10B] can occur in either the gas or liquid phase. Next, as shown inFIGS.3A and3B, the Li2CO3generated in equations [11A or 11B] is converted into sodium carbonate (Na2CO3) or potassium carbonate (K2CO3) by treatment with NaOH or potassium hydroxide (KOH), respectively. These reactions are shown below in equations [11A] and [11B], 1 mole of Li2CO3can react with 2 moles of NaOH or 2 moles of KOH to form 2 moles of LiOH and 1 mole of sodium carbonate (Na2CO3) or 1 mole of potassium carbonate (K2CO3): Li2CO3+2NaOH→2LiOH+Na2CO3[11A] Li2CO3+2KOH→2LiOH+K2CO3[11B] In addition to regenerating LiOH, the generated Na2CO3or K2CO3can be used in the next step to capture more CO2(see equations [8A] and [8B] below). The reaction of Li2CO3with NaOH/KOH to generate LiOH and Na2CO3/K2CO3as shown in equations [11A] and [11B] occurs in the liquid phase. Next the reaction products from equations [11A and 11B] are exposed to CO2again using the gas/liquid or liquid/liquid or gas/solid mass transfer methodology described above. The mass transfer results in reactions wherein 1 mole of Na2CO3or 1 mole of KHCO3can react with 1 mole of CO2and 1 mole of H2O to generate 2 moles of NaHCO3, or 2 moles of KHCO3as shown in equations [12A] and [12B]: Na2CO3+CO2+H2O→2NaHCO3[12A] K2CO3+CO2+H2O→2KHCO3[12B] This reaction can be perpetuated (subject to solids concentration in the aqueous phase) as long as the pH is elevated to basic by the addition of NaOH or KOH. As shown onFIGS.3A and3Band described in the Mass Balance (Table 4), the LiOH is recycled and the overall process requires one mole of NaOH or LOH per mole of captured CO2. The overall reaction produces one mole of NaHCO3per mole of CO2captured. The process chemistry uses a method to regulate the process residence time. This involves the flow of liquids through Loop 1 and Loop 2 of the 2-Loop Process sequence. Loop 2 is a slip stream of the Loop 1 process stream. Loop 2 is actually two or more process loops with the same mechanical configurations that may or may not handle the same volume of process liquid. The multiple Loop 2 process equipment systems can have equal or dissimilar reaction vessel cross sectional areas. The ratio or percent of the two or more Loop 2 process liquid flow paths can be monitored and regulated as required to provide ideal reaction residence time. The overall Loop 2 process flow cross sectional area is adjusted as required to achieve a liquid flow velocity that slows or increases the residence time within the reactor. The residence time is adjusted to allow the reaction(s) within the loop to achieve the desired percent process completion. The optimum process tuning is achieved by changing the overall cross-sectional area of the Loop 2 process path until any further change in cross-sectional area will adversely affect the desired percent of process completion within Loop 2. The Loop 1 process path residence time can also be adjusted as required obtaining the optimum percent completion for processes that occur in that loop. This is done by adjusting the process liquid flow rate through the loop and that is done by varying the split of liquid diverted to the Loop 2 reactors. The process control logic effectively monitors and adjusts the number of Loop 2 paths and the split ratio between Loop 1 and Loop 2 by responding to analytical sensors that determine concentrations of compounds in the liquid and gas stream plus flow rate sensor data and known loop cross sectional areas of the loops to create the desired residence time within Loop 1 and Loop 2 to effect the desired reaction completions in both loops. This process automatically adjusts to variations on the ratio of concentrations of the target gases and the total amount of each target gas. The disclosure provides methods for the removal of NaHCO3from the Loop 2 recycling process without removing the LiOH from the same process liquid. This is done through a forced precipitation using an alcohol at the add alcohol to the Loop 2 slip stream step. The selection of a suitable alcohol is critical to the success of this process. Two alcohols were identified as ideal for this process. Each has a unique set of ideal physical characteristics. Methanol is ideal because it is miscible in water without forming an azeotrope, has a low solubility for NaHCO3when compared to H2O and a solubility for LiOH that is equal to or higher than that of H2O. Methanol is the only alcohol that does not form an azeotrope with water, and that feature allows a more complete separation of the alcohol and water during distillation. Methanol has a boiling point of 64.7° C. This low temperature allows recovery of the methanol through distillation using waste heat available from a combustion process. Tert-butanol has a solidification temperature at 25°-26° C. This provides a solution for applications of this methodology that have access to large heat sinks, for example processes that are installed aboard seagoing ships. The ocean can provide chilling required for solidification of the tert-butanol at no cost. This feature allows its subsequent separation from the process stream by centrifuge or filtering. This separation sequence utilizes the fact that NaHCO3has a lower solubility in alcohol than does LiOH. For example, the LiOH solubility in water is between 108 and 128 g/L at process temperatures, and NaHCO3solubility in water is between 69 and 169 g/L at ambient temperatures. However, when an alcohol such as ethanol is added to an aqueous solution of LiOH, its solubility remains around 23 g/L, whereas the solubility of an aqueous solution of NaHCO3in ethanol is 0. The difference in solubility between NaHCO3and LiOH allows for this forced precipitation step: NaHCO3precipitates leaving the LiOH in solution. Methanol, tert-butanol (or other suitable alcohols) can be added to this slip stream liquid to affect the precipitation of the sodium or potassium salts. An alcohol, preferably methanol or tert-butanol, can be added to the Loop 2 liquid. The volume of alcohol is proportional to the Loop 2 liquid flow rate, process liquid temperature and the concentrations of compounds in the process stream that can influence precipitation of the NaHCO3or KHCO3. The alcohol can be added to the Loop 2 process liquid flow piping using any conventional dosing method that facilitates good liquid mixing with minimal introduction of static pressure in the process flow systems. The regenerated LiOH remains in the aqueous reaction mixture, which can be reused to sequester additional CO2through Loop 1, and the solid NaHCO3can be converted into a paste and washed or dried depending on the desired purity or physical state. For example, a thin film dryer, centrifuge or other similar device can remove the moisture present in the NaHCO3paste or slurry. The solid NaHCO3is then packaged for commercial use or deposited in the ocean in exchange for a tax donation. In the event the Loop 1 and optional SO2pre scrubber did not remove all of the SO2from the gas stream, any remaining SO2can react with the LiOH to form Li2SO3. This is also removed from the recirculated liquor in the forced two step precipitation of NaHCO3and Li2SO3step of the Loop 2 process. The process follows the following reaction steps shown below in equations [13] through [17]: 2LiOH(saturated)+SO2→Li2SO3+H2O  [13] Li2SO3+H2O+SO2→2LiHSO3[14] Li2SO3+H2SO4Li2SO4+SO2+H2O  [15] Li2SO4(conc.)+Na2CO3Li2CO3↓+Na2SO4[16] Li2CO3+2NaOH→2LiOH+Na2CO3[17] The chemistry used in the disclosed CO2sequestering process has been checked against other compounds commonly found in combustion exhaust and it was determined that no significant omissions occur that are not remedied in this process. FIGS.4A and4Billustrate an embodiment of how the CO2, NOx and SO2capture and reuse methodology disclosed herein for the 1-Loop Process and the 2-Loop Process can be configured. The sequence is important, but the steps can occur in one, two or more separate but linked reaction vessels. The process can also occur in two or more parallel reaction vessels provided all of the parallel vessels use the reaction sequence shown here. The 1-Loop Process and 2-Loop Processes can be sequentially combined within a single scrubbing vessel or separated into two or more components. FIGS.4A and4Balso shows how the 1Loop and 2Loop Processes are typically preceded by a SO2scrubber and/or exhaust gas cooling/economizer/quenching module when the exhaust gas is above ambient temperatures. The right side of the diagram also shows the generation of reagents and their flow into the 1-Loop Process and the 2-Loop Process. FIGS.4A and4Billustrate an embodiment of how the sequence of the five processes grouped within the black rectangle named “1 LOOP PROCESSES” ofFIG.1can be integrated into a scrubbing process within a single scrubbing vessel. This combination of chemical reactions is defined as the 1-Loop Process. It is designed to treat the effluent exhaust gas either from combustion, or from other chemical and biological sources of CO2, NOx and SO2. The 1-Loop and 2-Loop Process diagrams on the left side ofFIGS.4A and4Bare displayed in full detail inFIGS.1,3A and3B, respectively. The configuration shown inFIGS.4A and4Bis only an example of the possible configuration and is not meant to be limiting. The reagent generation, conversion and distribution technology shown inFIGS.4A and4Bis described in greater detail inFIG.5. FIGS.4A and4Balso shows hydrogen gas generated during the electrochemical (E-Chem) production of NaOH and Cl2vented to a burner downstream of the 2-Loop Process. This burn module can include a metallic grate across the gas flow. When present, the grate is heated by the hydrogen gas combustion. The hot metallic surface and/or burner flame are designed to combust remaining hydrocarbons and warm the exhaust gas to minimize a condensate cloud at the exhaust stack. FIG.5illustrates how seven separate gas scrubbing processes are grouped into two scrubbing groups: The SO2, NOx and CO2scrubbing chemical reactions identified as the 1-Loop Process is grouped within a rectangle enclosed in a double solid line. Two additional CO2capture process identified as the 2-Loop Process is shown within the rectangle enclosed in a dashed line FIG.5also shows that a single electrochemical generator (or membrane) can make the primary chemical consumables for all seven processes from seawater or other solution that contains NaCl without other compounds that will interfere with the E-Chem process. The methodology for E-Chem manufacture of NaOH and Cl2from NaCl is well practiced in industry. Newer and more energy efficient and less environmentally challenging technology is emerging. The improved technology is recommended, but the disclosed technology is not dependent upon any one electrochemical methodology. The conversion of Cl2into NaOCl is also well practiced methodology. This disclosure is not dependent on any one methodology but recommends the most energy efficient and environmentally noninvasive method be employed. FIG.5also show how reagent usage made by the E-Chem process can be balanced. Multiple methods for capturing and repurposing CO2and NOxare present; at least one of each type of process uses NaOCl as a reagent and another uses NaOH as a reagent. This dual reagent consumption option allows an allocation of the CO2and/or NOxscrubbing to either or both reagents as required to equalize the overall reagent production by the E-Chem process. Only one method for SO2capture is shown inFIG.5, but it can be augmented with an optional SO2pre-scrubbing stage. The integration of multiple CO2, NOx and SO2treatment methods within this overall process that use NaOH or NaOCl as consumables make it possible to accommodate fluctuations in the ratios of CO2, NOx and SO2in the waste gas stream without wasting reagents. For example, three processes for the removal of CO2were deliberately included in this technology package. One of the CO2processes utilizes NaOCl as a consumable and the other two use NaOH/KOH. This is important because the CO2mass loading in some process gas, for example combustion, is typically 40× higher than the NOx or SOx mass loading so it is essential to treat part of the CO2with NaOH/KOH and the rest with NaOCl in order to balance the chemical availability of reagents from the E-Chem conversion of NaCl. Variations in the NOx and SO2concentrations are monitored and easily accommodated by adjustments in the overall ratio selected for the CO2reactions. The process control system logic adjusts the percentage of each of the CO2sequestration processes through a multifaceted process previously described. The 1-Loop Process described herein is designed to operate as a prerequisite for the 2-Loop Process. However, the 1-Loop Process and 2-Loop Process can also be used in a standalone mode. The 1-Loop Process can also act as a polishing scrubber. In one example the 1-Loop Process can follow an SO2abatement scrubbing device of any design or a NOx abatement scrubbing device of any design. In another example, the 1-Loop Process can follow a quencher that captures waste heat from the exhaust gas stream for use in the recycling reactants used in the 1-Loop Process or for other purposes. Furthermore, the 2-Loop Process can be used as a standalone technology if the gas stream does not contain compounds that can react with the process chemicals, for example: SO2and NOx. EXAMPLES Example 1: The process flow instruments used in the 1-Loop Process are described inFIG.6and in Table 1 below: TABLE 1KEYDESCRIPTIONNOTEThe following summarize reactions that are occurring at each step in the overallreaction sequence. This information is also provided in the 1Loop Process diagram.Pumps and blowers required to move liquids and gases are not shown. There aremany sensors and a process control system that are not shown.ASO2+ NaOCl + H2O = NaCl + H2SO4B4NO + 4NaOCl + H2O = 4NaCl + 4HNO3CCO2+ NaOCl + H2O = HOCl + NaHCO3DNO + NO2+ 2NaOH + NaOCl = 2NaNO2+ H2OECO2+ NaOH = NaHCO3NOTEAll components and systems described below are assumed to be made frommaterials that are compatible with the chemi cal s/reagents, and process pressures,temperatures etc. that are applicable and relevant for the specific application.1Reaction vessel—typically cylindrical with one or more inlets for untreated gas atone end (Item 2) and one or more exits for treated gas at the other end (Item 41).The reaction vessel does not need to be partitioned because of the novel chemicalcompatibility between the five processes identified as A-E. The five chemicalprocesses synergistically assist each other. The byproducts of preceding reactionsenhance reaction kinetics of subsequent reactions. Each process requires its reactionresidence time prior to the initiation of the next process. The reaction byproducts ofthese chemical processes are salts, and these are dissolved/suspended into aqueousmist concurrently sprayed into the reaction vessel to introduce precursor (reagents)required for the chemical processes. The mist containing dissolved/suspendedreaction byproducts coalesce within the reaction vessel and migrates as liquid to thevessel drain where it is removed for further processing. The vessel can be of anyshape and configuration. It need not be linear as shown or oriented as shown. Thevessel can be one or more vessels in parallel or linear configurations. The vessel isdesigned to operate at the exhaust gas system pressures and meet site requirementsfor space through flexibility of equipment orientation. When the vessel is in avertical orientation, gas/liquid separators are provided near the gas inlet and gas exitends of the reaction vessel. The gas/liquid separators are used to prevent liquidcondensate from draining past the separator. The gas/liquid diverter can be of anydesign, for example the coolie caps design shown, or bubble caps.2Gas (typically air) containing one or more of the following: CO2, NOx, SO2(TargetGases) is introduced into the reaction vessel. The gas can be at any normal industrialprocess working pressure. Ideally the pressure is slightly negative with respect tothe surrounding atmosphere to prevent any exhaust gas from leaking into theatmosphere. The gas can be at any temperature between 10° C. and 90° C.3Gas sensor array. Local and/or remote instrumentation for qualitative andquantitative analysis of CO2, NOx, SO2and other compounds in the reactionmixtures. Instrumentation is also provided for gas temperature, pressure, and otherprocess variables. The sensors are connected to a process logic control (PLC)system that executes a process specific logic that regulates process variables in away that safely provides optimum reductions in Target Gases and minimizesconsumption of consumable compounds.4Reactant Injection Array. This equipment proportionally introduces and mixes twoor more different reactants (as liquids or gas) and then sprays the mixture into thereaction vessel in accordance with PLC program’s parameters for mixture ratios,flow rate, and flow duration.5Detail of “4”—Spray nozzle(s) of any type of air or mechanically atomized designthat are configured in countercurrent and/or co-current and/or tangential orientationwith respect to the gas flow. Tangential orientation is typically done at an angle orseries of angles that promote gas mixing.6Detail of “4”—Wall of reaction vessel (Item 1)7Detail of “4”—Nozzle assembly mixing chamber. This chamber provides anisolated environment for mixing reactants used for each of the five primarychemical processes identified as A-D and subordinate reactions that precede orfollow the primary reactions.8Detail of “4”—Static Mixer of any appropriate design.9Detail of “4”—Remotely controlled proportional high-pressure chemical pump ofany design. Preferably a pump that provides consistent pressure. The pressure rangecan be anywhere between 10 and 3000 psi. Preferably 20-300 psi above the gaspressure in the reaction vessel. The pump’s surfaces exposed to reactants are madeof any material that is compatible with the reactant(s) and pressure. Reactants usedinclude, but are not limited to, a hypochlorite compound, for example sodiumhypochlorite (NaOCl), or an alkaline compound, for example sodium hydroxide(NaOH), or a mineral acid, for example hydrochloric (HCl).10Detail of “4”—This is a second of two or more remotely controlled proportionalhigh-pressure chemical pumps of any design with attributes described in Item 9above.11Detail of “4”—Remotely controlled valve to regulate the addition of a gas into thenozzle assembly mixing chamber (Item 7). One or more of these devices add gasinto the mixing chamber at one or more locations. The selection of gas injectionpoint(s) is configured to provide optimum reaction kinetics.12Detail of “4”—Chemical storage, transfer pump(s) and interconnecting piping. Thereactants are stored in any appropriate quantity within tanks or vessels made ofmaterial that is compatible with the reactant. The reactants can be but are not limitedto a hypochlorite compound, for example sodium hypochlorite (NaOCl), or analkaline compound, for example sodium hydroxide (NaOH), or a mineral acid, forexample hydrochloric (HCl).13Detail of “4”—This is the second of several sets of chemical storage, transferpump(s) and interconnecting piping with same parameters described for Item 12.14One or more gas compressor(s), pressure vessel(s) and interconnecting piping,valving, and other devices. The portions of the equipment exposed to chemicals aremade of materials compatible with the gas(s) and pressure of the application. Therecan be one or more gasses introduced into the mixing chamber or several gasses canbe pre-combined and introduced collectively into the mixing chamber.15Piping with other required equipment to move drainage from the reaction vessel(Item 1) to process equipment.There are two forced precipitation loops in this diagram. The first is inclusive ofItems 15 through 27 and the second is inclusive of Items 28 through 40. Only oneloop is required if all four salts produced in reactions A-E (sodium bicarbonate,sodium sulfate, sodium nitrate and sodium chloride) are removed as a group with aketone like acetone. However, sodium bicarbonate and sodium sulfate can besegregated from the other salts by treating the mixture with a polar solvent, forexample an alcohol, preferably methanol. If this segregation option is elected, twoprecipitation loops are required. The first loop will use a polar solvent, for examplemethanol, and the second loop will use a ketone, for example acetone.The following process description explains the two loop option.16Piping to convey solvent (for example an alcohol like methanol) to a point ofinjection and mixing at the intersection between Item 16 piping and Item 15 piping.The point of introduction includes methods of statically mixing the liquids.17Device to separate precipitated salts and the aqueous supernatant. The device canuse any technology. Examples include centrifuge, belt press, and separatory funnel.The aqueous feedstock to the separation device contains salts made in the reactionchamber and dissolved or suspended in water that is introduced to the reactionchamber, preferably as a mist. The mist subsequently condenses and is collected ata vessel drain. Salt solubility is maintained prior to chemically forced precipitationto prevent clogging in piping and other equipment. The novel chemically forcedprecipitation process begins when the polar solvent with specific chemical attributesis added to the liquid mixture containing the salts at the intersection of pipingdescribed in Item 15, and the piping between Item 16. The precipitation processcontinues within the separation device (Item 17). The novel chemical forcedprecipitation occurs because the polar solvent interacts with the polar water todiminish the available water available to hold the salt ions in solution. The rate ofprecipitation is directly related to the chemical characteristics of the polar solvent,the ratio of polar solvent to water in the mixture, the process temperature andpressure.18Solids conveying device and storage vessel for precipitated salts (separatorysludge). This includes a screw conveyor or other device to transport the sludge tonext treatment process. The conveyance device is enclosed and externally heated toseparate residual solvent from the sludge. The solvent vapor is routed to pipingdescribed in Item 24. An inert gas, for example nitrogen, is introduced into thesealed conveyance device to prevent inadvertent solvent combustion. Theconveying device size and material of construction are commensurate withchemistry of conveyed materials and process flow requirements.19Sludge processing. This includes subsequent separation of the two or morecomponents in the sludge and/or product rinsing as required for end productrequirement.20Supplemental sludge processing. This includes drying and packaging as required tomeet end product requirements.21Conveyance device for final product(s). This includes and is not limited to storage,weighing, loading and other steps required for relocating product to a new location.22Transport supernatant from precipitate and separation areas as described in items 16& 17 above. This includes storage devices, piping, pumps, and other equipmentrequired to manage product flow and move liquid into distillation device (Item 23).23Distillation device(s) of any type that will separate solvent, for example methanolfrom the water, and other compounds dissolved in the supernatant liquid. Thetemperature is relevant to the polar solvent (methanol) used. The device(s) includesall necessary instrumentation, process control equipment, and liquid storage, tointerface this equipment with the rest of the process flow sequence.24Equipment to transfer polar compound (methanol) vapor from the distillationdevices (Item 23). This includes piping, pumps, and other devices.25Vapor condensation equipment and condensate storage equipment. This includes aheat exchanger of any relevant design, condensate storage vessel(s), and anyrequired vents, sensors, process control, and other devices necessary to integrate thecondensation and storage processes into the overall process flow.26Piping to transport the liquid polar solvent. This includes all piping, pumps, andflow control devices necessary.27Remotely controlled proportional metering pump at the required pressure and flownecessary to effectively introduce the polar solvent, for example methanol viapiping and other appurtenant devices described in Item 16 into the effluentconveyed from the reaction vessel (Item 1) in piping described in (Item 15). Ideallya pump with consistent fluid flow.28Piping and other appurtenant devices including sensors required to transport a polarsolvent, for example a ketone like acetone into the water byproduct of distillationItem 23. The integration of the acetone and distillation byproduct occurs at theintersection of piping that transports the acetone and piping that transports thedistillation byproduct. The point of introduction includes a method of static mixingthe two liquid streams together.29Device to separate precipitated salts and the aqueous supernatant. The device canuse any technology. Examples include centrifuge, belt press, and separatory funnel.The aqueous feedstock to the separation device contains salts made in the reactionchamber and dissolved or suspended in water that is introduced to the reactionchamber, preferably as a mist. The mist subsequently condenses and is collected ata vessel drain. Salt solubility is maintained prior to chemically forced precipitationto prevent clogging in piping and other equipment. The novel chemically forcedprecipitation process begins when the polar solvent with specific chemical attributesis added to the liquid mixture containing the salts at the intersection of pipingdescribed in Item 28, and the piping between Items 23 & 29. The precipitationprocess continues within the separation device (Item 29). The novel chemical forcedprecipitation occurs because the polar solvent interacts with the polar water todiminish the available water available to hold the salt ions in solution. The rate ofprecipitation is directly related to the chemical characteristics of the polar solvent,the ratio of polar solvent to water in the mixture, and the process temperature andpressure.30Solids conveying device and storage vessel for precepted salts (separatory sludge).This includes a screw conveyor or other device to transport the sludge to the nexttreatment process. The conveyance device is enclosed and externally heated toseparate residual solvent from the sludge. The solvent vapor is routed to pipingdescribed in Item 36. An inert gas, for example nitrogen, is introduced into thesealed conveyance device to prevent inadvertent solvent combustion. Theconveying device size and material of construction are commensurate withchemistry of conveyed materials and process flow requirements.31Sludge processing. This includes subsequent separation of the salts and or rinsing as required for end product requirement.32Supplemental sludge processing. This includes drying and packaging as required tomeet end product requirements.33Conveyance device for final product(s). This includes and is not limited to storage,weighing, loading and other steps required for relocating product to a new location.34Transport supernatant from precipitate separation device (Item 29). This includesstorage devices, piping, pumps, and other equipment required to manage productflow and move liquid into distillation device (Item 35).35Distillation device(s) of any type that will separate acetone from the water and othercompounds in the supernatant produced in Item 29 separation device used in theILoop process. The device(s) includes all necessary devices to interface thisequipment with the rest of the process flow sequence.36Piping and other devices to transfer vapor phase solvent, for example acetone fromthe Distillation devices (Item 35) to Item 36. This includes piping, pumps, and otherdevices necessary to integrate this system into the overall process flow.37Solvent vapor condensation and condensate storage equipment. This includes a heatexchanger of any relevant design, condensate storage vessel(s), and any requiredvents, level control instrumentation, process control equipment, and liquid storage,sensors, process control and other devices necessary to integrate the condensationand storage processes into the overall process flow.38Piping to transport the acetone (or similar solvent). This includes all piping, pumps,and flow control devices necessary.39Remotely controlled proportional metering pump at the required pressure and flownecessary to effectively introduce the polar solvent, for example acetone via pipingand other appurtenant devices described in Item 28 into the effluent conveyed fromthe distilling device (Item 23) in piping between Item 23 and (Item 29). Ideally apump with consistent fluid flow.40Commercially valuable water with reduced concentrations of NaHCO3, Na2SO4,NaCl and NaNO3. A portion of the water can be reused (recycled) in mixtures ofreactants introduced into the reaction vessel (Item 1) via nozzles described in Item4.41Gas containing lower concentrations of one or more of the following: CO2, NOx,SO2. The gas can be at any pressure. Ideally the pressure is slightly negative withrespect to the surrounding atmosphere to prevent any exhaust gas from leaking intothe atmosphere. Example 2: The process flow instruments used in the 2-Loop Process are described inFIG.7and in Table 2 below: TABLE 2KEYDESCRIPTIONNOTEThe following summarize reactions that are occurringat each step in the overall reaction sequence.This information is also provided inthe 2Loop Process diagram.A2LiOH + CO2= Li2CO3+ H2OBNa2CO3+ CO2+ H2O = 2NaHCO3NOTEThis process focuses on the removal of CO2from agas stream. However, lithium hydroxide (LiOH) isnot specific to CO2. LiOH reacts with nitrogencompounds, for example NO & NO2, and also reacts withsulfur compounds, for example SO2andH2S. Some of the reactions will actually prevent theLiOH from being recycled with NaOH, therefore it isimportant to pretreat an exhaust gas stream with the 1Loopprocess described in this patent to eliminate the sulfurand nitrogen compounds from the gas prior to treatmentof CO2with LiOH. All components and systemsdescribed below are assumed to be made from materialsthat are compatible with the chemicals/reagents, and processpressures, temperatures etc. that are applicable andrelevant for the specific application. Pumps and blowersrequired to move liquids and gases are not shown.There are many sensors and a process control system thatare not shown.1Reaction vessel-typically cylindrical with one or more inletsfor untreated gas at one end (Item 2) and one ormore exits for treated gas at the other end (Item 32).The vessel can be of any shape and configuration.It need not be linear as shown or oriented as shown andit can be one or more vessels in parallel and/or linearconfigurations. The vessel is designed to operate at awide range of exhaust gas system pressures and meetsite requirements for space through flexibility ofequipment orientation. The vessel is divided into 2sequential zones, that are defined by the vessel walls andseparated by three gas/liquid separators that allow gas topass from zone to zone while preventing liquid from passingfrom zone to zone. The gas/liquid separators are used toprevent liquid condensate formed within each zonefrom draining past the entrance end of any reactionvessel zone. The gas/liquid diverter can be of any design,for example when used with a vessel that has avertical orientation as shown, the coolie caps designshown, or bubble caps or equal are required. When thevessel is in a horizontal, or near horizontal orientation, aseparator with hole(s) for passage of gas is located at theupper portion of the vessel zone partitions. Said anotherway, partitions used in this application requirepenetrations for gas that are located at other than theareas near the vessel’s bottom. This hole patternrequirement allows gas to pass fromzone to zone but preventsliquid from migrating from zone to zone. In thisapplication, the coolie caps or equal, are not required toprevent liquid from falling between vessel zones.Chemical processes identified as A & B are designedto occur sequentially in separate reaction vessel zones.The reaction byproducts of these chemical processesare salts, and these are dissolved/suspended into theaqueous mist sprayed into the reaction vessel to introduceprecursor (reactants) required for the chemicalprocesses. The mist with dissolved/suspended reactionbyproducts coalesce within the reaction vessel zonesand migrates as liquid to the vessel zone drain where it isremoved for further processing.2Gas (typically air) containing an elevatedconcentration of CO2. Because LiOH usedin this 2Loop process is not selective to just CO2,it is strongly recommended thatexhaust gas be treated with the 1Loop processdescribed in this patent before the gasis treated with this 2Loop Process for CO2capture and sequestration.The gas introduced to this 2Loop Processcan be at any normal industrial processworking pressure. Ideally the pressure isslightly negative with respect to thesurrounding atmosphere to prevent anyexhaust gas from leaking into theatmosphere. The gas can be at any temperaturebetween 10° C. and 90° C..3Gas sensor array. Local and/or remoteinstrumentation for qualitative andquantitative analysis of CO2, NOx, SO2and other compounds in the reactionmixtures. Also, instrumentation for gastemperature pressure, and other processvariables. The sensors are connected to aprocess logic control (PLC) system thatexecutes a process specific logic that regulatesprocess variables in a way that safelyprovides optimum reductions in CO2whileminimizing consumption of consumable compounds.4Piping and other equipment to transport liquidcondensate from the first (lower) reaction vessel zone.5Reaction chamber of any shape, cylindrical ispreferred, with static mixer of anykind. Vessel size is based on process liquidtemperature, pressure, and theconcentrations of reactants. These and othervariables are considered whendetermining the volume and ideal shaperequired to provide efficient mixing ofreactants and the residence time necessaryfor the completion of the followingreaction: Li2CO3+ 2NaOH = 2LiOH + Na2CO3.The vessel is made of materials thatare compatible with the process chemistryand physical constraints.6Piping, pumps, and other equipment requiredto move the aqueous mixture made inItem 5 above. The liquid is sprayed into thesecond (upper) zone of the reactionvessel (Item 1). Spray nozzle(s) of any typeincluding but not limited to air ormechanically atomized design are orientedin countercurrent and/or co-currentand/or a tangential orientation with respectto the gas flow. The tangential orientation istypically done at an angle or series of anglesthat promote gas mixing.7Drain line with pumps and other equipmentrequired to transport liquid condensatefrom the second (upper) zone of the reaction vessel.8Device to separate the precipitated sodiumbicarbonate (NaHCO3) and the aqueoussupernatant. The device can use any technology.Examples include centrifuge, beltpress and separatory funnel. Sodium bicarbonateis made in the second (upper) zoneof the reaction chamber according to the“B” reaction (Na2CO2+ CO2+ H2O =2NaHCO3). The concentration of NaHCO3in the aqueous solution prior toproprietary chemically forced precipitationis deliberately maintained at a level thatwill not precipitate until it is mixed witha polar solvent (preferably methyl alcohol).This is done to prevent piping and otherequipment from becoming clogged withsolids. The chemically forced precipitationprocess begins when the polar solvent isadded to the liquid mixture conveyed inItem 7 piping to an intersection of piping inItem 7 and Item 15. The chemicallyforced precipitation continues within theseparation device (Item 8). The additionof a polar solvent like methanol to theaqueous solution with dissolved sodiumbicarbonate, creates a novel forcedprecipitation because the polar solventinteracts with the polar water to diminish theavailable water available to hold thebicarbonate and sodium ions in solution. Therate of precipitation is directly relatedto the chemical characteristics of the polarsolvent, the ratio of polar solvent towater in the mixture, process pressure, andprocess temperature. The LiOH remainsdissolved in the liquid supernatant becauseit is not affected by the addition of thecorrectly selected polar solvent.The separation device is enclosed. An inert gas,for example nitrogen is introducedinto the sealed separation device to preventinadvertent solvent combustion. Thisinert gas is transferred into the conveyance devicedescribed in Item 16 and thenreturned to the atmosphere during the condensationprocess described in Item 12.9Piping and other equipment to convey liquidsupernatant to distillation device designated as Item 10.10Distillation device(s) of any type that willseparate polar solvent, for examplealcohol from the water and other compoundsin the supernatant liquid. Thetemperature is relevant to the polar solvent (forexample methanol) used. Ideallymethanol is used because it does not forman azeotrope and is therefore moreeffectively separated from the water. Thedevice(s) includes, in addition to thedistillation equipment, all necessary instrumentation,process control equipment andliquid storage required to interface this equipmentwith the rest of the process flow sequence.Supernatant without the alcohol leaves thedistillation device through piping andother equipment described in Item 20).11Pipe and pump or other appurtenant equipmentrequired to transfer polar solventvapor from distillation device (Item 10) tocondensation and liquid storage device Item 12.12Vapor condensation equipment and condensatestorage equipment for alcohol (orother polar solvent). This equipment includesa heat exchanger of any relevantdesign, condensate storage vessel(s), andany required pumps, vents, level controland other devices necessary to integrate thecondensation and storage processesinto the overall process flow.13Piping to transfer condensed (liquid) polarsolvent (alcohol) from storage vesselincluded in Item 12 to the proportionalmetering pump (Item 14).14Remotely controlled proportional meteringpump to deliver polar solvent at therequired pressure and flow via pipingdescribed in Item 15 into the condensate fromthe upper portion of the reaction vesselconveyed in piping described in Item 7.Ideally a pump with consistent fluid flow.15Piping to convey polar compound (alcohol,preferably methanol) to a point ofinjection and mixing at the intersectionbetween Item 7 piping and Item 15 piping.The point of introduction includes methodsof statically mixing the polar compoundwith the aqueous process liquid conveyed in Item 7 piping.16Solids conveying device and storage vesselfor precipitated sodium bicarbonate(NaHCO3). This includes a screw conveyoror other device to transport the sludge tothe next treatment process. The conveyancedevice is enclosed and externally heatedto separate residual solvent from the sludge.The solvent vapor from the sludge joinssolvent vapor from the supernatant in Item11 piping. An inert gas, for examplenitrogen, is introduced into the sealed conveyancedevice to prevent inadvertentsolvent combustion. This inert gas isreturned to the atmosphere during thecondensation process described in Item 12.The conveying device size and materialof construction are commensurate with thechemistry of conveyed materials andprocess flow requirements.17Optional NaHCO3conditioning system asdesired to improve the purity of thecompound for commercial use. This can bea wash and re-precipitation and dryingdevice of any appropriate design. The productcan be supplied as powder or a paste.18Storage of optionally cleaned NaHCO3product.Vessel can be of any appropriate size and shape.19Clean sodium bicarbonate (NaHCO3).20Piping with pump and other devices totransfer the alcohol free supernatant to thefirst (lower) zone of the reaction vessel.The liquid is sprayed into the gas streamwithin the reaction vessel by any appropriatemeans. This includes but is not limitedto low or high-pressure nozzles and airassisted nozzles. Lithium carbonate (Li2CO3)is made in the first (lower) zone of thereaction vessel by the reaction of CO2in thegas stream with lithium hydroxide (LiOH)in a sprayed liquid according to thestoichiometry identified as “A” Reaction:2LiOH + CO2= Li2CO3+ H2O. Theliquid volume is maintained to ensure thelithium carbonate and other materials insolution remain in solution as it condensesand drains out of the reaction vessel.21Piping with a PLC controlled variable speed pumpfor introduction of NaOH into the condensate from the first(lower) portion of the reaction chamber. The NaOH isintroduced at a stoichiometrically required rate tosuccessfully deliver the reaction described in Item 5. Thisoccurs at the intersection of Item 21 piping and Item 4piping. A static mixer of any appropriate design isprovided in Item 4 piping downstream of thepoint where the NaOH is introduced into the liquid.22NaOH storage tank with appropriate level,heating, pumps, and other devices. Thetank is any appropriate size and shape.23Piping and other devices required to transfer NaOHfrom production in an Electrochemical NaCl cell(E-Cell), or BPED membrane device, orfrom commercial supply.24E-Cell when combined with an HCl fuel cellor separately a BPED membrane deviceare both designed to convert NaCl into NaOH and HCl.25Hydrogen (H2) gas produced in the NaCl E-Cell if it is notconnected to an HCl fuel cell. This gas is stored as acommercially viable product, utilized in anotherchemical process, or safely vented to atmosphere.26Piping and other equipment required to transfer NaOHmade in the E-Cell or BPED membrane systemto the NaOCl generator (Item 27). This option is usedto create NaOCl as a reactant for the 1Loopprocess described elsewhere in this patent.27NaOCl generator of any appropriate designthat utilizes Cl2gas or liquid HCl andNaOH as reactants. The reactants are provided bythe combination of an NaCl E-Celland HCl fuel cell, or separately a BPED membrane system.28NaOCl storage tank with vent to safe location orback into a process flow that utilizes NaOCl.29NaOCl supplied to the 1Loop processes(Diagram 1 and 1A).30Chlorine (Cl2) storage tank. Optionally the Cl2is feddirectly into the NaOCl generator (Item 27) and theproduced NaOCl is used on the 1Loop process or soldas a commercially viable product. There is no need forchlorine storage when theNaCl E-Cell is coupled directly with a HCl fuel cell.31Liquid brine (NaCl) solution. This can be a highconcentration brine or sea water.32Exhaust gas with little or no CO2. The integrated CO2, NOx and SO2processes disclosed herein are applicable to marine and land based applications. The inherent design of this series of processes provides it with the features necessary for marine applications. These same features can be applied to land applications if desired, or land applications can be segregated in ways that require larger equipment footprints. These features are summarized below: The reaction chambers process the exhaust gas at velocities that allow the reaction chambers to be fractionally larger than the volume required for typical exhaust gas flow. The reaction chambers can be oriented in any direction because they utilize mist reactions. The upward flow shown in the figures are only examples. The process can generate the NaOH and NaOCl from seawater thereby not requiring storage aboard the vessel for NaCl. The processes generate NaHCO3which is naturally used by the oceans for pH control. Direct disposal of this compound from the ship as it is underway will benefit the oceans. This eliminates the need for storage aboard the vessel for the NaHCO3. The processes disclosed herein segregate the NaNO3from the process stream and store it as a commercially viable paste. The processes disclosed herein have the ability to treat the exhaust of a generation system required to make the electricity necessary to run the processes thereby emitting essentially no CO2, NOx and SO2as a result of operating the combined group of processes. The use of E-Chem generation for NaOH/KOH production would be of concern if it was done using outdated technology. Over the past few years the technology for NaOH/KOH generation has become progressively more environmentally friendly. Upgrades in electrode technology are already used in commercial production. Other recent technological breakthroughs show how the need for a cell membrane is eliminated. This most recent change is reported to reduce the electrical requirement to between ⅓ and ⅕ of conventional power requirement. Table 3 shows the composition chemical composition of seawater that can be used to make the NaOH and NaOCl required for the disclosed processes. TABLE 3Total molarcomposition of seawater(salinity = 35)[15]Seawater elemental compositionConcentration(salinity = 3.5%)[citation needed]Component(mol/kg)Element▾▴Percent by mass▾▴H2O53.6Oxygen85.84Cl−0.546Hydrogen10.82Na+0.469Chlorine1.94Mg2+0.0528Sodium1.08SO42−0.0282Magnesium0.1292Ca2+0.0103Sulfur0.091K+0.0102Calcium0.04CT0.00206Potassium0.04Br−0.000844Bromine0.0067BT0.000416Carbon0.0028Sr2+0.000091Vanadium1.5 × 10−11−F−0.0000683.3 × 10−11 The Mass Balance in this study utilizes a 95% NO/5% NO2mix in the NOx, but value is approximate. The exact NO/NO2ratio will depend upon the actual time between NOx generation and scrubbing, gas temperature, and other compounds in the gas stream. It is also influenced by exposure to mist quenching prior to SOx scrubbing. Some of the NO2will dissolve into the quench water. The disclosure also presents individual Mass Balance tables for the 1-Loop Process and the 2-Loop Process scrubbing stages. Literature reports widely divergent ratios for NOx and CO2in marine exhaust therefore this study calculates Mass Balance for the removal of 1 Kg each of SO2, NOx and CO and then combines these based on a “typical car carrier type ship” with defined operational parameters. Table 4 illustrates the amount of CO2captured and repurposed based on 1 kg of CO2captured in the 2-Loop Process*. TABLE 4CompoundModuleMade/UsedMolesKgTotal (Kg)Net-Made/Used (Kg)CO2CaptureUsed11.360.501.0Used (CAPTURED)CO2ProductUsed11.360.50LiOHCaptureUsed22.740.550LiOHConvertMade22.740.55Li2CO3CaptureMade11.360.840Li2CO3ConvertUsed11.360.84H2OCaptureMade11.360.210H2OProductUsed11.360.21NaOHConvertUsed22.740.910.91UsedNa2CO3ConvertMade11.371.210Na2CO3ProductUsed11.371.21NaHCO3ProductMade22.741.911.91MadeMeOHRecycledRecycled25.000.801*All mass is calculated at dry weight for 100% material.*Methanol consumption through loss in H2O during distillation is an estimate. Table 5 illustrates the amount of CO2captured by NaOCl based on 1 kg of CO2captured in the 1-Loop Process*. TABLE 5CompoundMade/UsedMolesKgTotal (Kg)Net Made/UsedCO2Used22.721.001.00UsedCAPTURED(CAPTURED)NaOClUsed22.721.691.69UsedH2OUsed22.720.410.41UsedHOClMade22.721.191.19MadeNaHCO3Made22.721.911.91Made Table 6 illustrates the amount of SO2captured by NaOCl based on 1 kg of SO2captured in the 1-Loop Process*. TABLE 6CompoundMade/UsedMolesKgTotal (Kg)Net Made/UsedSO2Used15.611.001.00UsedCAPTURED(CAPTURED)NaOClUsed15.611.161.16UsedH2OUsed15.610.280.28UsedNaClMade15.610.910.91MadeH2SO4Made15.611.531.53Made*All mass is calculated at dry weight for 100% material. Table 7 illustrates the amount of NOxcaptured by NaOCl based on 1 kg of 95% NO/5% NO2treated by the abatement process in the 1-Loop Process*. TABLE 7CompoundMade/UsedMolesKgTotal (Kg)Net Made/UsedNOxUsed31.441.000.90Used(CAPTURED)NOxUntreated3.140.10UntreatedNaNO3Made28.242.402.40MadeNaNO2Made28.301.951.95MadeH2OUsed14.430.260MadeH2OMade14.430.26HClMade28.261.031.03MadeNaOClUsed28.212.102.21UsedNaOClUsed1.480.11NaOHUsed28.261.131.13Used*All mass is calculated at dry weight for 100% material. The two equations that describe the removal of NOx from exhaust gas collectively in a ratio assumed to be cumulative treats approximately 90% of the available NOx. If 99+% NOx removal is required, the NOx processes based on ClO2is required. Table 8 illustrates the ratio of NOx, SO2and CO2in marine exhaust from a 2 cylinder engine burning HFO fuel at 100% engine capacity. TABLE 8Pollutant SpeciesEmission FactorsUnitsg/kWhNitrogen oxides (NOx)19.77 ± 0.28Carbon dioxide (CO2)617 ± 11Carbon monoxide (CO)0.29 ± 0.02Sulfur dioxide (SO2)11.53 ± 0.20Particulate Matter (PM)2.399 ± 0.052Elemental Carbon (EC)0.0069 ± 0.0004Organic Carbon (OC)0.22 ± 0.01Ash0.098 ± 0.002Hydrated Sulfate (H2SO4,6.5 H2O)2.17 ± 0.19 Table 9 illustrates the physical characteristics of a “typical ship” used in the disclosed calculations TABLE 9Delivery year:2008Car Capacity:6500 CEU (Car Equivalent Unit)Length overall:199.99 mBreadth:32.26 mDraft (design):9 mDisplacement:32,791.6 ton (loaded at design draft)Main Engine:MAN B&W 7S60ME-C15,820 kWSpeed (design):20 knot FIG.8illustrates the fuel consumption from an actual vessel used at specified speeds and wind conditions. Table 10 illustrates the typical NOx, SO2and CO2emissions from fuel oil combustion in a two stroke marine engine. TABLE 10Pollutant SpeciesEmission FactorsUnitsg/kWhNitrogen oxides (NOx)19.77 ± 0.28Carbon dioxide (CO2)617 ± 11Carbon monoxide (CO)0.29 ± 0.02Sulfur dioxide (SO2)11.53 ± 0.20Particulate Matter (PM)2.399 ± 0.052Elemental Carbon (EC)0.0069 ± 0.0004Organic Carbon (OC)0.22 ± 0.01Ash0.098 ± 0.002Hydrated Sulfate (H2SO4,6.5 H2O)2.17 ± 0.19 Table 11 illustrates the amount (kg/hour) for NOx, SO2and CO2emissions from a typical ship described above.* TABLE 11• 312.8 Kg of NOx are made per hour• 9750.0 Kg of CO2are made per hour• 182.0 Kg of SO2are made per hour*The NOx ratio of NO/NO2is defined as 95/5. Table 12 illustrates the combined CO2, SO2and NO capture based on actual ratios in 2 stroke marine combustion of HFO per hour at 100% engine capacity.* TABLE 12Process DataMade-UsedTotalNet Made/UsedTableCompoundPer HourKg(Kg)Per hourNotes5 and 6CO2Used97509750Used7SO2Used182182Used8NOxUsed281.52312.890% Used8NOxUntreated31.285 and 6H2OUsed4192.54243.46Used17H2OUsed50.968NaOHUsed353.464643.46Used25 and 6NaOHUsed42908NaNO2Made609.96609.96Made8NaNO3Made750.72750.72Made5 and 6NaHCO3Made18622.518622.5Made8HClMade322.18322.18Made7NaClMade165.62165.62Made7H2SO4Made278.46278.46Made7NaOClUsed211.12211.12Used25 and 6HOClMade0487.23Used28HOClUsed487.231. The H2O is 90+% recycled. Makeup will come from desalinization plant.2. The NaOH, NaOCl and HOCl are all generated from NaCl carried on ship or captured fromthe seawater. Table 12 reports data used to adjust the ratios of NOx, CO2and SO2reported in the Tables to the actual chemical ratios shown for exhaust in the typical ship used in this report when operating at 100% engine capacity. However, the accumulated mass balance is hypothetical because the ratio of these compounds will vary with different fuels and engine operation. The following data refers to the energy required in the electrochemical process necessary to generate NaOH and NaOCl and HOCl required to treat 100% of the CO2, 90% of the NOx and 100% of the SO2. This calculation assumes there is no SO2pre-scrubber. All of the three chemicals described above are made from NaCl carried on the ship or removed from seawater. All other energy for recycling the chemicals through the 1-Loop Process and 2-Loop Process modules are entirely provided from the waste energy generated by the combustion source. The waste heat also contains required energy to generate the electricity necessary for pumps, mixers and other mechanical devices used in the chemical processing, but utilizing that waste heat would require additional equipment. Therefore, it is practical to use a small amount of additional fuel for the generation of this electrical energy. The ideal energy required to generate 1 Kg of NaOH, and all required NaOCl plus HOCl from saturated NaCl solution is 0.911 kWh. If seawater is used as the source for NaCl the electrical energy consumption will be greater. Table 13 illustrates the energy in various fuel oils*. TABLE 13Heating ValueGrade(Btu/US gal)CommentsFuel Oil No. 1132900-137000Small Space HeatersFuel Oil No. 2137000-141800Residential HeatingFuel Oil No. 4143100-148100Industrial BurnersFuel Oil No. 5 (Light)146800-150000Preheating in GeneralRequiredFuel Oil No.5 (Heavy)149400-152000Heating RequiredFuel Oil No. 6151300-155900Bunker C*1 kWh = 3412 BTU Pursuant to Tables 12 and 15, only 95.77 gallons of Fuel Oil No. 5 (Heavy) are required to treat all of the CO2, 90% of the NOxand all of the SO2generated per hour of 100% engine capacity by the typical ship described in Tables 10 and 11. While the inventive features have been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those in the art that the foregoing and other changes can be made therein without departing from the sprit and the scope of the disclosure. Likewise, the various diagrams may depict an example architectural or other configuration for the disclosure, which is done to aid in understanding the features and functionality that can be included in the disclosure. The disclosure is not restricted to the illustrated example architectures or configurations, but can be implemented using a variety of alternative architectures and configurations. Additionally, although the disclosure is described above in terms of various exemplary embodiments and implementations, it should be understood that the various features and functionality described in one or more of the individual embodiments are not limited in their applicability to the particular embodiment with which they are described. They instead can be applied alone or in some combination, to one or more of the other embodiments of the disclosure, whether or not such embodiments are described, and whether or not such features are presented as being a part of a described embodiment. Thus, the breadth and scope of the disclosure should not be limited by any of the above-described exemplary embodiments.
78,460
11857921
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS The exemplary embodiment disclosed hereinafter, which is only one of many exemplary embodiments of the present invention, was developed for application in the recovery of a substantial amount of the methyl bromide used as the fumigation gas for fumigating logs of wood, followed by its conversion to a value-added product. The waste fumigation gas treated in accordance with the present invention better complies with emission regulations. Although the process and apparatus described below are directed to the recovery and conversion of methyl bromide, it should be understood by a person of ordinary skill in the art that they are also effective for recovering and converting other alkyl halide fumigants. In the process of the present invention, the scrubbing solution is an alcohol-based buffer solution, which is not discarded, but rather is separated from the produced suspended solid, namely metal halide, and recycled, thereby further enhancing the economic efficiency and viability of the process. All of the reactants for the proposed process are inexpensive compared to existing processes, and metal halides, such as sodium bromide, can be highly valuable commodity products. Another by-product of the process disclosed herein is methanol, a solvent that is also recycled in the absorbing solution to aid further absorption of the fumigant. The one-step highly integrated wet reactive absorption process as developed herein requires reduced capital and operating cost and mild process conditions in comparison to currently available methods. With intensified mass transfer characteristics, highly efficient waste gas treatment can be achieved with reduction in equipment size, which makes it viable for onsite processing. In addition, the added-value byproduct from this process improves its cost-effectiveness, and makes the fumigant treatment close to being self-sustaining economically. While bearing in mind the foregoing prefatory comments, reference is made toFIG.1, in which apparatus10comprises an absorber/scrubber12, such as Model No. PPS-24 Vapor Scrubber from Vapor Tech, equipped to bring the fumigant gas and dissolved metal hydroxide into contact and thereby enabling their reaction. It should be understood that any absorber or scrubber apparatus known to persons having ordinary skill in the art is suitable for use as the absorber/scrubber12of the apparatus10. For example, in an embodiment, the absorber could be a metallic cylindrical column or tower. In some embodiments, the column could be a packed column, while in others it could be a tray tower. Various packings and trays are available and known and their selection is well within the knowledge of persons of ordinary skill in the art. With continued reference toFIG.1, a mixed air stream14comprising air and an alkyl halide, such as methyl bromide, is derived from a fumigation process16in which an alkyl halide stream18has been used to fumigate an agricultural product, such as wooden logs20, or fruit or grain (not shown), which has been stored in a fumigation container22. Air24is pumped continuously through the fumigation container22to aerate the fumigated agricultural products (i.e., the logs20), as well as the container22itself. In other embodiments, the mixed air stream14may be derived from other sources and processes besides a fumigation process. The mixed air stream14exiting the container22carries with it the removed alkyl halide fumigant (e.g., methyl bromide) as it enters the absorber/scrubber12from the bottom. During its upward travel, the mixed air stream14comes into contact with a counter-current flowing stream of absorbing solution26that is fed from the top of the absorber/scrubber12and travels downwardly through the absorber/scrubber12. In another embodiment, the mixed air stream14and the stream of absorbing solution26can flow through the10absorber/scrubber in the same direction. The stream of absorbing solution26is a metal hydroxide-alcohol buffer solution, which functions to enhance the external mass transfer of alkyl halide from the mixed air stream14to the absorbing solution, as well as to provide a stable alkyl halide conversion media. The alkyl halide (e.g., methyl bromide) is highly soluble in the absorbing alcohol, thereby facilitating its transfer from the mixed air stream14to the absorbing solution. A lean air stream28comprising air and a reduced amount of alkyl halide is discharged from the top of the absorber/scrubber12and passes through an optional de-entrainment/demi sting device30and an in-line alkyl halide detecting/quantification (i.e., measuring) instrument32before venting to the atmosphere A. As the alkyl halide is super active to react with the metal hydroxide in the absorbing solution, two reaction products result from a bimolecular nucleophilic substitution reaction (SN2), wherein the metal is an alkali metal (i.e., sodium, potassium or any of the Group 1 A (1) elements of the periodic table). One reaction product is a product alcohol which corresponds to the alkyl group of the alkyl halide and which is a liquid that is miscible with the absorbing alcohol. The other reaction product is a metal halide which corresponds to the metal of the metal hydroxide and the halide of the alkyl halide and which subsequently precipitates as a solid. The following reaction is the general reaction which occurs: CnH2n+IX+YOH CnH2n+OH+YX Alkyl Metal Alcohol Metal Halide Hydroxide Halide More particularly, where, for example, the alkyl halide is methyl bromide and the metal hydroxide is sodium hydroxide, the reaction will proceed as follows to produce methanol as the product alcohol and sodium bromide as the metal halide: CHsBR+NaOH+CHsOH+NaBr Methyl Sodium Methanol Sodium Bromide Hydroxide Bromide Referring still toFIG.1, stream34, which contains metal halide and alcohols, is supplied to absorbing solution drum36from the absorber/scrubber12. A small make-up stream38, which contains absorbing alcohol, is also supplied to the absorbing solution drum36to compensate for any absorbing alcohol that may have been lost due to reaction with the product alcohol or evaporation into the air stream or other losses. Similarly, a make-up alkali stream40, which contains metal hydroxide and alcohol at a certain concentration, is supplied to the absorbing solution drum36. A discharge stream42exits the absorbing solution drum36via pump44. After leaving the pump44, the stream42is divided into the absorbing solution stream26and a purge stream46. The purge stream46passes through a solid-liquid separation apparatus48, such as a Russell Eco Separator, resulting in (i) a stream50containing a negligible amount of dissolved salt (e.g., metal halide), which stream50is returned to the absorbing solution drum36, and (ii) collected solids52, namely metal halide, that can be packed for sale. The transfer of the alkyl halide fumigant from the mixed air stream14to the liquid absorbing solution in the absorber/scrubber12takes place primarily on the column packing or trays (not shown) of the absorber/scrubber12. The absorbing solution typically comprises an alkali-alcohol solution and may, for example, be methanol, ethanol, butanol, isopropanol, or combinations thereof. The mass fraction of the alcohol in the absorbing solvent will vary, in general, but in some embodiments the mass fraction will be from about 0 to about 1. Accordingly, the water content (i.e., aqueous component) of the absorbing solvent ranges from about 0 to about 1. The concentration of metal hydroxide in the absorbing solution will vary, in general, but in some embodiments the concentration will be from about 0 g/100 ml solvent to about 50 g/100 ml of solvent. The flow rate of the absorbing solution stream26as it flows into the absorber/scrubber12will vary depending on, amongst other things, (i) the concentration of the fumigant in the gas stream, (ii) gas stream flow rate, (iii) the desired fumigant concentration in the outlet gas stream, and (iv) the solubility of the fumigant in the absorbing solution. The flow rate is determinable by persons of ordinary skill in the art and is typically determined as part of the process design. It is desired that the concentration of fumigant in the lean air stream28will be from a trace amount (i.e., in the parts per billion range) to an undetectable amount. The temperature of the absorption column within the absorber/scrubber12will be maintained at a value selected to enhance the solubility of the fumigant in the alcohol, and also inhibit evaporation of the solvent into the gas stream. In some embodiments, this temperature will be kept at a value from about room temperature (e.g., about 20° C. to about 26° C.) to about 50° C. The operating pressure in the absorption column will depend on the pressure of mixed air stream14and may be higher than atmospheric pressure. In some embodiments, the operating pressure may be at least about atmospheric pressure (e.g., 1 atmosphere, or 14.7 pounds per square inch). The formed product alcohol will, in general, be miscible with the absorbing solution, and the metal halide will precipitate, thereby facilitating its separation from the product stream of the reactor. For any absorbing solution stream, the concentration of metal hydroxide should be controlled to meet any TSS and TDS specified by the manufacturer of the pump44, and any associated pipe design specification. As mentioned, the process of the present invention may be practiced in conjunction with fumigation of agricultural products in various containers or enclosures. In some embodiments, the containers may be sealed shipping containers, trailers, railway cars, mills, and warehouses. The fumigated product may be agricultural products, including wood products such as logs, as well as fruits or grains. The concentration of the fumigant in the mixed air stream14exiting the container22during aeration will vary with time. In certain embodiments, the concentration will vary from about 0.25 g fumigant/g mixture to about 0.0 g fumigant/g mixture. The flow rate of the air stream24will vary depending on the alkyl halide fumigant, and the size of the container22. In the fumigation of wood products in shipping containers, the air flow rate of the air stream24may be as high as 1200 ft3/min at room temperature. After the liquid level in the absorber/scrubber12remains unchanged for some time, gas flow is turned on, and the measuring of time-on-stream commences. The countercurrent flowing stream of absorbing solution26and the gas stream to be cleaned provides large contact area and creates a relatively higher concentration difference between the two phases, which is the driving force for mass transfer. FIG.2depicts a batch process and apparatus110for recovering and converting an alkyl halide in accordance with the present invention. Hereinafter, this setup will be referred to as the Batch Mode Setup. Raschig rings (PTFE, L×O.D.×thickness of 3 mm×3 mm×1 mm) are packed into an absorber112to a height of 6″. After such packing, 50 ml of absorbing/reaction solution is first transferred into the reservoir of the Batch Mode Setup, and the time-on-stream is measured from the time the gas flow is turned on. A stream of MeBr-rich gas114flowing from gas source116is regulated by a mass flow controller118(MFC) and passes through check valve120and control valve122on its way to an inlet124of the absorber112. The MeBr-rich gas stream114is supplied to a bottom portion126of the packed bed, and bubbles through the flooded packed bed before exiting through outlet128and then passing through a gas chromatography setup130or vent132via valve134. FIG.3depicts a schematic diagram of apparatus210which can be operated as a batch or recirculation process for recovering and converting an alkyl halide in accordance with the present invention. Hereinafter, this setup will be referred to as the Recirculating Mode Setup. As shown inFIG.3, the effective flow path of the absorber/reactor section212of the Recirculating Mode Setup has an ID of ¼″, a height of 21.26″ (54 cm) and is packed with 3 mm Raschig rings (PTFE, L×O.D.×thickness 3 mm×3 mm×1 mm). After such packing, 20 ml of solution is first transferred into the Recirculating Mode Setup and then circulated at a selected flow rate for the absorption process. A stream of MeBr-rich gas214flowing from gas source216is regulated by mass flow controller (MFC)218and passes through check valve220and control valve222on its way to an inlet224of the absorber212. High-pressure liquid chromatography pump226drives the fluid flow. After the liquid level at the bottom of the absorber212remains unchanged for 10 min, gas flow is turned on, and the measuring of time-on-stream commences. The countercurrent flow of absorbing solution228and the gas stream to be cleaned provides large contact area and creates a relatively higher concentration difference between the two phases, which is the driving force for mass transfer. Gas230exits the absorber212through outlet232and then passes through a gas chromatography setup238or vent236via valve234. In order to describe the invention in more details, the following examples are set forth: Example 1 Batch Mode Operation: Effect of Packing The effect of packing (FIG.4) on halide absorption was studied in the Batch Mode Setup using pure IPA (Isopropyl Alcohol), and the MeBr concentration in the liquid phase was measured. The liquid phase MeBr concentration was found to rapidly increase during the first 2 hours TOS (Time-On-Stream) for both cases, but at a much faster rate when using packing. With packing, the MeBr concentration approaches a stable value starting from the second hour and appears to reach that value, considered to be the maximum absorbing capacity of the solvent, at about the third hour of the process. The packing provides large interfacial contact area between the gas and liquid, by breaking the gas bubbles, the effect of which is the enhancement of inter-phase mass transfer. Therefore, packing materials with high specific surface area per unit volume can be used to improve the process efficiency for the capture of MeBr by the liquid phase. Example 2 Batch Mode Operation: Base Solvent Screening The data shown inFIG.5were collected from a set of experiments conducted in the Batch Mode Setup. The higher the number of carbon atoms, or molecular weight, or boiling point of the solvent, the higher is its absorbing capacity. Since Butanol is much more expensive than the other three solvents, based on cost considerations, IPA will likely be the most viable solvent. Example 3 Batch Mode Operation: Metal Hydroxides Screening The MeBr-rich liquid solution cannot be directly disposed of without incurring significant cost, effort was also made to develop a green process. Therefore, the captured MeBr can either react with the metal hydroxide (YOH) by mixing the MeBr-rich liquid solution with YOH in a separate vessel, or it can be directly reacted with YOH during absorption which may even enhance absorption because of the concomitant preservation of driving force for mass transfer. The present invention adopts the latter approach. The two most commonly used YOH (i.e., NaOH and KOH) were used to investigate the effect of the addition of YOH on the capture and conversion process in the Batch Mode Setup. According to Table 1, NaOH is generally much more soluble in water than in alcohols. Therefore, pure DI-H20, and DI-H20/alcohol mixture were first studied as the base solvent. For the latter mixture, because of the formation of two phases, an aqueous phase that contains almost all the NaOH, and the alcohol phase that contains little NaOH, this solvent system exhibited much lower absorbing capacity than the alcohol-based systems, as shown inFIG.6. Table 1: Solubility of YOH in different solvents NaOH (g/100 ml solvent) KOH (g/100 ml solvent) Water 111 112 Methanol 23.8 43.4 Ethanol «13.9 40 or 30.5 IPA 11 The results for all the solutions tested are presented inFIG.6, and were obtained from the Batch Mode Setup. For alcohol-based solutions, the increase of YOH concentration can greatly enhance the absorbing capacity. The results also reveal that the KOH is more active than NaOH, and ethanol appears to be the best solvent among all studied solvents when YOH is added. The stabilized values of % removal of MeBr from gas phase and the MeBr concentration in the MeBr-depleted gas using different absorbing solutions were corrected to account for the effect of solvent vapor pressure, and the results summarized inFIG.7and Table 2. The most effective absorbing solution is 20 g KOH/100 ml Ethanol. Table 2: Solvent ID reference MeBr Removal % MeBr_GC % Solvent ID Solution composition in Gas Phase: 1 1.5 g NaOH+50 ml Water 12.67% 3.69%2 250 ml IP A 13.35% 3.59%3 3 g NaOH+45 ml IPA+5 ml H2O 18.15% 3.43%4 50 ml MeOH 11.06% 3.35%5 16 g NaOH+38 ml Water+12 ml Ethanol 30.76% 2.95%6 1.5 g NaOH+50 ml Ethanol 63.85% 1.51%7 2.5 g NaOH+50 ml Ethanol 64.64% 1.48%8 5 g NaOH+50 ml MeOH 63.65% 1.42%9 10 g NaOH+50 ml MeOH 69.18% 1.22%10 5 g NaOH+50 ml Ethanol 74.64% 1.07%11 5 g KOH+50 ml IPA 79.24% 0.89%12 5 g KOH+50 ml Ethanol 79.62% 0.86%13 10 g KOH+50 ml Ethanol 86.12% 0.59% Example 4 Recirculating Mode Operation: Formation of Suspended Solids The major challenges for the recirculation test were from the precipitation of solids due to (i) the formation of lower solubility products (from the reaction of YOH and MeBr) as well as (ii) the loss of alcohol solvents at high gas flow rates when no make-up alcohol solution was added to the system. Tests with IOg and 20g KOH/100 ml Ethanol at 5 ml/min recirculation rate and 40 seem air flow rate (without MeBr) revealed that there was no KOH or NaOH in the precipitates which indicates that the precipitates are the products from the reaction of the YOH with MeBr. Example 5 Recirculating Mode Operation: Effect of Gas-Liquid (G-L) Contact Time The effect of G-L contact time in the Recirculating Mode Setup was experimentally studied by keeping the absorbing solution in batch mode. The results are summarized inFIG.8. It should be noted that, although there was a lag in the measurement of the 20 seem and 30 seem experiments, since the solution concentration was far in excess and approximately constant, the decrease of solution volume in the absorber was negligible (as there was solution above the packing, and the packing was always immersed in the solution), the gas composition at the top surface of the solution can remain constant during the 3 -hour duration of the experiment. Therefore, the data reported in the second plot for the 20 seem and 30 seem results can be considered the real performance data. As expected, the decrease in gas flow rate can effectively decrease the amount of MeBr in the gas exit stream, and the best result was 0.3 mol % at 20 seem. Compared with the set of experiments conducted in the Batch Mode Setup (depicted inFIG.2), where the exit gas composition was in the range of 1.05-1.07 mol %, the MeBr composition reduced to 0.67-0.7 mol % at 40 seem. This reduction can be attributed to the reduced ID and increased length of the absorber. Example 6 Recirculating Mode Operation: NaOH/H2O Solution as Model Solvent In order to study the performance of the process with the absorbing solution in recirculation mode while avoiding the pump blockage problem, 20 g NaOH/100 ml H2O solution was used. As shown inFIG.9, at 40 seem MeBr/Air flow rate, liquid (20 g NaOH/100 ml H2O) flow rate was increased from 3.5 ml/min to 10 ml/min. The results show that the 5 ml/min liquid flow rate is sufficient for achieving complete wetness of the absorber packing in the recirculation mode. At 10 ml/min, the gas flow rate was reduced to 20 seem. As expected, the MeBr mol % in gas phase was reduced compared to that at 40 seem. The experiment was also run at 20 seem with 35 ml solution but in non-recirculating (batch) mode. Compared with the 20 sccm/10 ml/min run, it seems the mixing due to the recirculation of liquid phase can be compensated for by the gas flow. For the comparison of batch mode and recirculation mode, based on the water recirculation results, there appears to be no difference for batch mode and recirculating mode at a liquid flow rate of 10 ml/min, although more experimental runs will be needed to confirm this observation. Also, although this may not be applicable for the YOH/Ethanol system, it should be noted that the recirculation mode requires only 20 ml (or even less) of solution, while the batch mode requires 35 ml solution, for capturing and converting similar amounts of MeBr. Furthermore, for practical operation, it is better to run in recirculation mode, which will enable the stream exiting the slurry reservoir to be passed into a precipitator for removal of the solid (salt) product, and add a make-up ethanol (or solvent) stream to the process stream after it exits the precipitator. The 20 sccm/35 ml result of 3.78 mol % is worse than that from the 40 sccm/50 ml (3 g NaOH/100 ml H2O) result of 3.69 mol % (FIG. 2 Batch Mode Setup), even with the NaOH concentration increased to 20 g NaOH/100 ml H2O. The main reason is that the superficial residence time in the Recirculating Mode Setup (FIG.3) is 1/3.2 that of the Batch Mode Setup (FIG.2). Example 7 Recirculating Mode Operation: YOH/Alcohol Solution The YOH/alcohol solution cannot be successfully processed in recirculating mode for 3 hours due to the formation of precipitates which clog the pump. For the IOg NaOH/100ml Ethanol solution, experiments were run (FIG.10) at different gas/liquid ratios while fixing the gas flow rate at 50 seem. As expected, the MeBr concentration in the exit gas stream decreases with the increase of L/G ratio, due to a higher coverage of the cross-section of the packing bed and increased liquid residence time. In addition to the data presented inFIG.11, 20 g KOH/100 ml Ethanol at flow rates of 5 ml/min and 10 ml/min was also tested, but the experiment had to be suspended because the pump pressure was too high (>1600 psi) even after only 5 minutes of recirculation. The liquid flow rate was fixed at 5 ml/min based on the previous experimental results using water. When the liquid flow rate was set to 10 ml/min, the pump pressure rose to a value >1600 psi very quickly. The observations shown inFIG.11confirm the previous conclusion that higher YOH concentration enhances the MeBr capture, and ethanol exhibits better performance than IPA. It will be understood that the embodiments described herein are merely exemplary and that a person of ordinary skill in the art may make many variations and modifications without departing from the spirit and scope of the invention. All such variations and modifications are intended to be included within the scope of the invention as defined in the following claims.
22,968
11857922
DETAILED DESCRIPTION Gas-liquid absorbers, such as scrubbers or sparging beds, are often used in the process of recovering a substance from a gas stream. For example, absorbers are employed to recover dust and various contaminants from process gas streams to produce a treated gas meeting environmental discharge requirements. Generally, a target contaminant present in the gas stream may be removed by contacting the gas with a scrubbing liquid. The contact may induce a transfer of the contaminant from the gas to the liquid. The treated gas may be released. In some applications, the liquid containing the target contaminant may be desirable as a commercial product. Thus, the liquid may be removed and further processed, if necessary, to form a liquid product. The concentration of the target substance in the liquid may be carefully controlled for a number of reasons. In some embodiments, the concentration may be controlled due to a thermodynamic limitation for the absorption of the substance in the liquid. The concentration of the substance may be controlled to reduce inhibition of further reactions happening within the liquid, for example, when inhibition is concentration dependent. In yet other embodiments, concentration may be controlled in view of dilution of the substance in the liquid, due to simultaneous condensation of liquid vapors during the absorption of the target substance from the gas. As a result, the liquid product comprising the target substance may be dilute. A concentrated product comprising the substance is often desirable for commercial applications. Specifically, concentrating the liquid product may reduce excessive costs associated with storage and transport of dilute products. Liquid products are often concentrated, but the process may be expensive due to high capital and operational expenses. Currently, liquid products are concentrated with complex processes such as reverse osmosis, electrodialysis or evaporation. Such processes generally require external energy to perform the concentration. Reverse osmosis and electrodialysis often face limitations in the degree of concentration that can be obtained due to osmotic effects. Thermal evaporative processes can further concentrate a liquid product beyond what reverse osmosis or electrodialysis are capable of concentrating, but the added costs of liquid evaporation are usually high and only employed for certain substances. A product with relatively low value is often not concentrated and either becomes a waste disposal problem or its use is limited to local markets due to storage and transportation costs. As disclosed herein, systems and methods employ an evaporative process for further concentrating a liquid product generated from recovery of a target substance from a gas stream. The methods and systems use the energy present in the gas stream to evaporate excess liquid from the dilute liquid product in a cost-effective manner. In accordance with an aspect, there is provided a method of producing a concentrate solution comprising a contaminant from a gas stream. The method may comprise introducing the gas stream into an absorption chamber. The absorption chamber may be a liquid-gas absorption or reaction chamber. The gas stream may comprise one or more contaminants. In some embodiments, the gas stream may be introduced at an elevated temperature. The method may further comprise introducing a dilute solution comprising the contaminants from the gas stream into the absorption chamber, where the gas stream and dilute solution are contacted. In some embodiments, the dilute liquid may be introduced at an elevated temperature. The contact may result in the production of a liquid-enriched gas, a concentrate solution, and water vapor. Generally, the dilute solution may have a lower concentration of the contaminant than the concentrate solution, and the liquid-enriched gas may have a lower concentration of the contaminant than the incoming gas stream. The liquid-enriched gas may additionally have a lower concentration of volatile organic carbon than the gas stream. In some embodiments, methods may comprise introducing the liquid-enriched gas into a scrubbing liquid to produce the dilute solution. The dilute solution may also be produced by introducing the gas stream into a scrubbing liquid. The gas stream with the target substance to be recovered may be put in contact with the liquid product that is generated in a substance recovery process. The gas may be cooled down by evaporating a fraction of the liquid in the dilute solution, using the gas stream sensible heat. The solution becomes more concentrated and the process is generally repeated until the liquid product reaches a desired concentration, at which point it may be removed as a concentrated liquid product. The gas stream, after contacting the dilute liquid, is generally enriched in liquid and it conveyed to the substance recovery process, where the target contaminant is removed, forming the dilute liquid product. Such dilute liquid product may be transferred upstream to be contacted with incoming gas from the gas stream and concentrated, as previously described. By using the sensible heat in the incoming gas, the main costs associated with an evaporative concentration process can be minimized. Systems and methods disclosed herein may employ temperature control mechanisms. In accordance with certain embodiments, the method may comprise controlling a temperature of one or more of the input gas, a process liquid, (for example, a dilute liquid or pre-concentrated liquid), or the liquid-enriched gas. The elevated temperature of the gas stream may be controlled to partially evaporate the dilute solution upon contact with the gas stream. In some embodiments, the dilute liquid may be introduced at an elevated temperature to heat the gas during evaporation. Water vapor may be evaporated from the dilute solution to produce the concentrate solution. Additionally, water vapor may be evaporated from the dilute solution to increase the relative humidity of the gas stream, producing the liquid-enriched gas. The elevated temperature of the gas stream or dilute liquid may be controlled to reach adiabatic saturation of the gas stream upon contact with the dilute solution. Thus, the controlled temperature will generally depend on the composition of the gas stream and/or the composition of the dilute solution. In some embodiments, the temperature may be controlled to about 230° F. The amount of heat available for evaporation of liquid product may be maximized when the input gas has reached adiabatic saturation. No further cooling of the input gas can be achieved once adiabatic saturation is reached. In some embodiments, for example, when the incoming gas has high relative humidity and the liquid product is dilute, there may be a need to supplement the heat from the input gas by adding external heat to the liquid product or the input gas. In accordance with some embodiments, additional heat to the one present in the input gas may be required to concentrate the liquid product and may be provided, for example, by a heat exchanger. Where the gas stream has an elevated temperature, the temperature of the gas stream will generally be dependent on the method used to produce the gas stream. In some embodiments, organic material may be dried to produce the gas stream. Organic material, for example, moist manure, may be introduced into a dryer. The organic material may be dried, evaporating moisture and ammonia from the manure and producing an ammonia gas stream. The gas stream may be rich in moisture and ammonia. In some embodiments, heat applied during drying may sterilize infectious agents in the organic material. The organic material may comprise, for example, poultry manure or poultry litter. In some embodiments, the poultry manure or poultry litter may comprise chicken manure or chicken litter. Poultry may generally refer to domestic fowl. In some embodiments, poultry may comprise wild game birds. Poultry manure or litter may comprise chicken, turkey, goose, duck, swan, quail, ostrich, or pigeon manure or litter, and combinations thereof. The organic material may comprise animal manure or litter, for example, of any domesticated or farm animal. The organic material may additionally or alternatively comprise sewage sludge. In some embodiments, the organic material may additionally or alternatively comprise food waste, for example, produce waste. Methods disclosed herein may comprise collecting manure, litter, sewage sludge, or food waste. Methods may comprise processing manure, litter, sewage sludge, or food waste to produce an organic material. In some embodiments, methods may comprise removing heat from one or more process components. High temperatures may affect the dissolution of gases in liquids. Any one or more of the following mechanisms may be employed to control temperature. In accordance with certain embodiments, water may be evaporated using the latent heat of vaporization of water and removal of water vapors along the rest of treated gases. In some embodiments, active heat exchange may be employed for removal of heat from hot input gases or to increase heat and vaporization of process liquids. In some embodiments, active heat exchange may be employed directly from absorption and/or reaction chambers. Active or passive heat exchange may be employed to transfer heat between various components of a system, for example, between an absorption chamber and an organic material dryer. Methods may comprise adding or removing heat from the gas stream or the dilute solution. In some embodiments, methods may comprise transferring heat between the gas and the dilute solution to control the temperature or partially evaporate liquid from the dilute solution. For example, the temperature may be controlled between about 85° F. and about 350° F. The temperature may be controlled to between about 100° F. and about 300° F., between about 150° F. and about 280° F., or between about 180° F. and about 250° F. In some embodiments, the method of producing a concentrate solution may comprise collecting the concentrate solution. The composition of the concentrate solution may generally be dependent on the composition of the dilute solution and gas stream. In some embodiments, where the liquid-enriched gas is scrubbed to produce the dilute solution, the composition of the concentrate solution will generally be dependent on the composition of the gas stream. Scrubbed gases typically comprise controlled contaminants that must be captured from polluting gases. The gas stream may comprise a contaminant that is scrubbed from the gas stream. For example, the gas stream may comprise a contaminant selected from nitrogen, sulfur, and carbon. In such embodiments, the concentrate solution may comprise at least one of nitrogen, sulfur, and carbon. The concentrate solution may be processed for further use. In accordance with one or more of the embodiments simultaneously with the evaporative concentration process previously described dust particles present in the input gas stream may also be captured and incorporated into the liquid product. These dust particles may be easily removed once in the liquid with a solid-liquid separation process. The method may further comprise post-treating the concentrate solution to remove solid particles. Solid particles may be removed, for example, by a sedimentation or filtration process. The ionic strength of the liquid product generally increases with an increasing concentration process, and the dust particles tend to coagulate in a liquid of high ionic strength, further easing the removal of solid particles from the liquid product. In accordance with certain embodiments, the concentration of the contaminant in the concentrate solution may be controlled to a predetermined concentration. For example, the concentration of the contaminant may be controlled to induce formation of crystals. The composition of the crystals may generally depend on the composition of the dilute solution and the gas stream. The method may further comprise post-treating the concentrate solution to remove the crystals. In some embodiments, the crystals are treated for further use, for example, for use a solid fertilizer product. In other embodiments, the concentration of the contaminant may be controlled to avoid formation of crystals. Avoiding formation of crystals may provide a desired composition of concentrate solution. The concentrate solution may be treated for further use, for example, for use as a liquid fertilizer product. In embodiments wherein the gas stream is produced by drying organic material, the fertilizer product may be a certified product suitable for organic farming. The method may comprise drying organic material to produce the gas stream. Heat applied during drying may sterilize infectious agents in the organic material. However, non-live contaminants may be released into the gas stream, for example, the gas stream may comprise solid particles such as dust and other volatiles. In some embodiments, the gas stream is pretreated to remove contaminants. The contaminants, for example, solids, may be separated from the gas stream. In some embodiments, the contaminants are separated from the gas stream and discarded. Such methods may minimize the incorporation of solid particles to the liquid. In some embodiments, the method of producing a concentrate solution may comprise introducing a non-water saturated gas into the gas stream. The non-water saturated gas may be employed to further enhance the evaporation of the dilute solution. The method of producing a concentrate solution may comprise pre-concentrating the dilute solution after producing it with a scrubbing liquid. The dilute solution may be pre-concentrated, for example, by one or more of a reverse osmosis, electrodialysis, or ultrafiltration process. The solution may be introduced into the absorption chamber as a pre-concentrated solution to contact the gas stream therein. In accordance with another aspect, there is provided a system for producing a concentrated solution from a gas stream. The system may comprise a source of a gas stream comprising a contaminant. In some embodiments, the source of the gas stream may be a processing plant which produces a contaminant gas as a byproduct. The source of a gas stream may be a plant which typically employs a scrubbing or other system to remove contaminants from a gas byproduct. The source of a gas stream may be an organic material dryer, as previously described. The system may comprise a source of a dilute solution comprising the contaminant. In some embodiments, the system may comprise an absorption chamber fluidly connectable to the source of the gas stream and the source of the dilute solution. It is to be understood that the absorption chamber may be fluidly connected to the source of the gas stream and the source of the dilute solution during operation. The absorption chamber may have an outlet for a concentrated solution and an outlet for a liquid-enriched gas. The absorption chamber may be constructed and arranged to combine the gas stream and dilute solution. In some embodiments, the absorption chamber may have an inlet for dilution water. The system may comprise more than one absorption chamber, wherein gases and liquids are transferred between the one or more absorption chambers. In some embodiments, the absorption chamber may comprise a gas-liquid contactor. The gas-liquid contactor may introduce a gas into a liquid (for example, the gas stream into the dilute solution) by dispersing the gas with a fine mist of solution or by flowing the gas though a volume of solution. The gas-liquid contactor may be a differential gas-liquid contactor or a stagewise gas-liquid contactor. The absorption chamber may comprise one or more of a gas sparger, a gas-liquid column (for example, a falling-film column, a packed column, a bubble column, or a plate column), a spray tower, an agitated vessel, a scrubber, a rotating disc contactor, a Venturi tube, a dispersion tube, or any other vessel configured to contact a gas and a liquid. The absorption chamber may comprise at least one of an enriched gas outlet and a product outlet. The reaction subsystem may further comprise at least one of a gas inlet and a liquid inlet. The system may comprise a wet electrostatic precipitator positioned within an absorption chamber. The wet electrostatic precipitator may be employed to prevent precipitation and/or aerosolization of product gas within the absorption chamber. The prevention of precipitation and/or aerosolization may limit and/or control unwanted byproducts from exiting the system. In some embodiments, the wet electrostatic precipitator may improve a yield of a target substance in the product by controlling undesired precipitation and/or aerosolization of the product. The system for producing a concentrated liquid contaminant product may comprise a temperature control subsystem. The temperature control subsystem may be configured to maintain a predetermined temperature range within the absorption chamber. The temperature control subsystem may employ active or passive heat transfer. In some embodiments, the temperature control subsystem comprises a chiller or a heater. The temperature control subsystem may further be configured to provide heat to the system for removing contaminants from a gas stream, for example, to produce input gases. The temperature control subsystem may be configured to heat or cool the gas stream or input liquid stream, as required. The temperature control subsystem may comprise a heat exchanger constructed and arranged to transfer heat between components and subsystems of the system. The heat exchanger may employ mechanisms to diffuse heat within the system, for example, to conserve heat energy. The heat exchanger may employ mechanisms to provide heat to the input gas or absorption chamber. In some embodiments, the temperature control subsystem may comprise a temperature sensor. One or more setting may be adjusted manually or automatically upon measuring a temperature outside the predetermined temperature range. The temperature control subsystem may comprise a control module electrically connected to the temperature sensor. In some embodiments, the control module may be configured to adjust a temperature within the absorption chamber, for example, manually or automatically, responsive to a measurement obtained by the temperature sensor. The temperature control subsystem may be configured to maintain a predetermined temperature range. The temperature control subsystem may comprise a heat exchanger. The system for producing a concentrated solution may comprise a solids-liquid separation unit positioned downstream from the absorption chamber through the outlet for the concentrated solution. The solids-liquid separation unit may be employed to separate solid pollutants, for example, undesired crystals, solids formed from dust particle flocs, or biological flocs. The solids-liquid separation unit may further be employed to collect desired crystal product. The solids-liquid separation unit may comprise at least one of a sedimentation unit and a filtration unit to process the concentrated product for further use. In some embodiments, the system may further comprise a gas-solids separation unit positioned downstream from the source of the gas stream. The solids-gas separator may comprise, for example, an air filter or a multicyclone separator. The solids-gas separator may be configured to remove dust and other contaminants from one or more gas streams within the system. Any waste collected through the solids waste outlet of the separator may be discarded. The source of the gas stream may comprise an organic material dryer, as previously described. In some embodiments, the system may further comprise a source of a non-water saturated gas fluidly connected to the source of the gas stream. The non-water saturated gas may be employed to further enhance the evaporation of the dilute solution. In some embodiments, the source of the dilute solution may comprise a subsystem for removing contaminants from the gas stream. The subsystem may be positioned downstream from the absorption chamber and constructed and arranged to receive at least one of the gas stream or the liquid-enriched gas and contact the gas with a scrubbing liquid. The scrubbing liquid may absorb contaminants from the gas and produce the dilute solution. Treated gas may be released, as will be apparent to one of ordinary skill in the art. In some embodiments, the subsystem for removing contaminants from the gas stream may comprise a second absorption chamber having an inlet for the at least one of the gas stream or the liquid-enriched gas and having an outlet for the dilute solution. The absorption chamber may be a gas-liquid contactor, as previously described. In accordance with certain embodiments, the subsystem for removing contaminants from the gas stream may comprise a pre-concentration unit positioned downstream from the second absorption chamber. The pre-concentration unit may comprise at least one of an ultrafiltration unit, a reverse osmosis unit, and an electrodialysis unit. In some embodiments, the pre-concentration unit may comprise at least two of an ultrafiltration unit, a reverse osmosis unit, and an electrodialysis unit. The pre-concentration unit may be configured to pre-concentrate dilute solution before it is conveyed to the absorption chamber for contact with the gas stream. In some embodiments, the subsystem for removing contaminants from the gas stream may further comprise a microbiological treatment subsystem fluidly connected to the second absorption chamber. The microbiological treatment subsystem may be positioned downstream from the absorption chamber, such that the gas that contacts the microorganisms is the liquid-enriched gas. The liquid-enriched gas may be safer for the microorganisms, since it comprises a dilute concentration of contaminants, as compared to the input gas stream. Systems and methods may comprise dosing the one or more process liquids with a biological catalyst. In accordance with certain embodiments, a naturally occurring microbial culture may be employed to enhance treatment of the product gas. Process liquids may be dosed with biological catalyst, for example a microbial or enzymatic organism. Catalysis may be accomplished by retaining the biological organisms catalyzing the oxidation in the reaction tank where oxygen is supplied. Once the organisms grow and are established in the system, they may be separated out of the final liquid and/or solid product. In accordance with certain embodiments, the separated biological organisms may be returned back to the reaction tank to enhance the culture, further speeding the treatment reaction. In some embodiments, the system may further comprise a source of an oxidant. The source of an oxidant may be fluidly connected to an absorption chamber, for example, to the second absorption chamber within the subsystem for removing contaminants from the gas stream. The system may comprise an oxidation control subsystem. The oxidation control subsystem may be configured to maintain a predetermined oxidation reduction potential (ORP) within the components or subsystems of the system, for example, within the second absorption chamber. In some embodiments, the oxidation control subsystem may comprise an ORP sensor configured to measure ORP of a solution within the system. One or more setting may be adjusted manually or automatically upon measuring an ORP that requires adjustment. The system may further comprise a control module electrically connected to the ORP sensor. The control module may be configured to adjust the ORP within the system, for example, manually or automatically, responsive to a measurement obtained by the ORP sensor. The control module may be configured to provide more or less oxidant to the system, to adjust the ORP therein. In some embodiments, the system may further comprise a source of a base. The source of a base may be fluidly connected to an absorption chamber, for example, to the second absorption chamber within the subsystem for removing contaminants from the gas stream. The system may further comprise a pH control subsystem configured to maintain a predetermined pH within the components or subsystems of the system, for example, within the second absorption chamber. The pH control subsystem may comprise a pH meter configured to measure pH of a solution within a component or subsystem of the system. One or more setting may be adjusted manually or automatically upon measuring a pH that requires an adjustment. The system may comprise a control module electrically connected to the pH meter. The control module may be configured to adjust pH within the subsystem, for example, manually or automatically, responsive to a measurement obtained by the pH meter. The pH may be adjusted as required by addition of an acid or a base, by adjusting a concentration of oxidant within the system (for example, increasing or decreasing aeration), or by dilution or evaporation of a solution within the system. The control module may be configured to adjust pH to a predetermined value. The pH control subsystem may be configured to maintain a pH that is favorable to the microbiological treatment subsystem. In some embodiments, the pH control subsystem is configured to maintain a pH between about 2 and about 9. The subsystem may be configured to maintain a pH between about 5 and about 8.5 or between about 6 and about 7.5. The subsystem may be configured to maintain a pH between about 6.7 and about 8.1, for example, where the system comprises a microbiological treatment subsystem. The system may further comprise a conductivity control subsystem configured to maintain a predetermined conductivity within a component or subsystem of the system, for example, within the second absorption chamber. In some embodiments, the conductivity control subsystem may comprise a conductivity meter. The conductivity meter may be configured to measure conductivity of a gas or solution within a component or subsystem of the system. One or more setting may be adjusted manually or automatically upon measuring a conductivity that requires adjustment. The system may comprise a control module electrically connected to the conductivity meter. The control module may be configured to adjust the conductivity of the gas or the solution within the system, for example manually or automatically, responsive to a measurement obtained by the conductivity meter. In some embodiments, the control module may adjust conductivity by adjusting one or more of pH, temperature, concentration of ions, or concentration of an oxidant in the system. In accordance with certain embodiments, the control module may be configured to maintain a predetermined concentration of a contaminant in the process liquids, for example, a predetermined concentration of TDS in the solution within the system. The predetermined concentration of the contaminant may be selected to induce formation of crystals. In other embodiments, the predetermined concentration of contaminant may be selected to avoid formation of crystals. The control module may adjust a concentration of a substance or TDS within the system by adjusting one or more of pH, temperature, concentration of ions, or concentration of an oxidant in the system. As shown in the exemplary embodiment ofFIG.1an inlet gas30with a target substance to be recovered may be introduced into an absorption chamber10where such target substance may be transferred into an absorbing liquid. The treated gas32with a fraction of the target substance removed may be conveyed out of such absorption chamber10. The absorption chamber10may be connected to a reaction chamber12. The absorbing liquid42,44may be actively exchanged back and forth between the absorption chamber10and reaction chamber12. In the reaction chamber12the conditions of the liquid may be adjusted with a variety of means in order to condition such liquid to continue absorbing the target substance in the absorption chamber10. In some embodiments, the pH of the liquid solution may be controlled, a base52may be added, or an oxidant50may be added to partially or fully oxidize the target compound. Heat20may be added or removed from the reaction chamber12to control temperature and dilution water may be added to control the concentration of the substances in the reaction chamber to optimize reaction conditions. A liquid product46may be removed from the reaction chamber as a final product, yet in some embodiments such liquid product may be conveyed to a dissolved solids concentrator in order to remove excess water and have a more concentrated final product. A reverse osmosis or electrodialysis unit is typically used in the dissolved solids concentrator but other technologies are possible. Some of the water60removed from the liquid product in the dissolved solids concentrator may be returned to the reaction chamber in order to control the concentration as previously described. In other embodiments a fraction or all of the water60may be discarded as wastewater. The water60may contain solids. The concentrated product may be conveyed away from the dissolved solids concentrator. In the exemplary embodiment ofFIG.2the inlet gas30with the substance to be recovered may be put in contact with the liquid product420coming from a downstream substance recovery process using a gas liquid absorption chamber100. The sensible heat200in the inlet gas300may be used to induce evaporation of the liquid product420, further concentrating such product. The inlet gas300may be enriched with liquid from the liquid product420, and such liquid enriched gas340may be conveyed to the downstream substance recovery process120. In the downstream substance recovery process120the target substance may be transferred from the liquid enriched gas340into the liquid product320. The recovered substance might undergo one or more reactions in the substance recovery process120to form a dilute liquid product420while in yet other embodiments no reactions occur. The dilute liquid product420may be conveyed back into the gas liquid contact chamber100for further concentrating. In some embodiments, heat200may be added to the inlet gas300or to the liquid in the gas-liquid absorption chamber100. Heat exchangers or other devices to transfer heat may be employed. In some embodiments the concentrated liquid product460obtained from the gas-liquid absorption chamber100is the final product, while in yet other embodiments the concentrated liquid product460may be further treated to remove dust particles that were collected in the liquid from the inlet gas30. A liquid-solid particle removal process140, such as but not limited to a settling chamber or a filter, may be used. The treated concentrated liquid480with a fraction of the particles removed may be conveyed away as final product. The exemplary embodiment ofFIG.3includes a pretreatment process160of the inlet gas30prior to introduction to the gas-liquid absorption chamber100. The pretreatment160may be employed to remove a fraction of the dust particles present in the gas30, for example, by using a gas-solid particle removal process, such as a bag filter or a cyclone. The exemplary embodiment ofFIG.4includes a pre-concentration process180of the dilute liquid product420downstream from the substance recovery process120. The dilute liquid product420may be pre-concentrated to produce a pre-concentrated liquid430in a dissolved solids concentrator, for example a reverse osmosis or electrodialysis unit, prior to introducing it into a gas-liquid absorption chamber100. The excess liquid425removed from the dilute liquid product420may be returned to the substance recovery process120as a diluent or discarded as waste. FIG.5is an illustration of an exemplary spray tower that may be used as a gas-liquid absorption or contact chamber. In the exemplary spray tower, a larger liquid surface area is created by the spray nozzles to induce evaporation of the liquid into the gas. Many alternative designs of gas-liquid absorption or contact chambers may be employed, as will be evident to someone skilled in the art.FIG.6is an illustration of an alternative exemplary gas-liquid absorption or contact chamber, where the gas is sparged into a pool of liquid using alternative sparger designs. The exemplary sparger forms a swarm of bubbles with a high surface area to induce gas to liquid heat transfer. FIG.7is an illustration of yet another embodiment of an exemplary gas-liquid absorption or contact chamber. The exemplary scrubber tower ofFIG.7includes alternative chamber locations125,120within the scrubber for obtaining the concentration of the liquid product460. The inlet gas300with the substance to be removed is introduced in the scrubber125and put in contact with a shower of liquid200to induce the heat transfer and evaporation of the liquid. In some embodiments, heat200may be added. The cooled and liquid enriched gas passes a mist eliminator127to retain small droplets of product. In some embodiments the concentrated product460in the scrubber sump120may be part of a liquid flow loop where a solid liquid separation process140is employed to retain dust particles and control the concentration of suspended solids in the scrubbing liquid. A fraction of the recirculation flow480may be removed away as concentrated final product. Systems and methods disclosed herein may be run according to the exemplary embodiment shown inFIG.8. At start up, flue gases from a source of a gas to be treated110may be put in contact with a scrubbing liquid in an absorption chamber100. The absorption chamber100may produce a treated gas and a liquid comprising contaminants from the flue gas. The liquid may be introduced into an ultrafiltration unit130and the effluent into a reverse osmosis unit135, to produce a pre-concentrated liquid product. Treated liquid may be discharged from the reverse osmosis unit as diluent, while the concentrated retentate may be introduced into a second absorption chamber120. In the second absorption chamber120, the flue gas from the source of a gas110may be scrubbed with the retentate. The hot flue gas may be cooled by the retentate while simultaneously evaporating water from the retentate, producing a concentrated liquid product. The concentrated liquid product may be discharged from the second absorption chamber120as the final product. The system may comprise one or more pumps, blowers, or fans to drive gases and solutions within the system. The system may further comprise one or more tanks for holding gases or solutions, for example, product tanks for holding liquid product and/or product comprising solids. The function and advantages of these and other embodiments will be more fully understood from the following non-limiting example. The example is intended to be illustrative in nature and is not to be considered to be limiting to the scope of the embodiments discussed herein. Example: Concentrated Nitrogen Product from Manure Flue Gas A pilot test was run for a nitrogen recovery process from a nitrogen containing gas stream. The results were estimated based on the pilot test. Water and nitrogen concentrations of each gas and liquid solution are presented in Table 1. Flue gases from a manure dryer carrying 105 tons per day (tpd) of water vapor and 3.7 tpd of ammonia nitrogen were put in contact with 16,547 gallons per day (gpd) of liquid in an ammonia recovery process. The ammonia recovery process included a pre-concentration reverse osmosis unit, which was run to produce 43 tpd of water (equivalent to 10,300 gpd) of a pre-concentrated liquid product. In the gas-liquid absorption chamber, the pre-concentrated liquid product was evaporated, obtaining a final concentrated product of 6,247 gpd. The evaporated water was transported by the flue gases exiting the gas-liquid absorption chamber into the ammonia recovery process. There, the majority of the ammonia was recovered and incorporated into a dilute liquid product to be concentrated. The system provides the advantage of further concentrating a liquid product using existing heat that otherwise would be lost. The concentrated product of only 6,247 gpd of liquid is easier to store and transport than the 16,547 gpd of dilute liquid product or even the 10,300 gpd of reverse osmosis pre-concentrated liquid product. TABLE 1Water and nitrogen concentrations in process gases and liquids.Process gasWaterWaterNitrogenor liquid(tons per day)(gallons per day)(tons per day)Flue gases (1)105—3.7Flue gases (2)148—3.7Scrubbed gases (3)21—0.07Effluent (5)730175,0003.6Dilute product (6)661158,4530.07Pre-concentrated6916,5473.6product (7)Concentrated266,2473.6product (8)Evaporated10,300430water (9) Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that actual parameters and/or configurations will depend on the specific application in which the disclosed methods and materials are used. Those skilled in the art should also recognize or be able to ascertain, using no more than routine experimentation, equivalents to the specific embodiments disclosed. For example, those skilled in the art may recognize that the method and components thereof, according to the present disclosure, may further comprise a network or systems or be a component of a system for concentrating a substance recovered from a gas stream. It is therefore to be understood that the embodiments described herein are presented by way of example only and that, within the scope of the appended claims and equivalents thereto; the disclosed embodiments may be practiced otherwise than as specifically described. The present systems and methods are directed to each individual feature, system, or method described herein. In addition, any combination of two or more such features, systems, or methods, if such features, systems, or methods are not mutually inconsistent, is included within the scope of the present disclosure. The steps of the methods disclosed herein may be performed in the order illustrated or in alternate orders and the methods may include additional or alternative acts or may be performed with one or more of the illustrated acts omitted. Further, it is to be appreciated that various alterations, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the spirit and scope of the disclosure. In other instances, an existing facility may be modified to utilize or incorporate any one or more aspects of the methods and systems described herein. Thus, in some instances, the systems may involve recovering a concentrated substance from a gas stream. Accordingly the foregoing description and figures are by way of example only. Further the depictions in the figures do not limit the disclosures to the particularly illustrated representations. The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term “plurality” refers to two or more items or components. The terms “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of” and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements. While exemplary embodiments of the disclosure have been disclosed, many modifications, additions, and deletions may be made therein without departing from the spirit and scope of the disclosure and its equivalents, as set forth in the following claims.
40,802
11857923
DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION This description will enable one skilled in the art to make and use the invention, and it describes several embodiments, adaptations, variations, alternatives, and uses of the invention, including what is presently believed to be the best mode of carrying out the invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly indicates otherwise. For example, “a fermentor” includes a plurality of actual fermentors, in series or in parallel. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this invention belongs. Unless otherwise indicated, all numbers expressing reaction conditions, stoichiometries, concentrations of components, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending at least upon a specific analytical technique. Some variations of the invention can be described by reference to the process configuration shown inFIG.1, which relates to both apparatus and methods to carry out the invention. Any reference to a method “step” includes reference to an apparatus “unit” or equipment that is suitable to carry out the step, and vice-versa. In the syngas-generation step, carbonaceous feedstock such as biomass is gasified with one or more oxidants to produce a raw syngas stream comprising at least syngas (CO and H2). Other gas species in the raw syngas stream may include acid gases CO2and H2S, relatively inert species such as CH4and N2, and trace constituents such as tars, ash, and particulates. The raw syngas stream from syngas generation may undergo one or more clean-up steps to remove specific contaminants, such as particulates, thereby forming an intermediate syngas stream. The raw syngas stream and/or the intermediate syngas stream (which may include some amount of recycle) optionally undergo an acid-gas removal step to remove bulk amounts of CO2and/or H2S, thereby forming a conditioned syngas stream. Typically, at least CO2(and H2O) will be removed in an acid-gas removal unit, but H2S removal may also be desired. Whether H2S should also be removed, and to what extent, typically depends on how much sulfur is present (if any) in the carbonaceous feedstock, the impact of sulfur-containing compounds on downstream operations, and the impact H2S removal may have on CO2removal. The intermediate stream, upstream of the addition of a recycle stream (if any), will typically have between about 5-30 vol % CO2. The conditioned syngas stream, upstream of the addition of a recycle stream (if any), will typically have between about 1-25 vol % CO2, or 2-20 vol % CO2in some embodiments. The tail gas stream, in various recycle scenarios, will typically have between about 10-90 vol % CO2, such as about 20-80 vol % CO2, or about 25-75 vol % CO2. Other ranges of CO2content in various streams are possible, depending on many factors. The conditioned syngas stream is suitable for direct biological conversion processes, wherein microorganisms (such as the microorganisms described herein) directly convert one or more of H2, CO, and CO2to ethanol, acetic acid, butyric acid, butanol, or another fermentation product. When tail gas comprising syngas is recycled, the syngas is given another pass for biological conversion to ethanol or another product. In some variations, as depicted inFIG.1, at least a portion of the tail gas may be recycled to the fermentor feed, or to a CO2-removal step upstream of the fermentor feed, or to both of these locations. When a CO2-removal unit is already in place, recycling to it is particularly advantageous because additional unit operations become unnecessary. Some variations of the invention are premised on the realization that recycle streams can be tuned so that syngas generation and balance-of-plant capital per unit product produced may actually decrease. With continued reference toFIG.1, R1is the ratio of tail gas recycle to the fermentor feed divided by the total tail gas flow, each on a volume basis. R2is the ratio of tail gas recycle to the acid-gas removal unit divided by the total tail gas flow, each on a volume basis. Recycle ratios R1and R2are non-negative numbers from 0 to 1. The sum of R1+R2cannot exceed unity. R1+R2=1 represents total recycle of the tail gas, while R1+R2=0 represents no recycle of the tail gas to either locations indicated inFIG.1. By mass balance, the fraction of tail gas that is not recycled plus R1plus R2must equal 1. R1may be selected from various values from 0 to about 1, preferably from 0 to about 0.5, and more preferably from 0 to about 0.2. R2may be selected from various values from 0 to about 1, preferably from about 0.2 to about 0.8, and more preferably from about 0.2 to about 0.5. The sum R1+R2may be selected from various values greater than 0 (e.g., 0.001 or more) to about 1, preferably from about 0.2 to about 0.8, and more preferably from about 0.25 to about 0.5. R1should not be equal or close to one at steady state, because total recycle of tail gas back to the fermentor will cause a buildup of CO2, other inerts, and syngas. However, in certain dynamic situations or due to equipment problems (e.g., problems with the tail gas combustion unit), it is possible to recycle all of the tail gas back to the fermentor feed (R1=1) for some amount of time. R2should also generally not be equal or close to one at steady state, unless the acid-gas removal unit is functionally designed to also remove inerts (e.g., CH4or N2) and anything else that must be purged somewhere from the system. Again, in certain dynamic situations, it is possible to allow total recycle of tail gas to the acid-gas removal unit from some amount of time. These dynamic situations could include downstream equipment problems, availability issues with feed streams in the process, fermentation issues (e.g., a stationary phase wherein syngas conversion drops significantly), and so on. The recycle ratios R1and R2may be subjected to various means of dynamic or steady-state process control. As is known, many feedforward and feedback control strategies are possible. R1and R2may independently be set to control points for a desired steady state, or for a desired or known unsteady state. A person of skill in the art of process control will also understand that the ratio of R1to R2, derivatives of R1and R2with time, the ratio of the time derivatives of R1and R2, the derivatives of process variables (such as CO or H2conversion, or ethanol productivity) with R1and R2, and so on, may be utilized in various control strategies. The following are exemplary control examples only and should not be construed as limiting in any way, or as being related to any particular fundamentals being applied. These examples demonstrate that R1and/or R2can be set to vary over time or as a function of other conditions in the process. In some embodiments, R1and/or R2are adjusted continuously, or at least dynamically (e.g., periodically or intermittently), in response to one or more upstream parameters such as feedstock type, oxidant profile, syngas-generation design or performance, syngas-cleanup design or performance, or acid-gas removal design or performance. In some embodiments, R1and/or R2are adjusted continuously, or at least dynamically (e.g., periodically or intermittently), in response to one or more fermentor parameters such as temperature, pressure, residence time, pH, redox potential, nutrient concentration, microorganism viability or vitality, and so on. In some embodiments, R1and/or R2are adjusted to one or more fermentor design or performance variables such as CO conversion, H2conversion, CO2conversion, ethanol selectivity, ethanol productivity, ethanol titer, or acetic acid selectivity. Such adjustment may be in combination with a response to fermentor parameter, such as those listed above. Certain embodiments adjust R1and/or R2to change or optimize the CO2content in the fermentor feed. The CO2level in the fermentor feed can be varied, by adjusting R1and/or R2, to about 5-50 vol % CO2, such as about 10-40 vol % CO2, or about 20-30 vol % CO2. Certain embodiments increase R2, relative to R1, so that more CO2can be removed in the acid-gas removal step and decrease the CO2level in the fermentor feed. Some embodiments adjust R1and/or R2to change or optimize the syngas to acid gas molar ratio, (CO+H2)/(CO2+H2S), at one or more points in the process. Certain, preferred embodiments adjust R1and/or R2to change or optimize the syngas to acid gas molar ratio, (CO+H2)/(CO2+H2S), in the feed stream entering the fermentor. The syngas to acid gas molar ratio entering the fermentor can be varied, by adjusting R1and/or R2, between about 2 to about 10 or more, such as about 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. The syngas feed to the fermentor is typically at a higher pressure than the tail gas pressure. The reason is that upstream operations (gasification and acid-gas removal) generally favor higher pressures compared to fermentation. For example, the feed pressure to the fermentor may be about 2-40 barg, while the pressure of the tail gas may be about 0.1-2 barg (usually not greater than 1 barg). In order to recycle a gas stream to an upstream point that is at higher pressure, the pressure of the gas stream being recycled needs to be raised. Rather than removing CO2from the tail gas, compressing the remainder, and then recycling it back to the fermentor, this invention contemplates recycling some portion of the tail gas and compressing it, without otherwise separating its components. That is, a “portion” of the tail gas stream in this context refers to a flow split only, by some flow-splitting means (e.g., valves)—not a component split by some separation means. InFIG.1, the recycled tail gas is compressed upstream of the R1/R2split. In other embodiments, the recycled tail gas may be split into two or more recycle streams and then each of these streams compressed. While this adds some cost, it allows for adjusting the pressure increase in the recycle streams individually, if desired. The amount of compression may be varied, but the pressure of a recycle stream should be at least raised to a pressure sufficient to allow its introduction into the stream(s) of interest. It is possible to compress the recycled tail gas, particularly when recycled back to the acid-gas removal unit, such that the pressure of the combined stream is actually increased. This would add operating costs but may improve the CO2removal. In some embodiments, the conversion of syngas is about 90-98% (molar conversion of CO and H2). The syngas conversion may be influenced by a number of factors, including the levels of inerts in the conditioned syngas stream, and the fermentor conditions, such as temperature, pH, mixing and mass transfer, the presence of competing microorganisms, and so on. In some embodiments, the syngas conversion is 90-98% upon recycling of tail gas as described herein, and less than 90% (such as only 75-85%) without tail gas recycling, all other factors being held constant. Preferably, syngas conversion is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or more percentage points higher by implementing one or more of the recycle methods taught herein. Higher overall syngas conversion will mean that the tail gas contains less of the syngas initially generated. In some embodiments with tail gas recycle, the tail gas contains about 2% to about 10% of the syngas contained in the raw syngas stream; whereas, without tail gas recycle (R1, R2=0), the tail gas contains about 10% to about 25% of the syngas contained in the raw syngas stream. The syngas concentration and energy content of the tail gas stream is not necessarily less when tail gas recycle is employed, because CO2can be removed from the acid-gas removal step. The non-recycled tail gas flow rate may be reduced, in some embodiments. Higher syngas conversions will translate into higher yields of products of interest, such as ethanol, because product selectivity is not expected to decrease using these recycle strategies. Product selectivity may actually improve when less CO2is fed to the fermentor, further increasing product yield. FIGS.2-4are provided to indicate other variations of the invention. InFIG.2, the carbonaceous feedstock is biomass, the oxidant is oxygen-enriched air, and the product of interest is ethanol. InFIG.3, there is recycle of some of the tail gas to the fermentor, but not any recycle to the acid-gas removal unit (R2=0). InFIG.4, there is recycle of some of the tail gas to the acid-gas removal unit, but not any recycle to the fermentor (R1=0). All other aspects of these configurations may be selected or characterized as described with reference toFIG.1herein. The syngas-generation unit or step may be selected from any known means, such as a gasifier. The gasifier could be, but is not limited to, a fluidized bed. Any known means for devolatilization or gasification can be employed. In variations, the gasifier type may be entrained-flow slagging, entrained flow non-slagging, transport, bubbling fluidized bed, circulating fluidized bed, or fixed bed. Some embodiments employ known gasification catalysts. “Gasification” and “devolatilization” generally refer herein to the reactive generation of a mixture of at least CO, CO2, and H2, using oxygen, air, and/or steam as the oxidant(s). If gasification is incomplete, a solid stream can be generated, containing some of the carbon initially in the feed material. The solid stream produced from the gasification step can include ash, metals, unreacted char, and unreactive refractory tars and polymeric species. Generally speaking, feedstocks such as biomass contain non-volatile species, including silica and various metals, which are not readily released during pyrolysis, devolatilization, or gasification. It is of course possible to utilize ash-free feedstocks, in which case there should not be substantial quantities of ash in the solid stream from the gasification step. When a fluidized-bed gasifier is employed as the devolatilization unit, the feedstock can be introduced into a bed of hot sand fluidized by a gas. Reference herein to “sand” shall also include similar, substantially inert materials, such as glass particles, recovered ash particles, and the like. High heat-transfer rates from fluidized sand can result in rapid heating of the feedstock. There can be some ablation by attrition with the sand particles. Heat is usually provided by heat-exchanger tubes through which hot combustion gas flows. Circulating fluidized-bed reactors can be employed as the devolatilization unit, wherein gas, sand, and feedstock move together. Exemplary transport gases include recirculated product gas, combustion gas, or recycle gas. High heat-transfer rates from the sand ensure rapid heating of the feedstock, and ablation is expected to be stronger than with regular fluidized beds. A separator may be employed to separate the product gases from the sand and char particles. The sand particles can be reheated in a fluidized burner vessel and recycled to the reactor. In some embodiments in which a countercurrent fixed-bed reactor is used as the gasifier, the reactor consists of a fixed bed of a feedstock through which a gasification agent (such as steam, oxygen, and/or recycle gas) flows in countercurrent configuration. The ash is either removed dry or as a slag. In some embodiments in which a cocurrent fixed-bed reactor is used as the gasifier, the reactor is similar to the countercurrent type, but the gasification agent gas flows in cocurrent configuration with the feedstock. Heat is added to the upper part of the bed, either by combusting small amounts of the feedstock or from external heat sources. The produced gas leaves the reactor at a high temperature, and much of this heat is transferred to the gasification agent added in the top of the bed, resulting in good energy efficiency. Since tars pass through a hot bed of char in this configuration, tar levels are expected to be lower than when using the countercurrent type. In some embodiments in which a fluidized-bed reactor is used as the gasifier, the feedstock is fluidized in recycle gas, oxygen, air, and/or steam. The ash is removed dry or as heavy agglomerates that defluidize. Recycle or subsequent combustion of solids can be used to increase conversion. Fluidized-bed reactors are useful for feedstocks that form highly corrosive ash that would damage the walls of slagging reactors. The primary fluidizing agent for a fluidized-bed gasifier may be recycle gas, possibly including a portion of the fermentor tail gas. Due to the high heat-transfer characteristics of a fluidized bed, the recycle gas will cool and give up a portion of its sensible heat to the carbon-containing feedstock particles. Utilizing hot recycle gas to fluidize a bed of incoming biomass particles leads to improved overall energy efficiency. In some embodiments in which an entrained-flow reactor is used as the gasifier, char is gasified with oxygen, air, or recycle gas in cocurrent flow. The gasification reactions take place in a dense cloud of very fine particles. High temperatures may be employed, thereby providing for low quantities of tar and methane in the product gas. Entrained-flow reactors remove a major part of the ash as a slag, as the operating temperature is typically well above the ash fusion temperature. A smaller fraction of the ash is produced either as a very fine dry fly ash or as a fly-ash slurry. Some feedstocks, in particular certain types of biomass, can form slag that is corrosive. Certain entrained-bed reactors have an inner water- or steam-cooled wall covered with partially solidified slag. In certain embodiments, the process configuration further includes a reformer disposed between the gasifier and the optional syngas-cleanup step or the acid-gas removal step. The reformer may be employed to convert or crack tars and methane to produce additional syngas, in some embodiments, optionally with a reforming catalyst. The optional reformer, which can be regarded as within the syngas-generation unit ofFIGS.1-4, is any reactor capable of causing at least one chemical reaction that produces syngas. Conventional steam reformers, well-known in the art, may be used either with or without a catalyst. Other possibilities include autothermal reformers, partial-oxidation reactors, and multistage reactors that combine several reaction mechanisms (e.g., partial oxidation followed by water-gas shift). The reactor configuration may be a fixed bed, a fluidized bed, a plurality of microchannels, or some other configuration. Heat can be supplied to the reformer reactor in many ways including, for example, by oxidation reactions resulting from oxygen added to the process. In some embodiments, a direct-fired partial-oxidation reactor is employed, wherein both oxygen and fuel are directly injected into the reactor to provide heat and assist in reforming and cracking reactions. The reformer may include homogeneous (non-catalyzed) partial oxidation, catalytic partial oxidation, or both. Steam-reforming reactions may also be catalyzed. Reforming and/or partial-oxidation catalysts include, but are not limited to, nickel, nickel oxide, nickel alloys, rhodium, ruthenium, iridium, palladium, and platinum. Such catalysts may be coated or deposited onto one or more support materials, such as, for example, gamma-alumina (optionally doped with a stabilizing element such as magnesium, lanthanum, or barium). When a reformer is employed, the gasifier chamber can be designed, by proper configuration of the freeboard or use of internal cyclones, to keep the carryover of solids to the downstream reformer at a level suitable for recovery of heat downstream of the reformer. Unreacted char can be drawn from the bottom of the devolatilization chamber, cooled, and then fed to a utility boiler to recover the remaining heating value of this stream. The syngas-cleanup unit is not particularly limited in its design. Exemplary syngas-cleanup units include cyclones, centrifuges, filters, membranes, solvent-based systems, and other means of removing particulates and/or other specific contaminants. The acid-gas removal unit is also not particularly limited, and may be any means known in the art for removing at least CO2from syngas. Examples include removal of CO2with one or more solvents for CO2, or removal of CO2by a pressure-swing adsorption unit. Suitable solvents for reactive solvent-based acid gas removal include monoethanolamine, diethanolamine, methyldiethanolamine, diisopropylamine, and aminoethoxyethanol. Suitable solvents for physical solvent-based acid gas removal include dimethyl ethers of polyethylene glycol (such as in the Selexol® process) and refrigerated methanol (such as in the Rectisol® process). Bioconversion of CO or H2/CO2to acetic acid, ethanol, or other products is well known. For example, syngas biochemical pathways and energetics of such bioconversions are summarized by Das and Ljungdahl, “Electron Transport System in Acetogens” and by Drake and Kusel, “Diverse Physiologic Potential of Acetogens,” appearing respectively as Chapters 14 and 13 ofBiochemistry and Physiology of Anaerobic Bacteria, L. G. Ljungdahl eds,. Springer (2003). Any suitable microorganisms may be utilized that have the ability to convert CO, H2, or CO2, individually or in combination with each other or with other components that are typically present in syngas. The ability of microorganisms to grow on CO as their sole carbon source was first discovered over one hundred years ago. A large number of anaerobic organisms including carboxydotrophic, photosynthetic, methanogenic, and acetogenic organisms have been shown to metabolize CO to various end products. Anaerobic bacteria, such as those from the genusClostridium, have been demonstrated to produce ethanol from CO, H2, or CO2via the acetyl CoA biochemical pathway. For example, various strains ofClostridium ljungdahliithat produce ethanol from gases are described in U.S. Pat. Nos. 5,173,429, 5,593,886, and 6,368,819. The bacteriumClostridium autoethanogenumsp is also known to produce ethanol from gases (Aribini et al., Archives of Microbiology 161, pp. 345-351 (1994)). Generally speaking, microorganisms suitable for syngas fermentation in the context of the present invention may be selected from many genera includingClostridium, Moorella, Carboxydothermus, Acetogenium, Acetobacterium, Butyribacterium, Peptostreptococcus, andGeobacter. Microorganism species suitable for syngas fermentation in this invention may be selected fromClostridium ljungdahlii, Clostridium autoethanogenum, Clostridium ragsdalei, Clostridium carboxidivorans, Butyribacterium methylotrophicum, Eubacterium limosum, and genetically engineered, mutated, or evolved variations thereof. Microorganisms that are engineered, created, or provided in the future will be applicable to the present invention, provided such new microorganisms can convert one or more of CO, H2, or CO2to a product of interest. A selected microorganism may be grown, to at least some extent, in the fermentor itself (simultaneous growth and production) or may be grown in a separate growth vessel or train. When separate cell growth is utilized, microorganism cells can be grown from any carbon substrate, which could be syngas but also could be various sugars such as glucose, galactose, arabinose, xylose, mannose, and other C5or C6sugars. The fermentor, or plurality of fermentors (in series or parallel), is not particularly limited but will generally be selected from a mechanically agitated reactor, a bubble column, a packed column, a plate column, a spray column, a gas-lift reactor, and a membrane reactor. In some embodiments, gas or liquid internal recycle is utilized to add mass transfer within the fermentor. Surfactants, water co-solvents, and microbubbles may all be utilized in various embodiments to enhance mixing and mass transfer. In certain embodiments, tail gas recycle improves mass transfer within the fermentor. In certain embodiments, compressed tail gas recycle increases the pressure within the fermentor, thereby allowing more syngas to enter the liquid phase for bioconversion. Some embodiments employ cell recycle back to the fermentor. Some embodiments employ recycle of cells, or fermentation sludge, back to the gasifier. Sludge recycling allows for conversion of used microorganisms back to syngas. The mechanical art necessary for implementing the tail gas recycle streams is well established. With reference toFIG.1, which is non-limiting, what is needed is a flow splitter in the tail gas stream, at least one compressor, a flow splitter to adjust R1and R2, and appropriate pipes and valves. The compressor is not limited but should be a mechanical device that increases the pressure of the tail gas by reducing its volume. Suitable compressors include centrifugal compressors, diagonal compressors, axial-flow compressors, reciprocating compressors, rotary screw compressors, rotary vane compressors, scroll compressors, and diaphragm compressors. The methods and apparatus of the invention can accommodate a wide range of feedstocks of various types, sizes, and moisture contents. “Biomass,” for the purposes of the present invention, is any material not derived from fossil resources and comprising at least carbon, hydrogen, and oxygen. Biomass includes, for example, plant and plant-derived material, vegetation, agricultural waste, forestry waste, wood waste, paper waste, animal-derived waste, poultry-derived waste, and municipal solid waste. Other exemplary feedstocks include cellulose, hydrocarbons, carbohydrates or derivatives thereof, and charcoal. In various embodiments of the invention utilizing biomass, the biomass feedstock can include one or more materials selected from: timber harvesting residues, softwood chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, off-spec paper pulp, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, miscanthus, animal manure, municipal garbage, municipal sewage, commercial waste, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, plastic, and cloth. The present invention can also be used for carbon-containing feedstocks other than biomass, such as a fossil fuel (e.g., coal or petroleum coke), or any mixtures of biomass and fossil fuels. For the avoidance of doubt, any method, apparatus, or system described herein can be used with any carbonaceous feedstock. Selection of a particular feedstock or feedstocks is not regarded as technically critical, but is carried out in a manner that tends to favor an economical process. Typically, regardless of the feedstocks chosen, there is screening to remove undesirable materials. The feedstock can optionally be dried prior to processing. Optionally, particle-size reduction can be employed prior to conversion of the feedstock to syngas. Particle size is not, however, regarded as critical to the invention. When multiple feedstocks are used (e.g., biomass-coal mixtures), they may be used in any ratio and they may be introduced in the same or different locations. It will be understood that the specific selection of feedstock ratios can be influenced by many factors, including economics (feedstock prices and availability), process optimization (depending on feedstock composition profiles), utility optimization, equipment optimization, and so on. A variety of operating temperatures, pressures, flow rates, and residence times can be employed for each unit operation ofFIGS.1-4or other variations of the invention. As is known to a skilled artisan, the optimum conditions for each unit will be influenced by the conditions of other units. Some embodiments of the invention relate to integration with the plant energy balance. The recycle loop(s) as described may be implemented to control the conversion of syngas to ethanol, adjusting for a steady-state or dynamic energy demand for syngas as an energy source. This invention allows real-time adjustment of how syngas is utilized in the overall process, thereby enhancing plant efficiency and economics. In general, solid, liquid, and gas streams produced or existing within the process can be independently passed to subsequent steps or removed/purged from the process at any point. Also, any of the streams or materials present may be subjected to additional processing, including heat addition or removal, mass addition or removal, mixing, various measurements and sampling, and so forth. In this detailed description, reference has been made to multiple embodiments of the invention and non-limiting examples relating to how the invention can be understood and practiced. Other embodiments that do not provide all of the features and advantages set forth herein may be utilized, without departing from the spirit and scope of the present invention. This invention incorporates routine experimentation and optimization of the methods and systems described herein. Such modifications and variations are considered to be within the scope of the invention defined by the claims. All publications, patents, and patent applications cited in this specification are herein incorporated by reference in their entirety as if each publication, patent, or patent application were specifically and individually put forth herein. Where methods and steps described above indicate certain events occurring in certain order, those of ordinary skill in the art will recognize that the ordering of certain steps may be modified and that such modifications are in accordance with the variations of the invention. Additionally, certain of the steps may be performed concurrently in a parallel process when possible, as well as performed sequentially. Therefore, to the extent there are variations of the invention, which are within the spirit of the disclosure or equivalent to the inventions found in the appended claims, it is the intent that this patent will cover those variations as well. The present invention shall only be limited by what is claimed.
30,735
11857924
DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF The general invention described herein refers to a photocatalytic reactor system (“photoreactor”) that is comprised of a photocatalyst that may be fluidized (“fluidizable photocatalyst”), and a photoreactor that contains the photocatalyst. The photocatalyst has low attrition (less than 3 wt %/h per ASTM D5757) and high-surface-area (50-600 m2/g N2BET (Brunauer, Emmett and Teller) surface area collected at 77 K). The photoreactor attributes preferably include: 1) an illumination source or sources with intensity that can be controlled, coupled to heat sink or other cooling means to remove waste heat, 2) non-imaging optical components to maximize the illumination intensity incident on the photocatalyst, 3) a reaction chamber that confines the fluidizable photocatalyst material inside a reaction zone (“containment vessel”), 4) a means for photocatalyst fluidization, 5) fluid flow through the reactor that contains a chemical or chemicals to be transformed, and 6) an electronic control system to operate the various components. The photoreactor may incorporate elements that help improve the rate of chemical transformations such as optics, photocatalyst heating and heat sources, reflectors, regeneration zones, and coatings. As used herein and in the appended claims, the reaction zone refers to the area where the light, fluid that contains the chemical or chemicals to be transformed, and photocatalyst interact to cause a chemical transformation. As used herein and in the appended claims, the regeneration zone refers to the area where the photocatalyst properties are modified so as to return to at least 50% of their chemical reactivity properties, (i.e., to perform a chemical transformation) by partially or completely reversing the effects of adsorbed by-products caused by performing the chemical transformation. As used herein and in the appended claims, the illumination source refers to any apparatus that emits light of the wavelength necessary to activate the photocatalyst. The light source or sources may include but are not limited to: light-emitting diodes (LEDs), laser diodes, low or medium pressure mercury lamps, Xe-discharge lamps, and excimer lasers. Illumination sources may optionally provide light that has utility to regenerate the photocatalyst, e.g. UVC radiation, and/or to heat the photocatalyst in order to regenerate the photocatalyst or to increase chemical transformation rates. As used herein and in the appended claims, chemical transformation refers to the oxidation, reduction, or substitution reaction or reactions performed on an organic molecule or multiple organic molecules containing any combination of C, H, N, O, S, P, Si, or halide using reactive oxygen species generated by the interaction of the photocatalyst with the illumination source. The result of this chemical transformation can be a high-value product desirable to the chemical industry, including alcohols, ketones, aldehydes, carboxylic acids, and epoxides. These high-value products can be the final commercial product of a chemical synthesis or serve as a feedstock for further chemical transformations. As used herein and in the appended claims, mineralization of an organic species refers to conversion of said organic species or volatile organic chemical (VOC) to CO2and H2O. Mineralization of an organic species or VOC containing nitrogen, sulfur, halides, and the like will also generate, in addition to CO2and H2O, small molecule compounds (e.g., mineral acids) related to these functional moieties. As used herein and in the appended claims, a fluid refers to a gas, liquid, or any combination of gas and liquid. As used herein and in the appended claims, fluidizable or fluidizable photocatalyst refers to a solid within a fluid flow whose downward force due to gravity is overcome by the drag force applied by an upward flowing fluid causing the solid to move. As used herein and in the appended claims, a fluidized bed refers to a system where the photocatalyst inside the reaction zone is mobilized by the fluid passing through the photocatalyst or by an external agitator such as vibration or rotation. As used herein and in the appended claims, composite photocatalyst refers to a mixture of the photoactive catalyst and a non-photoactive material or materials. As used herein and in the appended claims, bed density refers to the density of solids within the volume of the reaction zone. As used herein and in the appended claims, voidage refers to the fraction of the reaction zone that is not occupied by solids As used herein non-imaging optics refers to an ensemble of transmissive, scattering or reflective optical elements and materials that maximize the fraction of illumination that is incident on the photocatalyst and the uniformity of such illumination. In a preferred embodiment, the photocatalyst bed is itself an element in the photoreactor non-imaging optical system and properties of photocatalyst diffuse reflectance (i.e. scatter) and absorption are tailored to optimize performance. Other particles that do not contain the photocatalyst but are contained in the reactor and are transparent or reflective can also be part of the optical system whose concentration, size, transparency, and reflectivity can be tailored to optimize performance. Other surfaces of the containment vessel may possess high external transmittance via the use of antireflection coatings. These highly reflective or transmissive surface coatings may be comprised of high hardness materials that reduce the abrasion due to the fluidized photocatalyst during use. As used herein photocatalyst heating and heat sources may include 1) fluid preheating upstream of the reactor inlet, including by re-use of illumination source cooling gas, 2) wall heating using for example, electrical resistance or gas fired means, 3) heat introduced onto the photocatalyst by non-imaging optical components via illumination source or sources, for example infrared radiation. Photocatalytic Reactor Systems Photocatalytic reactor systems have several common attributes:1) the photocatalyst material2) Photoreactor designa. Containment vessel, which confines the photocatalyst, while allowing fluid flow through and over it, and photocatalytic illumination incident on it.b. Fluid flow direction and flow rate, referring to the fluid to be purified or chemically modified, through and over the surfaces of the photocatalystc. Photocatalytic illumination spectral irradiancy and direction with respect to the photocatalyst and fluid flow directions. In order to optimize efficiency of the intended chemical transformation and to minimize energy consumption, the photocatalyst in a photocatalytic reactor must be uniformly illuminated with adequate intensity photocatalytic illumination (i.e. intensity variation <25% of the average intensity in the photocatalyst), and the fluid to be reacted must be exposed to the photocatalyst. In a preferred embodiment of the subject innovation, the fluid is a gas, although the design principles herein may also be applied to liquid reacting systems. Hence the detailed reactor geometry, including illumination geometry and flow dynamics, are crucial design elements. The photoreactor containment vessel is a component of the photoreactor optical system since illumination interacts with these materials and surfaces for delivering photocatalytic illumination. In this case the transparent tube transmits illumination. Maximizing delivery of optical power to the photocatalyst is a key attribute of photoreactors, and several principles of non-imaging optics may be incorporated to achieve that objective. Non-imaging optical systems employ transmissive, reflective and scattering components, including coatings on those elements, to maximize radiative power transfer from an energy source to a location to usefully employ that energy. They are differentiated from imaging optical systems in that they are not concerned with creating an image. Use of non-imaging optical systems in photocatalytic reactor systems is a significant aspect of the subject innovations and will be described below. There are several basic photoreactor geometries that may be employed, each with its own unique combination of these three attributes (a-c). The subject innovations in these areas may in general be applied to many photoreactor designs, including designs that are not specifically described herein. Three of the most relevant are denoted as Type 1, Type 2, and Type 3, and are summarized in Table 1. TABLE 1Comparison of different photocatalytic reactor configurationsReactor TypeType 1Type 2Type 3DescriptionCylindrical cellCylindrical, annular fluid flowNon-imaging optical cellGeometryTransparent cylindricalAxial fluid flowFluid flow is axial withcell, axial fluid flowthrough an annularrespect to a non-imagingthrough a packed orregion that contains acell with interior reflectivefluidized photocatalyst bedpacked or fluidizedwalls. Illumination isphotocatalyst bedpredominantly axial andperpendicular to the topsurface of a packed orfluidized photocatalystbed.IlluminationExternal linearLinear illuminationHigh intensity/pointsourceillumination source orsource in a transparentsource or compact arraysources that are configuredcylindrical cell,and internal reflectors.parallel to cylindrical &Linear source may beAn array may befluid flow axis. Linearan LED array, a linearcomprised of a hybridsource may be an LEDdischarge source suchcombination of sourcesarray, a linear dischargeas a xenon lamp, or awith different spectralsource such as a xenoncylindrical lightguideoutput.lamp, or a cylindricalwith engineeredlightguide with engineeredleakage along theleakage along the length oflength of thethe lightguide. An arraylightguide. An arraymay be comprised of amay be comprised of ahybrid combination ofhybrid combination ofsources with differentsources with differentspectral output.spectral output.PhotocatalyticPrimary illumination isPrimary illuminationPrimary illumination isilluminationinwardly radial towardis outwardly radialaxial onto top surface ofgeometryaxis.from axis.catalyst bed.Secondary illumination isSecondarySecondary illumination,also predominantlyillumination (fromreflected from highinwardly radial, afterexterior cylindricalreflective cell interiorreflection from externalreflector) is inwardlywalls, has axial and radialreflectors.radialcomponents Type 1 A single cylindrical reactor chamber that has walls that are transparent or translucent for the desired photocatalytic illumination wavelengths. A fluidized or packed photocatalyst bed is contained in the reactor interior region. Fluid flow (for the material to be purified of chemically reacted) is in a generally axial direction. The simplest case is a single cylindrical vessel, i.e. the containment vessel cross section is circular. In addition to cylinders, other vessel geometries may be advantageous for uniform illumination, achieved via multisided cross sections such as triangles, rectangles, hexagons, etc. The corners of the multisided cross sections may have radii that improve fluidization and circulation of the particles. A radius greater than or equal to the particle is desired, and particle sizes may vary from 10-1000 microns. The cross section may also be an oval shape with a ratio of major to minor radius of >1. More preferably, the ratio of major to minor axis is >1.5. The photocatalyst is confined in a section of the chamber by one or more gas permeable containment elements, which may be porous frits, screens, perforated discs or other similar elements that do not let the photocatalyst pass, but which allow fluid flow through them. This element is positioned directly below the photocatalyst to counteract the force of gravity. Additional confining elements can be downstream of the photocatalyst but can also include particle separators such as a cyclone. The reaction chamber can also contain non-catalytic particles that help transmit or reflect light. The reactor in this invention is typically oriented vertically, and fluid flow is upward through the bed, opposite the force of gravity. Fluid flow will mechanically agitate the photocatalyst, which will then occupy larger volumes of the reactor. For example, at rest or below the minimum fluidization velocity, the reaction zone may have a voidage of at least 0.3 meaning 70% of the reaction zone is occupied by “stationary” solid particles. In a preferable embodiment of the invention, the reaction zone has a static voidage of 0.36 or greater. Adding fluid flow greater than the minimum fluidization velocity will cause the bed to expand increasing the voidage and also increasing the size of the reaction zone. For high flows the dispersed (fluidized) photocatalyst may occupy all the reactor volume. For the fluidized bed reactor of this invention the voidage is typically 0.6-0.8. It is also possible to entrain the photocatalyst in the fluid flow so that it is carried out of the reactor and separated from the fluid. Entrained particles can be circulated back into the reactor and may be regenerated while outside the reaction chamber. Voidage in the reactor of this invention can be controlled at values greater than 0.8 by controlling the fluid flow rate. For the photocatalytic reactor of this embodiment, the voidage should be greater than 0.4, but more preferably greater than 0.6 to ensure uniform deep light penetration. Photocatalytic illumination is provided through the transparent or translucent walls from light sources that are preferably linear and positioned parallel to the cylinder axis. Multiple linear sources may be employed to improve the uniformity of illumination throughout the photocatalyst bed. Non imaging cylindrical trough reflectors may also increase efficiency to deliver illumination into the catalyst. These external reflectors may serve to collect lamp radiation that is directly incident on the photocatalyst (“primary illumination”) or to collect and redirect illumination that is scattered from the photocatalyst (“secondary illumination”). The light source is preferably placed as close to the reaction chamber as possible since optical radiation decreases exponentially with distance. Individual emitters on the linear sources should have wide viewing angles)(>120° in order to more uniformly illuminate the reactor while also allowing light emitted outside of the reactor viewing angle to travel to reflectors around the reactor and be redirected by the non-imaging optics to the sides opposite the light source. When the photocatalyst is fluidized, light penetration is increased and the photocatalyst will be more uniformly illuminated, thus increasing the efficiency of photocatalytically driven chemical reactions. This increased light penetration due to fluidization may still not sufficiently allow light to penetrate all regions in the bed volume. Additional scattering and transparent particles within the reactor volume may be used to aid light penetration into the reactor. Fluidization also has the effect of exchanging the photocatalyst through the bed volume, so that all of the photocatalyst will be illuminated to some extent. The containment element at the reactor volume inlet will establish gas flow characteristics in the photocatalyst bed. The simplest elements result in inlet gas flow in a predominantly axial direction relative to the vessel. It may be advantageous to establish gas flow with radial or azimuthal components to increase the migration rates of the photocatalyst in the fluidized bed, thereby improving illumination uniformity and fluid interaction with the catalyst. Improved flow dynamics may also be achieved via use of a mixing element, which ideally will be optically transparent or translucent for the photocatalytic illumination wavelengths. The mixing element may be any variety of static mixer or gas distributer designs or other plates, fins or rods. FIG.1is a schematic of this Type 1 photoreactor.FIG.1ais an end view that shows a preferred embodiment, with a linear array of 365 nm LEDs1001and the photocatalyst contained in a transparent cylindrical tube1002. The tube materials1002of construction are preferably glass or fused silica, although other transparent materials may be employed as well, including alumina or polycarbonate for example. The preferred embodiment is for the tube to be optically transparent at the illumination wavelength, i.e., with internal transmittance greater than 99%. Reflection losses may be reduced by use of antireflection coatings on both the internal and external surfaces. In that case external transmittance of the photocatalytic illumination may be greater than 98%. Antireflection coatings can increase the photocatalytic illumination incident on the photocatalyst by approximately 6%. Photocatalytic illumination is generated by a linear light source1001on a high thermal conductance copper based PCB board that is mounted on a heat sink on the rear surface (not shown). Illumination from the source is directly incident on the photocatalyst1002, reflected from the reflector1003, and in the case of outwardly scattered (non-absorbed) illumination, is redirected back to the photocatalyst1006. These are surrounded by two reflectors, an elliptical trough reflector1003and a planar reflector1004. The planar reflector1004has openings provided such that the outer LED emitting surfaces near the plane of the planar reflector1004, which is configured parallel to the ellipse minor axis and at or near the minor axis i.e. less than 10% of the major axis away from the minor axis. Both reflectors1003and1004have reflectance approximately 90% a 365 nm. The linear LED array1001, photocatalyst tube1002, elliptical reflector1003and planar reflector1004are configured symmetrically with respect to the ellipse major axis1005. The reflectors may be constructed of simple aluminized metal, which may be electroformed for example. The aluminum coating may be highly specular, with reflectivity approximately 92%, or enhanced with dielectric layers to achieve reflectivity greater than 99% at the illumination wavelength. The cross-sectional shape of the reflector may be circular, parabolic, or a non-conic section shape that is optimized to maximize the transfer of energy from the illumination sources to the photocatalyst. The light source configuration and directional characteristics, and the on-imaging optical components will be adjusted to uniformly redirect scattered light back onto the photocatalyst. This reflector geometry is a preferred embodiment and the subject invention includes perturbations of these shapes and dimensions. Reflectors in these photoreactor applications may optionally incorporate transparent substrates, with high reflectivity achieved by all-dielectric interference coatings. Particularly useful coatings include dichroic characteristics to achieve high reflectivity at the design wavelength and moderate to high transmission at infrared wavelengths. These reflector designs would address illumination sources that emit at a range of wavelengths that are undesirable and contain a lot of energy, e.g., for medium- and high-pressure mercury lamps, xenon lamps, etc. The elliptical trough reflector1003serves to reflect illumination that is not directly incident on the photocatalyst1002and reflect those light rays1006back onto the photocatalyst tube. Illumination from such other directions is useful to improve illumination intensity and intensity uniformity in the tube1002. Light incident on the photocatalyst scatters in a range of directions and the elliptical trough and planar reflector work in concert to redirect that light bac to the photocatalyst1007. The planar reflector near the elliptical minor axis provides a virtual reflector1009with the virtual second ellipse focus at1008. Because the photocatalyst1002is also located near the other ellipse focus, scattered light1007from the photocatalyst tube1002may be redirected to the photocatalyst tube with two reflections, with energy loss less than 20% for reflectors with greater than 90% reflectance a the illumination wavelength. Optical reflectance of the photocatalyst, also described as diffuse reflectance or scatter, may be modified to optimize the illumination intensity and intensity uniformity incident on the photocatalyst. This optimization is typically done in an optical design ray tracing program such as Zemax. In such optical models all or many of the design parameters of the non-imaging optical system may be varied and the photocatalyst intensity in the photocatalyst may be maximized. These are the optical design parameters that may be varied for the subject Type 1 photoreactor: photocatalyst tube1002dimensions, photocatalyst reflectance (and associated absorbance) at the photocatalytic illumination wavelength, LED linear1001array spacing and distance from the photocatalyst tube, tube envelope external transmittance that is determined by tube material and the reflection of the interior and exterior surfaces (i.e. determined by the presence of antireflection coatings), the spacing and curvature of the elliptical reflector1003and spacing of the planar reflector1004. The exact curvature of the trough reflector and planar reflector may be perturbed from those ideal shapes. These optical system parameters including the photocatalyst reflectance can distribute the reflected power between various reflection geometries such as those indicated as1006and1007to achieve optimized illumination intensity and intensity uniformity. FIG.1bshows a side view of the Type 1 design, with no gas flowing. The photocatalyst1010is in the transparent containment vessel1011. In this schematic, it is evident that the photocatalyst occupies about ¼ of the containment volume under this no-flow condition. This view shows gas conductive containment elements at the inlet (bottom)1012and at the top1013. In this case those elements are metal screens with openings of 30 microns size, which confine the low attrition photocatalyst which are spherical and are 70 microns in diameter. The illumination source is a linear LED array1014on a PCB board1015, with an integral planar reflector1016. In this view the elliptical trough reflector is not shown. Also not shown are the LED array power supply, inlet fluid blower and plumbing, and the LED heat sink that is attached on the LED housing. FIG.1cprovides the same side view asFIG.1b, except gas is flowing (forcibly introduced) at the inlet (bottom) of the vessel1017and out the outlet (top)1018. The gas passes through the photocatalyst1019and exits the photoreactor at the outlet (top). In this case the catalyst is fluidized, and the volume increases to most of the volume in the containment vessel. This reduced photocatalyst bed density is a key method to enable greater penetration of photocatalytic illumination through the bed, and the fluidization also provides rapid circulation of the photocatalyst both top to bottom and center to edge. These factors and the optical reflectors and antireflection coated elements contribute to a highly uniform illumination of all the photocatalyst. The low-attrition photocatalyst of the subject innovation is a key enabling technology for fluidization of this type. It prevents premature decomposition of the catalyst, which would increase operating costs due to downtime and material replacement, and costs to address accumulation of attritted material beyond the downstream confinement element. In another embodiment, a plurality of reactors with the types of reflectors described above may be disposed around a central light source. A top down view is shown inFIG.1d, where the transparent reactor tube1017containing the photocatalyst1018and associated reflector1019are in axial alignment with a center light source1020. The central light source may be LEDs arranged along the axial direction of the reactors or it may be a single source such as a low or medium pressure mercury lamp. The number of reactor/reflector assemblies may vary from 2 to 20; four reactor/reflector assemblies are shown inFIG.1d. Type 2 A single annular cylindrical reactor chamber (i.e., defined be the volume between two coaxial cylinders) in which the inner cylinder walls are transparent or translucent for the desired photocatalytic illumination wavelengths, and the outer cylinder is reflective for the desired photocatalytic illumination wavelengths. In this case reflectance would be greater than 50%, or preferably greater than 80%, and most preferably greater than 95% for the wavelengths of interest. In a preferred embodiment, photocatalyst reflectance is between 40% and 95%. A fluidized or packed photocatalyst bed is contained in the annular region. Reflectance at this interior surface of the external cylinder may be determined by the intrinsic properties of the cylinder material of construction, e.g., aluminum should have reflectance >80%, and polished aluminum greater than 90%, both over a broad band of wavelengths from UV-C though the visible. Fluid flow (for the material to be purified or chemically reacted) is in a generally axial direction through the photocatalyst bed that is defined by the annular region and the containment elements that were described above. As in Type 1 the inlet may be designed to introduce azimuthal and radial flow components to advantageously increase fluid interaction with the photocatalyst and illumination uniformity on the photocatalyst. In Type 2 the illumination source is in the central cylinder, and light is directed predominantly radially outward and incident on the photocatalyst bed. This central illumination source may be a linear array of point sources, such as an LED chip-on-board array, or a linear discharge source, such as a low- or medium-pressure mercury discharge lamp or a Xe-discharge lamp. In one embodiment the LED board may have a reflective coating to redirect backscattered illumination back onto the photocatalyst. The central source may also be a lightguide that is illuminated at one or both ends of a transmissive solid cylinder and is engineered to “leak” illumination along its length in a controlled manner. FIG.2provides a schematic of the Type 2 photoreactor.FIG.2ais a cross-section of this reactor that is comprised of two coaxial cylinders, with the annular region containing the photocatalyst2001. The inner cylinder2002is a transparent envelope for separation of the centrally configured linear illumination elements2004. LikeFIG.1, its surfaces are preferably coated with an antireflection coating on the surface not in contact with the photocatalyst, which for Type 2 is the inner surface. The outer surface of the inner cylinder may be coated with a hard anti-wear coating, such as aluminum oxide or diamond like carbon (DLC) in order to reduce its wear while in contact with the fluidized bed constituents. A high durability antireflection coating may optionally be fabricated on this outer surface of the inner cylinder, with a hard outer surface to prevent wear from the fluidized photocatalyst. A high performance design may be achieved with a total of 3 layers, with Rmin of 0.4% at 410 nm. A schematic of the layer design and spectral reflectance is shown inFIG.6. Such antireflection coatings may be optimized for the appropriate photocatalytic illumination wavelength. That is compared with the normal single surface Fresnel reflectance of 4.2% for borosilicate glass. The outer cylinder2003provides a reflector on its inner surface to redirect illumination back inwardly towards the photocatalyst. It may be an aluminum housing with a polished interior surface, optionally with pairs of dielectric high index low index layers, to boost reflectance at the chosen design wavelength above 95%. Aluminum construction has the added advantage of high thermal conductance, which benefits high transfer out of the photoreactor to heat sinks. These heat sinks may be either passively cooled via convection in air or other fluids or actively cooled. A combination of passive cooling and active heating on this external cylindrical element can be implemented and would allow operation of the photoreactor at higher temperatures, e.g., up to 140° C. In addition to a metallic or dielectric-enhanced metallic reflector, an all-dielectric high reflector may be fabricated as described above. Extremely high durability at the inner surface2004may be achieved by forming a hard coating on the interior, such as alumina or DLC, and forming a high reflective metallic or dielectric metal structure on the external surface. FIG.2bshows a side view of the Type 2 design, with no gas flowing. The photocatalyst2005is in the annular region between the interior cylinder2006and the outer reflector cylinder2007. It is evident that the photocatalyst occupies about ¼ of the containment volume under this no flow condition in this schematic. This view shows gas conductive containment elements at the annular inlet at the reactor bottom2008, and at the annular outlet (top)2009. The linear LED array2010is centrally located as shown. This central illumination source or sources2004are segregated from the photocatalyst and may preferably be equipped with a means of cooling such as forced air flow past finned heat sinks on the LED chip on board liner arrays that are shown. For photoreactor operation at elevated temperatures, system inlet air may be drawn in through the illumination array region for cooling and would thus be preheated for redirection through the photocatalyst bed. FIG.2cprovides the same side view asFIG.2b, except gas is flowing (forcibly introduced) through the annular inlet (bottom) of the vessel2011. The gas passes through the photocatalyst2013, which under these conditions fills most of the containment vessel volume and exits the photoreactor at the annular outlet (top)2012. Typically, there will be a macroscopic bed density gradient along the flow path through the photocatalyst, with higher bed densities at the bottom, and lower bed densities toward the top. Type 3 incorporates a non-imaging reflective containment vessel with an illumination directed at a fluidized bed predominantly axial direction, i.e., predominantly aligned with the fluid flow. A primary attribute of this design is the vertical orientation of the reactor cell, and the conical shape that confines the at-rest photocatalyst in a smaller cross section region near the inlet (bottom) of the vessel confinement volume. This principle is illustrated in theFIGS.3-5. FIG.3shows a Type 3 photocatalytic reactor system comprised of the photocatalyst3001held in a conical cylindrical vessel3002, with gas permeable confinement elements at the inlet3003and the outlet3004. The conical vessel is metallic, with a polished reflective surface on the interior, with reflectance at the 385 nm illumination wavelength of greater than 95%. Fluid flow3007to the inlet confinement element is driven by a blower3005and directed to the inlet via the inlet manifold3006. Illumination incident on the photocatalyst3001is predominantly in an axial direction3010, counter to the predominantly upward gas flow through the photocatalyst. Off-axis illumination3011is also directed to the photocatalyst by the reflective interior surfaces. Fluid flow downstream of the photocatalyst3008is directed upward through the outlet confinement element3004. In this case the illumination source3007is an InGaN LED emitting at 385 nm. It is mechanically and thermally coupled to a heat sink3009. Typical commercially available sources of this type spectral bandwidth of 20 nm FWHM. Multiple LED die (e.g., quantity 9) may be mounted and packaged together on a board that is mounted on a high thermal conductance copper based heat sink in order to dissipate excess energy that powers the emitter. The preferred embodiment is to utilize illumination LED emitters in the 360-420 nm spectral range because of the high reliable and low cost of those sources. Other wavelength LED emitters may also be provided, such as UVC (240-280 nm) to be utilized for periodic catalyst regeneration for example. Alternatively, a broadband illumination source such as a xenon discharge lamp or a medium pressure mercury discharge lamp may be advantageous to provide photocatalyst illumination in the UVA range, as well as significant optical power at longer wavelengths to achieve photocatalyst heating. There are two means to achieve reactor heating from the photocatalytic illumination sources: longer wavelength emission from discharge sources and thermal waste heat from solid state sources (e.g. LEDs ad laser diodes) have a significant output in longer wavelength radiation. In an example of the former, a typical xenon arc discharge lamp may emit 1.3 W total optical power, of which 1 W (76%) is in the infrared, 700 nm-2800 nm wavelength. Optical power in the UV (200 nm-400 nm wavelength) may be 0.1 W and optical power in the visible (400 nm-700 nm wavelength) at 0.2 W. Use of infrared emission from the UV photocatalytic illumination source is a simple and effective means to achieve moderate heating of the photocatalyst, especially since typical aluminum based reflectors have very good reflectance in the infrared, over 98%. Solar radiation may also be usefully applied as a photocatalytic illumination sources, as typical spectral irradiancy of the solar spectrum is approximately 900 W/m2 total power, with approximately 10% of that power in the UV (200 nm-400 nm), 40% in the visible (400 nm-700 nm) and 50% in the infrared (700 nm-2800 nm). The UV part of the spectrum is useful for activation of the photocatalyst, and the infrared useful foe reactor heating. Photocatalytic reactor heating may also be achieved by harvesting the waste heat from LEDs. Neglecting thermal losses in power supplies, InGaN based LEDs emitting in the 365-420 nm wavelength range (such as Osram LZ4 products) have wall-plug efficiencies in the 48-54% range, i.e. 46-52% of the electrical energy provided is dissipated as heat. This heat is removed using forced air cooling of a finned aluminum heat sink or via a forced liquid cooled aluminum or copper block. The coolant may be water or a propylene-water solution. The heat sinks are in intimate contact with the LED PCB back surface, affixed with machine screws and contacted with thermal paste. Either of these cooling fluids may be recirculated past the reactor to achieve heating: heat is removed from the LED array, transported downstream via coolant, and reintroduced to the photoreactor. Glass based photoreactors such as Type 1 or Type 2 are well suited to have forced hot air circulated past them, conveyed by duct work after LED array cooling. Type 3 photoreactors may have the reactor vessel constructed of metal such as aluminum and are well suited for recirculation of liquid coolant. FIG.4ashows another Type 3 reactor that illustrates the use of an alternative geometry interiorly reflective containment vessel4002. Under static (no flow) conditions the photocatalyst4001resides at the bottom of the reactor and is partially supported by the inlet containment element4003. The containment volume is then completely defined by the outlet containment element4004. In this example the cross-sectional shape of the containment vessel is approximately elliptical, although modifications of that shape may be appropriate to increase illumination power transfer to the photocatalyst. In this case the three-dimensional shape is therefore ellipsoidal or nearly ellipsoidal with azimuthal symmetry around the central axis that corresponds to the predominant direction fluid flow. Other non-conic geometric shapes may also be used advantageously to address non-point sources and the extended nature of a fluidized photocatalyst bed to be illuminated. In cases where the illumination source4005is near a focus of the ellipsoid, the elliptical shape efficiently directs illumination from4006to a region4007near the top surface of the photocatalyst. Practical light sources are not in fact point sources but are extended, and the photocatalyst illumination target region is also extended, and therefore deviations from a perfect ellipsoid and point illumination source are in general desirable. The optimum shape of the interior reflective surface may thus be optimized together with the illumination source or source position, the photocatalyst mass and volumetric extent and the fluid flow characteristics. FIG.4bshows the same photocatalytic system under fluid flow conditions. Fluid4008is forcefully provided to the inlet and traverses the photocatalyst4009prior to exhaust4010. Under these conditions the photocatalyst4009has a greater macroscopic bed volume that is approximately 5 times the static volume (FIG.4a,4001). The packing density is therefore about ⅕th the packed density. This bed density decrease facilitates the uniform illumination of the photocatalyst bed. Uniform illumination is also provided by the interior reflective surfaces that serve to return scattered illumination4011back to the photocatalyst. Several interior reflective surfaces in these examples are exposed to fluidized catalyst, and it is desirable to prevent degradation of those reflective surfaces. (FIG.2a2003,FIG.2b2007,FIG.33002,FIG.4a4002) Highly durable and abrasion resistant optical coating designs may be formed on the interior reflective surfaces in photocatalytic fluidized bed reactors. These designs may employ a base layer of aluminum that possesses a nominal reflectance of 92% in the visible and near UV. Pairs of low-index/high-index dielectric layers may be engineered on the aluminum, to enhance reflectance to higher levels over a range of target wavelengths. Table 2 shows a representative design with an outer layer of DLC, to increase abrasion resistance. TABLE 2Optical coating design of a high abrasion resistance enhanced highreflector (EHR) for 385 nm wavelength that employs DLC andaluminum oxide as the coating layers.OpticalRefractivethicknessFIG.index(full wavesThicknessMaterial8aat 385 nmat 385 nm)(nm)Air1.00infiniteDiamond like carbon (DLC)80061.990.24948.22SiO280051.470.25065.33TiO280042.610.24035.40SiO280031.470.21455.85Aluminum80020.382.006infiniteGlass80011.53 FIG.5ashows another Type 3 reactor variant that employs a cylindrical containment vessel5002that is transparent to the photocatalytic illumination. That transparent cylindrical containment vessel is fully defined by confinement elements at the inlet5004and the outlet5005. These containment elements are conductive to the fluid flow but have pore or screen sizes that do not permit escape of the photocatalyst. The outlet element5005is also preferably transmissive with respect to the illumination, e.g., with transmittance greater than 50%. The containment vessel is positioned in a non-imaging optical system that in this case is an interiorly reflective surface that is optimized to provide uniform illumination to the photocatalyst5001in the containment vessel. FIG.5bshows the subject reactor system under fluid flow conditions. Fluid is forcefully directed through the inlet5010, and is incident on the photocatalyst5011, which has an expanded macroscopic volume due to the fluidization effects. The exhaust fluid travels out of the reactor5012. In this example a point source5008emits photocatalytic illumination that is incident on the photocatalyst both axially5009and radially5009, i.e., after reflection from the interior reflector5013. The transparent containment vessel5002may have enhanced external transmittance by use of antireflection coatings. The interior AR coating is preferably fabricated with high hardness optical thin film materials.FIG.6ashows a schematic 3 layer-antireflection coating, fabricated from relatively hard and abrasion resistant anti-wear materials: aluminum oxide (Al2O3), magnesium fluoride (MgF2) and diamond like carbon (DLC). The outer layer of DLC provides improved abrasion resistance in the presence of fluidized photocatalysts. One optical design is optimized for use with 385 nm photocatalytic illumination, with these layer thicknesses given in Table 3. TABLE 3Optical coating design of a high abrasion resistant anti-reflectioncoating (AR) for 385 nm wavelength that employs DLC as the outercoating layer (top). A similar design without the DLC is shownfor comparison (bottom).OpticalthicknessPhysicalFIG.Refractive(full wavesthicknessMaterial6aindexat 385 nm)(nm)Air1.00Diamond like carbon (DLC)60041.990.0214.0MgF260031.390.21659.8Al2O360021.640.21650.8Substrate60011.52Air1.00MgF260031.390.24369.2Al2O360021.640.24358.8Substrate60011.52 The top 3-layer design employs a 4 nm DLC outer coat, and a similar 2-layer design parameters are also shown in the table immediately below the 3-layer parameters, but without the DLC overcoat.FIG.6bshows spectral reflectance for these two AR coating designs. The 3-layer design with 4 nm DLC6005, and the two-layer design with no DLC6004. Both designs provide less than 0.5% reflectance at the 385 nm design wavelength, with the DLC degrading reflectance by about 0.2% absolute. Another abrasion resistant antireflection coating is provided inFIG.7. It is a two-layer design that employs DLC as the inner layer (adjacent to the glass substrate) and Al2O3as the outer layer. A 385 nm optimized design uses these layer parameters (Table 4). Spectral reflectance is shown inFIG.7b, with a reflectance minimum7004of less than 0.05% reflectance at 385 nm. TABLE 4Optical coating design of a high abrasion resistant anti-reflectioncoating (AR) for 385 nm wavelength that employs DLCand alumina as coating layers.OpticalRefractivethicknessPhysicalFIG.index(full wavesthicknessMaterial7a(at 385 nm)at 385 nm)(nm)Air1.00Al2O370031.640.25058.7Diamond like carbon70021.990.25048.3(DLC)Substrate70011.52 FIG.8ashows the schematic of the 5-layer enhanced high reflector, with outer layer of DLC8006. Thin film labels and optical/physical data are in Table 4. The other dielectric layers are SiO28003,8005and TiO28004.FIG.8bshows spectral reflectance8007with a maximum of reflectance 98.5% at 385 nm.FIG.8cshows reflectance vs incidence angle for 385 nm illumination, and reflectance is greater than 98% for both P-polarization8008and S-Polarization8009from normal incidence to 30° angles of incidence. Where abrasion resistant coatings are used to protect highly transmissive components, such as the walls of the reaction zone that are constructed from ceramic materials such as quartz and glass especially in Type 1 and 2 reactors, the reaction zone wall will be coated with optically useful and abrasion resistant films of materials that are transparent to UV and visible light (wavelengths of 360-700 nm) and have high mechanical strength to resist abrasion. Certain illumination schemes may employ UVC and UVB (200-360 nm), and optical coating materials will be selected for those based on their mechanical and optical properties. Aluminum oxide is particularly useful because it has high transmission to below 200 nm wavelength. The coating may be made of materials such as aluminum oxide, zirconium oxide, diamond like carbon (DLC), and chromium oxide. For Type 3 photocatalytic reactor systems that have metalized walls, aluminum oxide, zirconium oxide, diamond like carbon, and chromium oxide can be used to protect the walls. For photoreactors that use optical components such as mirrors, lenses, emissive surfaces within the reaction zone, or light guides, the optical components may be coated with 1-40 nm films of 150-600 nm transparent abrasion-resistant materials such as aluminum oxide, zirconium oxide, diamond like carbon, and chromium oxide. Attrition of optical systems, especially of reactor walls composed of quartz or glass, may result in a change in the efficiency of the photocatalytic process over the lifetime of the catalyst. Efficiency improvement may come about when attrition of the inner wall of a quartz tube causes the glass to frost, increasing the scattering coefficient of the quartz without loss of transmissivity which can lead to more uniform initial illumination. In one embodiment an LED light source or LED light sources are mounted directly onto a highly reflective surface such as a mirror that also contains a heat sink. The LED(s) can be placed either outside the reaction zone or be part of the walls of the reaction zone itself. The heat sink can be passively or actively cooled. The reflective surface onto which the LED(s) is mounted will allow the fraction of light that is scattered by the photocatalyst away from the reaction zone to be re-reflected toward the reaction zone while minimizing the volume occupied by the light source. In one embodiment the emission from an LED light source is focused using a series of lenses and mirrors into a lightguide that is inside the reaction zone. The lightguide can be parallel or perpendicular to the direction of fluid flow inside the reaction zone. The length of the lightguide is 90-100% the length of the critical axis in the reaction zone and allows light to emit from the entire length of the guide. It is also possible to have an LED source on both sides of the lightguide to increase the optical power entering the reaction zone. The surface of the lightguide can be engineered to control the scattering angle of light leaving the lightguide. In one embodiment, reactor temperature is controlled. Although not wishing to be bound by theory, it is believed that temperature may be modified to improve the kinetics of a chemical transformation, to provide requisite energy to activate a chemical transformation, or to help achieve the desired reaction selectivity. One approach to heating the reaction area is to use heat wire or heat tape that is inside the reaction zone. A preheater or heat exchanger at the fluid inlet may be used to control the temperature of input gases or liquids that are arriving from downstream processes or entering the reactor for the environment. A second post heater or heat exchanger may control the outlet fluid temperature before discharge into the environment or before another processing step. In this embodiment of the reactor, a desirable operating temperature range is between 20 and 150° C., in a further embodiment the temperature may be in a range of 51 to 139° C. In another approach to control temperature, the excess heat generated by the light source is transferred to the reaction zone, fluid inlet, and fluid outlet preferably by directing fluid exhaust from light source cooling to the photoreactor vessel, or through a heat exchanger. The light source cooling fluid may be air or a suitable liquid coolant such as water or propylene glycol. Temperature may be further controlled by passing a fraction of the fluid flow over the heat sink connected to the light source. The fluid used for temperature control may be recirculated back through the reactor after or discharged into the environment. Discharge is only advised if the process is carried out in a closed loop to avoid process waste. In another approach, waste heat may be communicated to an energy harvesting device, such as a thermoelectric material where the Seebeck effect is used to convert the thermal energy to electrical energy. The harvested electrical energy can be used to drive a fan or other device that provides the fluidization. Thus, a portion of the wasted energy can be recovered to provide a portion of the energy needed to fluidize the photocatalyst in the reactor. The thermoelectric device is placed in contact with a heat sink that removes heat from an LED source that illuminates the photoreactor. For Type 3 reactors, the reaction zone can be heated either by heat wires or tape inside the reaction zone or from a furnace surrounding the reaction area but the furnace does not heat the light source. If optics such as mirrors, lenses, or light guides are used, the optics are either inside or outside the photoreactor. One approach to conserve power or control deleterious side reactions is to control the availability of reactive sites on the photocatalyst surface. To achieve this goal, the optical power of the light source may be modulated based on feedback of the composition of the fluid in the outlet fluid stream. For some applications the spectral character of this illumination may also be modulated or actively controlled. In one embodiment, reactor pressure is controlled. Although not wishing to be bound by theory, the pressure of the reactor can influence the products of a chemical transformation, the reaction rate, the selectivity of a chemical transformation, and particle fluidization. Methods to control pressure include but are not limited to changing the inlet fluid flow rate, pressurizing the reaction zone, or changing the amount of photocatalyst in the reaction zone. An aspect of the photocatalytic reactor system is to have a discrete area, known as a regeneration zone, for the regeneration of the photocatalyst to recover the lost performance due to poisoning or some other form of deactivation by the time it reenters the reaction zone. There are several approaches for the catalyst to transport into the regeneration zone. In one approach, a fraction of the photocatalyst will “carry-over” or be entrained in the fluid stream out of the top of the reactor by the fluid flow and be directed by the fluid stream or gravity into the regeneration zone. Apparatuses such as cyclones can be used to separate the photocatalyst from the fluid stream. At no time will greater than 25% of the total catalyst in the photocatalytic reactor system be in the regeneration zone. In another approach, a gated opening in the side of the reactor can be opened to allow the photocatalyst to enter the regeneration zone until up to 25% of the total catalyst has entered the regeneration zone. The regeneration zone is an independent area with the same or different geometry from the initial reaction area. It can also be an annular tube on the inside or outside of a cylindrical photoreactor. The regeneration zone can have an independent heat or illumination source. An independent clean fluid, fluid from the reaction zone outlet, or fluid containing a chemical that reacts with or competitively adsorbs to the catalyst surface can be used to fluidize or pass over the photocatalyst in the regeneration zone. For heating, the adsorbed by-products will desorb from or decompose on the catalyst surface. The temperature is maintained sufficiently low to avoid sintering or denaturing the active sites. In another embodiment, the regeneration zone can be illuminated to use the photocatalytic effect to decompose or desorb the adsorbed by-products on the photocatalyst surface. The regeneration zone can also be fluidized by an inert fluid stream or with a fraction of the primary fluid stream, especially in the case of a closed loop system, but the fluidization of the regeneration zone will be low enough that there is not reverse spillover from the photocatalyst that would be routed toward the primary reaction zone. After treatment, the photocatalyst is reintroduced into the main reaction zone. One way to accomplish this is by a feed tube whose slope and inner diameter is such that the fraction of photocatalyst entering and leaving the regeneration zone is constant. The photocatalyst can also be reintroduced into the reaction zone by a gated opening that spills the photocatalyst from the regeneration zone to the reaction zone. The size of the regeneration zone and residence time therein is such that the photocatalyst recovers at least 50% of its initial activity. A related aspect of the invention for all types of photocatalytic reactors systems is the active photocatalytic media (i.e., “photocatalyst”). The media should be both fluidizable and have sufficiently low attrition, less than 3 wt %/h per ASTM D5757, to prevent the formation of fines that would shorten the photocatalyst lifetime and escape the photoreactor, degrading performance, and/or block downstream systems, causing higher pressure drops, blocked flow, and reactor failure. Fine-particle collection systems such as a cyclone or removable filters can be used to collect fines lost during operation without burdening downstream systems. Low attrition is an important feature of the photocatalyst to enable operation of the photocatalytic reactor system over a useful time period. The N2BET (Brunauer-Emmett-Teller) surface area of the photocatalyst is at least 10 m2/g, from 10-900 m2/g, preferably 20-800 m2/g, and most preferably 50-600 m2/g. Without wishing to be bound by theory, it is expected that this porosity can be utilized to adsorb the target species to bring it close to the surface-bound photoactive nanocrystals for oxidation. The rapid adsorption and large surface area provided by the porous photocatalysts preclude the need for a separate adsorption step before light-activated transformations are commenced. The photoactive component or components in the photocatalyst may include but are not limited to titanium oxide, zinc oxide, bismuth oxide, tungsten oxide, molybdenum sulfide, gallium phosphide, silicon carbide, cadmium sulfide, and modified compositions of these compounds with other dopants tuned to maximize performance at the desired wavelength of incident light. The photocatalyst may be comprised of 100% of this photoactive component, or the photoactive component may be present in the photocatalyst at less than 100%, in combination with a non-photoactive component. A photocatalyst that is a mixture of photoactive and non-photoactive components may be specified in this invention as a “composite photocatalyst” or more simply as a “photocatalyst”. In one embodiment, monolithic composite photocatalysts previously disclosed in provisional application 62/760,428 comprise discrete, immobilized photocatalyst (<5 nm) well-adhered to solid supports with low attrition, high surface area, and variable form factors. The shape and size of these composite photocatalysts can be tuned to achieve critical fluidization regimes and the necessary robustness to withstand losses from attrition. Composite photocatalysts can be specifically tuned to optimally mineralize or chemically transform the species of interest under the reaction conditions in the relevant environment. The form factor can be selected to optimize fluidization and physical robustness from various beads and extrudate shapes. Diameters in the range of 20-600 μm demonstrate good fluidization properties. Different composite photocatalyst supports, fillers, or binders can be used as the non-photoactive component. By way of example, these non-photoactive components can be zirconia, titania, silica-titania, alumina, silica, zeolites, or combinations thereof. The support composition may be chosen to impart wear-resistance to the fluidized media, decreasing attrition. The porosity of the support and pore size may play a role in performance. In one embodiment, the composite photocatalyst is mesoporous with pores from 2-50 nm, more preferably 4-450 nm, and most preferably 6-40 nm as determined from BJH (Barrett-Joyner-Halenda) analysis or DFT (density functional theory) analysis of N2isotherm data collected at 77 K. Pore volume is 0.2-1.5 cc/g, more preferably 0.4-1.0 cc/g as determined from DFT analysis of N2isotherms collected at 77 K. A single photocatalyst type may be used in the reactor and/or more than one photocatalyst differing in at least one property from among particle size, shape, pore size, surface area, pore volume, composition, surface properties can be combined in a reactor. Combining multiple photocatalyst types in a single reactor may offer advantages during chemical transformations, particularly when the stream contains multiple components differing in size and polarity. This approach may be appropriate where it has been shown that different photocatalyst types are optimized for different species and can preferentially adsorb and/or mineralize these species. Alternately, different reactors housing a single composite photocatalyst type may be placed in series to improve total mineralization rates of a mixed component stream. In one aspect of the invention, the photocatalyst and fluidized bed photoreactor are used to mineralize a single organic species or VOC or multiple organic species or VOCs in a fluid. A related aspect of the invention is the application of these photocatalytic fluidized bed reactor systems to achieve chemical transformations typically achieved with traditional thermal catalysts. The use of photocatalysts in fluidized beds may facilitate these transformations at lower pressures or lower temperatures than traditional thermal catalysts. The fluidized bed photoreactor, photocatalyst, and the reaction conditions employed can be tailored to achieve the desired product in high yield with high selectivity. Reaction conditions can include light alone or in combination with heat and or/pressure to achieve the desired outcome. Examples of organic transformations photocatalyzed in the fluidized bed reactors described herein include controlled oxidation reactions of organic molecules, epoxidation of alkenes, hydroxylations, CO2reduction, conversion of NO to N2and O2, and C—H activation reactions, particularly for light hydrocarbons. Photocatalysis can allow for chemical transformations to proceed at lower pressures, even atmospheric pressure, than traditional thermal catalysis. In processes that require elevated pressure, the operating pressure can be more moderate than the high pressure used in analogous thermal catalytic processes. Pressure greater than atmospheric may also enable photocatalytic transformations that are not possible using thermal catalysis. In one aspect of the invention, pressure within the reaction chamber may be modified to achieve specific chemical transformations. Conversion of CO2to methane or methanol, for example, may require pressures greater than 1 bar, preferably 1-20 bar, more preferably 2-10 bar. Without wishing to be bound by theory, it is thought that elevated pressures in chemical transformations can affect reagent solubility, reaction rate, product selectivity, and yield. In one embodiment, particles which are transparent to the incident radiation are added to the reaction chamber with the photocatalyst. Transparent particles allow the incident light to travel further into the fluidized bed while also allowing fluidization regime to be controlled. Alternatively, highly scattering (i.e. diffuse reflective) particles can be added to the reactor to improve light uniformity within the reactor. A combination of scattering and transmissive particles may be used. The added non-photocatalytic particles do not need to have the same size or density of the photocatalytic particles. In a preferred embodiment the optical absorbance and optical scattering properties of the photocatalyst are engineered to maximize the optical intensity and spatial uniformity of optical intensity incident on the photocatalyst.FIG.9shows spectral reflectance for four different variations of the monolithic composite photocatalyst. These data were measured at near normal incidence using a bifurcated fiber reflectance probe used with a diode array spectrometer and a pulsed Xenon discharge source. These monolithic composite photocatalysts employ alumina as the support, and the measurements are relative to uncoated alumina, i.e. spectral reflectance of uncoated alumina is defined as 100%. These materials are most useful near the absorption edge, i.e. where the reflectance is monotonically decreasing with wavelength. For these materials that spectral range is approximately from 380-420 nm. The wavelength dependence of the catalysts spectral reflectance and absorbance may be engineered via nanocrystal size of the active titania on the support, support pore size, support surface area and active titania loading. Relative absorbance A is calculated by A=1−R, (with R=reflectance), since transmittance was shown to be zero under these conditions. Table 5 summarizes the measured reflectance taken from theFIG.9spectral data and calculated absorbance at two technologically useful wavelengths, 365 nm and 385 nm. These correspond to commercially available high intensity LED emitters that are useful as photocatalytic illumination. These devices operate near peak wall plug efficiency for InGaN LED devices, approximately 48% and 52%. Both wavelengths are very effective at stimulating photocatalytic activity in the subject materials. A range of absorbance levels may be achieved by varying the illumination wavelength and material absorbance properties. In general, lower values for absorbance, i.e. less than 10%, may be achieved either by operating at 385 nm or for Sample Types 1 and 2, thereby enabling light penetration deeper into the fluidized photocatalyst bed. Higher absorbance values, i.e. greater than 10%, may be achieved at 365 nm for Sample types 2, 3 and 4. Higher absorbance is useful for shallow photocatalyst bed configurations. Other photocatalytic illumination wavelengths accordingly offer additional flexibility for photoreactor design and photocatalyst material type. Wavelengths in the 250 nm to 420 nm wavelength range are of the greatest interest. For a given material, illumination at multiple wavelengths enables a wide range of photocatalyst bed penetration depths. TABLE 5Reflectance and relative absorbance at 365 nm and 385 nm forfour engineered monolithic composite photocatalyst materials,from FIG. 9. A range of absorbance values are available tooptimize optical coupling in the subject photoreactors.SampleReflectanceAbsorbance (relative)TypeFIG. 9R (365 nm)R (385 nm)A (365 nm)A (385 nm)1900194%96%6%4%2900286%94%14%6%3900370%92%30%8%4900457%90%43%10% EXAMPLES Example 1 The photocatalytic oxidation of ethylene gas to CO2and H2O was performed in a closed loop, 100 L test environment comprising a photocatalytic reactor system of Type 3, an ultrasonic humidifier, a humidity controller, and a photoionization detector. The photocatalytic reactor system is similar to that depicted inFIG.3and consists of a 2.7 W, 365 nm LED mounted on a heat sink and suspended above the photocatalyst. The LED was operated at full power. The photocatalyst was housed in a conical reactor and held in place by stainless steel meshes above and below the reactor. Fluidization was provided by a variable speed axial fan mounted 2″ from the bottom of the photocatalyst, and all the air was directed through the photocatalytic reactor system using a tube. The relative humidity of the system was maintained at 60%. No additional water was added after the initial relative humidity level was reached. A 10 ppm ethylene cylinder, balanced with air, was used to introduce a charge of contaminated air into the system until the total ethylene level reached 6 ppm, at which point the LED source was switched on. The level of ethylene was continuously monitored using a PID detector for the course of 300 minutes. The resulting decrease in the ethylene level with time is shown inFIG.10. Example 2 The photocatalytic oxidation of toluene to CO2and H2O was performed using a continuous 600 sccm, 2 ppm toluene flow that passes once through a photocatalytic reactor of Type 1. The photocatalytic reactor consists of a linear array of 22 365 nm LEDs that are spaced ½″ apart mounted to a heat sink, however, only 3 LEDs are in direct line of site of the photocatalyst. The photocatalyst was housed in a 7 mm inner diameter quartz tube that was aligned vertically and parallel to the LED strip which sits 10 mm away. A reflector was placed on the back side of the reactor. Fluidization was achieved using the 600 sccm polluted gas flow and the photocatalyst was positioned vertically in the tube using a plug of quartz wool. An equilibrium flow of toluene was established for 10 minutes through the reactor before illumination. After illumination, the concentration of toluene was reduced to 0 ppb (limits of detection) of a PID detector calibrated for toluene and remained at that level for the duration of illumination time, 10 min. After the LEDs were turned off the 2 ppm toluene signal returned. Example 3 The photocatalytic oxidation of toluene to CO2and H2O was performed using the same setup as Example except the quartz tube used had been worn due to attrition by 300 mg of catalyst for 6 weeks at a flow of 1000 sccm. The toluene conversion of the worn tube and a new quartz tube were compared. The transmission of the worn tube was 2× lower than the new tube when measured normal to an LED source with the reactor tube in between. The concentration of toluene was 3 ppm for Example 3. Using the same lights source and reactor geometries, the concentration of toluene decreased to ˜100 ppb for reactor tubes despite the difference in light transmission indicating attrition did not adversely affect performance. Example 4 The photocatalytic oxidation of a humidified air stream containing isopropanol and ethylene in a 1:3 ratio can be enhanced using two composite photocatalysts in a fluidized bed reactor. The properties of each composite photocatalysts are optimized to maximize the conversion of either isopropanol or ethylene. Ethylene is a small, non-polar molecule that weakly interacts with the TiO2 surface, whereas isopropanol is larger, polar, and interacts strongly with TiO2, especially under UV illumination, where it outcompetes ethylene for photocatalytic sites. One photocatalyst is modified to have smaller pores to enhance ethylene adsorption and limit isopropanol adsorption. The second photocatalyst comprises larger pores to reduce ethylene adsorption and maximize isopropanol diffusion kinetics and photocatalytic conversion. Upon illumination of the mixed photocatalyst bed with 365 nm light, removal of both species can be achieved rather than preferential removal of one component over the other in a fluidized bed containing a single photocatalyst species. The subject invention may be embodied in the following examples that are by no means restrictive, but intended to illustrate the invention. In particular, aspects of the various examples and embodiments may be combined to comprise variations of this invention. It will be clear that the described invention is well adapted to achieve the purposes described above, as well as those inherent within. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Numerous other changes may be made which will readily suggest themselves to those skilled in the art and which are encompassed both in the spirit of the disclosure above and the appended claims.
67,146
11857925
DETAILED DESCRIPTION OF THE INVENTION Reduction of NOx from a lean burn diesel engine during engine cold start period is essential for meeting future legislative regulations. One approach to addressing this challenge may relate to a system configured to take advantage of the thermal swing from the engine to reduce the duration of the cold start period. In addition, exhaust gas recirculation circuits may be removed from the engine with such treatment system configurations, allowing for improved fuel economy and engine power output. A challenge for such system design, however, is that the space may be very limited. Therefore, it may be desirable to combine SCR/ASC/DOC functionality into as compact space as possible. However, because the minimal temperature for urea decomposition and for an SCR catalyst to be active is about 180° C. to about 200° C., there may still be a significant gap where the initial cold start emissions is not accounted for. Catalysts, systems, and methods of the present invention have been found to incorporate SCR/ASC/DOC functionalities without compromising NOx conversion and N2selectivity. In addition, a passive NOx adsorber (PNA) has been incorporated into the SCR/ASC component that may further improve the low temperature cold start performance. Catalysts, methods, and systems of the present invention relate to catalyst articles including various configurations of SCR catalyst(s), ASC, and DOC or DEC, with a PNA incorporated into the SCR/ASC component(s). The catalysts and specific configurations, methods, and systems are described in further detail below. Two Zone Configurations Embodiments of the present invention relate to a catalyst article comprising a substrate with an inlet end and an outlet end, a first zone and a second zone, where the first zone is located upstream of the second zone. The first zone can include a passive NOx adsorber (PNA), and an ammonia slip catalyst (ASC) including a platinum group metal on a support; and an SCR layer having an SCR catalyst, where the SCR layer is located over the ASC bottom layer and a first SCR catalyst. The second zone may include a diesel oxidation catalyst (DOC) or a diesel exotherm catalyst (DEC). The first zone may include a bottom layer including a blend of the platinum group metal on a support and the first SCR catalyst, and a top layer including a second SCR catalyst, with the top layer located over the bottom layer. PNA may be included in a catalyst article of the present invention in various configurations. For example, in some embodiments, PNA is included in the bottom layer. In some embodiments, PNA is included in the blend of the platinum group metal on a support and the first SCR catalyst. In some embodiments, the bottom layer includes a section comprising the PNA (“PNA section”), and the PNA section is located upstream of the blend. In some embodiments, the bottom layer comprises a section comprising the PNA and a third SCR catalyst (“PNA/SCR section”). The bottom layer may include the PNA/SCR section and the blend, with the PNA/SCR section located upstream of the blend, with the blend located on top of the PNA/SCR section, or with the PNA/SCR section located on top of the blend. In some embodiments, the first and second zone are located on a single substrate, with the first zone located on the inlet side of the substrate and the second zone located on the outlet side of the substrate. In another embodiment, the first zone is located on a first substrate and the second zone is located on a second substrate, wherein the first substrate is located upstream of the second substrate. The first and second substrate may be close coupled. When the first and second substrate are close coupled, the second substrate may be placed close to and/or directly downstream from the first substrate. A method of reducing emissions from an exhaust stream may include contacting the exhaust stream with a catalyst article as described herein. Three Zone Configuration Embodiments of the present invention relate to catalyst articles having a first zone, a second zone, and a third zone. The first zone may include an SCR catalyst. The second zone may include an ASC having a blend of a platinum group metal on a support and a first SCR catalyst. The third zone may include a catalyst (“third zone catalyst”) such as a DOC or DEC. The catalyst article includes a PNA. The first zone is located upstream of the second zone, and the second zone is located upstream of the third zone. In some embodiments, the ASC is included in a first layer, and the third zone catalyst is included in a second layer which extends from the outlet end to less than a total length of the substrate, where the second layer is located on top of the first layer and is shorter than length than the first layer. The SCR catalyst of the first zone may be included in a layer which extends from the inlet end to less than a total length of the substrate, and which at least partially overlaps the first layer. In various configurations, the first layer may extend from the outlet end to less than a total length of the substrate; the first layer may extend from the inlet end to less than a total length of the substrate; the first layer may extend the length of the substrate; and/or the first layer may cover the length of the first zone, the second zone, and/or the third zone. In some embodiments, the PNA is included in the first zone. In some embodiments, the PNA is included in the second zone. PNA may be included in a catalyst article of the present invention in various configurations. For example, in some embodiments, PNA is included in the first layer. In some embodiments, PNA is included in the blend of the platinum group metal on a support and the first SCR catalyst. In some embodiments, the first layer includes a section comprising the PNA (“PNA section”), and the PNA section is located upstream of the blend. In some embodiments, the first layer comprises a section comprising the PNA and a third SCR catalyst (“PNA/SCR section”). The first layer may include the PNA/SCR section and the blend, with the PNA/SCR section located upstream of the blend, with the blend located on top of the PNA/SCR section, or with the PNA/SCR section located on top of the blend. In some embodiments, the first zone is located on a first substrate, the second zone is located on a second substrate, and the third zone is located on a third substrate, where the first substrate is located upstream of the second substrate and the second substrate is located upstream of the third substrate. The first, second, and/or third substrate may be close coupled. When the first, second, and/or third substrate are close coupled, the second substrate may be placed close to and/or directly downstream from the first substrate, and the third substrate may be placed close to and/or directly downstream from the second substrate. A method of reducing emissions from an exhaust stream may include contacting the exhaust stream with a catalyst article as described herein. With reference toFIG.1a, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the combination of the SCR catalyst, PNA, and platinum group metal. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.1b, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the combination of the SCR catalyst and platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.1c, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the platinum group metal on a support. With reference toFIG.2a, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. A platinum group metal is impregnated on the combination of an SCR catalyst, a PNA, and a platinum group metal on a support which is not covered by the top layer SCR catalyst. With reference toFIG.2b, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the combination of the SCR catalyst and platinum group metal on a support. A platinum group metal is impregnated on the combination of an SCR catalyst and a platinum group metal on a support which is not covered by the top layer SCR catalyst. With reference toFIG.2c, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the platinum group metal on a support. A platinum group metal is impregnated on the platinum group metal on a support which is not covered by the top layer SCR catalyst. With reference toFIG.3a, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support and partially covering the PNA. A platinum group metal is impregnated on the outlet end of the substrate. With reference toFIG.3b, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the PNA. A platinum group metal is impregnated on the outlet end of the substrate. With reference toFIG.3c, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the PNA. A platinum group metal is impregnated on the outlet end of the substrate. With reference toFIG.4a, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends the length of the substrate, covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal. With reference toFIG.4b, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends the length of the substrate, covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.4c, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends the length of the substrate, covering the PNA and the platinum group metal on a support. With reference toFIG.5a, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.5b, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.5c, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the PNA and partially covering the platinum group metal on a support. With reference toFIG.6a, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support and partially covering the PNA. With reference toFIG.6b, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the PNA. With reference toFIG.6c, a catalytic article may include a PNA extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the PNA. With reference toFIG.7a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the combination of the SCR catalyst, PNA, and platinum group metal. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.7b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the combination of the SCR catalyst and platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.7c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the platinum group metal on a support. With reference toFIG.8a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. A platinum group metal is impregnated on the combination of an SCR catalyst, a PNA, and a platinum group metal on a support which is not covered by the top layer SCR catalyst. With reference toFIG.8b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the combination of the SCR catalyst and platinum group metal on a support. A platinum group metal is impregnated on the combination of an SCR catalyst and a platinum group metal on a support which is not covered by the top layer SCR catalyst. With reference toFIG.8c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the platinum group metal on a support. A platinum group metal is impregnated on the platinum group metal on a support which is not covered by the top layer SCR catalyst. With reference toFIG.9a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support and partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the outlet end of the substrate. With reference toFIG.9b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the outlet end of the substrate. With reference toFIG.9c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the outlet end of the substrate. With reference toFIG.10a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends the length of the substrate, covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal. With reference toFIG.10b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends the length of the substrate, covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.10c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends the length of the substrate, covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. With reference toFIG.11a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.11b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.11c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the inlet end towards the outlet end, covering the combination of the PNA and SCR catalyst and partially covering the platinum group metal on a support. With reference toFIG.12a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support and partially covering the combination of the PNA and SCR catalyst. With reference toFIG.12b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the combination of the PNA and SCR catalyst. With reference toFIG.12c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the inlet end toward the outlet end, and a platinum group metal on a support extending from the outlet end towards the inlet end. A top layer including an SCR catalyst extends from the outlet end towards the inlet end, extending less than the length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support and partially covering the combination of the PNA and SCR catalyst. With reference toFIG.13a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA/SCR combination. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.13b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA/SCR combination. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.13c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA/SCR combination. A DOC layer extends from the outlet end toward the inlet end, partially covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. With reference toFIG.14a, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.14b, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.14c, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA. A DOC layer extends from the outlet end toward the inlet end, partially covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the platinum group metal on a support. With reference toFIG.15a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.15b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.15c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.16a, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. A platinum group metal is impregnated on the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.16b, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. A platinum group metal is impregnated on the PNA and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.16c, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the platinum group metal on a support. A platinum group metal is impregnated on the PNA and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.17a, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.17b, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.17c, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. A DOC layer extends from the outlet end toward the inlet end, partially covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. With reference toFIG.18a, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.18b, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.18c, a catalytic article may include a PNA extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. A DOC layer extends from the outlet end toward the inlet end, partially covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the platinum group metal on a support. With reference toFIG.19a, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.19b, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.19c, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.20a, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.20b, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.20c, a catalytic article may include a PNA extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the platinum group metal on a support. A platinum group metal is impregnated on the combination of the PNA and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.21a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.21b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.21c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. With reference toFIG.22a, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends the entire length of the substrate, covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.22b, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends the entire length of the substrate, covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.22c, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends the entire length of the substrate, covering the PNA and the platinum group metal on a support. With reference toFIG.23a, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.23b, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.23c, a catalytic article may include a combination of a PNA and an SCR catalyst extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA/SCR combination. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. With reference toFIG.24a, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PNA/PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.24b, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The combination of SCR/PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.24c, a catalytic article may include a PNA extending from the outlet end toward the inlet end, extending less than the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. The PGM.support layer may be shorter in length than the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the platinum group metal on a support. With reference toFIG.25a, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.25b, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.25c, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. With reference toFIG.26a, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends the entire length of the substrate, covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.26b, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends the entire length of the substrate, covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.26c, a catalytic article may include a PNA extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends the entire length of the substrate, covering the PNA and the platinum group metal on a support. With reference toFIG.27a, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.27b, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.27c, a catalytic article may include a combination of a PNA and an SCR catalyst extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the combination of the PNA and SCR catalyst, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst and the platinum group metal on a support. With reference toFIG.28a, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst, a PNA, and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support. With reference toFIG.28b, a catalytic article may include a PNA extending the entire length of the substrate. A combination of an SCR catalyst and a platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the combination of the SCR catalyst and platinum group metal on a support. With reference toFIG.28c, a catalytic article may include a PNA extending the entire length of the substrate. A platinum group metal on a support extends from the outlet end towards the inlet end, on top of the PNA, extending less than the entire length of the substrate. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA and the platinum group metal on a support. With reference toFIG.29a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PNA/PGM.support layer. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the PNA and SCR catalyst. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.29b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PGM.support layer. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the PNA and SCR catalyst. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.29c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA/SCR combination may be longer in length than the platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the PNA and SCR catalyst. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.30a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PNA/PGM.support layer. A DOC layer extends from the outlet end toward the inlet end, partially covering the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.30b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PGM.support layer. A DOC layer extends from the outlet end toward the inlet end, partially covering the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.30c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA may be longer in length than the platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.31a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PNA/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.31b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.31c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA/SCR combination may be longer in length than the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.32a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PNA/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. A platinum group metal is impregnated on the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.32b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. A platinum group metal is impregnated on the PNA and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.32c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA may be longer in length than the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. A platinum group metal is impregnated on the PNA and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.33a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the PNA and SCR catalyst. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.33b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the PNA and SCR catalyst. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.33c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the combination of the PNA and SCR catalyst. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.34a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.34b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.34c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the platinum group metal on a support. A DOC layer extends from the outlet end toward the inlet end, partially covering the PNA. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.35a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.35b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.35c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. A platinum group metal is impregnated on the combination of the PNA and SCR catalyst and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.36a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. A platinum group metal is impregnated on the PNA and the combination of the SCR catalyst, PNA, and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.36b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. A platinum group metal is impregnated on the PNA and the combination of the SCR catalyst and platinum group metal on a support at the outlet end of the substrate. With reference toFIG.36c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. A platinum group metal is impregnated on the PNA and the platinum group metal on a support at the outlet end of the substrate. With reference toFIG.37a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PNA/PGM.support layer. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst. With reference toFIG.37b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PGM.support layer. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst. With reference toFIG.37c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA/SCR combination may be longer in length than the platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst. With reference toFIG.38a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PNA/PGM.support layer. An SCR catalyst extends the entire length of the substrate, covering the PNA. With reference toFIG.38b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PGM.support layer. An SCR catalyst extends the entire length of the substrate, covering the PNA. With reference toFIG.38c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA may be longer in length than the platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the PNA. With reference toFIG.39a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PNA/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.39b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA/SCR combination may be longer in length than the combination of SCR/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.39c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA/SCR combination may be longer in length than the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.40a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PNA/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.40b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. The PNA may be longer in length than the combination of SCR/PGM.support layer. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.40c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the outlet end toward the inlet end, extending less than the entire length of the substrate, and covering the platinum group metal on a support. The PNA may be longer in length than the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.41a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst. With reference toFIG.41b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst. With reference toFIG.41c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the combination of the PNA and SCR catalyst. With reference toFIG.42a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the PNA. With reference toFIG.42b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the PNA. With reference toFIG.42c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the platinum group metal on a support. An SCR catalyst extends the entire length of the substrate, covering the PNA. With reference toFIG.43a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.43b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, and covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.43c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A combination of a PNA and an SCR catalyst extends the entire length of the substrate, and covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the combination of the PNA and SCR catalyst. With reference toFIG.44a, a catalytic article may include a combination of an SCR catalyst, a PNA, and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends from the entire length of the substrate, covering the combination of the SCR catalyst, PNA, and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.44b, a catalytic article may include a combination of an SCR catalyst and a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the combination of the SCR catalyst and platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. With reference toFIG.44c, a catalytic article may include a platinum group metal on a support extending from the outlet end towards the inlet end, extending less than the entire length of the substrate. A PNA extends the entire length of the substrate, covering the platinum group metal on a support. An SCR catalyst extends from the inlet end towards the outlet end, extending less than the entire length of the substrate, partially covering the PNA. System Configurations System configurations of the present invention may an upstream SCR catalyst, and a catalytic article having a two- or three-zone configuration as described in the preceding sections. The upstream SCR catalyst may be located upstream of the catalytic article having a two- or three-zone configuration as described in the preceding sections; in some embodiments, the upstream SCR catalyst and the catalytic article may be close-coupled. In some embodiments, the upstream SCR catalyst and the catalytic article are located on a single substrate, with the upstream SCR catalyst located upstream of the first and second (and third, if present) zones of the catalytic article. In some embodiments, the system includes an SCR catalyst located downstream of the catalytic article having a two- or three-zoned configuration as described above. In some embodiments, a system may also include a filter. The system may include one or more reductant injectors, for example, upstream of any SCR catalyst in the system. In some embodiments, the system includes a reductant injector upstream of the SCR catalyst and/or the catalytic article having a two- or three-zone configuration as described above. In a system having a downstream SCR catalyst, a reductant injector may be included upstream of the downstream SCR catalyst. Ammonia Oxidation Catalyst Catalyst articles of the present invention may include one or more ammonia oxidation catalysts, also called an ammonia slip catalyst (“ASC”). One or more ASC may be included with or downstream from an SCR catalyst, to oxidize excess ammonia and prevent it from being released to the atmosphere. In some embodiments the ASC may be included on the same substrate as an SCR catalyst, or blended with an SCR catalyst. In certain embodiments, the ammonia oxidation catalyst material may be selected to favor the oxidation of ammonia instead of the formation of NOxor N2O. Preferred catalyst materials include platinum, palladium, or a combination thereof. The ammonia oxidation catalyst may comprise platinum and/or palladium supported on a metal oxide. In some embodiments, the catalyst is disposed on a high surface area support, including but not limited to alumina. In some embodiments, the ammonia oxidation catalyst comprises a platinum group metal on a siliceous support. A siliceous material may include a material such as: (1) silica; (2) a zeolite with a silica-to-alumina ratio of at least 200; and (3) amorphous silica-doped alumina with SiO2 content ≥40%. In some embodiments, a siliceous material may include a material such as a zeolite with a silica-to-alumina ratio of at least 200; at least 250; at least 300; at least 400; at least 500; at least 600; at least 750; at least 800; or at least 1000. In some embodiments, a platinum group metal is present on the support in an amount of about 0.5 wt % to about 10 wt % of the total weight of the platinum group metal and the support; about 1 wt % to about 6 wt % of the total weight of the platinum group metal and the support; about 1.5 wt % to about 4 wt % of the total weight of the platinum group metal and the support; about 10 wt % of the total weight of the platinum group metal and the support; about 0.5 wt % of the total weight of the platinum group metal and the support; about 1 wt % of the total weight of the platinum group metal and the support; about 2 wt % of the total weight of the platinum group metal and the support; about 3 wt % of the total weight of the platinum group metal and the support; about 4 wt % of the total weight of the platinum group metal and the support; about 5 wt % of the total weight of the platinum group metal and the support; about 6 wt % of the total weight of the platinum group metal and the support; about 7 wt % of the total weight of the platinum group metal and the support; about 8 wt % of the total weight of the platinum group metal and the support; about 9 wt % of the total weight of the platinum group metal and the support; or about 10 wt % of the total weight of the platinum group metal and the support. In some embodiments, the siliceous support can comprise a molecular sieve having a BEA, CDO, CON, FAU, MEL, MFI or MWW Framework Type. SCR Catalyst Systems of the present invention may include one or more SCR catalyst. In some embodiments, a catalyst article may include a first SCR catalyst, a second SCR catalyst, and/or a third SCR catalyst. In some embodiments, the SCR catalysts may comprise the same formulation as each other. In some embodiments, the SCR catalysts may comprise different formulations than each other. The exhaust system of the invention may include an SCR catalyst which is positioned downstream of an injector for introducing ammonia or a compound decomposable to ammonia into the exhaust gas. The SCR catalyst may be positioned directly downstream of the injector for injecting ammonia or a compound decomposable to ammonia (e.g. there is no intervening catalyst between the injector and the SCR catalyst). The SCR catalyst includes a substrate and a catalyst composition. The substrate may be a flow-through substrate or a filtering substrate. When the SCR catalyst has a flow-through substrate, then the substrate may comprise the SCR catalyst composition (i.e. the SCR catalyst is obtained by extrusion) or the SCR catalyst composition may be disposed or supported on the substrate (i.e. the SCR catalyst composition is applied onto the substrate by a washcoating method). When the SCR catalyst has a filtering substrate, then it is a selective catalytic reduction filter catalyst, which is referred to herein by the abbreviation “SCRF”. The SCRF comprises a filtering substrate and the selective catalytic reduction (SCR) composition. References to use of SCR catalysts throughout this application are understood to include use of SCRF catalysts as well, where applicable. The selective catalytic reduction composition may comprise, or consist essentially of, a metal oxide based SCR catalyst formulation, a molecular sieve based SCR catalyst formulation, or mixture thereof. Such SCR catalyst formulations are known in the art. The selective catalytic reduction composition may comprise, or consist essentially of, a metal oxide based SCR catalyst formulation. The metal oxide based SCR catalyst formulation comprises vanadium or tungsten or a mixture thereof supported on a refractory oxide. The refractory oxide may be selected from the group consisting of alumina, silica, titania, zirconia, ceria and combinations thereof. The metal oxide based SCR catalyst formulation may comprise, or consist essentially of, an oxide of vanadium (e.g. V2O5) and/or an oxide of tungsten (e.g. WO3) supported on a refractory oxide selected from the group consisting of titania (e.g. TiO2), ceria (e.g. CeO2), and a mixed or composite oxide of cerium and zirconium (e.g. CexZr(1-x)O2, wherein x=0.1 to 0.9, preferably x=0.2 to 0.5). When the refractory oxide is titania (e.g. TiO2), then preferably the concentration of the oxide of vanadium is from 0.5 to 6 wt % (e.g. of the metal oxide based SCR formulation) and/or the concentration of the oxide of tungsten (e.g. WO3) is from 5 to 20 wt %. More preferably, the oxide of vanadium (e.g. V2O5) and the oxide of tungsten (e.g. WO3) are supported on titania (e.g. TiO2). When the refractory oxide is ceria (e.g. CeO2), then preferably the concentration of the oxide of vanadium is from 0.1 to 9 wt % (e.g. of the metal oxide based SCR formulation) and/or the concentration of the oxide of tungsten (e.g. WO3) is from 0.1 to 9 wt %. The metal oxide based SCR catalyst formulation may comprise, or consist essentially of, an oxide of vanadium (e.g. V2O5) and optionally an oxide of tungsten (e.g. WO3), supported on titania (e.g. TiO2). The selective catalytic reduction composition may comprise, or consist essentially of, a molecular sieve based SCR catalyst formulation. The molecular sieve based SCR catalyst formulation comprises a molecular sieve, which is optionally a transition metal exchanged molecular sieve. It is preferable that the SCR catalyst formulation comprises a transition metal exchanged molecular sieve. In general, the molecular sieve based SCR catalyst formulation may comprise a molecular sieve having an aluminosilicate framework (e.g. zeolite), an aluminophosphate framework (e.g. AlPO), a silicoaluminophosphate framework (e.g. SAPO), a heteroatom-containing aluminosilicate framework, a heteroatom-containing aluminophosphate framework (e.g. MeAlPO, where Me is a metal), or a heteroatom-containing silicoaluminophosphate framework (e.g. MeAPSO, where Me is a metal). The heteroatom (i.e. in a heteroatom-containing framework) may be selected from the group consisting of boron (B), gallium (Ga), titanium (Ti), zirconium (Zr), zinc (Zn), iron (Fe), vanadium (V) and combinations of any two or more thereof. It is preferred that the heteroatom is a metal (e.g. each of the above heteroatom-containing frameworks may be a metal-containing framework). It is preferable that the molecular sieve based SCR catalyst formulation comprises, or consist essentially of, a molecular sieve having an aluminosilicate framework (e.g. zeolite) or a silicoaluminophosphate framework (e.g. SAPO). When the molecular sieve has an aluminosilicate framework (e.g. the molecular sieve is a zeolite), then typically the molecular sieve has a silica to alumina molar ratio (SAR) of from 5 to 200 (e.g. 10 to 200), 10 to 100 (e.g. 10 to 30 or 20 to 80), such as 12 to 40, or 15 to 30. In some embodiments, a suitable molecular sieve has a SAR of >200; >600; or >1200. In some embodiments, the molecular sieve has a SAR of from about 1500 to about 2100. Typically, the molecular sieve is microporous. A microporous molecular sieve has pores with a diameter of less than 2 nm (e.g. in accordance with the IUPAC definition of “microporous” [seePure&Appl. Chem.,66(8), (1994), 1739-1758)]). The molecular sieve based SCR catalyst formulation may comprise a small pore molecular sieve (e.g. a molecular sieve having a maximum ring size of eight tetrahedral atoms), a medium pore molecular sieve (e.g. a molecular sieve having a maximum ring size of ten tetrahedral atoms) or a large pore molecular sieve (e.g. a molecular sieve having a maximum ring size of twelve tetrahedral atoms) or a combination of two or more thereof. When the molecular sieve is a small pore molecular sieve, then the small pore molecular sieve may have a framework structure represented by a Framework Type Code (FTC) selected from the group consisting of ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, LTA, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SFW, SIV, THO, TSC, UEI, UFI, VNI, YUG and ZON, or a mixture and/or an intergrowth of two or more thereof. Preferably, the small pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of CHA, LEV, AEI, AFX, ERI, LTA, SFW, KFI, DDR and ITE. More preferably, the small pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of CHA and AEI. The small pore molecular sieve may have a framework structure represented by the FTC CHA. The small pore molecular sieve may have a framework structure represented by the FTC AEI. When the small pore molecular sieve is a zeolite and has a framework represented by the FTC CHA, then the zeolite may be chabazite. When the molecular sieve is a medium pore molecular sieve, then the medium pore molecular sieve may have a framework structure represented by a Framework Type Code (FTC) selected from the group consisting of AEL, AFO, AHT, BOF, BOZ, CGF, CGS, CHI, DAC, EUO, FER, HEU, IMF, ITH, ITR, JRY, JSR, JST, LAU, LOV, MEL, MFI, MFS, MRE, MTT, MVY, MWW, NAB, NAT, NES, OBW, -PAR, PCR, PON, PUN, RRO, RSN, SFF, SFG, STF, STI, STT, STW, -SVR, SZR, TER, TON, TUN, UOS, VSV, WEI and WEN, or a mixture and/or an intergrowth of two or more thereof. Preferably, the medium pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of FER, MEL, MFI, and STT. More preferably, the medium pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of FER and MFI, particularly MFI. When the medium pore molecular sieve is a zeolite and has a framework represented by the FTC FER or MFI, then the zeolite may be ferrierite, silicalite or ZSM-5. When the molecular sieve is a large pore molecular sieve, then the large pore molecular sieve may have a framework structure represented by a Framework Type Code (FTC) selected from the group consisting of AFI, AFR, AFS, AFY, ASV, ATO, ATS, BEA, BEC, BOG, BPH, BSV, CAN, CON, CZP, DFO, EMT, EON, EZT, FAU, GME, GON, IFR, ISV, ITG, IWR, IWS, IWV, IW W, JSR, LTF, LTL, MAZ, MEI, MOR, MOZ, MSE, MTW, NPO, OFF, OKO, OSI, -RON, RWY, SAF, SAO, SBE, SBS, SBT, SEW, SFE, SFO, SFS, SFV, SOF, SOS, STO, SSF, SSY, USI, UWY, and VET, or a mixture and/or an intergrowth of two or more thereof. Preferably, the large pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of AFI, BEA, MAZ, MOR, and OFF. More preferably, the large pore molecular sieve has a framework structure represented by a FTC selected from the group consisting of BEA, MOR and MFI. When the large pore molecular sieve is a zeolite and has a framework represented by the FTC BEA, FAU or MOR, then the zeolite may be a beta zeolite, faujasite, zeolite Y, zeolite X or mordenite. In general, it is preferred that the molecular sieve is a small pore molecular sieve. The molecular sieve based SCR catalyst formulation preferably comprises a transition metal exchanged molecular sieve. The transition metal may be selected from the group consisting of cobalt, copper, iron, manganese, nickel, palladium, platinum, ruthenium and rhenium. The transition metal may be copper. An advantage of SCR catalyst formulations containing a copper exchanged molecular sieve is that such formulations have excellent low temperature NOxreduction activity (e.g. it may be superior to the low temperature NOxreduction activity of an iron exchanged molecular sieve). Systems and method of the present invention may include any type of SCR catalyst, however, SCR catalysts including copper (“Cu-SCR catalysts”) may experience more notable benefits from systems of the present invention, as they are particularly vulnerable to the effects of sulfation. Cu-SCR catalyst formulations may include, for example, Cu exchanged SAPO-34, Cu exchanged CHA zeolite, Cu exchanged AEI zeolites, or combinations thereof. The transition metal may be present on an extra-framework site on the external surface of the molecular sieve or within a channel, cavity or cage of the molecular sieve. Typically, the transition metal exchanged molecular sieve comprises an amount of 0.10 to 10% by weight of the transition metal exchanged molecular, preferably an amount of 0.2 to 5% by weight. In general, the selective catalytic reduction catalyst comprises the selective catalytic reduction composition in a total concentration of 0.5 to 4.0 g in3, preferably 1.0 to 3.0 4.0 g in−3. The SCR catalyst composition may comprise a mixture of a metal oxide based SCR catalyst formulation and a molecular sieve based SCR catalyst formulation. The (a) metal oxide based SCR catalyst formulation may comprise, or consist essentially of, an oxide of vanadium (e.g. V2O5) and optionally an oxide of tungsten (e.g. WO3), supported on titania (e.g. TiO2) and (b) the molecular sieve based SCR catalyst formulation may comprise a transition metal exchanged molecular sieve. When the SCR catalyst is an SCRF, then the filtering substrate may preferably be a wall flow filter substrate monolith. The wall flow filter substrate monolith (e.g. of the SCR-DPF) typically has a cell density of 60 to 400 cells per square inch (cpsi). It is preferred that the wall flow filter substrate monolith has a cell density of 100 to 350 cpsi, more preferably 200 to 300 cpsi. The wall flow filter substrate monolith may have a wall thickness (e.g. average internal wall thickness) of 0.20 to 0.50 mm, preferably 0.25 to 0.35 mm (e.g. about 0.30 mm). Generally, the uncoated wall flow filter substrate monolith has a porosity of from 50 to 80%, preferably 55 to 75%, and more preferably 60 to 70%. The uncoated wall flow filter substrate monolith typically has a mean pore size of at least 5 μm. It is preferred that the mean pore size is from 10 to 40 μm, such as 15 to 35 μm, more preferably 20 to 30 μm. The wall flow filter substrate may have a symmetric cell design or an asymmetric cell design. In general for an SCRF, the selective catalytic reduction composition is disposed within the wall of the wall-flow filter substrate monolith. Additionally, the selective catalytic reduction composition may be disposed on the walls of the inlet channels and/or on the walls of the outlet channels. Blend Embodiments of the present invention may include a blend of (1) a platinum group metal on a support, and (2) an SCR catalyst. In some embodiments, within the blend, a weight ratio of the SCR catalyst to the platinum group metal on a support is about 3:1 to about 300:1; about 3:1 to about 250:1; about 3:1 to about 200:1; about 4:1 to about 150:1; about 5:1 to about 100:1; about 6:1 to about 90:1; about 7:1 to about 80:1; about 8:1 to about 70:1; about 9:1 to about 60:1; about 10:1 to about 50:1; about 3:1; about 4:1; about 5:1; about 6:1; about 7:1; about 8:1; about 9:1; about 10:1; about 15:1; about 20:1; about 25:1; about 30:1; about 40:1; about 50:1; about 75:1; about 100:1; about 125:1; about 150:1; about 175:1; about 200:1; about 225:1; about 250:1; about 275:1; or about 300:1. This weight ratio may include platinum group metal from the PNA as well, in embodiments where the blend includes PNA. NOx Adsorber (PNA) The NOx adsorber (PNA) comprises a metal-containing molecular sieve or palladium on ceria. When the PNA comprises a metal-containing molecular sieve, the metal may be selected from the group consisting of cerium, chromium, cobalt, copper, iron, lanthanum, manganese, molybdenum, nickel, niobium, palladium, tungsten, silver vanadium, and zinc, and mixtures thereof. In some embodiments, the metal is cobalt, manganese, palladium, or zinc. In some embodiments, the metal is palladium or zinc. In some embodiments, the metal in the SCR catalyst is copper and the metal in the PNA is palladium. The molecular sieve in the metal-containing molecular sieve in the PNA can comprise an aluminosilicate (e.g. zeolite), an aluminophosphate, or a silicoaluminophosphate, as described above in the description of molecular sieves in SCR catalysts. When the SCR catalyst comprises a metal-containing molecular sieve, the molecular sieve in the metal-containing molecular sieve in the SCR catalyst can be the same molecular sieve in the metal-containing molecular sieve in the PNA, or the molecular sieve in the metal-containing molecular sieve in the SCR catalyst can be the different than the molecular sieve in the metal-containing molecular sieve in the PNA. In some embodiments, a same formulation and/or component may function as both a PNA and an SCR catalyst. The molecular sieve in the metal-containing molecular sieve in the PNA can be a small-pore, a medium-pore or a large-pore molecular sieve, as described above in the SCR catalyst. The molecular sieve in the metal-containing molecular sieve in the PNA is preferably a small pore molecular sieve, as described above in the SCR catalyst. The small pore molecular sieve can comprise a Framework Type selected from the group consisting of: ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, LTA, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, and ZON, and mixtures or intergrowths thereof. Preferably the small pore molecular sieve is a chabazite (CHA) or an AEI. Preferred medium pore molecular sieves include FER, MEL, MFI and STT. Preferred large pore molecular sieves include AFI, BEA, MAZ, MOR and OFF. Preferably the molecular sieve in the metal-containing molecular sieve comprises an aluminosilicate or an aluminophosphate having an SAR from 5 to 100, inclusive. When the palladium containing molecular sieve is a palladium containing silicoaluminophosphate, preferably the silicoaluminophosphate comprises between 5% and 15%, inclusive, of silica. The metal in the PNA can be present at a concentration of 0.01 to 20 wt. %. The metal-containing molecular sieve can be present in the catalyst article at a concentration of about 0.5 to about 4.0 g/in3. Mixture of SCR Catalyst and NOXAdsorber Catalyst Catalyst articles of the present invention may include a mixture of an SCR catalyst with a NOx adsorber catalyst (PNA). In some embodiments, the mixture may also include an ASC, such as when the PNA is included in the SCR/ASC blend. In some embodiments, a catalyst article can comprise an SCR catalyst and a PNA, where the SCR catalyst comprises a metal-containing molecular sieve, where the metal is selected from the group consisting of cerium, copper, iron, and manganese, and mixtures thereof, and the PNA comprises a metal-containing molecular sieve, wherein the metal is selected from the group consisting of palladium or silver, and mixtures thereof, wherein the SCR catalyst and the PNA comprise the same molecular sieve and both the metal of the SCR catalyst and the metal of the PNA are exchanged and/or substituted in the molecular sieve. In some embodiments, the molecular sieve in the metal-containing molecular sieve in the SCR catalyst and the PNA can comprise an aluminosilicate, an aluminophosphate, or a silicoaluminophosphate. The molecular sieve in the metal-containing molecular sieve in the PNA is preferably a small pore molecular sieve. In some embodiments, the molecular sieve in the metal-containing molecular sieve in PNA comprises a Framework Type selected from the group consisting of: ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, LTA, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, and ZON, and mixtures or intergrowths thereof. In some embodiments, the molecular sieve comprises an AEI or CHA Framework Type. A method of preparing a catalyst article comprising an SCR catalyst and a PNA, where the SCR catalyst comprises a metal-containing molecular sieve, where the metal is selected from the group consisting of cerium, copper, iron, and manganese, and mixtures thereof, and the PNA comprises a metal-containing molecular sieve, where the metal is selected from the group consisting of palladium or silver, and mixtures thereof, where the SCR catalyst and the PNA comprise the same molecular sieve and both the metal of the SCR catalyst and the metal of PNA catalyst are exchanged and/or substituted in the molecular sieve is described. In some embodiments, the method comprises: (a) adding a first metal selected from the group selected from the group consisting of cerium, copper, iron, and manganese, and mixtures thereof, to a molecular sieve to form a molecular sieve containing the first metal; (b) calcining the molecular sieve containing the first metal to form a first calcined molecular sieve; (c) adding a second metal selected from the group selected from the group consisting of palladium or silver, and mixtures thereof, to the first calcined molecular sieve to form a molecular sieve containing the first metal and the second metal; and (d) calcining the molecular sieve containing the first metal and the second metal. The method can further comprise steps (a1) and (c1), where step (a1) comprises drying the molecular sieve containing the first metal and step (c1) comprises drying the molecular sieve containing the first metal and the second metal. Steps (a) and (c), adding the first and second metal, can be performed by one or more of impregnation, adsorption, ion-exchange, incipient wetness, precipitation, spray drying or the like. A catalyst article can comprise an SCR catalyst and a PNA having the compositions described above, where: (a) when the molecular sieve in the NOx adsorber catalyst is the same as the molecular sieve in a metal-containing molecular sieve in the SCR catalyst, the metal in the NOx adsorber catalyst and the metal in the SCR catalyst are in combination with the molecular sieve or (b) when the molecular sieve in the NOx adsorber catalyst is different than the molecular sieve in a metal-containing molecular sieve in the SCR catalyst, the metal in the NOx adsorber catalyst is in a first combination with the molecular sieve in the NOx adsorber catalyst, the metal in the SCR catalyst is in a second combination with the molecular sieve in the SCR catalyst and the first combination and the second combination are present in a third combination. Preferably, the metal in the PNA is palladium. In some embodiments, the metal in the SCR catalyst is copper, the metal in the PNA is palladium and the molecular sieve is a chabazite or an AEI. Palladium can be in introduced into the molecular sieve by spray drying or by impregnating with Pd nitrate. The molecular sieve can be hydrothermally aged. The catalyst article can further comprise hydrocarbon-SCR activity. The catalyst article can reduce stored NOx by hydrocarbon SCR. In some embodiments, the copper loading is between 0.1 and 10.0 wt. %, based on the total weight of the article. In some embodiments, the palladium loading is between 0.01 and 20.0 wt. %, based on the total weight of the article. In embodiments where the SCR catalyst and PNA are combined, the SCR catalyst and PNA are present in a weight ratio of about 10:1 to about 1:10; about 9:1 to about 1:9; about 8:1 to about 1:8; about 7:1 to about 1:7; about 6:1 to about 1:6; about 5:1 to about 1:5; about 4:1 to about 1:4; about 3:1 to about 1:3; about 2:1 to about 1:2; about 10:1; about 9:1; about 8:1; about 7:1; about 6:1; about 5:1; about 4:1; about 3:1; about 2:1; about 1:1; about 1:2; about 1:3; about 1:4; about 1:5; about 1:6; about 1:7; about 1:8; about 1:9; or about 1:10. DOC Catalyst articles and systems of the present invention may include one or more diesel oxidation catalysts. Oxidation catalysts, and in particular diesel oxidation catalysts (DOCs), are well-known in the art. Oxidation catalysts are designed to oxidize CO to CO2and gas phase hydrocarbons (HC) and an organic fraction of diesel particulates (soluble organic fraction) to CO2and H2O. Typical oxidation catalysts include platinum and optionally also palladium on a high surface area inorganic oxide support, such as alumina, silica-alumina and a zeolite. Substrate Catalysts of the present invention may each further comprise a flow-through substrate or filter substrate. In one embodiment, the catalyst may be coated onto the flow-through or filter substrate, and preferably deposited on the flow-through or filter substrate using a washcoat procedure. The combination of an SCR catalyst and a filter is known as a selective catalytic reduction filter (SCRF catalyst). An SCRF catalyst is a single-substrate device that combines the functionality of an SCR and particulate filter, and is suitable for embodiments of the present invention as desired. Description of and references to the SCR catalyst throughout this application are understood to include the SCRF catalyst as well, where applicable. The flow-through or filter substrate is a substrate that is capable of containing catalyst/adsorber components. The substrate is preferably a ceramic substrate or a metallic substrate. The ceramic substrate may be made of any suitable refractory material, e.g., alumina, silica, titania, ceria, zirconia, magnesia, zeolites, silicon nitride, silicon carbide, zirconium silicates, magnesium silicates, aluminosilicates, metallo aluminosilicates (such as cordierite and spudomene), or a mixture or mixed oxide of any two or more thereof. Cordierite, a magnesium aluminosilicate, and silicon carbide are particularly preferred. The metallic substrates may be made of any suitable metal, and in particular heat-resistant metals and metal alloys such as titanium and stainless steel as well as ferritic alloys containing iron, nickel, chromium, and/or aluminum in addition to other trace metals. The flow-through substrate is preferably a flow-through monolith having a honeycomb structure with many small, parallel thin-walled channels running axially through the substrate and extending throughout from an inlet or an outlet of the substrate. The channel cross-section of the substrate may be any shape, but is preferably square, sinusoidal, triangular, rectangular, hexagonal, trapezoidal, circular, or oval. The flow-through substrate may also be high porosity which allows the catalyst to penetrate into the substrate walls. The filter substrate is preferably a wall-flow monolith filter. The channels of a wall-flow filter are alternately blocked, which allow the exhaust gas stream to enter a channel from the inlet, then flow through the channel walls, and exit the filter from a different channel leading to the outlet. Particulates in the exhaust gas stream are thus trapped in the filter. The catalyst/adsorber may be added to the flow-through or filter substrate by any known means, such as a washcoat procedure. Reductant/Urea Injector The system may include a means for introducing a nitrogenous reductant into the exhaust system upstream of the SCR and/or SCRF catalyst. It may be preferred that the means for introducing a nitrogenous reductant into the exhaust system is directly upstream of the SCR or SCRF catalyst (e.g. there is no intervening catalyst between the means for introducing a nitrogenous reductant and the SCR or SCRF catalyst). The reductant is added to the flowing exhaust gas by any suitable means for introducing the reductant into the exhaust gas. Suitable means include an injector, sprayer, or feeder. Such means are well known in the art. The nitrogenous reductant for use in the system can be ammonia per se, hydrazine, or an ammonia precursor selected from the group consisting of urea, ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate, and ammonium formate. Urea is particularly preferred. The exhaust system may also comprise a means for controlling the introduction of reductant into the exhaust gas in order to reduce NOx therein. Preferred control means may include an electronic control unit, optionally an engine control unit, and may additionally comprise a NOx sensor located downstream of the NO reduction catalyst. Benefits Catalyst articles of the present invention may provide many benefits, including advantages compared to a catalyst article which is generally equivalent except does not include a PNA. Catalyst articles of the present invention may allow for the reduction or removal of an EGR circuit within an exhaust system, which may be beneficial in improving fuel economy and power output as well as lowering hydrocarbon and particulate matter emissions. Additionally, catalyst articles of the present invention may provide equivalent or near-equivalent NO conversion as compared to an SCR catalyst when the catalyst article is placed in a close-coupled position after the engine. Catalyst articles may provide equivalent or near-equivalent N2O formation compared to an SCR catalyst during NH3under-injection. Catalyst articles of the present invention may provide significantly reduced N2O formation during NH3over-injection. Catalyst articles of the present invention may be said to behave as an SCR/DOC catalyst under urea under-injection conditions, while behaving as an SCR/ASC/DOC with high NH3selectivity when excess NH3is present. Catalyst articles of the present invention may achieve SCR/ASC/DOC functionalities in a single block, which is particularly desirable when space is limited. Additionally, the catalyst articles may provide a fast response to engine thermal swing, which may be beneficial for NOx conversion during a cold start period. The catalyst articles may provide NOx storage before the urea-injection temperature is reached, providing additional cold-start NOx control. In some embodiments, the catalyst article may provide HC storage during cold start. In some embodiments, because of the fast warm-up of the close-coupled catalyst, the NOx storage capacity of the PNA component can be much lower than the configuration with Engine→PNA/DOC→filter→SCR/ASC. In some embodiments, because NOx release and conversion occurs on the same brick, the NOx release temperature of the PNA component may be much lower than the configuration with Engine→PNA/DOC→filter→SCR/ASC In some embodiments, optimal benefit may be derived for a system with the inventive catalyst as the first block when an ammonia:NOx ratio is ≥1 and when a temperature of the exhaust stream entering the catalyst article is ≤180° C. During these conditions, i.e. the cold start period, a downstream SCR/ASC may be too cold to be active. Once the system warms up such that the exhaust stream entering the catalyst article is ≥180° C., the ammonia:NOx ratio of is more optimally >0.5, to allow the catalyst to convert the maximum amount of NOx with minimal amount of N2O production. During the high ammonia:NOx ratio cold start period and occasional transient NH3slip event, a catalyst article of the present invention may be able to selectively oxidize excess NH3to N2without a separate/additional ASC component. Catalysts of the present invention may provide excellent SCR and ASC functionalities while being able to store NOx during cold start period and convert released NOx at higher temperatures if NH3is provided in the feed. This invention may essentially eliminate the temperature gap between NOx release temperature on the PNA catalyst and the necessary temperature for SCR reaction to be active in the downstream SCR catalyst in a PNA/DOC→filter→SCR/ASC system. As used in this specification and the appended claims, the singular forms “a”, “an” and “the” include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to “a catalyst” includes a mixture of two or more catalysts, and the like. The term “ammonia slip”, means the amount of unreacted ammonia that passes through the SCR catalyst. The term “support” means the material to which a catalyst is fixed. The term “calcine”, or “calcination”, means heating the material in air or oxygen. This definition is consistent with the IUPAC definition of calcination. (IUPAC. Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.) Calcination is performed to decompose a metal salt and promote the exchange of metal ions within the catalyst and also to adhere the catalyst to a substrate. The temperatures used in calcination depend upon the components in the material to be calcined and generally are between about 400° C. to about 900° C. for approximately 1 to 8 hours. In some cases, calcination can be performed up to a temperature of about 1200° C. In applications involving the processes described herein, calcinations are generally performed at temperatures from about 400° C. to about 700° C. for approximately 1 to 8 hours, preferably at temperatures from about 400° C. to about 650° C. for approximately 1 to 4 hours. When a range, or ranges, for various numerical elements are provided, the range, or ranges, can include the values, unless otherwise specified. The term “N2selectivity” means the percent conversion of ammonia into nitrogen. The terms “diesel oxidation catalyst” (DOC), “diesel exotherm catalyst” (DEC), “NOx absorber”, “SCR/PNA” (selective catalytic reduction/passive NOx adsorber), “cold-start catalyst” (CSC) and “three-way catalyst” (TWC) are well known terms in the art used to describe various types of catalysts used to treat exhaust gases from combustion processes. The term “platinum group metal” or “PGM” refers to platinum, palladium, ruthenium, rhodium, osmium and iridium. The platinum group metals are preferably platinum, palladium, ruthenium or rhodium. The terms “downstream” and “upstream” describe the orientation of a catalyst or substrate where the flow of exhaust gas is from the inlet end to the outlet end of the substrate or article. The following examples merely illustrate the invention; the skilled person will recognize many variations that are within the spirit of the invention and scope of the claims. Example 1 Close-couple catalyst configurations were prepared with the following configurations: SCR/DOC, SCR-ASC/DOC and PNA/SCR-ASC/DOC. The specific configurations are shown inFIG.45. The SCR catalysts include Cu.zeolite. The blend ASC catalyst was prepared having a first zone with an SCR catalyst top layer of Cu on a zeolite, and a bottom layer with a blend of (1) platinum on a zeolite and (2) Cu on a zeolite; and a second zone with a DOC. A traditional ASC catalyst was prepared having a first zone with an SCR catalyst top layer of Cu on a zeolite, and a bottom layer with a platinum on a zeolite (and no SCR catalyst). Both catalysts were prepared with 3 g/ft3of Pt loading in the ASC zone. The DOC zone in the SCR/DOC and SCR-ASC/DOC configuration includes 3:1:0/20 PtPd.alumina. The DOC zone in the PNA/SCR-ASC/DOC configuration includes 3:1:0/40 PtPd.alumina. All catalysts were aged at 650° C./10% H2O in air/50 h. The configurations were tested under simulated engine out conditions with ANR>1 and ANR<1. Specifically, the test conditions were as follows: 600 ppm or 1200 ppm NH3, 1000 ppm NO, 500 ppm (C1-based) C10H22, 200 ppm CO, 10% O2, 4.5% CO2, 4.5% H2O, total 40,000 h−1. Results for NOx conversion, N2O, NH3slip, HC conversion, and CO conversion are shown inFIGS.46-50. The SCR-ASC/DOC configuration with the traditional ASC produces most amount of N2O (FIG.50) and has the lowest NO conversion (i.e. highest NO re-make) (FIG.47) across the temperature window. When the traditional SCR-ASC in the SCR-ASC/DOC is replaced with SCR or blend SCR-ASC, both N2selectivity and NO conversion (FIG.47) is significantly improved by reducing the unselective NO+NH3reaction on Pt. A three zoned catalyst with PNA/SCR-ASC/DOC functionalities was tested to compare to the above references without PNA functionality. The PNA/SCR-ASC/DOC catalyst showed excellent N2selectivity and NO conversion (FIG.47) that is comparable to SCR/DOC and SCR-ASC/DOC with the blend ASC, demonstrating that in the inventive catalyst, the addition of Pd.zeolite does not have negative effect on its SCR and ASC performance. The DOC performance of the PNA/SCR-ASC/DOC catalyst is slightly lower than the other references, mostly due to the shorter zone length, but is not expected to affect the total system performance as it can be easily compensated by a separate downstream DOC catalyst and/or a CSF catalyst. Example 2 The aforementioned PNA/SCR-ASC/DOC catalyst was tested under simulated NOx storage-release conditions, where the catalyst was exposed to a simulated engine out gas mixture containing NOx at 80° C. for 100 seconds, followed by a temperature ramp to 500° C. Specifically, the test conditions were as follows: 200 ppm NO, 500 ppm (C1-based) C10H22, 200 ppm CO, 10% O2, 5% CO2, 5% H2O, with or without 300 ppm NH3injection at T≥180° C.; SV=40,000 h−1. The catalysts were aged at 650° C./10% H2O in air/50 h. As shown inFIG.51, the catalyst provides significant NOx storage capacity during the “cold-start” period until the exhaust temperature reaches about 200° C. when NO release starts to occur. The test was then repeated under the same conditions except NH3was added to the feed once the temperature reaches 180° C.; this time, the catalyst still provides the same amount of NOx storage as in the first test, but the released NOx was converted through NH3-SCR reaction on the catalyst instead of releasing to the reactor outlet. These results demonstrate that the inventive catalyst provides excellent SCR and ASC functionalities while being able to store NOx during cold start period and convert released NOx at higher temperatures if NH3is provided in the feed. This invention essentially eliminates the temperature gap between NOx release temperature on the PNA catalyst and the necessary temperature for SCR reaction to be active in the downstream SCR catalyst in the PNA/DOC→filter→SCR/ASC system.
133,873
11857926
EMBODIMENTS FOR CARRYING OUT THE INVENTION A nanocarbon separation method, a nanocarbon purification method, and a dispersion liquid according to an embodiment will be described below with reference to the drawings. In the embodiment, nanocarbon materials refer to carbon materials mainly composed of carbon including single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nanotwists, graphenes, fullerenes, and the like. As an example regarding nanocarbons, the case of separating single-walled carbon nanotubes of a semiconducting type and single-walled carbon nanotubes of a metallic type from a dispersion liquid containing single-walled carbon nanotubes will be described in detail. (1) Single-walled carbon nanotubes It is known that single-walled carbon nanotubes can be divided into two different types, i.e., those having metallic properties and those having semiconducting properties in accordance with a diameter and a winding manner of tubes. When single-walled carbon nanotubes are synthesized using currently known manufacturing methods, mixed materials including single-walled carbon nanotubes which include single-walled carbon nanotubes having metallic properties (hereinafter referred to as “metallic single-walled carbon nanotubes”) and single-walled carbon nanotubes having semiconducting properties (hereinafter referred to as “semiconducting single-walled carbon nanotubes”) in a statistical ratio of 1:2 are obtained. It should be noted that, in the following description, single-walled carbon nanotubes in which metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes are mixed together are referred to as a single-walled carbon nanotube mixture. The single-walled carbon nanotube mixture is not particularly limited as long as the single-walled carbon nanotube mixture contains metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes. Furthermore, single-walled carbon nanotubes in the embodiment may be independently single-walled carbon nanotubes or may be single-walled carbon nanotubes in which some of carbon atoms are substituted with arbitrary functional groups, or single-walled carbon nanotubes in which some of carbon atoms are modified by arbitrary functional groups. An example in which a dispersion liquid in which a single-walled carbon nanotube mixture is dispersed in a dispersion medium is separated into single-walled carbon nanotubes of a semiconducting type and single-walled carbon nanotubes of a metallic type will be described in detail below. (2) Dispersion liquid of single-walled carbon nanotube mixture A dispersion liquid of a single-walled carbon nanotube mixture in the embodiment is a liquid in which a single-walled carbon nanotube mixture is dispersed in a dispersion medium. It is desirable to use water or heavy water as the dispersion medium for the dispersion liquid. However, a dispersion medium such as an organic solvent and an ionic liquid may be used as long as the dispersion medium is a dispersion medium which can disperse single-walled carbon nanotubes. As an auxiliary material used for dispersing a single-walled carbon nanotube mixture in a dispersion medium, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, another dispersion auxiliary agent, and the like may be used. Particularly, it is desirable to use a non-ionic surfactant. The non-ionic surfactant will be described later. A method of preparing the dispersion liquid will also be described later. A separation apparatus used in the embodiment will be described below. FIGS.1A and1Bboth show separation apparatuses in the embodiment. A separation apparatus1inFIG.1Aincludes an electrophoresis tank10, an electrode20disposed in an upper part in the electrophoresis tank10, an electrode30disposed in a lower part in the electrophoresis tank10, a first injection port40through which a liquid is injected into the electrophoresis tank10, a second injection port50which is provided below the first injection port40and through which a liquid having a pH lower than that of the liquid injected through the first injection port40is injected into the electrophoresis tank10, and a recovery port60provided in a surface facing a surface having the first injection port40and the second injection port50. The liquid injected through at least one of the first injection port40and the second injection port50is a dispersion liquid having nanocarbons dispersed therein. A separation apparatus1inFIG.1Bincludes an electrophoresis tank10, an electrode20disposed in an upper part in the electrophoresis tank10, an electrode30disposed in a lower part in the electrophoresis tank10, a first injection port40through which a liquid is injected into the electrophoresis tank10, a second injection port50which is provided below the first injection port40and through which a liquid having a pH lower than that of a liquid injected through the first injection port40is injected into the electrophoresis tank10, a first recovery port70provided at a position in which the first recovery port70faces the first injection port40, and a second recovery port80provided at a position in which the second recovery port80faces the second injection port50. At least one of the liquids injected through the first injection port40and the second injection port50is a dispersion liquid having nanocarbons dispersed therein. The electrophoresis tank10has a space having a liquid accommodated therein. A dispersion liquid of a single-walled carbon nanotube mixture to be separated is injected into the electrophoresis tank10and a carbon nanotube mixture is separated. Any material may be adopted for the electrophoresis tank10as long as the material is an insulating material. For example, glass, quartz, acrylic resin, and the like can be used as the material of the electrophoresis tank10. When a voltage is applied to the electrode20and the electrode30, the single-walled carbon nanotube mixture is separated into metallic single-walled carbon nanotubes and semiconducting carbon nanotubes. The metallic single-walled carbon nanotubes collect near a negative electrode. On the other hand, the semiconducting single-walled carbon nanotubes collect near a positive electrode. For this reason, it is desirable to dispose the electrode20and the electrode30at an upper end portion and a lower end portion of the electrophoresis tank10. It is more desirable to dispose a positive electrode in a lower part of the electrophoresis tank10and to dispose a negative electrode in an upper part of the electrophoresis tank10. When the electrode30is used as the positive electrode and the electrode20is used as the negative electrode, an electric field Z is directed upward from the bottom of the electrophoresis tank10. On the other hand, when the electrode30disposed in the lower part of the electrophoresis tank10is used as the negative electrode and the electrode20disposed in the upper part of the electrophoresis tank10is used as the positive electrode, the electric field Z is directed downward from the top of the electrophoresis tank10. Here, in the case of the upward direction and the downward direction, a direction upward in a direction of gravitational force indicates the upward direction and a direction downward in the direction of gravitational force indicates the downward direction when a separation apparatus1is installed in a usable state. Platinum or the like can be used as a material of the electrodes20and30. An injection port40is an opening through which a liquid is injected into the electrophoresis tank10. The injection port40in the embodiment is an opening provided in an upper end of the electrophoresis tank10. A recovery port50is an opening through which a liquid is recovered from the electrophoresis tank10. The recovery port50may be provided at a lower end of the electrophoresis tank10. When a plurality of recovery ports50are provided, it is desirable to provide the recovery ports near the electrodes20and30. Since the separated metallic single-walled carbon nanotubes move to the vicinity of the negative electrode and the semiconducting single-walled carbon nanotubes move to the vicinity of the positive electrode, the moved single-walled carbon nanotubes can be efficiently recovered. Although a constitution in which the injection port40and the recovery ports50are provided has been shown in the example shown inFIG.1, the constitution of the separation apparatus1is not limited thereto. The separation method according to the embodiment will be described below.FIG.3is a flowchart showing the separation method in the embodiment. First, in a first step (S1), a plurality of liquids having different pHs are prepared. At least one of the plurality of liquids is a dispersion liquid of a single-walled carbon nanotube mixture. The plurality of liquids having different pHs are liquids in which a predetermined solute is contained in a predetermined solvent. As the predetermined solute, for example, a surfactant can be used. Furthermore, as the predetermined solvent, water and heavy water can be used. By adjusting the concentration of a surfactant that is a solute, a pH can be adjusted. For example, heavy water can be used as a solvent and polyoxyethylene (100) stearyl ether (Brij 700 [trade name]) that is a surfactant which is a non-ionic surfactant can be used as a solute. In this case, a 1 wt % aqueous solution of Brij 700 at room temperature (25° C.) has a pH lower than that of a 0.5 wt % aqueous solution of Brij 700. Next, a method of acquiring a dispersion liquid of a single-walled carbon nanotube mixture is not particularly limited and known methods can be applied as the method. For example, when a single-walled carbon nanotube mixture and a dispersion medium are mixed and subjected to ultrasonic treatment, the single-walled carbon nanotube mixture is dispersed in the dispersion medium. Alternatively, single-walled carbon nanotubes may be dispersed in the dispersion medium using a mechanical shear force. The dispersion liquid may contain a dispersion auxiliary agent such as a surfactant in addition to the single-walled carbon nanotube mixture and the dispersion medium. Subsequently, in a second step (S2), the liquids prepared in the first step are injected into the electrophoresis tank10so that the pHs of the liquids increase from the bottom to the top thereof in a direction of gravitational force irrespective of whether or not the liquids contain single-walled carbon nanotubes. To be specific, a liquid having a lowest pH among the prepared liquids is put into the electrophoresis tank10. Subsequently, a liquid having a second higher pH among the prepared liquids is put into the electrophoresis tank10. After that, the other liquids are put into the electrophoresis tank10in order from a liquid having a lowest pH. This makes it possible to form a pH gradient in which the pHs of the liquids increase from the bottom to the top thereof in the direction of gravitational force in the electrophoresis tank. In a third step (S3), a direct current (DC) voltage is applied to the electrophoresis tank. Metallic single-walled carbon nanotubes in the carbon nanotube mixture dispersed in the liquid move to the vicinity of the negative electrode and semiconducting single-walled carbon nanotubes move toward the positive electrode side. As a result, the carbon nanotube mixture dispersed in each of the liquids can be separated into a metallic type and a semiconducting type. In the case of using a liquid having a non-ionic surfactant dissolved therein, metallic single-walled carbon nanotubes have a positive charge in the liquid and semiconducting single-walled carbon nanotubes have a very weak negative charge. Furthermore, after voltage application, the semiconducting single-walled carbon nanotubes tend to have a pH higher than that of the metallic single-walled carbon nanotubes. The single-walled carbon nanotube mixture is separated into a metallic type and a semiconducting type due to a combined force of a moving force generated due to a difference between the pHs and an electrophoretic force generated due to an electric field and charges. In the case of a voltage to be applied, an optimal value thereof needs to be determined using a composition of the dispersion medium and an amount of charge of the single-walled carbon nanotube mixture. When water, heavy water, or the like is used as the dispersion medium, an application voltage applied between electrodes which are farthest away from each other can be an arbitrary value between greater than 0 V and 1000 V or less 0 to 1000 V). Particularly, since water and heavy water minimize the effects of electrolysis, it is desirable to apply a voltage in a range of greater than 0 V and 120 V or less (0 to 120 V). In a fourth step (S4), the dispersion liquid is injected into the electrophoresis tank through a first injection port provided in one side surface of the electrophoresis tank and a liquid having a pH lower than that of the dispersion liquid is injected into the electrophoresis tank through a second injection port provided below the first injection port. Injection is continuously performed while the separation process is being performed. Finally, in a fifth step (S5), the separated liquids are recovered. A separated liquid is recovered through the recovery port50in a state in which a voltage is applied. When the separation proceeds, a metallic carbon nanotube layer having metallic carbon nanotubes accumulated therein is generated in the upper part of the electrophoresis tank10at which the electrode20(the negative electrode) is provided. Furthermore, a semiconducting single-walled carbon nanotube layer having semiconducting single-walled carbon nanotubes accumulated therein is generated in the lower part of the electrophoresis tank10at which the electrode30(the positive electrode) is provided. Thus, a separated liquid containing metallic carbon nanotubes is recovered through the first recovery port70and a separated liquid containing semiconducting single-walled carbon nanotubes is recovered through the second recovery port80. A rate at which the dispersion liquid is injected through the first injection port40, a rate at which a liquid having a pH lower than that of the dispersion liquid is injected through the second injection port50, and a rate at which the separated liquids are recovered through the first recovery port70and the second recovery port80are controlled so that the rates are the same. Thus, the separated liquid containing metallic single-walled nanocarbon tubes can be continuously recovered through the first recovery port70, and at the same time, the separated liquid containing semiconducting single-walled nanocarbon tubes can be continuously recovered through the second recovery port80while the dispersion liquid is being injected into the electrophoresis tank10through the first injection port40, and simultaneously, a liquid having a pH lower than that of the dispersion liquid is being injected through the second injection port50. Although the flowchart of the separation method has been described above on the basis of the separation apparatus shown inFIG.1B, a separation apparatus1A ofFIG.2may be used instead of the separation apparatus1ofFIG.1B. The separation apparatus1A ofFIG.2and the separation apparatus1ofFIG.1Bdiffer in that the separation apparatus1A includes a third injection port40A between a first injection port40and a second injection port50and a third recovery port70A between a first recovery port70provided at a position in which the first recovery port70faces the first injection port40and a second recovery port80provided at a position in which the second recovery port80faces the second injection port50. When a separation operation is performed using the separation apparatus1A, a liquid adjusted to be weakly alkaline or neutral is injected through the first injection port40, a liquid adjusted to be weakly acidic is injected through the second injection port50, and a dispersion liquid in which a single-walled carbon nanotube mixture is dispersed in a dispersion medium is injected through the third injection port40A. The separated liquids are independently recovered through the first recovery port70, the second recovery port80, and the third recovery port70A. Thus, the single-walled carbon nanotube mixture can be separated into metallic single-walled carbon nanotubes and semiconducting single-walled carbon nanotubes. It should be noted that the first to fifth steps may be repeatedly performed using the recovered liquid obtained in the fifth step. By repeatedly performing the first to fifth steps, the purity of the metallic single-walled carbon nanotubes and the semiconducting single-walled carbon nanotubes can be improved. It should be noted that, although an example in which the single-walled carbon nanotube mixture is separated into the metallic single-walled carbon nanotubes and the semiconducting single-walled carbon nanotubes has been described in the foregoing description, the present invention is not limited thereto. For example, this may be performed as a purification method of single-walled carbon nanotubes in which only single-walled carbon nanotubes having desired properties are recovered after separation is performed in the electrophoresis tank10. The separation efficiency of the recovered sample can be evaluated using a method such as a microscopic Raman spectroscopic analysis (a change in Raman spectrum in a radial breathing mode (RBM) region and a change in Raman spectrum shape in a BWF region), ultraviolet visible near-infrared absorption spectrophotometry (a change in peak shape of an absorption spectrum), and the like. Furthermore, it is also possible to evaluate the separation efficiency by evaluating the electrical properties of the single-walled carbon nanotubes. For example, it is possible to evaluate a sample by preparing a field effect transistor and measuring the transistor characteristics thereof. In the above description, an example of using polyoxyethylene (100) stearyl ether (Brij 700 [trade name]) as a non-ionic surfactant has been described. However, the non-ionic surfactant is not limited thereto. As a non-ionic surfactant, it is possible to use one non-ionic surfactant including a non-ionizing hydrophilic site and a hydrophobic site such as an alkyl chain or a combination of a plurality of non-ionic surfactants. For example, a non-ionic surfactant having a polyethylene glycol structure represented by a polyoxyethylene alkyl ether type, an alkyl glucoside type non-ionic surfactant, and the like can be used. Furthermore, it is desirable to use non-ionic surfactants defined by polyoxyethylene (n) alkyl ether (n is 20 or more and 100 or less and in which an alkyl chain length is C12 or more and C18 or less). For example, polyoxyethylene (23) lauryl ether (Brij 35 [trade name]), polyoxyethylene (20) cetyl ether (Brij 58 [trade name]), polyoxyethylene (20) stearyl ether (Brij 78 [trade name]), polyoxyethylene (10) oleyl ether (Brij 97 [trade name]), polyoxyethylene (10) cetyl ether (Brij 56 [trade name]), polyoxyethylene (10) stearyl ether (Brij 76 [trade name]), polyoxyethylene (20) oleyl ether (Brij 98 [trade name]), polyoxyethylene (100) stearyl ether (Brij 700 [trade name]), and the like can be used. Although an embodiment applicable to separation of metallic type and semiconducting type single-walled carbon nanotubes has been described above, the present invention can also be applied to other nonocarbons, that is, multi-walled carbon nanotubes, double-walled carbon nanotubes, graphene, and the like. By using the separation method according to the embodiment, the separation efficiency can be improved or the time required for separation can be shortened and mass production can be achieved when nanocarbons having different properties are separated. Embodiments will be shown below. The following embodiments are examples and the present invention is not limited to the following embodiments. Embodiment 1 FIG.4is a schematic diagram showing an example of electrophoresis conditions shown in the embodiments. Description will be provided below with reference toFIG.4. (1) Preparation of Liquid for Separation As a dispersion medium, an aqueous solution in which 0.25 wt % of Brij 700 that was a non-ionic surfactant was dissolved in water was prepared. A single-walled carbon nanotube mixture (eDIPS single-walled carbon nanotube) was mono-dispersed in this dispersion medium. The mono-dispersed liquid was subjected to ultrasonic dispersion treatment using a horn type ultrasonic crusher (output: about 300 W; over 30 minutes). After that, the mono-dispersed liquid was subjected to a ultracentrifugation operation and a supernatant that was 50% of the mono-dispersed liquid was obtained as a dispersion liquid (hereinafter referred to as a “CNT dispersion liquid”). Also, an aqueous solution in which 1 wt % of Brij 700 that was a non-ionic surfactant is dissolved in water (hereinafter referred to as a “1 wt % Brij aqueous solution”) and an aqueous solution in which 0.25 wt % of Brij 700 that was a non-ionic surfactant was dissolved in water (hereinafter referred to as a “25 wt % Brij aqueous solution”) were prepared. In the case of the pHs of the liquids, that of the 1 wt % Brij aqueous solution was the lowest (pH 4 to 4.5) and that of the 0.25 wt % Brij aqueous solution was pH 6 to 7. (2) Injection of Liquid The prepared liquids were injected into the electrophoresis tank10of the separation apparatus1A shown inFIG.2. First, the 1 wt % Brij aqueous solution (pH 4 to 4.5) is put into the electrophoresis tank10through the second injection port50. Thus, a 1 wt % Brij layer was formed using the put 1 wt % Brij aqueous solution. Subsequently, the 0.25 wt % Brij aqueous solution (pH 6 to 7) was gently injected into the electrophoresis tank10of the separation apparatus1A through the first injection port40so that the 0.25 wt % Brij aqueous solution was laminated above the 1 wt % Brij layer. As described above, a pH gradient was formed to increase from the bottom to the top in the direction of gravitational force in the liquids in the electrophoresis tank10. (3) Separation Operation A DC voltage (30 V) was applied between a lower electrode30(a positive electrode) and an upper electrode20(a negative electrode) of the separation apparatus1A. After the voltage application was completed, in a state in which the pH gradient of the liquids was formed in the electrophoresis tank10, the 0.25 wt % Brij aqueous solution (pH 6 to 7) was injected through the first injection port40, the 1 wt % Brij aqueous solution (pH 4 to 4.5) was injected through the second injection port50, and the dispersion liquid in which the single-walled carbon nanotube mixture was dispersed in the dispersion medium was injected through the third injection port40A. FIG.5shows a photograph of the electrophoresis tank10during a separation operation. A dispersion liquid in which a single-walled carbon nanotube mixture injected through the third injection port40A was dispersed in a dispersion medium moved to a first recovery port70and a second recovery port80with the passage of time and three layers, i.e., a region (201) containing a large amount of metallic single-walled carbon nanotubes, a transparent region (202), and a region (203) containing a large amount of semiconducting single-walled carbon nanotubes were formed. Furthermore, the separated liquids were recovered through the first recovery port70, the second recovery port80, and the third recovery port70A. In the present invention, the dispersion liquid in which the single-walled carbon nanotube mixture was dispersed in the dispersion medium was injected through the third injection port40A in a state in which the liquids having different pHs were injected through the first injection port40and the second injection port50in a state in which the liquid layers having different pHs were formed in the electrophoresis tank10so that the liquids had a pH gradient from a lowest pH to a highest pH directed upward from the bottom of the electrophoresis tank10and the separated liquids were recovered through the first recovery port70, the second recovery port80, and the third recovery port70A. Thus, according to the present invention, it was confirmed that semiconducting single-walled carbon nanotubes and metallic carbon nanotubes could be separated and recovered continuously. REFERENCE SYMBOLS 1,1A Separation apparatus10Electrophoresis tank20,30Electrode40First injection port40A Third injection port50Second injection port70First recovery port70A Third recovery port80Second recovery port
24,882
11857927
DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS The present invention relates to a reverse osmosis filter ram apparatus. Specifically, the present invention comprises a base rack having a controllable linear actuator thereon, preferably a hydraulic ram apparatus. The ram apparatus comprises detachable and changeable connection brackets configured to alternately connect to steel reverse osmosis tubes and fiberglass reverse osmosis tubes. The linear actuator comprises a plunger head that is configured to push one or more spools within a reverse osmosis tube for moving tubular reverse osmosis filters therein, either for adding the same to the reverse osmosis tube or removal of the same from the reverse osmosis tube. Systems and methods of using the same are further provided. Now referring to the figures, wherein like numerals refer to like parts,FIG.1illustrates a reverse osmosis filter ram apparatus10in an embodiment of the present invention. The ram apparatus10is specifically designed for use in steel reverse osmosis tubes12, as illustrated inFIGS.1-13, or in fiberglass reverse osmosis tubes, as illustrated and describe with reference toFIGS.16and17, below. The filter ram apparatus10comprises a first end plate20and a second end plate22, with a plurality of base rods24disposed in a semi-circular arc around the first end plate20and the second end plate22, thereby forming a base on which a plunger26may sit. The plunger comprises a plunger tube30which may contain a rod32(as illustrated inFIG.13) and a plunger head34on an end of the rod32. The plunger26may have a controller36that may control the linear actuation of the rod32and plunger34out of the plunger tube30. The linear actuator may preferably be hydraulically controlled, such that activating the plunger26using the controller36causes the rod32and plunger head34to extend out of the tube30. The plunger head34may be in the shape of a disk and may be made from a thermoplastic material that may easily be pushed into the steel tube12to push one or more osmosis filters and/or pushing spools (as described below) in or out of the steel tube12. It should also be noted that the plunger head34may also be utilized to push osmosis filters and/or pushing spools into and out of fiberglass reverse osmosis tubes, as described below with reference toFIGS.14and15. The second end plate22may be sized and positioned, as illustrated inFIGS.2and3, to sit against the bottom outside circular wall of the steel tube12. Extending from the second end plate22may be relatively short rods40, which connect to a semi-circular clamp plate or ring42that may be sized and positioned, as illustrated inFIG.2, to sit against the top outside circular wall of the steel tube12. The second end plate22and the clamp plate or ring42may act together to clamp the filter ram apparatus10to the open end of the steel tube12. Therefore, the plunger head34may be pushed into the steel tube12, thereby moving reverse osmosis filters or pushing spools through the steel tube12. The second end plate22and the clamp plate or ring42may hold the filter ram apparatus10in place so that the plunger head34has a direct unimpeded path into the steel tube12. As shown inFIG.1, the filter ram apparatus10may rest upon a cart50that may be movable and allow the filter ram apparatus10to be positioned adjacent to a reverse osmosis tube, as shown inFIG.1. Once clamped to the tube12, the cart may be moved out of the way, as shown inFIG.2. The cart may further have a plurality of pushing spools60(described below) and may provide storage for other elements required, such as tools, alternate parts, or the like. FIGS.4-9illustrate the use of the filter ram apparatus10to push a pushing spool into the steel tube12. As shown inFIG.4, the plunger tube, along with the rod32and the plunger head34, may be rotatably attached via rotatable connectors62a,62bto one of the base rods24so that the plunger tube30, the plunger rod32and the plunger head34may be moved off of the base formed by the base rods24, thereby clearing the space for a pushing spool60. The pushing spool60may comprise a pushing spool rod64having, on terminal ends thereof, first and second pushing spool heads66, respectively. The pushing spool heads66may be disks that are sized and shaped to just fit within the opening of the steel tube12, thereby moving into and through the steel tube12. As shown inFIGS.5-7, pushing spool60may be placed into the steel tube12manually until the rear pushing spool head66is placed just inside the opening of the steel tube12. As illustrated byFIG.8, the plunger tube30, with plunger rod32and plunger head34, may be rotated back toward the base formed by the base rods24so that the plunger head34and plunger rod32are aligned with the opening of the steel tube12. A user may then operate the controller36to push the plunger head34and thus the pushing spool60into steel tube12. A plurality of pushing spools60may therefore be pushed into the steel tube12in the same manner to dislodge and move spent reverse osmosis filters through and out of the steel tube12on an opposite side thereof, which would also be opened. Once all of the spent reverse osmosis filters are removed from the steel tube12, a plurality of clean reverse osmosis filters may be pushed into the steel tube12, as described below with reference toFIGS.9-13. Specifically, inFIGS.9-13, the plunger26may be rotated away from the base formed by the base rods24thereby clearing the area for a clean reverse osmosis filter70, which may be placed onto the base rods24and aligned with the opening in the steel tube12, as shown inFIG.10. The clean reverse osmosis filter70may then be manually pushed into the steel tube12, as shown inFIG.11, so that an end thereof is just inside the opening of the steel tube12, as shown inFIG.12. Then, the plunger26may be rotated back toward the base formed by the base rods24so that the plunger head34aligns with the opening of the steel tube12. The controller36may then be used to push the plunger rod32and plunger head34into the steel tube12, thereby pushing the reverse osmosis filter into the steel tube12. A plurality of clean reverse osmosis filters may therefore be added to the steel tube12in the same or similar manner. At the same time, any pushing spools60that may be within the steel tube12may be pushed out the opposite end thereof as the steel tube12becomes full of clean reverse osmosis filters. Referring now toFIGS.14and15, an alternate embodiment of the present invention is illustrated. Specifically filter ram apparatus100is shown having many of the same parts as described above with respect to the filter ram apparatus10, shown inFIGS.1-13, except that instead of attaching to a steel tube, the filter ram apparatus100connects to a fiberglass reverse osmosis tube112. The fiberglass reverse osmosis tube112also comprises a plurality of reverse osmosis filters therein, but because of the less sturdy nature of the fiberglass material, and because the fiberglass tube112has a flared end, it is difficult to utilize the same connection means as described above with respect to the filter ram apparatus10for the steel tube12. As illustrated inFIG.14, the second end plate22may comprise relatively long connector rods102that extend beyond the flare of the fiberglass tube and attach to a ring104having a shape and size sufficient to ring around the outside surface of the fiberglass tube112beyond the flare therein. Thus, the ring104may hold the apparatus100in place, aligning the plunger head34with the opening of the fiberglass tube112. As shown inFIG.15, the plunger26may have a semi-disk-shaped end plate108having a mesh material110that may cover the plunger head34and the opening of the fiberglass tube112when in proper positioning. The end plate108and mesh material110may protect a user from material that may expel from the fiberglass tube112when the plunger head34is pushed into the fiberglass tube112, either when adding pushing spools60or pushing through clean reverse osmosis filters, as described above. In an alternate embodiment of the present invention, a reverse osmosis filter ram apparatus bracket200is illustrated. The bracket200may be attached to a fiberglass reverse osmosis tube202at an end thereof, allowing a reverse osmosis filter ram apparatus, such as the reverse osmosis filter ram apparatus10, illustrated herein and described above, to attach thereto to align the plunger26with the tube202. The fiberglass tube202may have a flare206at its end and the bracket200may utilize the flare to lock the bracket200onto the fiberglass tube. Specifically, the bracket200may comprise a first ring210and a second ring212connected by one or more threaded rods214, each of which may be attached to a first tab216on the first ring and a second tab218on the second ring212. The first ring210may sit on the end204of the fiberglass tube202and the second ring212may sit behind the flare206of the fiberglass tube202. To allow the second ring212to be placed on the fiberglass tube202behind the flare206, the second ring212may have a hinge213on one end thereof and a bracket and bolt connection215on an opposite end thereof, holding the ring212together on the fiberglass tube202. Nuts220,222may be utilized to tighten the threaded rods214on the first and second tabs216,218, respectively, and pull the second ring212toward the first ring210. The second ring212may be tightened until the second ring212cannot travel closer to the first ring210due to the flare206of the fiberglass tube202. Thus, the first ring210and the second ring212may be rigidly held on the end of the fiberglass tube202. Extending from the first ring210may be a short tube230extending past the end204of the fiberglass tube202and having roughly the same internal diameter as the internal diameter of the fiberglass tube202. The short tube230may further have a clamp recession232that may provide a seat for the reverse osmosis filter ram apparatus10to be connected thereto. Specifically, the clamp plate or ring42of the reverse osmosis filter apparatus10may sit within the clamp recession232and be held therein. Therefore, the short tube230may allow the reverse osmosis filter ram apparatus10to be clamped thereto in the same manner that the reverse osmosis filter ram apparatus10is clamped to the end of the steel reverse osmosis tube12, described above. Therefore, with the bracket200clamped rigidly to the fiberglass tube and the reverse osmosis filter ram apparatus10clamped rigidly to the short tube230of the bracket200, the reverse osmosis filter ram apparatus10may be utilized to push reverse osmosis filters therethrough. It should be noted that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. Further, references throughout the specification to “the invention” are nonlimiting, and it should be noted that claim limitations presented herein are not meant to describe the invention as a whole. Moreover, the invention illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein.
11,353
11857928
DESCRIPTION OF THE EMBODIMENTS Reference will now be made in detail to exemplary embodiments of the disclosure, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. The present disclosure is shown in particular e.g. inFIGS.11to13. However, the features of the frame elements101,102are described first which may form the membrane distillation apparatus. FIG.1shows a schematic representation of the principle design of the frame elements according to embodiments of the present disclosure. The frame element is shown in a front view. The frame elements101,102have an outer frame39and an inner frame43. Accordingly, the outer frame surrounds the inner frame. The inner frame encases (i.e. borders or defines in its inside) an inner region which desirably is used as an active area of the frame element (as described in more detail in other passages of the present disclosure). Hence, there remains an available area between the outer frame and the inner frame. In this available area passage openings and vapor and/or liquid channels are arranged. This configuration leads to a more efficient utilization of the total area inside the frame element, as the complete area between outer and inner frame may be utilized for passage openings and channels. For example, the vapor and/or liquid channels can have an increased size, which can lead to a higher possible output and efficiency of the modular flow system, as described in other passages of the present disclosure. The inner frame43may comprise a rectangular form. The outer frame may comprise a octagonal form, more desirably an octagonal form. In other words, the frame element may have a octagonal shape. Accordingly, the form of the outer frame may approximate a circular form, when having a octagonal form. Therefore, the pressure inside the frame element can be balanced (equalized), which can reduce the maximum pressure and hence allows thinner walls and increased openings, channels and inner region. The frame elements101,102may be made of a plastic, i.e. a synthetic material. FIG.2shows a schematic representation of a first frame element101in particular with vapor and/or liquid channels according to embodiments of the present disclosure. The frame element101is shown in a front view in the orientation it has when being stacked in a modular flow system. Accordingly, vapor and/or liquid channels17,18are arranged above the inner region40in the modular flow system (i.e. desirably with regard to the gravitational direction pointing downwards). Desirably the vapor and/or liquid channels have a trapezoidal form. In this case they can efficiently fill the area above the (desirably rectangular) inner region in a frame element having a octagonal form. Thus the vapor and/or liquid channels can efficiently use the space in the frame element above the inner region40. Consequently the frame element can have an outer shape which converges toward a circle form (e.g. by having the form of a octagon). In a circle form the pressure inside the frame element is ideally balanced. Therefore, the frame configuration of the present disclosure allows a reduced material use (i.e. thinner walls), as the maximum pressure in the frame element can be reduced compared to e.g. an elongated frame element form. As a further consequence, due to the material reduction the relative size of the inner region, the channels and passage opening can be increased, which can ameliorate the efficiency of the modular flow system. The cross-sectional area ratio of at least one of the vapor and/or liquid channels17,18of a frame element101,102with regard to the central inner region40may be at least 13%, more desirably 15%. In other words, the cross-sectional area ratio of the entirety of vapor and/or liquid channels17,18with regard to the central inner region40may be at least 26%, more desirably 30%. It is noted that the schematic figures do not necessarily represent these dimensions correctly. Accordingly, the relative sizes of the vapor and/or liquid channels may be increased in comparison to the systems of the prior art. This is possible due to the new arrangement of the channels above the inner regions, which can allow a more balanced pressure inside the frame element and hence a decreased maximum pressure. In particular, the inventors have found that the defined relative sizes lead to an optimum efficiency of the complete modular flow system. Indeed, a relative increase of the sizes of the vapor and/or liquid channels17,18also implies a reduction of the active area (40,40′) of the membrane frame. However, due to the increased sizes of the vapor and/or liquid channels, more vapor can be transported to and from the active areas (i.e. the condensation/evaporation areas). Hence, the modular flow system may contain more frame elements in one stage and/or in one module (as described below in more detail), which can increase the efficiency and the output of the flow system. The inventors have found that the described relative sizes lead to an optimum size balance leading to improved total efficiency of the modular flow system. The inner region40is desirably bordered (i.e. covered) on its front and back side by a film, foil, or other heat transmitting but gas and liquid tight material. In particular, the central inner region40may be hollow or comprises a grid-like spacer. The film may be arranged, in particular welded, on the two sides of the spacer. The film may cover the total spacer but the passage openings and the channels may be kept free. There is provided a vapor and/or liquid channel opening22abetween the vapor and/or liquid channel17and the inner region40. Said vapor and/or liquid channel opening22amay be e.g. a through hole inside an upper first frame wall of the inner frame43. Said frame wall may hence separate the inner region40from the vapor and/or liquid channels17,18. Accordingly, vapor may be transported via a vapor and/or liquid channel17and the vapor and/or liquid channel opening22afrom or to the inner region40. Further, condensate collection passages19a,19bare arranged below the inner region40. The central inner region may further be connected to at least one of the condensate collection passages by a condensate channel opening (or openings)22bconstituting a through hole in the inner frame. The condensed vapor generated inside said inner region when the vapor cools down may thus run out through the condensation collection passage. On the left and or right side of the inner region at least one passage opening14,15may be provided for other functions of the modular flow system than a membrane distillation stage (as e.g. formed by the exemplary first and second frame elements shown inFIGS.2and3). Below the inner region40and between the condensate collection passages19a,19bthere may be arranged first passage openings16a,16bwhich are described in more detail in context ofFIG.5A. Further, below the inner region40and between the first passage openings16a,16bthere may be arranged a central drain passage which is described in more detail in context ofFIG.4C. FIG.3shows a schematic representation of a second frame element in particular with vapor and/or liquid channels according to embodiments of the present disclosure. The frame element102is desirably again shown in a front view in the orientation it has in when being stacked in a modular flow system, i.e. in the same view as frame101ofFIG.2. The second frame element102may be to adjacent to the first frame element101in the modular flow system. Accordingly, the first and second frame element may be stacked. More desirably, a plurality of first frame elements101and a plurality of second frame elements102may be stacked alternately, as it is shown e.g. inFIG.8. The second frame element102principally corresponds to the first frame element101. However, the inner region40of second frame element102is desirably bordered (i.e. covered) on its front and back side by a vapor-permeable (and liquid tight) membrane. Thus the border may serve to transmit vapor and block liquid (i.e. the feed). Beside this, it might be possible that the second frame element102corresponds to the first frame element and is merely turned inFIG.3around a vertical symmetry axis. However, it is desired that the first and second frame elements comprise further structural differences, at least regarding the configuration of the liquid passages45,46(as shown inFIGS.5and6). As a further desired difference of the second frame element with regard to the first frame element, instead of the condensate channel openings22bthe frame element102comprises a drain channel opening (or openings)22cconstituting a through hole in the inner frame (i.e. a second frame wall below the inner region40) connecting the central inner region40to the drain passage20. As further shown inFIGS.2and3, at least one of the vapor and/or liquid channels17,18comprises at least one internal strut member48a,48bextending between the inner frame43and the outer frame39. Hence, the structure of the frame element101is reinforced by the at least one internal strut member. Hence, the size of the vapor and/or liquid channels may be increased without decreasing the steadiness (stability) of the frame element. In particular, the strut members may be provided to connect the outer frame with the inner frame, which can lead to a higher stability. Accordingly, the frame walls may be made thinner. The at least one strut member may comprise at least one connecting internal strut member48aconnecting the inner frame43with the outer frame39, and/or at least one non-connecting internal strut member48bprotruding from the inner frame43toward the outer frame39or from the outer frame39toward the inner frame43without connecting the inner frame43with the outer frame39. In the present example of e.g.FIG.2the channel17comprises two non-connecting internal strut members48band the channel18comprises two connecting internal strut members48a. In the present example of e.g.FIG.3the channel17comprises two connecting internal strut member48aand the channel18comprises two non-connecting internal strut members48b. When the frame elements101,102are stacked alternately, the connecting and non-connecting internal strut members are desirably also stacked alternately. Accordingly, due to a possible use of connecting internal strut members, the stability of the frame element can be effectively increased. Further, due to a possible use of non-connecting internal strut members, the liquid or vapor inside the channel can still pass from one side of the internal strut member to the other. Hence, pressure differences can be equalized (balanced). Thus the channel may also be regarded as one functional channel in spite of the (connecting) internal strut member separating it in at least two sub channels (which may be arranged at adjacent frame elements in the stack). Finally, since frame elements may be stacked such that connecting internal strut members and non-connecting internal strut members are arranged alternately in a vapor and/or liquid channel (17,18), the overall stability of the modular flow system, provided by the structure forming said vapor and/or liquid channel (17,18) can be increased. Desirably the internal strut members48may be provided at least partially with the welding web structure11(cf.FIG.7). The welding web structure is used to attach the frame elements to each other, in particular to close any channels, where necessary and to increase the all over stability of the modular flow system. In particular, when the adjacent first and second frame elements101,102are stacked, a welding web structure11of the connecting internal strut members48aare aligned and match with the welding web structure of the non-connecting internal strut members48b. For example, the welding web structure extends across the complete non-connecting internal strut members48band only on a matching section on the connecting internal strut members48a(as shown e.g. inFIG.7). Thus a reliable connection across the complete stack of frame elements can be obtained in the area of the non-connecting internal strut members48b, which can provide an increased stiffness of the modular flow system. At the same time a vapor inside the channels17,18can still be equalized within the channel due to the open sections in each second frame element. Due to the connecting internal strut members48a(e.g. inFIG.2) the channel18may be regarded as comprising three adjacent sub-channels18a,18b,18cwhich, when the frame elements are stacked together, traverse across the frame elements. These sub channels have openings between each other in some of the frame elements (e.g. in an adjacent frame element102as shown inFIG.3). Accordingly, due to the openings between the sub channels, the liquid or vapor inside the channel can still pass from one side of the internal strut member to the other. Hence, pressure differences can be equalized (balanced). Thus the channel may also be regarded as one functional channel in spite of the plurality of comprised sub channels. Only some of the sub-channels (e.g. sub-channels18aand18cof the first frame element101) may be connected to the central inner region (40) (e.g. via a vapor and/or liquid channel opening (22) of an adjacent second frame element of the stack). It is noted that this feature is not illustrated in the schematicFIGS.2and3. Furthermore, in order to further strengthen the stability of the frame element101,102, the outer frame39may include additional outer strut members48c,48d,48e,48f(48fis shown inFIG.7). Moreover, the inner frame43and the outer frame39may be connected by additional intermediate strut members (e.g. a strut member separating a vapor and/or liquid channels17,18and the first passage opening13. InFIG.4A to4Cthe process of a membrane distillation using adjacent stacked frame elements101and102is shown. Generally, the inner region40(and desirably also the feeding area in front of the inner region in a front view of the frame element) may serve as the active area, in particular for membrane distillation. Said inner region and the feeding area may namely either be separated by a film, foil, or other heat transmitting and gas and liquid tight material, or by a vapor-permeable membrane. Hence, in case a film or there like is used, the border between inner region and feeding area may serve for heat transfer. In case a membrane is used, the border may serve to transmit vapor and block liquid (i.e. the feed). FIG.4Ashows a schematic representation of the vapor and liquid flow in a first frame element101according to embodiments of the present disclosure. Vapor V1is supplied by the first vapor and/or liquid channel and enters into the inner region40of the first frame element101. Since this inner region40is bordered on its front and back side by a film, the vapor cannot pass the film (i.e. in a direction perpendicular to the frame element. Instead, the vapor condenses at the foil, such that a condensate (liquid) C1runs out of the inner region into one or several condensate collection passages (19aand/orb). However, the heat of the vapor is transferred by the film to its opposite side, when the vapor condenses. FIG.4Bshows a schematic representation of the feed flow F in between a first frame element101and a second frame element102according to embodiments of the present disclosure. The frame elements101,102are configured such (e.g. by the welding web structure(s) in between) that a gap remains between the frame elements when they are stacked in the modular flow system. This gap in particular forms a feeding area40′ being aligned with the inner regions of the stacked frame elements and being in front of and outside of the inner regions40of the adjacent frame elements. Since the inner region40of the second frame element102is bordered on its front and back side by a vapor-permeable membrane, the feeding area40′ is bordered on a first side by a film (toward the first frame element101) and on a second side by a vapor-permeable membrane (toward the second frame element102). A feed F is supplied via the first passage opening13to the feeding area40′. Said feed may be a liquid, e.g. salt water or dirt water which is distilled and/or cleaned by the modular flow system. The feed may have a temperature slightly lower than the vapor V1, e.g. a difference of 4 to 6° C. Due to the heat transferred from the condensing vapor V1, the feed F is heated and vaporizes. In this regard it is possible that the pressure within the feeding area or in parts of the modular flow system is reduced such that the feed boils when heated. The vapor passes the vapor-permeable membrane, which can lead to a membrane distillation MD. FIG.4Cshows a schematic representation of the vapor and liquid flow in the second frame element102adjacent to the first frame element101according to embodiments of the present disclosure. Due to the membrane distillation MD, vapor enters from the feeding area40′ into the inner region40of the frame element102. Said vapor may have a slightly lower temperature than the vapor V1, e.g. 2 to 3° C. and leaves the inner region40via the second vapor and/or liquid channel18. The arrangement shown inFIG.4A to4Cshows a first stage of the modular flow system. Said vapor leaving the second frame element102may be transmitted to a second stage of the modular flow system where it may be used as (heating) vapor in a first frame element101again. Thus, the modular flow system may have several stages (e.g. 10 or more) wherein in each subsequent stage the temperatures of the supplied vapor and feed are slightly decreased with regard to the preceding stage. As further shown inFIG.4C, in case any feed undesirably passes the membrane (e.g. due to defects in the membrane) said feed (i.e. leakage) DR can leave the inner region40of the second frame element via the drain passage20. Due to the arrangement of the vapor and/or liquid channel18above the inner region40, the whole inner region40may serve as a barrier for leakage. In other words, the leakage would need to fill the complete inner region, in order to pass the barrier given by the configuration of the frame element, i.e. to flow into the vapor and/or liquid channel18. Hence, any contamination of the final product (i.e. the distillate) can be effectively prevented. FIG.5Ashows a schematic representation of a first frame element101in particular with liquid passages45a,46aaccording to embodiments of the present disclosure. The liquid passages45,46are desirably provided (e.g. as notches) on a first upper frame wall and a second lower frame wall of the inner frame43. The first upper frame wall may separate the vapor and/or liquid channels17,18and the first passage opening13from the inner region40. The second lower frame wall may separate the passages19,20and openings16from the inner region40. A first liquid passage45is provided by the first upper frame wall and is configured to distribute a feed from the first passage opening13to the feeding area40′. The liquid passage45may extend asymmetrically by extending from a central section of the first frame side (below the first opening13) into only one first direction along the first frame side (e.g. inFIG.5Ato the right) without extending into the opposite direction. The first liquid passage45may be connected to the first passage opening13, in particular by connecting notches47provided on a front side of the first upper frame wall or a connecting channel provided inside said frame wall. A second liquid passage46is provided by the second lower frame wall and is configured to collect a liquid from the feeding area40′ to the first passage openings16a,16b. The second liquid passage46may extend discontinuously by extending only across the central region but not across the peripheral regions of the second lower frame wall. The second liquid passage46may be connected to the second passage openings16a,16b, in particular by a connecting notches47provided on a front side of the second lower frame wall or a connecting channel provided inside the second lower frame wall. FIG.5Bshows a cross section of the first frame element ofFIG.5Aalong the line B-B. It is noted thatFIG.5Bonly shows the front side structure of the frame element101but does not consider its structure on the back side (as it is shown e.g. inFIG.5C). Said back side structure may be symmetrical to the shown front side structure. FIG.5Cshows a cross section of the first frame element ofFIG.5Aalong the line C-C.FIG.5Cschematically shows the structure of the frame element101on its front side and on its back side. As it can be seen, the front and back side of the frame elements can correspond to each other, desirable they are symmetric in a top view of the frame elements (which corresponds to the direction of view inFIG.5B). In other words a frame element may be symmetric to a center plane of the frame element which is parallel to a plane defined by the front or back side of the frame element. As it is shown in5C, a feed supplied by the first opening13can enter the notch45avia the connecting notch47. Due to a barrier on the lower side of the notch (shown inFIG.5C) which actually forms one side wall of the notch (or cavity)45a, the feed is first fills the notch before it enters the (relatively thin) feeding area40′ by passing the barrier. FIG.6shows a schematic representation of a second frame element102in particular with liquid passages45,46according to embodiments of the present disclosure; As shown, the second frame elements desirably comprises complementary liquid passages45,46, such that the liquid passages of stacked first and adjacent second frame elements101,102form together a liquid passage extending across (i.e. over the full length of) the complete first upper and second lower sides the feeding area40′ (regarding peripheral liquid passages46b, this is only schematically shown). Accordingly, the liquid passage45of the second frame element102may extend asymmetrically by extending from a central section of the first frame side (below the first opening13) into only a second direction along the first frame side (e.g. inFIG.6to the left) without extending into the opposite first direction. A second liquid passage46of the second frame element102may extend discontinuously by extending only across the peripheral regions of the second lower frame wall but not across the central region. As a consequence, it is possible to provide channel openings22a,22b,22cconstituting through holes in the inner frame in those areas where no liquid passage is provided. As a consequence, there is no interference of the liquid passage and the other function. Hence, the thickness of the frame wall (in particular in a front view of the frame member) may be reduced and hence, desirably of the complete frame element. As a consequence, more frame elements may be used in a modular flow system and the heat transfer may be increased due to the reduced thickness. This leads to a higher efficiency and an increased output of the flow system. FIG.7shows a schematic representation of a second frame element in particular with a welding web structure11according to embodiments of the present disclosure. The first frame element101may have a corresponding welding web structure (with respective differences on e.g. the strut members48a,48b). The welding web structure11is schematically shown by a solid line inFIG.7. The other structural elements and features of the frame elements are indicated by dashed lines. The welding web structure11defines regions including the passage openings13to16and the central inner region40and defines at least two regions each including a vapor and/or liquid passage17,18. As shown inFIG.7, the region defining the central region40may also include the first passage opening13and the second passage openings16a,16b. In this way, a feed supplied by the first passage opening13can enter the feeding area40′ between two adjacent frame elements and leave the feeding area via the second passage openings16a,16b. The further passage openings14,15, channels17,18and passages20are each desirably enclosed by a welding web structure11such that they are separated from each other in the area between two adjacent frame elements. As further shown inFIG.7, the welding web structure desirably extends across the complete non-connecting internal strut members48band only on a matching section on the connecting internal strut members48a. Due to the different arrangement of the non-connecting internal strut members in the first frame element101, the arrangement of the welding web structure desirably differs correspondingly. As further shown inFIG.7, in order to additionally strengthen the stability of the frame element101,102, the outer frame39may include additional outer strut members48f. Such outer strut members may be provided with the welding web structure11. Accordingly, outer strut members may be provided inside the outer frame, e.g. on an additional base element provided at the bottom of the frame element (shown inFIG.7but not inFIGS.1to6). Desirably, said welding web structure11is provided on only one side of a frame element (as schematically shown e.g. inFIG.5C) but it may also be arranged (e.g. symmetrically) on both sides. FIG.8shows a schematic representation of a multistage membrane distillation apparatus, in particular comprising a modular flow system, according to embodiments of the present disclosure. The multistage membrane distillation apparatus5000comprises a plurality of multistage membrane distillation modules500,600. The modules are configured to be flowed through in parallel by a liquid (i.e. a feed, e.g. salt or dirt water) F to be concentrated. The modules are also supplied in parallel by a (heating) steam V1, as described below. Each module comprises a plurality of serial condensation/evaporation stages50,60etc. configured to be flowed through in series by the liquid to be concentrated. This is shown inFIG.8for module500only. Further stages may be subsequently connected in series to stage60. A steam (i.e. vapor) V2generated in a first stage50may be supplied to a subsequent second stage60to heat said second stage. In this way the stages are also (at least functionally) connected (or coupled) in series with regard to the steam V1, V2. The steam supplied to the first stage (by the centralized heating stage300) may have a temperature of 80-85° C. The temperature difference between an incoming and a generated outgoing steam in a stage (i.e. V1and V2) may be 4-5° C. Accordingly, in case the steam supplied to the last stage has 40-45° C., it is possible that a module comprises 8 to 10 stages. Each condensation/evaporation stage50,60etc. comprises a plurality of parallel condensation/evaporation elements101,102configured to be flowed through in parallel by the liquid to be concentrated. Desirably the condensation/evaporation elements101,102are also configured to be flowed through in parallel by the steam. This is schematically shown inFIG.8for condensation/evaporation stage50,60. Each condensation/evaporation element comprises at least one condensation unit101(e.g. a first frame element101) and at least one evaporation unit102(e.g. a second frame element102), as shown in stages50and60. In the example ofFIG.8two condensation/evaporation elements are shown which are formed each by an evaporation unit102sandwiched by two condensation units101. Accordingly, the condensation/evaporation elements share a condensation unit101arranged between them. It is noted that a stage may comprise a hundred parallel condensation/evaporation elements or more, i.e. more than hundred condensation units101(e.g. first frame elements101) and evaporation units102(e.g. second frame elements102). Accordingly, the apparatus may be or comprise at least one modular flow system according to the present disclosure. Also each module500,600may be a modular flow system according to the present disclosure. A stage50,60may be terminated on its both ends by covers (i.e. closing frame members)103, which close at least some of the openings, channels, passages, etc. in the outmost frame members101,102(inFIG.8frame members101). The multistage membrane distillation apparatus5000has thus a hierarchical organization with three levels. On the first (highest) level, the apparatus comprises a plurality of parallel multistage membrane distillation modules500,600. On the second (lower) level, the apparatus comprises a plurality of serial condensation/evaporation stage50,60. On the third (lowest) level, the apparatus comprises a plurality of parallel condensation/evaporation elements101,102. A condensation/evaporation element may comprise a first frame element101and a second frame element102. Due to this arrangement the apparatus may comprise up to several thousand condensation/evaporation elements, e.g. by simply combining several thousand first and second frame elements, respectively. The apparatus5000may further comprise a centralized heating stage300configured to generate steam (i.e. a vapor) and to provide the steam to each of the modules in parallel, and/or a centralized condensation stage400configured to receive steam from each of the modules in parallel and to condense the steam. Furthermore, by providing such an apparatus, it is possible that several modules commonly use a centralized (or single) heating stage and/or a centralized (or single) condensation stage. Therefore, the energy consumption of the centralized (or single) heating stage and/or a centralized (or single) condensation stage may be shared by a plurality of parallel modules, which can lead to an optimized energy efficiency of the apparatus and at the same time (due to the use of more than one module) to a higher total output of the apparatus. The centralized heating stage300generates steam (i.e. a vapor) and provides the steam to each of the modules in parallel. Accordingly the modules are heated with the supplied steam. In comparison to heating with supplied (hot) liquid, this has the advantage that due to the thermodynamics steam will automatically be attracted most by the coldest surface in a steam space (in the present case the steam channel from the heating stage300to the condensation units101of each module's first stage). Hence, a module which is colder than the others will automatically be heated more. As a consequence, the temperature of the modules is automatically balanced. In comparison, heating with (hot) liquid may involve a very precise control implying high effort and reduced reliability. The same applies to a centralized condensation stage400. Due to thermodynamics the vapor (or steam) generated in the last stage of each module will automatically be attracted by the centralized condensation stage depending on the temperature of the vapor. Hence, a module which generates hotter vapor (or steam) in its last stage will automatically supply more steam to the centralized condensation stage and will therefore, be cooled more than the other (colder) modules. As a consequence, the temperature of the modules is automatically balanced. In other words, the set temperature of the modules can be automatically controlled. The centralized heating stage300may be configured to provide the steam in each module to a first stage50of the serial condensation/evaporation stages. Accordingly, the first stage of each module may be heated by the centralized heating stage. In particular; the steam is provided in each module to the condensation units101of the first stage in parallel. Said condensation units of the first stages are thus heated to a first predetermined temperature, e.g. in the range of 80-85° C. Accordingly, the condensation units of a first stage50of each module may be heated by the generated steam. Condensation units of subsequent stages60may be heated with the steam (vapor) generated in preceding stages50. The feed F may be heated to a second temperature which is slightly lower than the temperature of the generated steam, e.g. 4 to 6° C. lower. In this way the steam V1can heat the feed F in the first stage such that the liquid vaporizes and passes the membrane walls of the evaporation units102, thereby causing a membrane distillation. The centralized condensation stage400may be configured to receive steam from a last stage of the serial condensation/evaporation stages50,60of each module. In particular, the centralized condensation stage400may be configured to receive steam from the evaporation units102(of each last stage) in parallel, in particular for cooling said evaporation units to a third predetermined temperature, e.g. in the range of 30 to 35° C., being lower than the first and the second predetermined temperatures. Accordingly, the evaporation units102of a last stage of each module may be cooled by the centralized condensation stage. Evaporation units102of preceding stages50may be cooled by subsequent stages60(i.e. the condensation units101of subsequent stages). Each of the condensation units101may comprise a first steam space corresponding to the inner region40of the frame element101at least partly limited by a condensation wall, in particular a film. Accordingly, a condensation unit may be a first frame element101, as described above. Each of the respective evaporation units102may comprise a second steam space corresponding to the inner region40of the frame element101at least partly limited by a steam-permeable, liquid tight membrane wall. Accordingly, a evaporation unit may be a second frame element102, as described above. At least one flow channel (formed by a feeding area40′ between adjacent frame elements101,102) for the liquid to be concentrated may be provided between a condensation unit101and an adjacent evaporation unit102such that the liquid inside the flow channel is heated via the condensation wall and the steam arising from the liquid to be concentrated moves through the membrane wall into the second steam space. It is noted that for simplicity reasons the schematic illustration ofFIG.8does not show any channels, in which the condensate C can flow out of the condensation units101(e.g. via condensate collection passages19a,19b). This condensate C may constitute, in particular together with the condensed vapor Vn in the centralized condensation stage400, the final product of the apparatus (i.e. the distillate). Said final product may be collected in a container (not shown inFIG.8). Furthermore,FIG.8does not show a drainage channel which may be configured to guide the drainage DR of the evaporation units102(e.g. via the drain passages20) to a drainage container or to recirculate it to the feed supply channels which supply the feed F to the apparatus. In the example ofFIG.8in each condensation/evaporation stage50,60the evaporation units102and condensation units101are stacked alternately. The evaporation units102have steam outlet passages in form of the vapor and/or liquid channels18connected with another, in particular facing one another and/or being aligned with each other. The condensation units101have steam inlet passages in the form of the vapor and/or liquid channels17connected with another, in particular facing one another. The evaporation units102further comprise passage openings in the form of the vapor and/or liquid channels17facing the steam inlet passages17of the condensation units101. The condensation units also comprise passage openings in the form of the vapor and/or liquid channels18facing steam outlet passages18of the evaporation units102. Said passage openings are hence vapor and/or liquid channels17,18which are not connected to the inner region by channel openings22a. In other words, in an evaporation unit102the steam outlet passage18and the passage opening17are be symmetrical, and in an condensation unit101the steam inlet passage17and the passage opening18are symmetrical. Since the vapor and/or liquid channels, and also the further openings and passages13to16and19,20match each other in both frame elements101,102. Hence, each condensation/evaporation element comprises a single stack of frame elements providing the respective condensation units and evaporation units of the condensation/evaporation element. Furthermore, also each condensation/evaporation stage50is formed by a single stack of frame elements providing the parallel condensation/evaporation elements. By this configuration a set of parallel connected evaporation and condensation units can be obtained in a stage. Furthermore, as shown in the example ofFIG.8, the steam outlet passages18of the evaporation units102of a preceding stage50may be connected to the steam inlet passages17of the condensation units101of a successive stage60for forming a steam channel providing steam from the preceding stage to the successive stage. Hence, the subsequent stage60can be heated by the steam generated in the preceding stage50. At the same time, said steam is the distillate (e.g. distilled and hence cleaned water). Said units101,102may be in particular arranged such that the respective steam outlet passages18of the preceding stage50and the respective steam inlet passages17of the successive stage face60one another. This is e.g. possible by turning the frame elements of a subsequent stage around their vertical symmetry axis. Therefore, each module can be formed by a single stack of frame elements. Consequently, the heating steam V1(e.g. generated by a centralized heating stage) can be easily supplied to each module500,600. The heating steam may namely be supplied only to the first frame element (forming a condensation unit101) of a stacked module500(the outset closing frame members103may have a respective opening to allow the heating steam to enter the vapor and/or liquid channel17of the first frame member101). In this way, the steam V1is supplied to the parallel condensation units101of the first stage50of the module500. The same applies to the steam generated in the last stage which may be supplied e.g. to a centralized condensation stage400. The centralized condensation stage may be connected to the vapor and/or liquid channel18of the last frame element of the module stack. Said last frame element may e.g. form a condensation unit101. Therefore, the overall structure of the apparatus can be simplified and made more compact, which can enhance its efficiency, in particular with regard to the energy consumption. FIG.9Ashows a schematic representation of a centralized heating stage300according to a first embodiment of the present disclosure. This centralized heating stage300may be used e.g. in the multistage membrane distillation apparatus5000ofFIG.8. The centralized heating stage300may comprise a heating device310and an evaporation device320, e.g. a flash tank. The heating device310may comprise a heating liquid space configured to heat a liquid and to supply it to the evaporation device320. The evaporation device320may comprise a steam space322at least partly limited by a mesh tab and/or a steam-permeable, liquid-tight membrane wall321such that the steam V1arising from the liquid moves through the mesh tab and/or the membrane wall into the plurality of multistage membrane distillation modules500,600via a plurality of parallel steam passages. It is desirable to use a liquid-tight membrane wall such321. In this way it becomes possible to integrate a droplet elimination device (as described in more detail in context ofFIGS.11to13) into the heating stage. In one exemplary embodiment, the evaporation device320may be fed by an unheated liquid (or feed) FO which is to be concentrated (i.e. to be distilled). In this way the liquid FO can be heated in the evaporation device, in order to generate the steam V1and to supply the heated liquid F to the modules500,600. The liquid F may in particular be heated to a second predetermined temperature being lower than the first predetermined temperature of the steam V1. For this purpose the evaporation device320may be connected to the modules in parallel via a supply channel331. Additionally the evaporation device320may be connected to the heating device310via a return channel332. The supply channel331and the return channel332may comprise a common pump330. The supply channel331may further comprise a valve340and any further means to adapt the pressure of the liquid F to a desired level. The centralized heating stage may be configured as a vapor-liquid separator, in particular as a demister. FIG.9Bshows a schematic representation of a centralized heating stage according to a second embodiment of the present disclosure. In this example, the centralized heating stage300′ is configured as a kettle-type heating device and/or a submerged tube evaporator. FIG.9Cshows a schematic representation of a centralized heating stage according to a third embodiment of the present disclosure. In this example, the centralized heating stage300″ is configured as a thermosiphon heating device and/or as a natural circulation steam boiler. The centralized heating stage may also have any other configuration for generating steam. FIG.10shows a schematic representation of a centralized condensation stage400according to embodiments of the present disclosure. This centralized condensation stage400may be used e.g. in the multistage membrane distillation apparatus5000ofFIG.8. The centralized condensation stage400may comprise e.g. a mixing condenser or a plate-type condenser. In one example, the centralized condensation stage400may comprise a cooling device410with a cooling liquid space412and a condensation device with a steam space413. The cooling liquid space may be supplied with e.g. a cooled water supplied by a flow-through cooler (not shown). The spaces412,413are separated by a liquid-tight, heat-conducting wall411. The steam space413may be connected to the last stage of each module500,600in parallel via a plurality of respective steam passages. In this way the centralized condensation stage400can receive and condense a vapor Vn generated in the last stages. The condensate, i.e. the distillate leaves the steam space413via a distillate channel414. Furthermore, the steam space413may be connected via a vacuum channel415to a vacuum pump. In this way the pressure of the steam space413and desirably thus also of the modules may be controlled. E.g. the modules may be applied with a predetermined negative pressure. Due to a pressure reduction the boiling temperature of the liquid is namely reduced, as well, which can enhance the membrane distillation process. FIG.11shows a schematic representation of a droplet elimination device320′ according to a first embodiment of the present disclosure.FIG.11may show a side view or a top view of the droplet elimination device. The droplet elimination device comprises a membrane321′ configured to separate droplets from the steam generated by the heating stage. The membrane comprises in particular a steam-permeable, liquid-tight membrane wall. The membrane is arranged in a steam chamber which is separated by the membrane into a steam incoming chamber322′ and a steam outgoing chamber324′. In particular, the droplet elimination device comprises a steam incoming chamber322′ which is supplied with steam VD (potentially comprising droplets) generated by the heating stage via a steam incoming channel326. It further comprises a steam outgoing chamber324′ on the other side of the membrane which provides the steam VNDseparated from droplets to the condensation/evaporation stages via a steam outgoing channel327. The steam VNDmay be used e.g. as steam V1inFIG.8which is provided to the first stage of each module. The separated droplets DL can flow down on the membrane in the steam incoming chamber322′ due to the gravitational force (in this caseFIG.11shows a side view of the droplet elimination device). The droplet elimination device may be used in a membrane distillation apparatus for producing water for injection. In particular, it may be used in the multi-stage membrane distillation apparatus, as described above, which may hence be used for producing water for injection purposes. For example, the droplet elimination device may be integrated into the heating stage300or a respective droplet elimination device may be integrated into each module500,600. Alternatively (or additionally), a droplet elimination device may be arranged in a steam channel between and externally to the heating stage and the modules, in particular before the steam channel is split to distribute the steam to each of the modules. FIG.12Ashows a top view of a schematic representation of a droplet elimination device320″ according to a second embodiment of the present disclosure. As shown, the membrane has a folded form when seen from said top view. The folds extend hence in a vertical direction. It may however comprise (additional) folds extending in a horizontal direction. Accordingly, due to the increased surface a flow speed of the steam can be reduced, as the flow speed depends on the flow volume per surface size. Hence, since the pressure loss caused by the membrane correlates with the flow speed of the steam, a pressure loss can be reduced due to the decreased flow speed. Furthermore, due to the folded form, the droplet elimination device may have a compact form. Droplets DL may be caught in the folds which extend into the direction of the steam outgoing channel327and may there flow down on the membrane. FIG.12Bshows a side view of the droplet elimination device ofFIG.12A. As shown in this side view, the membrane comprises a steam-permeable, liquid-tight membrane wall section321″ and arranged above a steam- and liquid-tight wall section325. The membrane may have a folded form like that ofFIG.12Aor a straight form like inFIG.11(for simplicity, the membrane is schematically illustrated as only one dotted line321″ and not in a folded form) Furthermore, the steam incoming channel326and the steam outgoing channel327are arranged above the membrane321″. The spatial relationship “above” relates to the positioning in the droplet elimination device when the droplet elimination is installed in the membrane distillation apparatus. Accordingly, a separation of any droplets can be achieved by using the gravitational force on the droplets. Since at least the steam outgoing channel is arranged above the membrane, the droplets cannot enter the outgoing channel, even if the membrane is damaged. In particular, due to the steam- and liquid-tight wall section a droplet can be hindered from directly passing from the steam incoming channel to the steam outgoing channel. Furthermore, even if the membrane is damaged, any droplets passing the membrane (i.e. leakage) cannot enter the outgoing channel326due to its positioning above the membrane. Accordingly, the steam outgoing chamber324″ forms a barrier for any leakage DR due to the raised position of the outgoing channel327. The steam outgoing chamber324′ may comprise an additional outlet channel on its bottom for any potential leakage. FIG.13shows a side view of a schematic representation of a module comprising an integrated droplet elimination device according to embodiments of the present disclosure. The module may correspond to the module500described above and shown inFIG.8, wherein it additionally comprises an integrated droplet elimination device. The module comprises a plurality of condensation/evaporation stage50,60, N, wherein for each stage for simplicity reasons of the schematic illustration only one condensation/evaporation element is shown inFIG.13. For each condensation/evaporation element a condensation units101and an evaporation unit102is schematically shown. From the condensation units101a condensate is extracted (e.g. via collection passages19a,19b) which constitutes (together with the condensed vapor Vn generated in the last stage N) the distillate, i.e. the water for injection. From the evaporation units102a leakage may be extracted (e.g. via second passage openings16a,16b). The module further comprises as a first unit (i.e. with regard to the steam flow coming from the heating stage) the droplet elimination device320″. Said droplet elimination device may e.g. be provided by one or two frames added to the stack which forms the module shown inFIG.8. The steam VD generated by the heating stage300passes the droplet elimination device, in particular its membranes321″, whereby any potential droplets are separated from the steam. The thus purified steam V1is then transmitted to the first stage50, in order to heat the condensation units101. Accordingly, a compact arrangement of the droplet elimination device320can be provided, which has a simple structure due to the use of additional frame elements added to the module stack. Furthermore, since the droplet elimination device has a substantially equal steam pressure on both sides of the membrane321″, there is a reduced risk of any membrane damage, any additional pressure adaptation in the droplet elimination device320″ is unnecessary and the droplet elimination device320″ does not substantially reduce the efficiency of the module. Finally, since the steam incoming channel and the steam outgoing channel are aligned with the steam inlet passages and the steam outlet passages and are arranged above the membrane321″ and the feed areas40′, standardized (frame) elements can be used and a safe leakage barrier is obtained. Throughout the description, including the claims, the term “comprising a” should be understood as being synonymous with “comprising at least one” unless otherwise stated. In addition, any range set forth in the description, including the claims should be understood as including its end value(s) unless otherwise stated. Specific values for described elements should be understood to be within accepted manufacturing or industry tolerances known to one of skill in the art, and any use of the terms “substantially” and/or “approximately” and/or “generally” should be understood to mean falling within such accepted tolerances. Although the present disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims.
50,732
11857929
DESCRIPTION OF EMBODIMENTS FIG.1is a sectional view of a zeolite membrane complex 1.FIG.2is a sectional view illustrating part of the zeolite membrane complex 1 in enlarged dimension. The zeolite membrane complex 1 includes a porous support11and a zeolite membrane12formed on the support11. InFIG.1, the zeolite membrane12is illustrated with bold lines. InFIG.2, the zeolite membrane12is cross-hatched. The membrane thickness of the zeolite membrane12illustrated inFIG.2is thicker than the actual membrane thickness. The support11is a cylindrical member. The support11is a porous member that is permeable to gases and liquids. The support11has an inside surface113that is generally cylindrical about a central axis J1extending in a longitudinal direction (i.e., a right-left direction inFIG.1), and an outside surface112that is generally cylindrical and surrounds the inside surface113. The central axis J1as used herein refers to a central axis of a virtual cylinder arranged so as to circumscribe the inside surface113. The outside surface112is located outward of the inside surface113in a radial direction about the central axis J1(hereinafter, also simply referred to as the “radial direction”) and surrounds the inside surface113. The outside surface112has the zeolite membrane12formed thereon. The zeolite membrane12covers approximately the entire outside surface112of the support11. In the following description, a generally columnar space located radially inward of the inside surface113is referred to as an “inner flow path111.” The support11has a length (i.e., length in the right-left direction inFIG.1) of, for example, 10 cm to 200 cm. The support11has an outer diameter of, for example, 0.5 cm to 30 cm. A distance in the radial direction between the inside surface113and the outside surface112of the support11(hereinafter, also referred to as a “support thickness”) is, for example, in the range of 0.1 mm to 10 mm. Surface roughness (Ra) of the support11is, for example, in the range of 0.1 μm to 5.0 μm and preferably in the range of 0.2 μm to 2.0 μm. As the material for the support11, various substances (e.g., ceramic or metal) may be employed as long as they are chemically stable during the step of forming the zeolite membrane12on the surface of the support11. In the present embodiment, the support11is formed of a ceramic sintered compact. Examples of the ceramic sintered compact that is selected as the material for the support11include alumina, silica, mullite, zirconia, titania, yttrium, silicon nitride, and silicon carbide. In the present embodiment, the support11contains at least one of alumina, silica, and mullite. The support11may contain an inorganic binder. The inorganic binder may be at least one of titania, mullite, easily sinterable alumina, silica, glass frit, clay minerals, and easily sinterable cordierite. A mean particle diameter of the support11in the vicinity of the surface where the zeolite membrane12is formed is smaller than a mean particle diameter of the support11in the other portions. To achieve this structure, the support11has a multilayer structure. When the support11has a multilayer structure, the material for each layer may be any of the materials described above, and each layer may be formed of the same material or may be formed of a different material. The mean pore diameter of the support11can be measured using an apparatus such as a mercury porosimeter, a perm porometer, or a nano-perm porometer. The mean pore diameter of the support11is, for example, in the range of 0.01 μm to 70 μm and preferably in the range of 0.05 μm to 25 μm. In a pore size distribution of the support11in the vicinity of the surface where the zeolite membrane12is formed, D5is, for example, in the range of 0.01 μm to 50 μm, D50is, for example, in the range of 0.05 μm to 70 μm, and D95is, for example, in the range of 0.1 μm to 2000 μm. A porosity of the support11in the vicinity of the surface where the zeolite membrane12is formed is, for example, in the range of 25% to 50%. FIG.3is a diagram illustrating a section of the support11that is perpendicular to the longitudinal direction (i.e., section perpendicular to the central axis J1). InFIG.3, a position at which the distance in the radial direction between the inside surface113and the outside surface112of the support11becomes a maximum is indicated by arrows, and the support thickness at this position is assumed to be a maximum value A of the support thickness. A position at which the distance in the radial direction between the inside surface113and the outside surface112of the support11becomes a minimum is also indicated by arrows, and the support thickness at this position is assumed to be a minimum value B of the support thickness. The maximum value A and the minimum value B of the support thickness in one cross-section of the support11, which is perpendicular to the central axis J1, satisfy “(A−B)/(A+B)≤0.3.” In other words, this relation between the maximum value A and the minimum value B is satisfied in at least part of the support11in the longitudinal direction. Preferably, this relation between the maximum value A and the minimum value B is satisfied along the entire length of the support11in the longitudinal direction (i.e., in each cross-section in the longitudinal direction). Preferably, the maximum value A and the minimum value B of the support thickness satisfy (A−B)/(A+B)≤0.2 in at least part of the support11in the longitudinal direction. More preferably, this relation between the maximum value A and the minimum value B of the support thickness is satisfied along the entire length of the support11in the longitudinal direction (i.e., in each cross-section in the longitudinal direction). A mean radius X and roundness Y of the inside surface113of the support11in the above one cross-section perpendicular to the central axis J1satisfy Y/X≤0.5. In other words, this relation between the mean radius X and the roundness Y is satisfied in at least part of the support11in the longitudinal direction. Preferably, this relation between the mean radius X and the roundness Y is satisfied along the entire length of the support11in the longitudinal direction (i.e., in each cross-section in the longitudinal direction). The mean radius X in one cross-section of the support11is an arithmetical mean of the maximum radius and the minimum radius in this cross-section. The roundness Y is obtained in conformity with JIS-B-0621. Specifically, in this cross-section, a rough circle (i.e., circular form) serving as the inside surface113is sandwiched between two concentric geometric circles, and a difference between the radii of these two geometric circles, obtained when the interval between the two geometric circles becomes a minimum, is regarded as the roundness Y. The zeolite membrane12is a porous membrane with small pores. The zeolite membrane12can be used as a separation membrane that separates a specific substance from a mixture of substances including a plurality of types of substances, using its molecular sieving function. The zeolite membrane12is less permeable to the other substances than to the specific substance. In other words, a permeance of the other substances through the zeolite membrane12is lower than a permeance of the above specific substance through the zeolite membrane12. The zeolite membrane12has a membrane thickness of, for example, 0.05 μm to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.5 μm to 10 μm. The membrane thickness of the zeolite membrane12as used herein refers to a minimum value for the distance from the surface of the support11to the surface of the zeolite membrane12(i.e., minimum thickness) in the overall zeolite membrane12with the exception of defective portions. The same also applies to the following description. In the present embodiment, the membrane thickness of the zeolite membrane12is less than or equal to 1 μm. A mean membrane thickness of the zeolite membrane12is preferably less than or equal to 5 μm, more preferably less than or equal to 3 μm, and yet more preferably less than or equal to 2 μm. Increasing the membrane thickness of the zeolite membrane12improves the selectivity. Reducing the thickness of the zeolite membrane12increases the permeance. Surface roughness (Ra) of the zeolite membrane12is, for example, less than or equal to 5 μm, preferably less than or equal to 2 m, and more preferably less than or equal to 1 μm. Yet more preferably, the surface roughness (Ra) of the zeolite membrane12is less than or equal to 0.5 μm Examples of the zeolite of the zeolite membrane12include a zeolite in which atoms (T atoms) located in the center of an oxygen tetrahedron (TO4) constituting the zeolite are composed of only Si or composed of Si and Al, an AlPO-type zeolite in which the T atoms are composed of Al and P, an SAPO-type zeolite in which the T atoms are composed of Si, Al, and P, an MAPSO-type zeolite in which the T atoms are composed of magnesium (Mg), Si, Al, and P, and a ZnAPSO zeolite in which the T atoms are composed of zinc (Zn), Si, Al, and P. Some of the T atoms may be replaced by other elements. When n represents a maximum number of membered rings in the zeolite of the zeolite membrane12, an arithmetical mean of the major and minor axes of an n-membered ring pore is assumed to be a mean pore diameter. The n-membered ring pore as used herein refers to a pore whose number of oxygen atoms that are bonded to T atoms and make a ring structure is n. When the zeolite has a plurality of n-membered ring pores where n is the same number, an arithmetical mean of the major and minor axes of all n-numbered rings is assumed to be the mean pore diameter of the zeolite. In this way, the mean pore diameter of the zeolite membrane is uniquely determined by the framework structure of the zeolite and can be obtained from a value disclosed in “Database of Zeolite Structures” [online] by the International Zeolite Association on the Internet <URL:http://www.iza-structure. org/databases/>. The mean particle diameter of the zeolite membrane12is preferably greater than or equal to 0.2 nm and less than or equal to 0.8 nm, more preferably greater than or equal to 0.3 nm and less than or equal to 0.6 nm, and yet more preferably greater than or equal to 0.3 nm and less than or equal to 0.5 nm. The mean particle diameter of the zeolite membrane12is smaller than the mean pore diameter of the support11in the vicinity of the surface where the zeolite membrane12is formed. There are no particular limitations on the type of the zeolite of the zeolite membrane12, but from the viewpoint of increasing the CO2flux and improving the CO2selectivity, a maximum number of atoms in the ring of the zeolite is preferably less than or equal to 8 (e.g., 6 or 8). The zeolite membrane12is, for example, a DDR-type zeolite. In other words, the zeolite membrane12is a zeolite membrane composed of a zeolite having a framework type code “DDR” assigned by the International Zeolite Association. In this case, the zeolite of the zeolite membrane12has an intrinsic pore diameter of 0.36 nm×0.44 nm and a mean pore diameter of 0.40 nm. For example, the zeolite membrane12may be any of the following types including AEI-type, AEN-type, AFN-type, AFV-type, AFX-type, BEA-type, CHA-type, ERI-type, ETL-type, FAU-type (X-type, Y-type), GIS-type, LEV-type, LTA-type, MEL-type, MFI-type, MOR-type, PAU-type, RHO-type, SAT-type, and SOD-type. The zeolite membrane12contains, for example, silicon (Si). For example, the zeolite membrane12may contain any two or more of Si, aluminum (Al), and phosphorus (P). The zeolite membrane12may contain alkali metal. The alkali metal is, for example, sodium (Na) or potassium (K). When the zeolite membrane12contains Si atoms, an Si/Al ratio in the zeolite membrane12is, for example, higher than or equal to 1 and lower than or equal to 100,000. The Si/Al ratio is preferably higher than or equal to 5, more preferably higher than or equal to 20, and yet more preferably higher than or equal to 100. This ratio is preferably as high as possible. The Si/Al ratio in the zeolite membrane12can be adjusted by, for example, adjusting the composition ratio of an Si source and an Al source in a starting material solution, which will be described later. Next, one example of the procedure for producing the zeolite membrane complex 1 will be described with reference toFIG.4. In the production of the zeolite membrane complex 1, first, the support11is formed (step S11). Specifically, first, green body that is a material for the support11is prepared by kneading ceramic particles, an inorganic binder, water, a dispersant, and a thickener. Then, the green body is subjected to extrusion molding so as to form a generally cylindrical compact. This compact is then fired to obtain a generally cylindrical fired compact. Then, the outside surface of the fired compact is grinded into a support member. Thereafter, a porous ceramic membrane that has smaller pore diameters than the pore diameters of the support member is formed as an intermediate layer on the outside surface of the support member, and another porous ceramic membrane that has yet smaller pore diameters is formed as a surface layer on the intermediate layer. In this way, the support11having a multilayer structure is formed. In the aforementioned preparation of the green body, for example, 0.1 to 50 parts by mass (in the present embodiment, 20 parts by mass) of the inorganic binder is added to 100 parts by mass of the ceramic particles (in the present embodiment, alumina particles). The alumina particles have a mean particle diameter of, for example, 1 μm to 200 μm and in the present embodiment, 50 μm. A firing temperature of the aforementioned compact is in the range of, for example, 1000° C. to 1800° C., and in the present embodiment, 1250° C. A firing time of the aforementioned compact is, for example, in the range of 0.1 to 100 hours, and in the present embodiment, one hour. For example, the outside surface of the fired compact is grinded with a belt-type grinder by a belt centerless method using fixed abrasive grains of a diamond grinding wheel. Various modifications may be made to the grinding method and the type of the grinder, used in this grinding. The intermediate layer and the surface layer described above are, for example, porous alumina membranes with thicknesses of several micrometers to several hundred micrometers. The intermediate layer and the surface layer are formed by, for example, vacuum filtration deposition. Alternatively, the intermediate layer and the surface layer may be formed by other methods. The intermediate layer has a mean pore diameter of, for example, 0.1 jam to 10 μm, and in the present embodiment, 0.5 μm. The surface layer has a mean pore diameter of, for example, 0.01 μm to 5 μm, and in the present embodiment, 0.1 μm. Then, seed crystals that are used to produce the zeolite membrane12are prepared (step S12). For example, the seed crystals are acquired from DDR-type zeolite powder synthesized by hydrothermal synthesis. This zeolite powder may be used as-is as seed crystals, or may be processed into seed crystals by pulverization or other methods. Note that step S12may be performed in parallel with step S11, or may be performed before step S11. Next, the seed crystals are deposited on the outside surface112of the support11(step S13). In step S13, for example, the seed crystals are deposited by filtration on the support11. Specifically, first, the lower-end opening of the support11that stands upright with the central axis J1running parallel to the up-down direction is sealed in a liquid-tight manner, and the upper-end opening thereof is attached in a liquid-tight manner to a generally cylindrical opening member83made of a liquid-tight material. Then, as illustrated inFIG.5, the support11is inserted from the lower end side (i.e., the side on which a seal member82is attached) into a reservoir80that stores a solution81in which the seed crystals are dispersed, and is immersed in the solution81. An upper-end opening of the opening member83attached to the upper end of the support11is located above the liquid level of the solution81, and the outside surface112of the support11is located within the solution81. Accordingly, a solvent in the solution81permeates through the support11from the outside surface112of the support11and moves to the inner flow path111, as indicated by arrows pointing in the right-left direction inFIG.5. On the other hand, the seed crystals in the solution81remain on and adhere to the outside surface112of the support11without permeating through the support11. In this way, a seed-crystal-deposited support is prepared. When step S13has ended, the support11with the seed crystals deposited thereon is taken out of the solution81and dried. The dried support11with the seed crystals deposited thereon is immersed in a starting material solution. For example, the starting material solution is prepared by dissolving or dispersing substances such as an Si source and a structure-directing agent (hereinafter, also referred to as an “SDA”) in a solvent. The solvent in the starting material solution may be water or alcohol such as ethanol. The SDA contained in the starting material solution may, for example, be an organic compound. For example, 1-adamantanamine may be used as the SDA. Then, using the seed crystals as nuclei, the DDR-type zeolite is grown by hydrothermal synthesis into the DDR-type zeolite membrane12on the support11(step S14). The temperature of the hydrothermal synthesis is preferably in the range of 120° C. to 200° C., and for example, 160° C. The time of the hydrothermal synthesis is preferably in the range of 10 hours to 100 hours, and for example, 30 hours. When the hydrothermal synthesis has ended, the support11and the zeolite membrane12are rinsed with deionized water. After the rinsing, the support11and the zeolite membrane12are dried at, for example, 80° C. After the support11and the zeolite membrane12have been dried, the zeolite membrane12is subjected to heat treatment so as to almost completely burn and remove the SDA in the zeolite membrane12and cause micropores in the zeolite membrane12to come through the membrane (step S15). In this way, the aforementioned zeolite membrane complex 1 is obtained. In the aforementioned production of the zeolite membrane complex 1, if the support11has a greatly varying support thickness, the amount of seed crystals to be deposited in step S13will also vary. Specifically, a thin portion of the support11with a small support thickness has low resistance when the solvent in the above solution permeates through the support11. This increases the amount of the solvent permeating through the thin portion of the support11and also increases the amount of seed crystals deposited on the outside surface112of the thin portion of the support11. On the other hand, a thick portion of the support11with a large support thickness has high resistance when the solvent permeates through the support11. This reduces the amount of the solvent permeating through the thick portion of the support11and also reduces the amount of seed crystals deposited on the outside surface112of the thick portion of the support11. As a result, the zeolite membrane12increases in thickness in portions of the zeolite membrane complex 1 that have small support thicknesses, and the zeolite membrane12decreases in thickness in portions of the zeolite membrane complex that have large support thicknesses. Accordingly, variations occur in the membrane thickness of the zeolite membrane12. Table 1 shows the relation of variations in support thickness and variations in the membrane thickness of the zeolite membrane12in the zeolite membrane complex 1. Generally cylindrical supports11according to Examples 1 to 7 have an outer diameter of 20 mm and a longitudinal length of 15 cm. The same applies to the support according to Comparative Example 1. Zeolite membranes12according to Examples 1 to 3 and a zeolite membrane according to Comparative Example 1 are DDR-type zeolite membranes. Zeolite membranes12according to Examples 4 and 5 are CHA-type zeolite membranes. Zeolite membranes12according to Examples 6 and 7 are AEI-type zeolite membranes. The zeolite membrane complexes 1 according to Examples 1 to 7 and the zeolite membrane complex according to the comparative example were produced by a production method approximately similar to the production method illustrated in steps S11to S15described above. Detailed production conditions and the like will be described below. For the production of the DDR-type zeolite membranes12according to Examples 1 to 3, in step S13, a slurry solution for seed deposition, prepared such that DDR-type zeolite seed crystals dispersed in water had a concentration of 0.1% by mass, was used as the aforementioned solution81. Then, the support11with the seed crystals deposited thereon was subjected to through-circulation drying with predetermined conditions (at room temperature, at an air velocity of 5 m/sec, for 10 minutes). In step S14, 88.0 g of 30% by weight of silica sol (trade name: SNOWTEX S manufactured by Nissan Chemical Corporation), 6.59 g of ethylenediamine (produced by FUJIFILM Wako Pure Chemical Corporation), 1.04 g of 1-adamantanamine (produced by Sigma-Aldrich, Japan), and 104.4 g of deionized water were mixed for preparation of the aforementioned starting material solution. The zeolite membrane12was synthesized by hydrothermal synthesis for 10 hours in an oven set at 130° C. The removal of the SDA was implemented by heating the support11with the zeolite membrane12formed thereon at 450° C. for 50 hours in an electric furnace. The same applies to the production of the DDR-type zeolite membrane according to Comparative Example 1. For the production of the CHA-type zeolite membranes12according to Examples 4 and 5, in step S12, CHA-type zeolite seed crystals were prepared by interzeolite conversion of a Y-type zeolite or by hydrothermal synthesis of an aluminosilicate solution or the like. In step S13, a slurry solution for seed deposition, prepared such that the CHA-type zeolite seed crystals dispersed in water had a concentration of 0.1% by mass, was used as the aforementioned solution81. Then, the support11with the seed crystals deposited thereon was subjected to through-circulation drying conducted with predetermined conditions (at room temperature, at an air velocity of 5 m/sec, for 10 minutes). In step S14, 21.3 g of 30% by weight of silica sol (trade name: SNOWTEX S manufactured by Nissan Chemical Corporation), 0.90 g of potassium hydroxide (produced by FUJIFILM Wako Pure Chemical Corporation), 1.18 g of sodium aluminate (produced by FUJIFILM Wako Pure Chemical Corporation), 3.58 g of 25% by mass of an N, N, N-trimethyl-1-ammonium hydroxide solution (produced by SACHEM, INC.), and 173.1 g of deionized water were mixed for preparation of the aforementioned starting material solution. The zeolite membrane12was synthesized by hydrothermal synthesis for 30 hours in an oven set at 160° C. The removal of the SDA was implemented by heating the support11having the zeolite membrane12formed thereon at 550° C. for 10 hours. For the production of the AEI-type zeolite membranes12according to Examples 6 and 7, in step S12, AEI-type zeolite seed crystals were prepared by hydrothermal synthesis of an aluminophosphate solution or the like. In step S13, a slurry solution for seed deposition, prepared such that the AEI-type zeolite seed crystals dispersed in water had a concentration of 0.1% by mass, was used as the aforementioned solution81. Then, the support11with the seed crystals deposited thereon was subjected to through-circulation drying conducted with predetermined conditions (at room temperature, at an air velocity of 2 m/sec to 7 m/sec, for 30 minutes). In step S13, the application of the slurry solution for seed position and the through-circulation drying were conducted twice. In step S14, 4.72 g of aluminum tri-isopropoxide (produced by KANTO CHEMICAL CO., INC.), 30.71 g of 35% by mass of a tetraethylammonium hydroxide solution (produced by Sigma-Aldrich, Japan), 8.41 g of 85% phosphoric acid (produced by Sigma-Aldrich, Japan), and 156.17 g of deionized water were mixed for preparation of the aforementioned starting material solution. The zeolite membrane12was synthesized by hydrothermal synthesis at 150° C. for 30 hours. The removal of the SDA was implemented by heating the support11having the zeolite membrane12formed thereon at 400° C. for 10 hours. TABLE 1Variation inVariation inSupportMembraneType ofThicknessThicknessZeolite(A − B)/| a − b |/Membrane(A + B)((a + b)/2)Example 1DDR-type0.093%zeolitemembraneExample 2DDR-type0.184%zeolitemembraneExample 3DDR-type0.287%zeolitemembraneComparativeDDR-type0.3614%Example 1zeolitemembraneExample 4CHA-type0.094%zeolitemembraneExample 5CHA-type0.288%zeolitemembraneExample 6AEI-type0.094%zeolitemembraneExample 7AEI-type0.289%zeolitemembrane Variation in support thickness in Table 1 represents “(A−B)/(A+B)” described above in one cross-section of the support11. That is, the variation in support thickness corresponds to a value obtained by dividing the difference between the maximum value A and minimum value B of the support thickness in one cross-section of the support11by the sum of the maximum value A and the minimum value B. The variation in support thickness increases as this value increases. Variation in membrane thickness in Table 1 represents a value obtained by dividing the absolute value of the difference between membrane thicknesses “a” and “b” by an arithmetical mean of the membrane thicknesses “a” and “b” in the above cross-section of the support11(i.e., “|a-b|/((a+b)/2)”), where “a” is the membrane thickness of a given portion of the zeolite membrane12where the support thickness is the maximum value A, and “b” is the membrane thickness of a given portion of the zeolite membrane12where the support thickness is the minimum value B. In Table 1, this value is expressed in percentage. The variation in the membrane thickness of the zeolite membrane12increases as this value increases. The maximum value A and minimum value B of the support thickness and the membrane thicknesses “a” and “b”, described above, were obtained by cutting the support11along a plane perpendicular to the central axis J1and observing the cross section using a scanning electron microscope (SEM). When the variation in support thickness, i.e., (A−B)/(A+B), is greater than 0.3 as in Comparative Example 1, the variation in the membrane thickness of the DDR-type zeolite membrane12, i.e., |a-b|/((a+b)/2), is greater than 10%. On the other hand, when the variation in support thickness, i.e., (A−B)/(A+B), is less than or equal to 0.3 as in Examples 1 to 3, the variation in the membrane thickness of the DDR-type zeolite membrane12, i.e., |a-b|/((a+b)/2), is less than or equal to 10%. Similarly, with the CHA-type zeolite membrane12, when the variation in support thickness, i.e., (A−B)/(A+B), is less than or equal to 0.3, the variation in the membrane thickness of the zeolite membrane12, i.e., |a-b|/((a+b)/2), is less than or equal to 10% (Examples 4 and 5). Similarly, with the AEI-type zeolite membrane12, when the variation in support thickness, i.e., (A−B)/(A+B), is less than or equal to 0.3, the variation in the membrane thickness of the zeolite membrane12, i.e., |a-b|/((a+b)/2), is less than or equal to 10% (Examples 6 and 7). Next, the separation of a mixture of substances using the zeolite membrane complex 1 will be described with reference toFIGS.6and7.FIG.6is a diagram illustrating a separator2.FIG.7is a diagram illustrating a procedure for separating a mixture of substances, performed by the separator2. The separator2, in which a mixture of substances including a plurality of types of fluids (i.e., gases or liquids) is supplied to the zeolite membrane complex 1, separates a substance having high permeability in the mixture of substances from the mixture of substances by causing the substance to permeate through the zeolite membrane complex 1. For example, the separator2may made the separation for the purpose of extracting a substance having high permeability from the mixture of substances, or for the purpose of condensing a substance having low permeability. The mixture of substances (i.e., mixed fluid) may be a mixed gas including a plurality of types of gases, may be a mixed solution including a plurality of types of liquids, or may be gas-liquid two-phase fluid including both gases and liquids. In the separator2, the CO2permeance of the zeolite membrane complex 1 at temperatures of 20° C. to 400° C. is, for example, greater than or equal to 100 nmol/m2·s·Pa. The ratio (permeance ratio) between the amount of CO2permeance and the amount of CH4permeance (leakage) of the zeolite membrane complex 1 at temperatures of 20° C. to 400° C. is, for example, higher than or equal to 100. The permeance and the permeance ratio are values for the case where a difference in the partial pressure of CO2between the supply side and the permeation side of the zeolite membrane complex 1 is 1.5 MPa. The mixture of substances includes, for example, one or more kinds of substances including hydrogen (H2), helium (He), nitrogen (N2), oxygen (O2), water (H2O), water vapor (H2O), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxide, ammonia (NH3), sulfur oxide, hydrogen sulfide (H2S), sulfur fluoride, mercury (Hg), arsine (AsH3), hydrocyanic acid (HCN), carbonyl sulfide (COS), C1 to C8 hydrocarbons, organic acid, alcohol, mercaptans, ester, ether, ketone, and aldehyde. Nitrogen oxide is a compound of nitrogen and oxygen. The aforementioned nitrogen oxide is, for example, a gas called NOx such as nitrogen monoxides (NO), nitrogen dioxides (NO2), nitrous oxide (also referred to as dinitrogen monoxide) (N2O), dinitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4), or dinitrogen pentoxide (N2O5). Sulfur oxide is a compound of sulfur and oxygen. The aforementioned sulfur oxide is, for example, a gas called SOx such as sulfur dioxide (SO2) or sulfur trioxide (SO3). Sulfur fluoride is a compound of fluorine and sulfur. The aforementioned sulfur fluoride may, for example, be disulfur difluoride (F—S—S—F, S═SF2), sulfur difluoride (SF2), sulfur tetrafluoride (SF4), sulfur hexafluoride (SF6), or disulfur decafluoride (S2F10). C1 to C8 hydrocarbons are hydrocarbons containing one or more and eight or less carbon atoms. C3 to C8 hydrocarbons each may be any of a linear-chain compound, a side-chain compound, and a cyclic compound. C2 to C8 hydrocarbons each may be either a saturated hydrocarbon (i.e., the absence of a double bond and a triple bond in a molecule) or an unsaturated hydrocarbon (i.e., the presence of a double bond and/or a triple bond in a molecule). C1 to C4 may, for example, be methane (CH4), ethane (C2H6), ethylene (C2H4), propane (C3H8), propylene (C3H6), normal butane (CH3(CH2)2CH3), isobutane (CH(CH3)3), 1-butene (CH2═CHCH2CH3), 2-butene (CH3CH═CHCH3), or isobutene (CH2═C(CH3)2). The aforementioned organic acid may, for example, be carboxylic acid or sulfonic acid. The carboxylic acid may, for example, be formic acid (CH2O2), acetic acid (C2H4O2), oxalic acid (C2H2O4), acrylic acid (C3H4O2), or benzoic acid (C6H5COOH). The sulfonic acid may, for example, be ethane sulfonic acid (C2H6O3S). The organic acid may be either a chain compound or a cyclic compound. The aforementioned alcohol may, for example, be methanol (CH3OH), ethanol (C2H5OH), isopropanol (2-propanol) (CH3CH(OH)CH3), ethylene glycol (CH2(OH)CH2(OH)), or butanol (C4H9OH). The mercaptans are organic compounds with terminal sulfur hydride (SH) and are substances called also thiol or thioalcohol. The aforementioned mercaptans may, for example, be methyl mercaptans (CH3SH), ethyl mercaptans (C2H5SH), or 1-propane thiol (C3H7SH). The aforementioned ester may, for example, be formic acid ester or acetic acid ester. The aforementioned ether may, for example, be dimethyl ether ((CH3)2O), methyl ethyl ether (C2H5OCH3), or diethyl ether ((C2H5)2O). The aforementioned ketone may, for example, be acetone ((CH3)2CO), methyl ethyl ketone (C2H5COCH3), or diethyl ketone ((C2H5)2CO). The aforementioned aldehyde may, for example, be acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), or butanal (butyraldehyde) (C3H7CHO). The following description takes the example of the case where the mixture of substances to be separated by the separator2is a mixed gas including a plurality of types of gases. The separator2includes the zeolite membrane complex 1, sealers21, an outer cylinder22, seal member23, a supply part26, a first collecting part27, and a second collecting part28. The zeolite membrane complex 1, the sealer21, and the seal members23are placed in the outer cylinder22. The supply part26, the first collecting part27, and the second collecting part28are disposed outside the outer cylinder22and connected to the outer cylinder22. The sealers21are members mounted on the both ends of the support11in the longitudinal direction (i.e., left-right direction inFIG.6) and covering and sealing the both end faces of the support11in the longitudinal direction and the outside surface of the support11in the vicinity of the both end faces. The sealers21prevent the inflow and outflow of gases from the opposite generally ring-shaped both end faces of the support11. The sealers21are, for example, plate-like members formed of glass or resin. The material and shape of the sealers21may be appropriately changed. The right sealer21inFIG.6has an opening that overlaps with the inner flow path111of the support11, and therefore a right end opening of the inner flow path111is not covered with the sealer21. Accordingly, the gas in the inner flow path111can flow out from this end opening to the outside of the zeolite membrane complex 1. On the other hand, the left sealer21inFIG.6has no opening, and therefore the gas cannot flow in and out through the left end of the inner flow path111. The outer cylinder22is a generally cylindrical tubular member. The outer cylinder22is formed of, for example, stainless steel or carbon steel. The longitudinal direction of the outer cylinder22is approximately parallel to the longitudinal direction of the zeolite membrane complex I (i.e., direction pointing in the central axis J1). The outer cylinder22has a supply port221and a first exhaust port222on the outside surface. The supply port221and the first exhaust port222are, for example, arranged on the opposite sides in the radial direction with the zeolite membrane complex 1 sandwiched therebetween (i.e., at 180° different positions in the circumferential direction). The outer cylinder22also has a second exhaust port223on one end in the longitudinal direction (i.e., right end inFIG.6). The supply port221is connected to the supply part26. The first exhaust port222is connected to the first collecting part27. The second exhaust port223is connected to the second collecting part28. An internal space of the outer cylinder22is an enclosed space isolated from the space around the outer cylinder22. The seal member23is arranged around the entire circumference between the outside surface of the zeolite membrane complex 1 and the inside surface of the outer cylinder22in the vicinity of an end of the zeolite membrane complex 1 in the longitudinal direction. The seal member23is a generally ring-shaped member formed of a material that is impermeable to gases. For example, the seal member23is O-ring formed of a resin having flexibility. The seal member23is in tight contact with the outside surface of the zeolite membrane complex 1 and the inside surface of the outer cylinder22around the entire circumference. In the example illustrated inFIG.6, the seal member23is in tight contact with the outside surface of the right sealer21in the drawing and is indirectly in tight contact with the outside surface of the zeolite membrane complex 1 via this sealer21. A space between the seal member23and the outside surface of the zeolite membrane complex 1 and a space between the seal member23and the inside surface of the outer cylinder22are sealed so as to almost or completely disable the passage of gases. Note that the seal member23may be provided between the outer cylinder22and an end face of the zeolite membrane complex 1 in the longitudinal direction. The supply part26supplies a mixed gas to the internal space of the outer cylinder22through the supply port221. For example, the supply part26is a blower or pump that transmits the mixed gas toward the outer cylinder22under pressure. The blower or pump includes a pressure regulator that regulates the pressure of the mixed gas supplied to the outer cylinder22. The first collecting part27and the second collecting part28are, for example, reservoirs that store the gas derived from the outer cylinder22, or are blowers or pumps that transfer the gas. In the case of separating a mixed gas, the aforementioned separator2is provided to prepare the zeolite membrane complex 1 (step S21). Then, the supply part26supplies a mixed gas that includes a plurality of types of gases having different permeability to the zeolite membrane12, to the internal space of the outer cylinder22. For example, the mixed gas is composed predominantly of CO2and CH4. The mixed gas may also include other gases different from CO2and CH4. The pressure of the mixed gas supplied from the supply part26to the internal space of the outer cylinder22(i.e., supply pressure) is, for example, in the range of 0.1 MPa to 20.0 MPa. The temperature of separating the mixed gas is, for example, in the range of 10° C. to 150° C. The mixed gas supplied from the supply part26to the outer cylinder22flows toward the outside surface of the zeolite membrane complex 1, as indicated by an arrow251. A gas having high permeability (e.g., CO2and hereinafter referred to as a “high-permeability substance”) in the mixed gas permeates through the zeolite membrane12provided on the outside surface112of the support11and through the support11, and is then emitted from the inside surface113of the support11to the inner flow path111. Accordingly, the high-permeability substance is separated from a gas having low permeability (e.g., CH4and hereinafter referred to as a “low-permeability substance”) in the mixed gas (step S22). The gas emitted from the inside surface113of the support11to the inner flow path111(hereinafter referred to as a “permeated substance”) is collected by the second collecting part28through the second exhaust port223, as indicated by an arrow253. The pressure (i.e., permeation pressure) of the gas collected by the second collecting part28through the second exhaust port223is, for example, approximately one atmospheric pressure (0.101 MPa). The permeated substance may include a substance other than the aforementioned high-permeability substance. In the mixed gas, a gas other than the gas having permeated through the zeolite membrane12and the support11(hereinafter, referred to as a “non-permeated substance”) passes through the space between the outside surface of the zeolite membrane complex 1 and the inside surface of the outer cylinder22from the upper side to the lower side in the drawing and is collected by the first collecting part27through the first exhaust port222, as indicated by an arrow252. The pressure of the gas collected by the first collecting part27through the first exhaust port222is, for example, approximately the same pressure as the supply pressure. The non-permeated substance may also include a high-permeability substance that has not permeated through the zeolite membrane12, in addition to the aforementioned low-permeability substance. As described above, the porous cylindrical support11used to support the zeolite membrane12has the generally cylindrical inside surface113having the central axis J1extending in the longitudinal direction as its center, and the generally cylindrical outside surface112surrounding the inside surface113. The zeolite membrane12is formed on the outside surface112. The radial distance between the inside surface113and the outside surface112, i.e., the maximum value A and the minimum value B in the circumferential direction of the thickness of the support, satisfy (A−B)/(A+B)≤0.3 in at least part of the support11in the longitudinal direction. By reducing the variation in the support thickness in this way, as described previously, it is possible for the support11to improve uniformity in the membrane thickness of the zeolite membrane12formed on the support11. Accordingly, even in the case where the zeolite membrane12is formed to a small mean thickness, it is possible to prevent part of the zeolite membrane12from becoming a defect by becoming too thin. As a result, the dense and thin zeolite membrane12can be formed on the support11. As described above, it is preferable for the support11that the maximum value A and the minimum value B of the support thickness in the circumferential direction satisfy (A−B)/(A+B)≤0.3 along the entire length of the support11in the longitudinal direction. This further improves uniformity in the membrane thickness of the zeolite membrane12formed on the support11. As described above, it is preferable for the support11that the maximum value A and the minimum value B of the support thickness in the circumferential direction satisfy (A−B)/(A+B)≤0.2, and in particular (A−B)/(A+B)≤0.1 in at least part of the support11in the longitudinal direction. This further improves uniformity in the membrane thickness of the zeolite membrane12formed on the support11. As described above, it is more preferable for the support11that the maximum value A and the minimum value B of the support thickness in the circumferential direction satisfy (A−B)/(A+B)≤0.2, and in particular (A−B)/(A+B)≤0.1, along the entire length of the support11in the longitudinal direction. This further improves uniformity in the membrane thickness of the zeolite membrane12formed on the support11. As described above, it is preferable for the support11that the mean radius X and the roundness Y of the inside surface113satisfy Y/X≤0.5, yet more preferably Y/X≤0.3, and in particular Y/X≤0.1, in at least part of the support11in the longitudinal direction. In this way, if the cross-sectional shape of the inside surface113perpendicular to the central axis J1is relatively close to a perfect circle, it is possible to improve uniformity in support thickness in the circumferential direction when the outside surface112is made closer to a perfect circle by grinding or other methods at the time of forming the support11. Accordingly, the support11, at least part of which in the longitudinal direction satisfies (A−B)/(A+B)≤0.3, can be formed with high yields. As described above, it is more preferable for the support11that the mean radius X and the roundness Y of the inside surface113satisfy Y/X≤0.5, yet more preferably Y/X≤0.3, and in particular Y/X≤0.1, along the entire length of the support11in the longitudinal direction. Accordingly, the support11that satisfies (A−B)/(A+B)≤0.3 along the entire length in the longitudinal direction can be formed with higher yields. As described above, the support11is preferably formed of a ceramic sintered compact. This enables increasing the strength of bonding between the zeolite membrane12and the support11more than in the case where the support is formed of a material other than a ceramic sintered compact, and thereby enables stably supporting the zeolite membrane12. The zeolite membrane complex 1 includes the aforementioned support11, and the zeolite membrane12formed on the outside surface112of the support11. This enables providing the zeolite membrane complex 1 that includes the zeolite membrane12having high uniformity in membrane thickness. Accordingly, it is also possible to provide the zeolite membrane complex 1 that includes the dense and thin zeolite membrane12. In other words, the zeolite membrane complex 1 can reduce the thickness of the zeolite membrane12. Since, as described above, the zeolite membrane complex 1 can reduce the thickness of the zeolite membrane12, the structure of the zeolite membrane complex 1 is in particular suitable for use as a zeolite membrane complex that includes a zeolite membrane12having a thickness less than or equal to 1 μm (minimum membrane thickness). As described above, a maximum number of membered rings in the zeolite of the zeolite membrane12is preferably less than or equal to 8. Accordingly, when the zeolite membrane12is used for the separation of a mixture of substances, it is possible to favorably achieve selective permeation of a to-be-permeated substance having a relatively small molecular diameter, such as CO2, and to efficiently separate the to-be-permeated substance from the mixture of substances. The aforementioned method of producing the zeolite membrane complex 1 includes the step of preparing seed crystals (step S12), the step of depositing the seed crystals on the support11(step S13), and the step of forming the zeolite membrane12on the support11by growing a zeolite from the seed crystals by hydrothermal synthesis (step S14). Accordingly, it is possible to provide the zeolite membrane complex 1 that includes the zeolite membrane12having high uniformity in membrane thickness. It is also possible to provide the zeolite membrane complex 1 that includes the dense and thin zeolite membrane12. The aforementioned separation method includes the step of preparing the above-described zeolite membrane complex 1 (step S21), and the step of supplying a mixture of substances including a plurality of types of gases or liquids to the zeolite membrane12and separating a substance with high permeability in the mixture of substances from the mixture of substances by causing the substance with high permeability to permeate through the zeolite membrane complex 1 (step S22). This enables favorably separating a substance with high permeability (i.e., high-permeability substance) from the mixture of substances. This separation method is in particular suitable for use in the separation of a mixture of substances including one or more kinds of substances including hydrogen, helium, nitrogen, oxygen, water, water vapor, carbon monoxide, carbon dioxide, nitrogen oxide, ammonia, sulfur oxide, hydrogen sulfide, hydrogen fluoride, mercury, arsine, hydrocyanic acid, carbonyl sulfide, C1 to C8 hydrocarbons, organic acid, alcohol, mercaptans, ester, ether, ketone, and aldehyde. The support11, the zeolite membrane complex 1, the method of producing the zeolite membrane complex 1, and the separation method for a mixture of substances, described above, may be modified in various ways. For example, the support11does not necessarily have to be formed of a ceramic sintered compact, and may be formed of other materials such as metal. The mean radius X and the roundness Y of the inside surface113of the support11do not necessarily have to satisfy Y/X≤0.5. The central axis of the outside surface112of the support11does not necessarily have to match the central axis J1of the inside surface113, and may be different from the central axis J1. In the zeolite membrane complex 1, the membrane thickness of the zeolite membrane12is not limited to be less than or equal to 1 μm, and may be modified in various ways. A maximum number of membered rings in the zeolite of the zeolite membrane12may be greater than 8, or may be smaller than 8. The aforementioned support11may be produced by a production method different from the method described in the above example. For example, the outside surface does not necessarily have to be grinded. The aforementioned zeolite membrane complex 1 may be produced by a production method different from the method described in the above example. For example, a technique different from the technique described in the above example may be used to deposit seed crystals on the support11. The zeolite membrane12may be formed on the inside surface113of the support11, or may be formed on both of the outside surface112and the inside surface113of the support11. The structure of the separation apparatus2illustrated inFIG.6may be modified in various ways. For example, like the right sealer21inFIG.6, the left sealer21inFIG.6may also have an opening that overlaps with the inner flow path111, and seal member23may be provided for sealing. Also, the left end face of the outer cylinder22may also have a second exhaust port223that is connected to the second collecting part28. The separator2and the separation method described above may separate a substance other than the substance exemplified in the above description from a mixture of substances. The zeolite membrane12in the zeolite membrane complex 1 does not necessarily have to be used for the separation of a high-permeability substance from a mixture of substances, and may be used in other applications such as for use as an absorption membrane or a pervaporation membrane. The configurations of the preferred embodiments and variations described above may be appropriately combined as long as there are no mutual inconsistencies. While the invention has been shown and described in detail, the foregoing description is in all aspects illustrative and not restrictive. It is therefore understood that numerous modifications and variations can be devised without departing from the scope of the invention. INDUSTRIAL APPLICABILITY The support according to the present invention is, for example, applicable for use in supporting a zeolite membrane that can be used as a gas separation membrane. The zeolite membrane complex according to the present invention is applicable in various fields that use zeolites, such as for use as a gas separation membrane, a separation membrane for substances other than gases, and an adsorption membrane for various substances. REFERENCE SIGNS LIST 1Zeolite membrane complex11Support12Zeolite membrane112Outside surface (of support)113Inside surface (of support)A Maximum value (for support thickness in circumferential direction)B Minimum value (for support thickness in circumferential direction)J1Central axisS11to S15, S21, and S22Step
50,497
11857930
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Hereinafter, an embodiment of a crystallization apparatus continuously performing poor solvent crystallization will be described with reference to the drawings. FIG.1is a configuration example of a downflow-type crystallization apparatus in which a raw material liquid is supplied from the upper portion side of a treatment container2and a mixed liquid obtained by a poor solvent being mixed with the raw material liquid is extracted from the lower portion side of the treatment container2. The crystallization apparatus of this example includes a raw material liquid supply unit11that supplies a raw material liquid101, a poor solvent supply unit (treatment liquid supply unit)12that supplies a poor solvent102, which is a treatment liquid, the treatment container2in which the raw material liquid101and the poor solvent102are mixed, and an aging unit that precipitates and grows crystals of a target substance from the mixed liquid extracted from the treatment container2. The raw material liquid supply unit11includes a raw material liquid tank114storing the raw material liquid101and a raw material liquid supply line110for supplying the raw material liquid101extracted from the raw material liquid tank114to the treatment container2. On the raw material liquid supply line110, a diaphragm pump111, a pressure gauge112, and an opening-closing valve113are provided in this order from the upstream side. The poor solvent supply unit12includes a poor solvent tank124storing the poor solvent102and a poor solvent supply line120for supplying the poor solvent102extracted from the poor solvent tank124to the treatment container2. On the poor solvent supply line120, a diaphragm pump121, a pressure gauge122, an opening-closing valve123, and a pressure gauge125for monitoring the pressure in the treatment container2are provided in this order from the upstream side. The treatment container2is made of, for example, a straight pipe and is disposed with a pipe axis vertically oriented. As illustrated inFIGS.1and2, the raw material liquid supply line110has a terminal end portion connected to the upper end portion of the treatment container2via an exhaust unit22(described later). On the other hand, the poor solvent supply line120has a terminal end portion connected to a side surface on the upper portion side of the treatment container2. A porous membrane21smaller in diameter than the treatment container2and molded in a straight pipe shape is disposed in the treatment container2of this example. The porous membrane21partitions the space in the treatment container2into a first flow space201inside the porous membrane21and a second flow space202between the inner peripheral surface of the treatment container2and the outer peripheral surface of the porous membrane21. The raw material liquid101supplied from the raw material liquid supply line110flows into the upper portion side of the first flow space201. The poor solvent102supplied from the poor solvent supply line120flows into the upper portion side of the second flow space202. Porous membranes made of various materials such as porous glass, porous ceramics, and porous polymers can be used as the porous membrane21. For example, a porous membrane having an average pore diameter in the range of 0.01 to 50 μm can be used as the porous membrane21. In addition, more preferably, a porous membrane having an average pore diameter of 0.01 to 10 μm is used as the porous membrane21. The pore diameter distribution of the porous membrane21can be measured by, for example, a mercury penetration method or a gas adsorption method. The porous membrane21having the above-described configuration plays a role of mixing the raw material liquid and the poor solvent by allowing the poor solvent supplied to the second flow space202side to pass to the first flow space201side via the multiple pores that are formed in the porous membrane21. The pressure gauge125provided on the downstream side of the opening-closing valve123on the poor solvent supply line120is used in order to keep the pressure of the second flow space202higher than the pressure of the first flow space201in view of the pressure loss of the porous membrane21. By managing the pressure of the second flow space202, it is possible to prevent raw material liquid backflow from the first flow space201side to the second flow space202side. It should be noted that the porous membrane21that has an average pore diameter of more than 50 μm can also be used in a case where the concentration distribution of the poor solvent that will be described later with reference toFIG.3can be formed. A sintered metal can be exemplified as a material that the porous membrane21is made of. Next, the configuration of the exhaust unit22will be described. In some cases, air bubbles brought in together with the liquid (raw material liquid101or poor solvent102) from the raw material liquid supply line110or the poor solvent supply line120accumulate in the treatment container2and form a gas pool. In this case, the part of the porous membrane21that is in contact with the gas pool is incapable of exhibiting the function of mixing the raw material liquid and the poor solvent. In this regard, the gas that has been brought into the treatment container2is discharged to the outside by means of the exhaust unit22. As illustrated inFIG.2, the exhaust unit22includes a T-shaped connection221that connects the downstream end portion of the raw material liquid101and the upper end portion of the treatment container2, a gas-liquid separation unit222that is a container connected to a branch pipe221abranching from the side surface of the T-shaped connection221, a liquid level gauge223that is a sensor unit measuring the liquid level in the gas-liquid separation unit222(height of the interface between the gas pool and the liquid), and a valve controller224that opens and closes a degassing valve225based on the result of the liquid level detection by the liquid level gauge223. The gas-liquid separation unit222is provided at a position higher than the first flow space201and the second flow space202. The liquid level gauge223is made of, for example, an ultrasonic level sensor. The valve controller224is configured to open the degassing valve225and discharge the gas of the gas pool to the outside in a case where the liquid level detected by the liquid level gauge223has become equal to or lower than a preset liquid level. Returning to the description of the treatment container2side, an extraction line230for continuously extracting the mixed liquid of the raw material liquid101and the poor solvent102from the first flow space201is connected to the lower end portion of the treatment container2. On the extraction line230, a pressure gauge231and a needle valve232are provided in order from the upstream side. The extraction line230, the pressure gauge231, and the needle valve232correspond to an extraction unit23of this example. The pipeline of the extraction line230on the downstream side of the needle valve232constitutes an aging pipe (aging unit)3through which the mixed liquid flows until the crystals of the target substance precipitate from the mixed liquid of the raw material liquid and the poor solvent (induction time) and until the crystals precipitated from the mixed liquid grow to a desired crystal diameter. Although not particularly limited, the length of the aging pipe3is set to, for example, approximately tens of centimeters to approximately tens of meters based on the flow rate of the mixed liquid and the induction time or the time required for the crystal growth. Although the aging pipe3that is disposed in a meandering manner is illustrated inFIG.1, the aging pipe3may be wound around, for example, a cylindrical holding member (see the winding of the aging pipe3around a cooling unit32that is illustrated inFIG.6and will be described later). Provided in the downstream end portion of the aging pipe3is a solid-liquid separation unit31that is configured by, for example, an aspirator and a filter for solid-liquid separation being combined and is for separating the mixed liquid into crystals and waste liquid. The action of the crystallization apparatus having the configuration described above will be described. First, the opening-closing valve113is opened, the diaphragm pump111is driven, and the raw material liquid101in the raw material liquid tank114is continuously supplied to the treatment container2at a predetermined flow rate. In parallel with this operation, the opening-closing valve123is opened, the diaphragm pump121is driven, and the poor solvent102in the poor solvent tank124is continuously supplied to the treatment container2at a predetermined flow rate. The raw material liquid101supplied from the raw material liquid supply unit11flows in the first flow space201from the upper portion side toward the lower portion side (along one surface side of the porous membrane21). In addition, the poor solvent102supplied from the poor solvent supply unit12flows in the second flow space202from the upper portion side toward the lower portion side (along the opposite surface side that is opposite to the one surface side of the porous membrane21). Further, by the supply pressure from the poor solvent supply unit12being adjusted so as to be higher than the pressure loss of the porous membrane21, the poor solvent102flowing in the second flow space202passes through the porous membrane21from each position on the outer surface of the porous membrane21and flows into the first flow space201(see the dashed arrow inFIG.3). Here, since the pore diameter distribution of the porous membrane21is uniform in the surface of the porous membrane21, the poor solvent102flows into the first flow space201at substantially the same flow velocity from each position in the surface of the porous membrane21. As a result, as also illustrated inFIG.3, a concentration distribution is formed in which the average concentration of the poor solvent102in the mixed liquid at each height position continuously increases from the upper portion side of the first flow space201toward the lower portion side of the first flow space201(FIG.3illustrates an example in which the concentration of the poor solvent increases proportionally). On the other hand, in the MSMPR process of the related art in which the poor solvent102is dripped and mixed with the raw material liquid101by means of a stirring blade or the like, there may be a case where a region where the poor solvent102has a high concentration is locally formed at the position of the dripping and it is difficult to form crystals of uniform size. In this regard, it becomes difficult to increase the amount of treatment if the amount of dripping of the poor solvent102is reduced so that the formation of such a high-concentration region is suppressed. In this respect, the poor solvent102is uniformly supplied from each position in the surface of the porous membrane21in the crystallization apparatus of this example, and thus a supply amount distribution in which the supply amount of the poor solvent increases only in a local region in the surface of the porous membrane21is unlikely to be formed. Used in this example in particular is a porous membrane having an average pore diameter in the range of 0.01 to 50 μm and more preferably having an average pore diameter of 0.01 to 10 μm. By using the porous membrane21having such characteristics, it is possible to suppress local supply of a large amount of poor solvent as compared with the porous membrane21that includes relatively large pores, and thus it is possible to precisely control the crystal diameter of the target substance or the like. In this manner, the raw material liquid101supplied from the upper portion of the first flow space201and the poor solvent102that has passed through the porous membrane21are mixed and the mixed liquid in which the solubility of the target substance is lowered is continuously extracted from the lower portion side of the first flow space201to the extraction line230. It should be noted that the raw material liquid101may contain fine crystals (seed crystals) of the target substance. Here, some time needs to elapse until the initiation of the precipitation of the crystals of the target substance after the concentration of the target substance in the mixed liquid reaches saturation as a result of the mixing of the poor solvent and this time is called induction time. For example, in a case where the induction time is short, crystals may precipitate in the mixed liquid in the first flow space201. Crystals can be easily discharged out of the first flow space201even in such a case since a downflow in which the mixed liquid flows from the upper portion side toward the lower portion side is formed in the first flow space201. In addition, as for the action of the exhaust unit22, air bubbles rise in the treatment container2and the T-shaped connection221and flow into the gas-liquid separation unit222even in a case where the air bubbles have been brought in together with the raw material liquid101from the raw material liquid supply line110. In addition, in a case where air bubbles have been brought into the second flow space202together with the poor solvent102from the poor solvent supply line120, the air bubbles pass through the porous membrane21, flow into the first flow space201, and then flow into the gas-liquid separation unit222. The valve controller224executes the operation of opening the degassing valve225once a gas pool is formed in the gas-liquid separation unit222in this manner and the liquid level detected by the liquid level gauge223becomes equal to or lower than a preset level. As a result, the gas accumulated in the gas-liquid separation unit222is discharged to the outside, and thus it is possible to suppress gas pool formation in the treatment container2and mix the raw material liquid101and the poor solvent102by using the entire surface of the porous membrane21. The mixed liquid that has flowed out of the treatment container2passes through the needle valve232provided on the extraction line230and flows into the aging pipe3side. A case where the needle valve232is blocked by the crystals of the target substance precipitated in the first flow space201at this time is detected as a rise in the pressure of the pressure gauge231, and thus it is possible to avoid damage to the equipment by stopping the diaphragm pumps111and121in that case. The induction time elapses in the process of the mixed liquid that has flowed into the aging pipe3flowing in the aging pipe3and the crystals of the target substance precipitate and grow. It should be noted that the crystals may be small to the point of being invisible after the elapse of the induction time. Accordingly, it may be difficult to pinpoint where the induction time elapses among the first flow space201, the extraction line230, and the aging pipe3. In this respect, in the crystallization apparatus of this example, it can be said that the aging pipe3fulfills the action of “precipitating and growing the crystals of the target substance” insofar as at least the mixed liquid is capable of flowing to the aging pipe3side without blocking the needle valve232and the crystals can be grown in the aging pipe3. The crystals of the target substance precipitated and grown in the aging pipe3are separated from the liquid in the solid-liquid separation unit31and are contained in a receiving container4. In addition, the liquid from which the crystals have been separated is treated as waste liquid. The crystallization apparatus according to the present embodiment has the following effects. The poor solvent102is mixed, via the porous membrane21, with the raw material liquid101flowing through the first flow space201in the treatment container2, and thus the crystals of the target substance can be precipitated in the mixed liquid continuously extracted from the treatment container2. Here, the operation of “continuously supplying” the raw material liquid101and the poor solvent102includes not only a case where the liquids101and102are continuously supplied at a constant flow rate but also a case where supply and stop at a predetermined flow rate and supply amount increase and decrease are intermittently repeated. In addition, the operation of “continuously extracting” the mixed liquid includes not only a case where the mixed liquid is continuously extracted at a constant flow rate but also a case where extraction and stop at a predetermined flow rate and extraction amount increase and decrease are intermittently repeated at regular intervals. In addition, the aging unit provided in the latter stage of the treatment container is not limited to cases of configuration by means of the aging pipe3illustrated in FIG.1and so on. For example, a container containing the mixed liquid may be disposed on the downstream side of the needle valve232and solid-liquid separation between crystals and waste liquid may be performed after the crystals of the target substance are precipitated and grown by the container being used as an aging unit. Further, variations of the crystallization apparatus and the treatment container2will be described with reference toFIGS.4to10. InFIGS.4to10, components common to the variations and the example described with reference toFIGS.1to3are denoted by the same reference numerals as those used in the drawings. FIG.4is a configuration example of an upflow-type crystallization apparatus in which the raw material liquid101and the poor solvent102are supplied from the lower portion side of the treatment container2and the mixed liquid is extracted from the upper portion side. In this example, the raw material liquid supply line110has a terminal end portion connected to the lower end portion of the treatment container2and the poor solvent supply line120has a terminal end portion connected to a side surface on the lower portion side of the treatment container2. On the other hand, the extraction line230is connected to the upper end portion of the treatment container2(upper end portion of the T-shaped connection221in a case where the exhaust unit22is provided). In a case where a liquid (such as ethanol) smaller in specific gravity than the raw material liquid101is mixed as the poor solvent102with the raw material liquid101that is, for example, an aqueous solution containing the target substance, mixing of the raw material liquid101and the poor solvent102may be facilitated by mixed liquid flow being formed from the lower portion side toward the upper portion side in the first flow space201. In this regard, the upflow-type crystallization apparatus illustrated inFIG.4may be employed in a case where the problem of crystal precipitation and deposition in the first flow space201described above is insignificant. FIG.5is a configuration example of a crystallization apparatus in which two sets of crystallization modules1aand1beach including a set of the treatment container2and the aging pipe3are connected in series. In this example, the liquid after the collection of the crystals of the target substance in the upstream-side crystallization module1ais re-supplied as the raw material liquid101to the downstream-side crystallization module1bvia a connection line130. In the crystallization module1b, the mixed liquid is obtained by the poor solvent102being further mixed with the raw material liquid101. In other words, in the crystallization module1bon the latter stage side (second or subsequent set), the mixed liquid that has flowed out of the aging pipe3of the crystallization module1aof the set upstream by one instead of the raw material liquid supply unit11and from which precipitated crystals have been removed is supplied as the raw material liquid101. It is possible to reduce a target substance loss by repeatedly performing continuous crystallization on the raw material liquid101. In a case where the purity of the crystals of the target substance collected in the downstream-side crystallization module1bis low in the above-described serial connection-type crystallization apparatus, high-purity crystals may be collected in the upstream-side crystallization module1aby the concentration of the target substance being increased by re-dissolution of the crystals in the raw material liquid101in the raw material liquid tank114of the upstream-side crystallization module1a. In addition, the number of sets of the crystallization modules connected in series is not limited to two and may be three or more. FIG.6is a configuration example of a crystallization apparatus provided with the cooling unit32cooling the mixed liquid flowing in the aging pipe3. The cooling unit32of this example is configured as a cylindrical cooling pipe through which cooling water flows and the aging pipe3is wound around the outer surface of the cylinder. By the temperature of the mixed liquid being lowered, the solubility of the target substance is lowered, and thus more crystals can be collected. It should be noted that the cooling unit is not limited to the case where the cooling unit is provided on the aging pipe3side. For example, the mixed liquid may be cooled at the outlet side part of the treatment container2. FIG.7is a configuration example of the treatment container2that includes an ultrasonic supply unit242supplying ultrasonic vibration via a rod-shaped ultrasonic vibrator241inserted in the first flow space201. Mixing of the raw material liquid101and the poor solvent102can be promoted by means of the ultrasonic vibration. The ultrasonic supply unit242and the ultrasonic vibrator241correspond to the mixing promotion unit of this example. Here, the configuration example of the mixing promotion unit is not limited to the examples of the ultrasonic vibrator241and the ultrasonic supply unit242. For example, a line mixer or a small stirrer may be disposed along the flow direction of the mixed liquid in the first flow space201. It should be noted that description of the exhaust unit22is omitted in relation to the treatment container2, a treatment container2a, and a treatment container2billustrated inFIGS.7to10. However, it is a matter of course that the exhaust unit22may be provided with respect to the treatment containers2,2a, and2b. FIG.8is an example in which the internal and external disposition relationship between the first flow space201and the second flow space202in the treatment container2illustrated inFIG.3is reversed. In other words, in this configuration, the second flow space202to which the poor solvent102is supplied is formed inside the porous membrane21and the first flow space201to which the raw material liquid101is supplied is formed between the porous membrane21and the treatment container2. In this example, the lower end side of the first flow space201is sealed and the mixed liquid is extracted from the extraction line230connected to the side surface on the lower portion side of the treatment container2. FIG.9illustrates a configuration example of the treatment container2ain which the first flow space201and the second flow space202are partitioned by means of a flat plate-shaped porous membrane21a. For example, an example is conceivable in which the inner portion of the plate-shaped treatment container2ahaving a hollow inner portion is partitioned by the single porous membrane21aas illustrated in the vertical cross-sectional side view ofFIG.9. FIG.10is an example in which a plurality of the first flow spaces201and a plurality of the second flow spaces202outside the plurality of first flow spaces201are configured by a plurality of the pipe-shaped porous membranes21being disposed in the treatment container2b. Each porous membrane21has a terminal end portion connected to a fixed pipe plate211, and a space212where the raw material liquid101flows into the treatment container2band the second flow space202and a space213where the mixed liquid flows out of the treatment container2bare partitioned by the fixed pipe plate211. A poor solvent containing fine crystals of a target substance capable of passing through pores of a porous membrane to be used may be used for each of the crystallization apparatuses and the treatment containers2,2a, and2bdescribed above. In addition, each of the crystallization apparatuses and the treatment containers2,2a, and2bdescribed above are also applicable to a technique for continuously performing reactive crystallization for precipitating crystals of a target substance by mixing a raw material liquid containing a raw material substance with a reaction liquid generating a target substance that is lower in solubility by reacting with the raw material substance. EXAMPLES Example 1 and Comparative Example 1 Continuous crystallization was performed by means of the crystallization apparatus described with reference toFIGS.1to3and by mixing between ethanol as a poor solvent and a saline solution-ethanol mixed liquid as a raw material liquid. A. Experimental Conditions Example 1 The porous membrane21made of porous ceramics and having an inner diameter of 9 mm, a length of 250 mm, and an average pore diameter of 1 μm was disposed in the treatment container2including a stainless steel pipe body having an inner diameter of 17.5 mm and a length of 296 mm. The aging pipe3including a transparent vinyl pipe having an inner diameter of 6 mm and a length of 5 m was disposed in the latter stage of the treatment container2. It should be noted that an exhaust pipe (not illustrated) instead of the exhaust unit22illustrated inFIG.1was connected to the side surface on the upper portion side of the treatment container2in the crystallization apparatus used in the experiment and the exhaust pipe includes a pressure gauge for exhaust pressure monitoring and an opening-closing valve for exhaust operation. 7.5 L of purified water was mixed with 7.5 L of ethanol having a purity of 99.5 wt %, 2 kg of salt was added, stirring and mixing were performed, and then a supernatant was obtained by the mixture being left as it is for 24 hours. The supernatant was used as the raw material liquid101. In addition, ethanol having a purity of 99.5 wt % was used as the poor solvent102. The raw material liquid101was supplied to the first flow space201of the treatment container2at a flow rate of 40 mL per minute, and the poor solvent102was supplied to the second flow space202at a flow rate of 3.2 mL per minute. Then, the precipitation and growth of salt crystals in the obtained mixed liquid was observed visually and photomicrographically. Comparative Example 1 The liquids101and102were mixed under the same conditions as in Example 1 except that the raw material liquid101and the poor solvent102were supplied to a stainless steel pipe body lacking the porous membrane21made of porous ceramics. B. Result of Experiment According to the result of the example, the mixed liquid of the raw material liquid101and the poor solvent102flowed out of the treatment container2and the mixed liquid flowed into the aging pipe3without blocking the needle valve232provided on the outlet side of the treatment container2for a long time. Meanwhile, the inner portion of the transparent aging pipe3was visually observed. As a result, it was possible to observe how salt crystals flowed while gradually becoming large (growing). The needle valve232was blocked115minutes after the initiation of the supply of each of the liquids101and102, and the experiment was finished with the pressure of the pressure gauge231risen.FIGS.11(a) to11(c)are photomicrographs of salt crystals in the mixed liquid collected 15 minutes, 65 minutes, and 115 minutes after the initiation of the supply of the liquids101and102, respectively. It could be confirmed that crystals having a crystal diameter of approximately 100 μm were obtainable. On the other hand, in the experiment according to the comparative example, crystals were generated immediately after the initiation of the supply of the raw material liquid101and the poor solvent102, the treatment container2itself was blocked, and it was impossible to continue with the experiment. According to the result of the example and the comparative example described above, it is possible to realize continuous crystallization while suppressing blocking of a flow path attributable to crystal precipitation by mixing the raw material liquid101and the poor solvent102by means of the porous membrane21. Example 2 Continuous crystallization was performed by means of the crystallization apparatus illustrated inFIG.12, which is a modification of the crystallization apparatus described with reference toFIGS.1to3, and by water as a poor solvent being mixed with an acetaminophen-water-isopropyl alcohol (IPA) mixed liquid as a raw material liquid. A. Experimental Conditions The porous membrane21made of porous ceramics and having an inner diameter of 9 mm, a length of 250 mm, and an average pore diameter of 1 μm was disposed in the treatment container2including a stainless steel pipe body having an inner diameter of 17.5 mm and a length of 296 mm, two units of the disposition were prepared, and the two units were connected in series (FIG.12). The aging pipe3including a transparent vinyl pipe having an inner diameter of 6 mm and a length of 25 m was disposed in the latter stage of the treatment container2of the second unit. It should be noted that an exhaust pipe128instead of the exhaust unit22illustrated inFIG.1was connected to the side surface on the upper portion side of the treatment container2, as illustrated inFIG.12, in the crystallization apparatus used in the experiment and the exhaust pipe128includes a pressure gauge126for exhaust pressure monitoring and an opening-closing valve127for exhaust operation. 1.25 L of purified water was mixed with 1.25 L of IPA having a purity of 99.7 wt %, 569 g of acetaminophen was added, stirring and mixing were performed, and then a supernatant was obtained by the mixture being left as it is for 24 hours. The supernatant was used as the raw material liquid101. In addition, purified water was used as the poor solvent102. The raw material liquid101was supplied to the first flow space201of the treatment container2at a flow rate of 10 mL per minute, and the poor solvent102was supplied to the second flow space202at a flow rate of 15 mL per minute. Then, the precipitation and growth of acetaminophen crystals in the obtained mixed liquid was observed visually and photomicrographically. B. Result of Experiment According to the result of the example, the mixed liquid of the raw material liquid101and the poor solvent102flowed out of the treatment container2and the mixed liquid flowed into the aging pipe3without blocking the needle valve232provided on the outlet side of the treatment container2for a long time. Meanwhile, the inner portion of the transparent aging pipe3was visually observed. Nevertheless, no acetaminophen crystals could be observed. A solution was collected by sampling being performed at the outlet of the aging pipe360 minutes after the initiation of the supply of each of the liquids101and102. As a result of the microscopical observation of the collected solution, it was observed that crystals of approximately 20 microns were contained. This experiment continued for approximately 4 hours until the raw material was used up, and a solution was collected by regular sampling at the outlet of the aging pipe3. The collected solution was microscopically observed, and it was continuously observed that crystals of approximately 20 microns were contained.FIG.13shows a photograph of acetaminophen crystals contained in the solution sampled at the outlet of the aging pipe3. REFERENCE SIGNS LIST 1a,1bCrystallization module101Raw material liquid102Poor solvent11Raw material liquid supply unit12Poor solvent supply unit2,2a,2bTreatment container201First flow space202Second flow space21,21aPorous membrane3Aging pipe
32,048
11857931
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A process for production of a nano-microemulsion system of plant oil triglycerides according to the present invention is performed as follows:(i) preparing a dispersed phase by heating plant oil triglycerides to a temperature between 60-100° C., the heating allows the dispersed phase to be combined with a better carrier.(ii) preparing a carrier by heating a mixture of propylene glycol monocaprylate and lecithin by a weight ratio of 5-6:1-1.5, most preferably 5:1, to a temperature between 60-100° C. under vacuum by a vacuum rotary evaporator from 30 to 60 minutes, then cooling to 30° C., followed by, respectively, ultrasonication within 30 minutes, stirring and heating between 60-100° C. within 30 minutes, and introduction of the solution into the vacuum rotary evaporator while stirring at 100° C. from 30 to 60 minutes. When used, the plant oil triglycerides are likely to be denatured by light, temperature, and often destroyed in the digestive tract. Therefore, there is a demand for a process for production of microdroplets containing oil triglyceride active agents of small size with biofilm, structural stability, nonaggregation, and high solubility. Since the microemulsion system according to the present invention is used in food and pharmaceutical industries, the carriers selected for use must be highly safe, and non-toxic with few side effects. Propylene glycol monocaprylate is a mixture of propylene glycol monoester and fatty acid diester composed mainly of caprylic acids. The contents of the monoester and the diester vary for the two types (Type I and Type II) of propylene glycol monocaprylate with certified safety records. Having properties of a specific soluble carrier for injections, (pharmaceutical and veterinary) solutions, and agents for adjustment and stabilization of viscosity, and for production of microemulsion liquids, propylene glycol monocaprylate helps emulsify and form good microemulsion systems, allowing for an increase in absorption. However, if the carrier is used on the skin in high dosages, it will cause irritation. Therefore, in order to form a microemulsion system that is stable and safe to the users, so that the product can be applied on the skin and administered orally, according to the investigation, the inventors combined propylene glycol monocaprylate with lecithin by a weight ratio of 5-6:1-1.5, most preferably 5:1. Lecithin is a very popular food additive and has been acknowledged as safe to human in Europe. Lecithin is a type of phospholipid by nature, which is found in every cell of the human body. The chemical formula of lecithin shows that lecithin is a fat, of which a structural component, however, is water soluble. This allows lecithin to emulsify plant oil triglycerides, and advocate dispersion thereof in water. If the ratio of propylene glycol monocaprylate to lecithin is less than 5:1.5, it is possible that the resulting carrier cannot carry the whole oil amount, leading to non-uniform droplet sizes, and the resulting system being unstable and likely to have layer separation. However, if the said ratio is more than 6:1, the lecithin amount will remain in the system, which goes wasted and also makes the system less stable. In the step of preparing the carrier, the present invention uses propylene glycol monocaprylate and lecithin by a studied ratio that is different from those used in known solutions. In particular, the solution mentioned in US20170112764A1 only relates to a process for determination of the weight ratio of the aqueous phase to the oil phase, which solution is different from that of the present invention, that mentioned in EP2659903B1 to form a microemulsion system for use of cyclosporin A for ophthalmic purpose, which is different from the objective of the present invention to produce microemulsion system of plant oil triglycerides, and that mentioned in CN105476959A of using OvumGallus domesticus Flavuslecithin for high speed breakdown until the solution is homogenously mixed. Such breakdown makes it difficult to produce uniform molecules, is time-consuming, and affects the quality of lecithin (since lexithin is easy to denature). The use of propylene glycol monocaprylate and lecithin by a ratio studied by the inventors under said conditions helps reduce the impact on the structure of lecithin, while simultaneously propylene glycol monocaprylate also helps increase the capability of carrying active agents, and the loading efficiency compared to the use of lecithin alone.(iii) adding the carrier to the dispersed phase by a weight ratio of 3-4:1-1.5, most preferably 3:1, wherein the temperature of the dispersed phase after the addition is continuously maintained between 60-100° C. while simultaneously stirring at 400-800 rpm under vacuum from 30 to 60 minutes, followed by introduction of the whole mixture through the high-pressure microjet homogenizer. By the weight ratio of the carrier to the dispersed phase being 3-4:1-1.5, most preferably 3:1, the reaction yield is most optimal, ensuring that all substances in the dispersed phase are fully carried, and that there is no carrier left in the system. The incorporation of the carrier now as a mixture of propylene glycol monocaprylate and lecithin in specialized processing steps helps achieve the most optimal contact efficiency and vesiculation of the dispersed phase. The use of the high-pressure microjet homogenizer helps improve the vesiculation efficiency, while simultaneously improving the durability of the biofilms, allowing the lipophilic heads to be fully exposed, and form optimal bonds. The inventors have studied to create a microjet nozzle for integration thereof into the machine in order to not only utilize the high-pressure homogenization to produce droplets, but also allow the droplets to disperse right after formation thereof to avoid droplet aggregation before being added the expanding agents in the next step. This is highly important in improving the stability of the nano system, thereby allowing an increase in yield and stability duration of the system. (iv) adding Tween 80 and Tween 60 to the solution mixture obtained in step (iii) by a weight ratio of 3-4:1-1.5:1-1.5, most preferably 3:1:1, wherein the temperature of the dispersed phase after the addition is continuously maintained between 60-100° C. while simultaneously stirring at 400-800 rpm under vacuum from 30 to 60 minutes. By theoretical and empirical studies, the inventors have found that in order to prepare plant oil nano-triglyceride which dissolves well in water, this emulsion needs to have the form of an oil-in-water emulsion. The selection of an emulsifier to improve the stability of the microemulsion system is based on the properties of the microemulsion system (e.g., forms of oil-in-water microemulsion system, water-in-oil microemulsion system, etc.). Therefore, the inventors selected the emulsifier Tween, particularly a combination of Tween 80 (HLB—hydrophilic-lipophilic balance: 15) and Tween 60 (HLB: 14.5), since Tween is a hydrophilic, nontoxic, and highly safe. The addition of Tween 80 and Tween 60 to the solution mixture obtained in step (iii) by a weight ratio of 3-4:1-1.5:1-1.5, most preferably 3:1:1, ensures that the HLB of the emulsion is suitable for it to disperse in the aqueous phase, wherein if the ratio is less than 3:1.5:1.5, the emulsion becomes lipophilic and will make it difficult to disperse well in water, and wherein if the ratio is more than 4:1:1, the emulsion becomes more hydrophilic but less stable. Since the emulsifier Tween is a molecule with two distinct moieties, a lipophilic moiety and a hydrophilic moiety, it is able to form bonds with oil and the carrier mixture. The lipophilic moiety of Tween forms bonds with plant oil, and the hydrophilic moiety of Tween forms bonds with the hydrophilic moiety of the carrier mixture of propylene glycol monocaprylate and lecithin, which produces microdroplets of plant oil triglyceride nano-emulsions of a structure that protects the activity of plant oil triglycerides well. According to the most related reference solution disclosed in CN105476959A, only Tween 80 was used, so the dispersion efficiency was not high enough, and the content of dispersed substances was up to only 10%. However, for the process of the present invention, the incorporation of Tween 80 and Tween 60 improves the dispersibility of the compounds, and increases the contents and stability of the compounds. (v) forming a nano-microemulsion system of plant oil triglycerides by cooling the obtained mixture to 25° C., followed by homogenization of the mixture by ultrasonication using a homogenizer (Ultrasonication) from 30 to 60 minutes to achieve a droplet size of less than 100 nm, quality control of the resultant product by dissolution thereof in water and measurement of the transparency, in which if the required transparency is not met, continue to heat and measure the transparency every 30 minutes until the required transparency is met, then stop the reaction, and lower the temperature slowly until the temperature reached 50° C. or lower, preferably to room temperature, and emulsification of the solution mixture in an emulsifying device at a stirring rate between 400-800 rpm at this temperature to obtain a nano-microemulsion system of plant oil triglycerides. Nano-droplets tend to agglomerate, thus to disperse these nano-droplets, it is necessary to provide enough energy to break the bondings. The use of the homogenizer as an effective means of dispersing the nano-droplets and reducing the nano-droplet size produces droplets of a smaller and more uniform size. The dispersion and disruption of nano-droplet agglomeration are the result of gas corrosion by ultrasound. As the ultrasound propagates through the solvent, it continuously forms alternating cycles between high and low pressures, which affects the binding forces of the nano-droplets. At the same time, when many bubbles burst, this puts a great pressure on the nano-droplet beams, making it easy for them to get separated easily. From the experiments, the inventors identified the timelines of ultrasonication to help form a droplet structure that meets the product requirements. By theoretical and empirical studies, the inventors have found that to produce a plant oil triglyceride nano-emulsion with good water solubility, the microemulsion system needs to be in the form of an oil-in-water emulsion. The selection of an emulsifier to improve the stability of the microemulsion system is based on the properties of the microemulsion system (e.g., the forms of oil-in-water microemulsion system, water-in-oil microemulsion system, etc.). The microemulsion system obtained by a process according to the present invention has a pH of 7-7.4. With this pH value, the microdroplets are stable since in this neutral environment, the bonds between the plant oil triglyceride and the carrier are maintained in the dispersion process, while in the microemulsion system having a pH<7, these bonds weaken leading to the destruction of plant oil triglyceride nano-droplets in the digestive tract. The nano-microemulsion system of plant oil triglycerides obtained by a process according to the present invention, which has a hydrophilic-lipophilic balance HLB of 13-18, is a hydrophilic microemulsion system. This microemulsion system consists of hydrophilic, and non-aggregated plant oil triglyceride-containing microdroplets, wherein the droplets are uniform in size and stable, which can increase water solubility, thereby improving its applicability to many different types of products. When comparing the efficiency of the present invention with other most related references, the objectives of the solutions disclosed in US20170112764A1 and EP2659903B1 are different from that of the inventors. Meanwhile, the solution disclosed in CN105476959A employed a high-speed mixer at 100,000 rpm under 5-minute mixing for 3 successive times under 103 Mpa, and a high-pressure followed by homogenization of compounds for 3 successive times. A process that employs very high-speed stirring at 100,000 rpm, homogenization at 103 Mpa, and multiple repetitions with this power is not applicable on a large scale since the manufacturing machines would not meet this power, and at the same time the process would generate a great amount of heat, affecting the quality of the triglyceride. However, in the present invention, the obtained mixture homogenized by ultrasonic waves under cold conditions ensures the quality of triglyceride, and the inventors have studied to combine ultrasonication with emulsification to make it applicable to the process for industrial production in manufacturing instead of using only for experimental models. EXAMPLES Example: Producing 200 g of Nano-Microemulsion System of Plant Oil Triglycerides Preparation of a dispersed phase: 10 g of plant oil triglycerides was subjected to stirring at 400 rpm, and heating at 50° C. until uniform. Preparation of a carrier: a mixture of 25 g of Capryol 90 (Propylene Glycol Monocaprylate) and 5 g of lecithin was subjected to heating to 60° C. in 40 minutes. 30 g of the carrier was added to 10 g of the dispersed phase prepared above. Continue heating the dispersed phase to 60° C. while stirring at 600 rpm under vaccume for 40 minutes. Tween 80 (sinopol 85 USP) and Tween 60 were added to the mixture in step (iii) by a weight ratio of 3:1:1 in correspondence with 120 g of Tween 80:40 g Tween 60:40 g of the above mixture, wherein the temperature of the dispersed phase after the addition was continuously maintained between 60-100° C., and stirred at 600 rpm under vacuum in 40 minutes to obtain 200 g of mixture. The obtained mixture was cooled to 25° C. using a homogenizer (Ultrasonic homogenizer) with a power of 200-400 W to homogenize the solution. The ultrasonication duration would affect the droplet size, so in order to achieve droplets of 100-500 nm ultrasonication was performed from 10 to 20 minutes; to achieve droplets of less than 100 nm, ultrasonication was performed from 30 to 60 minutes. The quality of the resultant product was controlled by dissolution thereof in water and measurement of the transparency, in which if the required transparency had not been met, the product would be heated continuously and the transparency would be measured every 30 minutes until the required transparency was met, then the reaction was stopped, and the temperature was lowered slowly until it reached 50° C. At 50° C., emulsification was performed on the solution mixture at 500 rpm for 30 minutes. Before filling, 200 g of nano-microemulsion system of plant oil triglycerides with good water dispersibility was collected. By UV-vis spectrometry, the inventors found that the positions of the peaks of the plant oil triglyceride ingredients and the peaks of the nano-microemulsion system of plant oil triglycerides matched perfectly. This shows that the microemulsion system obtained by the process according to the present invention was able to maintain its structure and the activity of the plant oil triglycerides during nanonization. The UV-Vis spectrometry was used to quantify the plant oil triglyceride content in the microemulsion system. The results show that the concentration of the essential oil in the nano-microemulsion system of plant oil triglycerides fell between 20-25%. The measurement of the size of plant oil triglyceride nano-droplets was conducted by Transmission Electron Microscopy (TEM) as shown inFIG.2. The figure shows that the droplet size of between 10-50 nm accounts for almost the highest percentage as much as 100% of the solution. The droplet size was measured by Dynamic Light Scattering (DLS): The suspended droplets in a liquid are constantly subjected to random motions, and the droplet size directly affects the droplet velocity. Smaller droplets move faster than larger ones. In DLS, light passes through the sample, and the scattered light is detected and recorded at a certain angle. Zeta potential or dynamic potential: The potential between the dispersed phase and the dispersion medium. The table below shows the data measurements by Dynamic Light Scattering (DLS): Plant oil triglyceridenano-emulsion withtreatments toachieve a droplet size ofDiameter%Widthless than 100 nm(nm)Intensity(nm)Average droplet sizePeak 122.0296.74.791(d · nm): 22.02Pdl: 0.136Peak 244183.3912.0Blocking rate: 0.939Peak 30.000.000.00Evaluation result: good Analysis: Data from this table reflects an average droplet size of 22.02 nm, accounting for 96.7% intensity of the system. ZetaSizeSizepotentialStability(nm, TEM)(nm, DLS)(mV)(month (s))Water solubility10-5010-50−40>24good solubility inwater; afterdissolution in water,the emulsion wasstable >60 days From the above results, it was shown that the use of the carrier Capryol 90 (Propylene Glycol Monocaprylate) and lecithin in combination with Tween made it possible to obtain the microemulsion system composed of microdroplets of 10-50 nm, good stability (>24 months), good water solubility, and after the dissolution thereof in water, the emulsion was stable for >60 days. A large Zeta potential value indicated that the charged droplets were large and the emulsion tended to be stable. FIG.1shows the comparison of the water dispersibility of between known plant oil triglycerides and a plant oil triglyceride nano-emulsion obtained by a process according to the present invention, in which Vial A shows the known plant oil triglycerides dispersed in water, and Vial B shows the plant oil triglyceride nano-emulsion dispersed in water, obtained by a process according to the present invention. The plant oil triglyceride nano-emulsion obtained by a process according to the present invention completely dispersed in water to produce a transparent, homogeneous solution, while the known plant oil triglycerides were water insoluble and floated on the surface. FIG.2represents a TEM spectrum by size distribution of plant oil triglyceride nano-droplets obtained by a process according to the present invention, which shows the average droplet size of 10-50 nm. Advantageous Effects of the Invention The process for production of the nano-microemulsion system of plant oil triglycerides according to the present invention has succeeded in producing a microemulsion system composed of plant oil triglyceride nano-microdroplets of 10-50 nm with uniformity, and good solubility in water while maintaining its structure, and the activity of plant oil triglycerides during nanoization. The compounds used during the production of plant oil triglyceride nano-emulsion have good dispersibility in water, good safety records, and no toxicity with few side effects. Therefore, the nano-microemulsion system of plant oil triglycerides obtained from the process according to the present invention is safe to use. The process according to the present invention is simple, easy to implement, and suitable for the practical conditions in Vietnam.
19,135
11857932
DETAILED DESCRIPTION The disclosure is therefore based on the task of creating a correspondingly improved valve arrangement. The mixing valve according to the disclosure is suitable for mixing several coating components to a multi-component mixture. For example, the mixing valve according to the disclosure can be used to mix the masterbatch and hardener of a two-component paint (2-component paint). However, the mixing valve according to the disclosure can also be designed for mixing other coating components, e.g. for mixing components of an adhesive or a thick material. In accordance with the state of the art, the mixing valve according to the disclosure has two coating inlets in order to supply the various coating components (e.g. hardener and master batch). In addition, in accordance with the state of the art, the inventive mixing valve has two coating valves to control the flow of coating agent through the two coating inlets. Furthermore, in accordance with the state of the art, the inventive mixing valve also has a coating agent outlet in order to discharge the multi-component mixture in a specific outflow direction. The inventive mixing valve is now characterized by a special design of the first coating agent valve and/or the second coating agent valve. Thus at least one of these coating agent valves is designed as a rotary slide valve and has two plane-parallel valve discs which can be rotated relative to each other about an axis of rotation in order to control the respective coating agent flow as a function of the angular position of the valve discs relative to each other. An advantage of the mixing valve is the so-called zero closure of the respective coating component by a rotary movement (shearing) of the valve discs relative to each other. A further advantage of the mixing valve according to the disclosure is the very fine adjustment possibility even with very small coating agent flows, as will be explained in detail below. In general, it should be mentioned that the mixing valve according to the disclosure allows a dynamic, variable adjustment of the mixing ratio of the different coating components. Another advantage of the mixing valve according to the disclosure is the easy maintenance. Furthermore, the disclosure also enables simple nozzle replacement, which may even be possible without tools and is described in detail below. In a variant of the disclosure, the axis of rotation of the valve disks is essentially parallel to the outflow direction at the coating agent outlet. The valve discs are thus arranged with their disc plane transverse to the direction of flow. In this variant of the disclosure, the two coating components are usually combined downstream behind the downstream valve disc. This is distinguished from a combination of the various coating components within one of the valve disks, as is possible with another disclosure variant, which is described in detail below. In this first disclosure variant, the two coating agent inlets are preferably arranged next to each other with regard to the outflow direction. The rotatable valve discs are preferably rotatable about two axes of rotation, which are aligned parallel to the direction of outflow and arranged next to each other. The rotatable valve discs can therefore each be rotated about their own axis of rotation, with the axes of rotation of the individual valve discs preferably running parallel to each other and also parallel to the outflow direction. With this disclosure variant, the coating agent inlets on the one hand and the coating agent outlet on the other hand are preferably located on opposite sides of the valve discs, in each case in relation to the disc plane. In another variant of the disclosure, on the other hand, the axis of rotation of the valve discs runs transversely, in particular at right angles, to the outflow direction at the coating outlet. The valve discs are thus aligned with their disc plane parallel to the outflow direction. With this disclosure, the rotary axes of the rotatable valve discs can run coaxially. In the preferred example of this disclosure, a rotatable valve disc is arranged on both sides of a central, stationary valve disc. Here the coating agent inlets are preferably arranged on opposite sides of the valve disks. This means, for example, that one coating component is fed from the left, while the other coating component is fed from the right. With this variant of the disclosure, the two coating components can be combined within the stationary valve disc. The stationary central valve disc is thus a component of the two coating agent valves. In the preferred example of the disclosure, the downstream valve disc is stationary, while the upstream valve disc is rotatable. Alternatively, it is also possible for the downstream valve disc to be rotatable while the upstream valve disc is stationary. In the upstream valve disc and also in the downstream valve disc there is in each case at least one through-hole, wherein the through-holes in the two valve discs can be brought more or less into alignment by a relative rotational movement and then form a free valve cross-section which is dependent on the angle of rotation of the two valve discs relative to one another. It should be mentioned here that the disclosed mixing valve has a specific valve characteristic curve, whereby the valve characteristic curve reflects the relationship between the angle of rotation on the one hand and the free valve cross-section on the other. By appropriately shaping the through holes in the two valve disks lying on top of each other, a non-linear valve characteristic can be achieved with the disclosure of the mixing valve. In one example of the design, this valve characteristic curve is progressive. This means that the free valve cross-section changes relatively little at the beginning depending on the angle of rotation, which then allows very fine dosing with small coating agent flows. However, with increasing angle of rotation and thus also increasing coating agent flow, the valve characteristic becomes steeper so that a maximum free valve cross-section can be realized within the available angle of rotation. The non-linearity of the valve characteristic curve can—as already briefly mentioned—be achieved by a suitable shaping of the through-holes in the valve discs. For example, the through-hole in one of the valve disks can become narrower in the circumferential direction, for example in the form of a drop, in order to achieve the desired non-linear dependence of the free valve cross-section on the angle of rotation. In addition, the through-hole in the downstream valve disc can also narrow in the direction of flow, especially conically. It is also possible that the through-hole in the downstream valve disc is angled in the circumferential direction so that the first or second coating agent exits the through-hole with a swirl in the circumferential direction. The disclosure also allows the mixing valve to have an integrated outlet nozzle which is fed with the multi-component mixture from the coating outlet. The outlet nozzle may be made of plastic, for example plastic injection moulding, which allows simple and cost-effective production. The outlet nozzle has a flow channel which can be shaped in such a way that it gives the multicomponent mixture flowing through it a twist. The multicomponent mixture then flows out of the outlet nozzle with a corresponding twist. It should also be mentioned that the outlet nozzle may be attached to the mixing valve so that it can be replaced. The outlet nozzle can therefore be manufactured as an exchange part. The mixing valve in accordance with the disclosure enables the outlet nozzle to be changed without tools, for example by means of a bayonet lock or a manually operated cap nut. It should also be mentioned that the mixing valve can also have a flushing agent inlet to supply flushing agent. In this case, the valve disc can have s a separate through-hole for the flushing agent. Depending on the angle of rotation of the valve disc, either coating agent or flushing agent can then be allowed through. It should also be mentioned that the coating agent valves are preferably adjusted by an electric motor which rotates the valve discs relative to each other. Two electric motors can also be used here, which make it possible to rotate the valve discs of the coating agent valves independently of each other, which enables the mixing ratio to be adjusted by means of a suitable control of the electric motors. Finally, it should be mentioned that the disclosure does not only claim protection for the mixing valve described above. Rather, the disclosure also claims protection for a complete coating robot with such a mixing valve or for a complete painting or coating system with at least one such mixing valve. FIGS.1A and1Bshow different views of an initial example of a mixing valve1that can be used, for example, in a paint shop for painting vehicle body components in order to mix different coating components of a thick material. The mixing valve1has two coating agent inlets2,3, through which the two coating agent components are fed separately from each other. In addition, the mixing valve1has a coating agent outlet4, whereby the multi-component mixture consisting of the two coating agents is discharged via the coating agent outlet4. Between the two coating agent inlets2,3on the one hand and the coating agent outlet4on the other hand there are two coating agent valves which control the coating agent flow through the coating agent inlet2or3. The coating agent valve between the coating agent inlet2and the coating agent outlet4has a fixed valve disc5and a rotatable valve disc6. The other coating fluid valve between the coating fluid inlet3and the coating fluid outlet4also has a stationary valve disc7and a rotatable valve disc8. There are through holes9,10,11,12in the valve discs5-8. The through-holes9,11can be brought more or less into line by a relative rotary movement of the two valve discs5,6relative to each other, so that the freely flowable valve cross-section depends on the angle of rotation of the valve disc6relative to the valve disc5. The same applies to the through holes10,12in the two valve discs7,8, which can also be rotated relative to each other. It should be noted that the angle of rotation of the valve discs5,6relative to each other can be adjusted independently of the angle of rotation of the valve discs7,8relative to each other. This makes it possible to adjust the mixing ratio of the coating components to be applied very precisely and variably by turning the valve discs6,8appropriately. In addition, the coating agent flow of the multi-component mixture, which is discharged via the coating agent outlet4, can also be adjusted. The mixing valve1according to the disclosure thus allows on the one hand an adjustment of the mixing ratio and on the other hand an adjustment of the discharge quantity. It should also be mentioned that the valve discs5-8are accommodated in two housing parts13,14, which is only shown schematically here. In addition, it should be mentioned that the drive of the rotating valve discs6,8is not shown in the drawing. It should also be mentioned that the mixing valve1has an outlet nozzle15which is fed with the multi-component mixture from the coating agent outlet4. The multi-component mixture flows through a nozzle channel16in the outlet nozzle15. The nozzle channel16is shaped in such a way that the multi-component mixture flowing through receives a twist, as indicated in the drawing by the spiral line in the nozzle channel16. It should also be noted that through holes9,10are drop-shaped in the circumferential direction, as shown inFIG.1B. This leads advantageously to a non-linear, progressive valve characteristic curve, as shown inFIG.3. It can be seen from the drawing that the free opening cross-section A of the mixing valve1at a small angle of rotation a initially has only a small gradient depending on the angle of rotation a, which enables very fine dosing. As the angle of rotation a increases, the gradient of the valve characteristic curve then becomes steeper so that within the available angle of rotation a maximum free valve cross-section Amax can also be achieved. FIG.2shows a variation of the execution example according toFIGS.1A and1B, so that the above description is referred to in order to avoid repetitions, whereby the same reference signs are used for the corresponding details. A special feature of this design example is that the rotatable valve discs6,7are arranged on both sides of a central, stationary valve disc17. The stationary valve disc17is thus a component of both coating agent valves. A further feature of this design example is that the two rotatable valve discs6and8can be rotated about axes of rotation which run coaxially and at right angles to the outflow direction18. In addition, two electric motors19,20are shown here, which serve to rotate the two rotatable valve discs6,8relative to the central, stationary valve disc17. In this design example, the various coating components are combined within the central, stationary valve disc17. It should also be mentioned that the outlet nozzle15is attached to a housing22of the mixing valve1by means of a cap nut21. The description of the second example also shows that the valve discs5-8do not have to be exactly plate-shaped. Rather, it is sufficient if the valve discs5-8run plane-parallel on their side surfaces facing each other in order to enable a rotary movement relative to each other. The disclosure is not limited to the preferred design examples described above. Rather, a large number of variants and modifications are possible which also make use of the disclosure idea and therefore fall within the scope of protection. In particular, the disclosure also claims protection for the subject-matter and the features of the dependent claims independently of the claims referred to in each case and in particular also without the characteristic feature of the main claim.
14,193
11857933
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS Referring now to the drawings, and more particularly toFIGS.1A-1F,FIG.1Ashows an isometric view of an embodiment of the present mixing apparatuses with integrally formed differential pressure ports and an injection inlet;FIG.1Bshows an inlet end view of the mixing apparatus ofFIG.1A;FIG.1Cshows an outlet end view of the mixing apparatus ofFIG.1A;FIG.1Dshows a cross-sectional side view of the mixing apparatus ofFIG.1Ataken along a plane passing through differential pressure ports defined by the mixer body;FIG.1Eshows a cross-sectional side view of the mixing apparatus ofFIG.1Ataken along a plane passing through an injection passage defined by the mixing body;FIG.1Fshows a perspective view of the mixing apparatus ofFIG.1A; andFIGS.3A,3B, and3Crespectively show perspective, side, and bottom views of the mixing apparatus ofFIG.1Aassembled between two flanges. In some embodiments, such as the one shown inFIGS.1A-1FandFIGS.3A-3C, mixing apparatus100comprises: a mixer body104having an exterior surface104aand an interior surface104b. As shown, mixer body104defines an inlet108and an outlet112. In the depicted embodiment, interior surface104bdefines a flow passage116extending between inlet108and outlet112to permit a first fluid to flow sequentially through inlet108, flow passage116, and outlet112. As best illustrated inFIGS.1D and1E, in a direction120of flow, a first portion116aof flow passage116narrows from inlet108to a point of constriction116b; and, in direction120, a second portion116cof flow passage116expands from point of constriction116bto outlet112. As shown, a channel axis124extends longitudinally through the center of first and second portions116a,116cof flow passage116. The narrowing of first portion116areduces the available cross-sectional area in passage116for fluid to flow, and thereby accelerates the fluid in the direction of flow (120). Conversely, the expansion of second portion116cincreases the available cross-sectional area in passage116for fluid to flow, and thereby permits the fluid to decelerate. In the depicted embodiment, flow passage116has a substantially circular cross-section such that first portion116anarrows linearly to define a frusto-conical profile, and second portion116cexpands linearly to define a second frusto-conical profile. As shown inFIGS.1D and1E, each of first and second portions116a,116cdefine a linear cross-sectional profile that is angled relative to axis124. For example, first portion116amay taper linearly toward axis124at an angle of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 degrees relative to axis124; and/or second portion116cmay taper linearly away from axis124at an angle of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 degrees relative to axis124. In some embodiments, such as the one shown, first portion116anarrows linearly toward axis124in direction120at a greater angle relative to axis124, than the angle relative to axis124at which second portion116cexpands linearly away from axis124in direction120. In the embodiment shown; mixer body104also defines a plurality of support arms128a,128b,128c, that are unitary (i.e., formed as a single, monolithic piece of material) with the mixer body104and that extend radially inward from interior surface104b. In this embodiment, arms128a,128b,128care disposed in first portion116aof passage116, but in other embodiments, may be disposed in second portion116b(e.g., with a central portion extending forward to support the flow member described below). In the embodiment shown, mixing apparatus100also comprises a substantially conical flow member132coupled to support arms128a,128b,128c. In this embodiment, flow member132has a leading end132a, a base132bopposite the leading end132a, and a peripheral surface132cextending between the leading end132aand the base132b. A flow axis136extends through respective centers of leading end132aand base132b, and flow member132is coupled to support arms128a,128b,128c, such that leading end132afaces inlet108of mixer body104, base132bfaces outlet112of the mixer body104, and flow axis136is substantially parallel to (e.g., collinear with, as shown) channel axis124. In other embodiments, the flow member may be substantially pyramidal. In some embodiments, such as the one shown, mixer body104defines at least one body injection passage144aextending from an injection inlet140aon exterior surface104aof mixer body104, through one of the support arms (e.g.,128a,128b,128c). Additionally; flow member132defines a flow member injection passage148extending through at least a portion of flow member132to an injection outlet156defined at leading end132or peripheral surface132cof flow member132(e.g., at leading end132, as shown). Flow member132is coupled to the support arms (e.g.,128a,128b,128c) such that injection inlet140ais in fluid communication with injection outlet156via mixer body injection passage144aand flow member injection passage148. For example, in the embodiment shown, flow member132is unitary with support arms (128a,128b,128c) and mixer body104, such that mixer body injection passage144aand flow member injection passage148are two portions of a common passage. In other embodiments, part or all of the flow member132may be separately coupled to the support arms (e.g.,128a,128b,128c) to also bring the flow member injection passage148into fluid communication with the mixer body injection passage144a. In the embodiment shown, mixer body104also defines two differential pressure ports176a,176bextending from two pressure outlets180a,180bon exterior surface104aof mixer body104. In some embodiments, first differential pressure port176ais configured to be in fluid communication with first portion116aof passage116and second differential pressure port176bis configured to be in fluid communication with second portion116cof passage116. In other embodiments, injection outlet156may be disposed on peripheral surface132cof flow member132. For example, the mixer body injection passage may extend radially inward through support arm128a, and flow member injection passage may continue radially across the flow member to an injection outlet on the peripheral surface circumferentially between support arms128band128c(i.e., rather than extending longitudinally to the leading end). Other embodiments, such as embodiment100ashown inFIG.2, may include multiple injection outlets172a,172b, and172con the peripheral surface of flow member132in addition to injection outlet156. For example, one injection passage (e.g.,144a,144b, or144c) extending through each support arm128a,128b,128c, to a respective injection outlet172a,172b,172c, on the peripheral surface of the flow member between the other two support arms. In some such embodiments, the injection passages144a.144b.144c. may intersect (e.g., within the flow member) so that all injection passages are in fluid communication; in which case, two of the injection inlets (e.g.,140band140cas depicted) may be plugged outward of the point of intersection with inlet plugs168a,168bso that fluid may be injected to all of the injection outlets via a single injection inlet (e.g.,140aas depicted). As shown, mixing apparatus100does not include pipe flanges, and the longitudinal ends of mixer body104that are not threaded. Instead, in the depicted embodiment, mixer body104is configured to be clamped between two pipe flanges (as described below with reference toFIGS.3A-3C). To facilitate such assembly, the mixing apparatus can include two or more flanges. For example, in the depicted embodiment, mixing apparatus100includes flanges164a,164b, and164cthat extend radially outward from exterior surface104aof mixer body104. In this embodiment, two of the flanges164b,164care longitudinally spaced along exterior surface104aof the mixer body104. As shown, flanges (e.g.,164a,164b,164c) can define a plurality of guide openings. For example, flanges164b,164cdefine a plurality of pairs of guide openings (e.g.,170band170c), with each pair of guide openings (170b,170c) being aligned along a respective guide axis174that is parallel to the channel axis124to receive a bolt that resists rotational misalignment of the mixer relative to the flanges. Referring now toFIGS.4A-4G,FIG.4Ashows an isometric, cutaway view of another embodiment of the present mixing apparatuses with the inlet end facing toward the viewer.FIG.4Bshows an isometric, cut away view of the mixing apparatus ofFIG.4Awith the outlet end facing toward the viewer.FIG.4Cshows a cross-sectional side view of the mixing apparatus ofFIGS.4A and4Bwith the longitudinal ends coupled to flanges on either end.FIG.4Dshows an isometric view of the mixing apparatus ofFIGS.4A and4Bwith the longitudinal ends coupled to flanges on either end.FIG.4Eshows an end view of a flange coupled to the inlet end of the mixing apparatus ofFIGS.4A and4B.FIG.4Fshows an end view of a flange coupled to the outlet end of the mixing apparatus ofFIGS.4A and4B.FIG.4Gshows an exploded view of the mixing apparatus ofFIGS.4A and4Band two flanges. In some embodiments of the present mixing apparatuses, longitudinal ends340a,340bof mixer body304define threads configured to receive a pipe fitting and hammer union washer or flange fitting. In other embodiments of the present mixing apparatuses, such as the one shown inFIGS.4A-4G, longitudinal ends340a,340bmay be configured to be butt-welded or tapped. In some embodiments of the present mixing apparatuses, longitudinal ends340a,340bof mixer body304define male threads. In some embodiments of the present mixing apparatuses, the longitudinal ends340a,340bof mixer body304define female threads. As shown inFIGS.4A and4B, mixer body304has an exterior surface304aand interior surface304b, where the mixer body304defines at least one body injection passage324extending from an injection inlet320on exterior surface304aof mixer body304, through one of the support arms (e.g.,356a,356b). Mixer body304also defines longitudinal ends340a,340b, which may be configured to be male or female threaded, butt-welded, and/or tapped. Additionally; flow member332defines a flow member injection passage328extending through at least a portion of flow member332to an injection outlet336defined at the leading end or peripheral surface of flow member332(e.g., at the leading end, as shown). Flow member332is coupled to the support arms (e.g.,356a,356b) such that injection inlet320is in fluid communication with injection outlet336via mixer body injection passage324and flow member injection passage328. For example, in the embodiment shown, flow member332is unitary with support arms356a,356band mixer body304, such that mixer body injection passage324and flow member injection passage328are two portions of a common passage. In other embodiments, part or all of flow member332may be separately coupled to the support arms (e.g.,356a,356b) to also bring flow member injection passage328into fluid communication with mixer body injection passage324. As best illustrated inFIGS.4C and4D, and further depicted inFIGS.4E-4G, in some embodiments of the present mixing apparatuses, mixing apparatus300further comprises flange fittings352a,352bcoupled to longitudinal ends340a,340b, each flange comprising a pressure port344a,344bin fluid communication with passage316via pressure outlet348a,348b. Longitudinal ends340a,340bmay be configured to be threaded male ends, threaded female ends, butt-welded, and/or tapped ends coupled to flange fittings352a,352b. In this embodiment, mixing apparatus300is configured similarly to the mixing apparatus ofFIGS.1D and1E, where flow passage316has a substantially circular cross-section such that first portion316anarrows linearly to define a frusto-conical profile, and second portion316cexpands linearly to define a second frusto-conical profile. As shown inFIG.4C, each of first and second portions316a,316cdefine a linear cross-sectional profile that is angled relative to axis364. For example, first portion316amay taper linearly toward axis364at an angle of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 degrees relative to axis364; and/or second portion316cmay taper linearly away from axis364at an angle of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 degrees relative to axis364. In some embodiments, such as the one shown, first portion316anarrows linearly toward axis364in direction368at a greater angle relative to axis364, than the angle relative to axis364at which second portion316cexpands linearly away from axis364in direction368. In the embodiment shown, mixer body304also defines a plurality of support arms356a,356b, as best illustrated inFIGS.4E and4F, that are unitary (i.e., formed as a single, monolithic piece of material) with mixer body304and that extend radially inward from the interior surface of the mixer body. As shown inFIG.4C, support arms356a,356bare disposed in first portion316aof passage316, but in other embodiments, may be disposed in second portion316b(e.g., with a central portion extending forward to support flow member332). In the embodiment shown, mixing apparatus300also comprises a substantially conical flow member332coupled to support arms356a,356b. In this embodiment, flow member332has a leading end332a, a base332bopposite the leading end332a, and a peripheral surface332cextending between the leading end332aand the base332b. A flow axis364extends through respective centers of leading end332aand base332b, and flow member332is coupled to support arms356a,356b, such that leading end332afaces inlet308of mixer body304, base332bfaces outlet312of the mixer body304. In other embodiments, the flow member may be substantially pyramidal. In some embodiments, such as the one shown, mixer body304defines at least one body injection passage324extending from an injection inlet320on exterior surface304aof mixer body304, through one of the support arms (e.g.,356a,356b). Additionally; flow member332defines a flow member injection passage328extending through at least a portion of flow member332to an injection outlet336defined at leading end332aor peripheral surface332cof flow member332(e.g., at leading end332a, as shown). Flow member332is coupled to the support arms (e.g.,356a,356b) such that injection inlet320is in fluid communication with injection outlet336via mixer body injection passage324and flow member injection passage328. For example, in the embodiment shown, flow member332is unitary with support arms (356a,356b) and mixer body304, such that mixer body injection passage324and flow member injection passage328are two portions of a common passage. In other embodiments, part or all of flow member332may be separately coupled to the support arms (e.g.,356a,356b) to also bring the flow member injection passage328into fluid communication with the mixer body injection passage324. In the embodiment shown, flange fittings352a,352beach define a pressure port344a,344bextending from two respective pressure outlets348a,348bon the exterior surface of flange fittings352a,352b. In other embodiments, injection outlet336may be disposed on peripheral surface332cof flow member332. For example, the mixer body injection passage324may extend radially inward through support arm356a, and flow member injection passage328may continue radially across the flow member to an injection outlet on the peripheral surface of the flow member (i.e., rather than extending longitudinally to the leading end). Referring now toFIGS.5A-5B,FIG.5Ashows an exploded perspective view of an embodiment of the present mixing apparatuses configured to receive a pipe fitting and hammer union washer.FIG.5Bshows an assembled perspective view of the mixing apparatus ofFIG.5A. In some embodiments of the present mixing apparatuses, longitudinal ends424a,424b, of mixer body404define hammer union joints. As shown inFIG.5A, mixer body404is similar internally to the mixer body inFIGS.4A and4B, but longitudinal ends424a,424b, are configured as threaded male hammer union ends configured to receive locking nuts432a,432b. Longitudinal ends424a,424b, may also be configured as threaded female ends or other types of pipe fitting ends for hammer union joints. As shown inFIG.5A, pipe fittings428a,428b, are configured to be slideably engaged with respective longitudinal ends424a,424b. Locking nuts432a,432bare then tightened over longitudinal ends424a,424b, to secure pipe fittings428a,428bto form mixing apparatus assembly400as shown inFIG.5B. In some embodiments, mixer body404defines at least one body injection passage extending from an injection inlet408on exterior surface404aof mixer body404, coupled to injection passage sleeve416. Injection inlet valve412is coupled to injection passage416to permit an open and close position for injection of fluid. Referring now toFIGS.6A-6B,FIG.6Ashows an isometric view of the mixing apparatus ofFIGS.4A and4Bassembled with hammer union pipe fittings configured with external pressure ports.FIG.6Bshows a side view of the mixing apparatus assembly ofFIG.6A. As shown inFIGS.6A, and6B, mixer body504is similar internally to the mixer body inFIGS.5A and5B, but longitudinal ends536a,536b, of mixer body504are configured as threaded male ends coupled to female threaded pipe tees528a,528bwith external pressure ports532a,532b. In some embodiments, external pressure ports532a,532bmay be omitted from the pipe tees. In some embodiments, such as the one shown, male threaded pipe fittings520a,520bare coupled to pipe tees528a,528b. Locking nuts524a,524bare then tightened over the ends of the male threaded pipe fittings to secure mixing apparatus assembly500. Referring now toFIGS.7A-7H,FIG.7Ashows a cross-sectional side view of an embodiment of the present mixing apparatuses assembled between two flange fittings taken along a plane passing through an injection passage defined by the mixing body.FIG.7Bshows an inlet end view of the mixing apparatus assembly ofFIG.7A.FIG.7Cshows a cross-sectional side view of the mixing apparatus ofFIG.7Ataken along a plane passing through an injection passage defined by the mixing body.FIG.7Dshows an inlet end view of the mixing apparatus ofFIG.7C.FIG.7Eshows an exploded perspective view of the mixing apparatus assembly ofFIG.7A.FIG.7Fshows an assembled isometric view of the mixing apparatus assembly ofFIG.7A.FIG.7Gshows an isometric cut-away view of the mixing apparatus assembly ofFIG.7F.FIG.7Hshows an isometric cut-away view of the mixing apparatus ofFIG.7C. As best illustrated inFIGS.7B,7D,7E, and7H, in some embodiments of the present mixing apparatuses, longitudinal ends of mixer body604define flange faces608a,608b. In some embodiments of the present mixing apparatuses, flange faces608a,608b, define a plurality of threaded holes656disposed radially around flange faces608a,608b. As shown inFIGS.7A and7E, to ensure a tight seal, gasket612ais disposed between flange face608aand flange fitting616a, and gasket612bis disposed between flange face608band flange fitting616bto form mixing apparatus assembly600as shown inFIGS.7A,7F,7G. As shown inFIGS.7A and7C, mixer body604has an exterior surface604a, interior surface604bthat narrows towards a point of constriction664from the inlet end624facing side to the outlet end628facing side, and an extension piece668coupled to the outlet facing side of mixer body604. Extension piece668has an exterior surface668a, an interior surface668bthat aligns with the interior surface604bof mixer body604such that when the extension piece668is coupled to the mixer body604, the interior surface668bof the extension piece668expands outward from the point of constriction664towards the outlet end628facing side. Mixer body604also defines at least one body injection passage636extending from injection inlet632on exterior surface604aof mixer body604, through one of the support arms (e.g.,648a,648b,648c). Additionally, flow member644defines a flow member injection passage640extending through at least a portion of flow member644to an injection outlet652defined at the leading end or peripheral surface of flow member644(e.g., at the leading end, as shown). Flow member644is coupled to the support arms (e.g.,648a,648b,648c) such that injection inlet632is in fluid communication with injection outlet652via mixer body injection passage636and flow member injection passage640. For example, in the embodiment shown, flow member644is unitary with support arms648a,648b,648cand mixer body604, such that mixer body injection passage636and flow member injection passage640are two portions of a common passage. In other embodiments, part or all of flow member644may be separately coupled to the support arms (e.g.,648a,648b,648c) to also bring flow member injection passage640into fluid communication with mixer body injection passage636. Referring now toFIGS.8A-8D,FIG.8Ashows an isometric cut-away view of an embodiment of the present mixing apparatuses with threaded studs.FIG.8Bshows an outlet end view of the mixing apparatus ofFIG.8A.FIG.8Cshows a top view of the mixing apparatus ofFIG.8A.FIG.8Dshows a side view of the mixing apparatus ofFIG.8A. As best illustrated inFIG.8A, in some embodiments of the present mixing apparatuses, the plurality of threaded holes756disposed radially around flange faces752a,752b, comprise a plurality of threaded studs748extending therefrom. In the embodiment shown, mixer body704is similar internally to the mixer body inFIGS.4A and4B. Mixer body704defines a plurality of support arms732a,732b, that are unitary (i.e., formed as a single, monolithic piece of material) with mixer body704and that extend radially inward from interior surface704b. In some embodiments, support arms732a,732bmay be disposed in a first portion of the passage in the mixer body, but in other embodiments, may be disposed in a second portion of the passage in the mixer body (e.g., with a central portion extending forward to support the flow member). As shown inFIG.8A, mixer body704has an exterior surface704aand interior surface704b, where mixer body704defines at least one body injection passage720extending from an injection inlet716on exterior surface704aof mixer body704, through one of the support arms (e.g.,752a,752b). As best illustrated inFIGS.8A,8C,8D, the longitudinal ends of mixer body704also defines flange faces752a,752b, comprising a plurality of threaded studs748extending from a plurality of threaded holes756disposed radially around the flange faces. In the embodiment shown, mixer body704also defines differential pressure ports740a,740b, as shown inFIGS.8A and8C, extending from two respective pressure outlets744a,744bon the exterior surface of mixer body704. In some embodiments, mixer body704also defines at least one threaded loop hook760extending from exterior surface704aof mixer body704. In the embodiment shown, flow member736defines a flow member injection passage724extending through at least a portion of flow member736to an injection outlet728defined at the leading end or peripheral surface of flow member736(e.g., at the leading end, as shown). Flow member736is coupled to the support arms (e.g.,752a,752b) such that injection inlet716is in fluid communication with injection outlet728via mixer body injection passage720and flow member injection passage724. For example, in the embodiment shown, flow member736is unitary with support arms752a,752b, and mixer body704, such that mixer body injection passage720and flow member injection passage724are two portions of a common passage. In other embodiments, part or all of flow member736may be separately coupled to the support arms (e.g.,752a,752b) to also bring flow member injection passage724into fluid communication with mixer body injection passage720. In the embodiment shown, mixing apparatus700also comprises a substantially conical flow member736coupled to support arms752a,752b. In this embodiment, flow member736has a leading end736a, a base736bopposite the leading end736a, and a peripheral surface736cextending between the leading end736aand the base736b. A flow axis extends through respective centers of leading end736aand base736b, and flow member736is coupled to support arms752a,752b, such that leading end736afaces inlet708of mixer body704, base736bfaces outlet712of mixer body704. In other embodiments, the flow member may be substantially pyramidal. In other embodiments, injection outlet728may be disposed on peripheral surface736cof flow member736. For example, the mixer body injection passage720may extend radially inward through support arm732a, and flow member injection passage724may continue radially across the flow member to an injection outlet on the peripheral surface of the flow member (i.e., rather than extending longitudinally to the leading end). In some embodiments of the present mixing apparatuses, each of the support arms has a longitudinal axis disposed at an angle 85 to 95 degrees relative to the flow axis. In some embodiments of the present mixing apparatuses, such as the embodiment shown inFIG.2, each of the support arms are configured such that each support arm has a corresponding injection inlet140a,140,140c, in fluid communication with injection outlet156via mixer body injection passage144a,144b,144c, and the flow member injection passage148a,148b,148c. In some embodiments of the present mixing apparatuses, one or more of the support arm injection inlets140a,140b,140c, may be plugged from a first injection passage end (e.g.,144a,144c,144e) toward a second injection passage end (e.g.,144b,144d,144f) to prevent passage of fluid to flow member injection passage148a,148b,148c. In some embodiments of the present mixing apparatuses, the mixer body is coupled to a pipe fitting configured to permit injection of more than one chemical by one or more of the following: an off-center drill tap, an upstream injection quill, a bleed ring, an injection weldolet, or other entry point. In some embodiments of the present mixing apparatuses, the mixing apparatus is connected in series, each mixing apparatus configured to receive a chemical to be mixed with an upstream mixture of chemicals. In some embodiments of the present mixing apparatuses, the mixer body defines an elongated, narrow pipe with an inner diameter less than the pipe inner diameter of the upstream and downstream longitudinal ends, where increased velocity and turbulence is provided by larger mass transfer contact prior to allowing the downstream cone opening to occur at an 8 degree angle. In some embodiments of the present mixing apparatuses, the injection inlet is omitted from the exterior surface of the mixer body. In some embodiments of the present mixing apparatuses, the flow member is configured as an interchangeable component within a flange connection. In some embodiments of the present mixing apparatuses, the mixer body is machined as a full pipe outer diameter from a single piece of metal and coupled between two flanges. In some embodiments of the present mixing apparatuses, the mixer body is configured to be interchangeable based on process flow conditions. The above specification and examples provide a complete description of the structure and use of illustrative embodiments. Although certain embodiments have been described above with a certain degree of particularity, or with reference to one or more individual embodiments, those skilled in the art could make numerous alterations to the disclosed embodiments without departing from the scope of this invention. As such, the various illustrative embodiments of the methods and systems are not intended to be limited to the particular forms disclosed. Rather, they include all modifications and alternatives falling within the scope of the claims, and embodiments other than the one shown may include some or all of the features of the depicted embodiment. For example, elements may be omitted or combined as a unitary structure, and/or connections may be substituted. Further, where appropriate, aspects of any of the examples described above may be combined with aspects of any of the other examples described to form further examples having comparable or different properties and/or functions, and addressing the same or different problems. Similarly, it will be understood that the benefits and advantages described above may relate to one embodiment or may relate to several embodiments. The claims are not intended to include, and should not be interpreted to include, means-plus- or step-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase(s) “means for” or “step for,” respectively.
28,755
11857934
DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments will be described with reference to the drawings. The same or corresponding elements are denoted by the same reference signs throughout the drawings, and redundant detailed description will be omitted. Embodiment 1 FIGS.1A and1Bshow a manufacturing site to which a viscous material stirring apparatus1(hereinafter, simply referred to as “stirring apparatus1”) according to Embodiment 1 is applied. In this manufacturing site, a viscous material95is applied to a joining part93of workpieces91and92formed by overlapping or abutting the two workpieces91and92. <Manufacturing Site> As an example of a manufacturing site, a manufacturing site of a vehicle (for example, an aircraft or an automobile) or industrial machinery (for example, a construction machine, an agricultural machine, or a machine tool) can be cited. <Workpiece> In the present embodiment, as an example, the workpieces91and92are plate-shaped, and the joining part93is formed by overlapping the workpieces91and92. The joining part93is formed by a surface of the first workpiece91and a side end surface of the second workpiece92, forms a right angle, and extends along the side end surface of the second workpiece92. At an aircraft manufacturing site, the workpieces91and92may be segments constituting a cylindrical fuselage. <Viscous Material> The viscous material95is a material having viscosity such as a sealant or an adhesive. As an example, the viscous material95has a viscosity of 1500 to 2000 Pa·s when applied under a normal temperature environment (for example, 20 to 25° C.). However, both the sealant and the adhesive harden (the viscosity increases) with the lapse of time after being applied to the joining part93due to influence of moisture or heating at the manufacturing site. <Coating Work> FIG.1Ashows work of applying the viscous material95. As shown inFIG.1A, a discharge head80that discharges the viscous material95is used in the work of applying the viscous material95. By a head moving mechanism (not shown), the discharge head80can be moved close to or away from the joining part93, and can be moved in an extending direction of the joining part93. In the coating work, while the discharge head80is operated to discharge the viscous material95to the joining part93, the head moving mechanism is operated to move the discharge head80in the extending direction of the joining part93while appropriately maintaining a clearance between the discharge head80and the joining part93. By adjusting discharge speed and moving speed, an amount (a volume or weight) of the viscous material95applied to the joining part93while the discharge head80moves by the unit distance is adjusted to fall within a range required for a product. Hereinafter, the amount is referred to as “coating amount”. By this coating work, the viscous material95is applied along the extending direction of the joining part93. In the present embodiment, the viscous material95is provided so as to straddle the surface of the first workpiece91and the side end surface of the second workpiece92, and is provided in a bead shape along the extending direction of the joining part93. Thus, the viscous material95fills a gap between the workpieces91and92. Hereinafter, the extending direction of the viscous material applied in the bead shape is also referred to as “coating direction”. As shown in a cross section of the viscous material95inFIG.1B, when viewed from outside, even if the viscous material95is provided so as to straddle the two workpieces91and92as described above, air96may enter an inside thereof. In that case, a contact area of the viscous material95with the workpieces91and92becomes smaller than expected. Then, the viscous material95is easily peeled off from the workpieces91and92, and a period in which required performance (for example, sealing performance or joining performance) can be obtained satisfactorily may be shorter than expected. Note that, as an example of a situation in which the air96enters, a case where a coating amount required for a product is large can be cited. At this manufacturing site, after the work of applying the viscous material95, work of bleeding the air96that has entered the inside of the viscous material95is performed incidentally. Previously, the air bleeding work has been manually performed by an operator using a comb tool made of wood or synthetic resin, but the stirring apparatus1is applied to the manufacturing site for automation of the air bleeding work. <Viscous Material Stirring Apparatus> The stirring apparatus1includes a stirring member2. The stirring member2rotates around a rotation axis A, and its tip is radially separated from the rotation axis A. The stirring apparatus1causes the tip of the stirring member2to be immersed in the viscous material95applied to the joining part93in the coating work, and in this state, causes the stirring member2to turn around the rotation axis A and move the stirring member2along the coating direction. Here, the “turn” includes not only rotation about the rotation axis Abut also revolution about the rotation axis A or eccentric rotation about the rotation axis A. Thereby, the air96that has entered the inside of the viscous material95can be removed, whereby the viscous material95properly contacts the workpieces91and92, and a service life of the viscous material95is extended (a repair frequency is reduced). Hereinafter, a configuration and operation of the stirring apparatus1will be described in more detail. FIG.2is a conceptual view showing the stirring apparatus1, andFIG.3is a block diagram showing the stirring apparatus1. As shown inFIGS.2and3, the stirring apparatus1includes a rotary actuator3, a moving mechanism4, and a control device8, in addition to the stirring member2described above. The rotary actuator3rotates the stirring member2around the rotation axis A. The rotary actuator3is configured by, for example, an electric motor. The moving mechanism4moves the stirring member2. The moving mechanism4is, for example, a vertical articulated robot, and includes a robot arm5having a plurality of (e.g., six) joints and a plurality (the same number of joints) of moving actuators6(seeFIG.3) each driving each of the plurality of joints. In the present embodiment, the stirring member2and the rotary actuator3are unitized by being held by a holding member7, and the stirring member2, the rotary actuator3, and the holding member7constitute a stirring head10. The holding member7is detachably attached to a tip of the robot arm5. When the robot arm5of the moving mechanism4operates, the holding member7and the stirring member2held by the holding member7move together with the rotary actuator3. As an example, a base of the robot arm5is installed on a floor of a work site. The workpieces91and92are held by a jig90installed on the floor of the manufacturing site, and positioned within a movable range of the robot arm5. However, the base of the robot arm5may be slidably supported by a traveling rail installed on the floor of the manufacturing site, in which case the moving mechanism4includes the traveling rail and a traveling actuator that causes the robot arm5to travel along the traveling rail. The base of the robot arm5may be supported by a pedestal installed on the floor of the manufacturing site. As shown inFIG.3, the rotary actuator3and the moving actuator6of the moving mechanism4are controlled by the control device8. The control device8is, for example, a computer having a memory such as a ROM or a RAM and a CPU, and a program stored in the ROM is executed by the CPU. The control device8may be a single device or may be divided into a plurality of devices. In the present embodiment, the program stored in the ROM includes a program that teaches a movement locus and moving speed of the tip of the robot arm5, and execution of the program (i.e., playback) can cause the holding member7and the stirring member2held by this to move as taught in advance. The program stored in the ROM includes a program for deriving a command value of rotation speed of the rotary actuator3, and the rotation speed of the rotary actuator3and thus the stirring member2is controlled by executing the program. The control device8is connected to an operation panel9. The operation panel9is operated by an operator at the manufacturing site. When a command to start the air bleeding work is input by the operator at the operation panel9, the CPU of the control device8executes the above-described program, and the stirring member2is turned and moved. <Stirring Head> FIG.4Ais a cross-sectional view of the holding member7according to Embodiment 1. As shown inFIG.4A, the holding member7has a holding unit11for holding the stirring member2and the rotary actuator3and a mounting unit12integrated with the holding unit11. Although not shown in detail, the mounting unit12is formed in a disk shape and is detachably attached to the tip of the robot arm5. The holding unit11is formed in a tubular shape with both ends opened. The holding unit11may be a cylinder other than the illustrated rectangular tube. When the rotary actuator3is configured by the electric motor as described above, the rotary actuator3includes a housing31containing a rotor and a stator, a flange32provided at one end of the housing31, and an output shaft33protruding from the flange32to a side opposite to the housing31. The rotary actuator3is held by the holding member7by fastening the flange32to one end of the holding unit11in a state in which the output shaft33is inserted into the holding unit11through one end opening of the holding unit11. A spacer13may be interposed between the holding unit11and the flange32. The stirring member2includes a driven body21and a stirring body22. In the present embodiment, the driven body21has a driven shaft23and a disk body24. The driven shaft23is partially accommodated in the holding unit11through another end opening of the holding unit11, and one end of the driven shaft23is connected to the output shaft33of the rotary actuator3via a shaft coupling14in the holding unit11. Another end of the driven shaft23is located outside the holding unit11. The driven shaft23is rotatably supported by bearings15and16provided in the holding unit11. The disk body24is fixed to the other end of the driven shaft23, and is positioned outside the holding unit11. The stirring body22is attached to the disk body24of the driven body21and protrudes from the disk body24to a side opposite to the driven shaft23and the rotary actuator3. The stirring body22forms a tip of the stirring member2. In the present embodiment, the output shaft33, the driven shaft23, and the disk body24are coaxially arranged, and a central axis thereof forms the rotation axis A of the stirring member2. However, the output shaft33does not have to be arranged coaxially with the driven shaft23. For example, the two shafts33and23may be connected via an orthogonal shaft gear or a staggered shaft gear. In this case, the gear can be provided with a speed reducing function. However, even in a case of the coaxial arrangement, the speed reducing function may be provided by interposing a strain wave gearing. When the rotary actuator3operates and the output shaft33rotates, the stirring member2(the driven body21and the stirring body22) is driven to rotate around the rotation axis A. The stirring body22is attached to the disk body24via an eccentric amount adjusting mechanism25, and as shown inFIG.4B, a tip of the stirring body22(that is, the tip of the stirring member2) is radially away from the rotation axis A. When the stirring member2rotates around the rotation axis A, if the tip of the stirring body22is focused, this tip revolves or rotates eccentrically around the rotation axis A. Hereinafter, a radial distance of the tip of the stirring member2from the rotation axis A is referred to as “eccentric amount e”. The eccentric amount adjusting mechanism25can adjust a mounting position of the stirring body22to the driven body21(disk body24), which thereby can adjust the eccentric amount e [mm]. As an example, the eccentric amount e can be adjusted within a range of 0 to 10 mm. <Eccentric Amount Adjusting Mechanism> FIG.5Ais an exploded perspective view of the eccentric amount adjusting mechanism25, andFIG.5Bis a perspective view showing the eccentric amount adjusting mechanism25in an assembled state. As an example, the eccentric amount adjusting mechanism25includes a slider26and a male screw27provided on the stirring body22, and a groove28provided on the disk body24. The eccentric amount adjusting mechanism25further includes a washer29and nuts30. The stirring body22is formed in a rod shape and extends linearly, for example. The tip of the stirring body22is tapered. In the illustrated example, it is formed in a hemispherical shape and rounded, but may be formed in a conical shape and sharpened. The slider26is fixed to a base end of the stirring body22. In other words, the stirring body22is provided so as to protrude from a center of the slider26. As an example, the slider26is formed in a square block shape when viewed in a direction of the rotation axis A. The male screw27is located at the base end of the stirring body22and slightly closer to the tip side thereof than the slider26, and is provided on an outer peripheral surface of the stirring body22. The groove28is formed linearly along a diameter direction of the disk body24(one direction orthogonal to the rotation axis A). The groove28includes a penetrating part28athat extends linearly inside the disk body24and opens through a peripheral surface of the disk body24and an opening part28bformed on an end surface of the disk body24to open the penetrating part28aoutside the disk body24. The penetrating part28aand the opening part28bare parallel. The slider26is received inside the penetrating part28athrough an opening formed on the peripheral surface of the disk body24, and is slidable in an extending direction of the groove28in the penetrating part28a. A height h28bof the opening part28bis smaller than a height h26of the slider26and larger than an outer diameter φ22of the stirring body22. Therefore, when the slider26is received by the penetrating part28a, the stirring body22can protrude out of the disk body24through the opening part28b, whereas the slider26is prevented from falling off. When the slider26is received inside the penetrating part28a, the male screw27is positioned outside the disk body24and near the end surface of the disk body24. The washer29is inserted through the stirring body22from the tip side of the stirring body22, and then the nuts30are fastened to the male screw27. By this fastening, the disk body24is sandwiched between the slider26and the washer29, and the stirring body22is fixed to the driven body21. A through bolt type fastening structure is employed, and the slider26has the same function as a bolt head in the fastening structure. Before the fastening, a position of the slider26in the penetrating part28ais adjusted while sliding the slider26, thereby adjusting the eccentric amount e (seeFIG.4B). The eccentric amount e can be changed in accordance with a coating amount of the viscous material95to be subjected to air bleeding work, and air can be removed regardless of the coating amount of the viscous material95. Since a double nut type fastening structure is employed, the screw is not easily loosened, and the eccentric amount e after the fastening can be prevented from undesirably changing. <Air Bleeding Work> Air bleeding work using the stirring apparatus1having the above configuration starts when a command is input by an operator on the operation panel9. Note that operation of the actuator described below is based on the control of the control device8. When the command is input, the moving actuator6operates, a posture of the robot arm5and a position and a posture of the stirring member2change, and the tip of the stirring member2faces a stirring start position of the viscous material95applied to the joining part93as a result of the coating work (seeFIG.1B or2). When the viscous material95is applied in a line segment shape having both ends, the stirring start position is any end of the viscous material95. The viscous material95may be applied in a closed loop shape. In this case, the stirring start position is an arbitrary position of the viscous material95or a starting point/end point position of the coating work. The moving actuator6continues to operate, and the tip of the stirring member2is immersed at the above-described stirring start position of the applied viscous material95(seeFIG.1BorFIG.6). The tip of the stirring member2(stirring body22) forms an immersion part2aimmersed inside the viscous material95(seeFIG.6). Referring toFIG.6, after this immersion step, the rotary actuator3operates, and the stirring member2turns around the rotation axis A. At the same time, the moving actuator6operates, and the stirring member2moves along the coating direction of the viscous material95while the tip of the stirring member2is immersed in the viscous material95. The immersion part2amoves in the coating direction from the stirring start position while rotating eccentrically with respect to the rotation axis A. A movement locus T of the immersion part2ais a series of a plurality of ellipses arranged in the coating direction. The turning and moving steps of the stirring member2are performed until the immersion part2areaches a stirring end position of the viscous material95. When the viscous material95is applied in a line segment shape, the stirring end position is an end of the viscous material95opposite to the stirring start position. When the viscous material95is applied in a closed loop shape, the stirring end position is the same as the stirring start position. When the immersion part2amoves to the stirring end position, the moving actuator6operates to retreat the stirring member2from the viscous material95. In this retreat step, before or during the retreat movement by the moving actuator6, the rotary actuator3stops and the turn of the stirring member2stops. When the stirring member2is turned and moved while the tip of the stirring member2is immersed in the viscous material95, the immersion part2amoves along the movement locus T while pushing away the viscous material95. Accordingly, the viscous material95is stirred by the immersion part2a. In the viscous material95, a passage mark95aof the immersion part2ais formed on a downstream side of the movement locus T with respect to the immersion part2a. The air that has entered the inside of the viscous material95flows out of the viscous material95around the immersion part2a, particularly through the passage mark95a. The rotary actuator3rotates the stirring member2at a constant rotation speed n [rpm] (an angular velocity ω [rad/s] of the stirring member2is 2πn/60). The moving actuator6moves the stirring member2at a constant moving speed v [mm/s]. In this case, when a two-dimensional orthogonal coordinate system in which the coating direction is an x direction and a direction orthogonal to the coating direction and the direction of the rotation axis A is a y direction is assumed, the movement locus T of the immersion part2ais represented in the following equation (1). x=ecos ωt+vt, y=esin ωt(1) Here, t is elapsed time [s] from the start of rotation and movement of the immersion part2a, and x is an x coordinate and y is a y coordinate after t seconds from the start of rotation and movement of the immersion part2aNote that e, ω, and v are the above-described eccentric amount [mm], angular velocity [rad/s], and moving speed [mm/s]. As an example, the rotation speed n is set within a range of 50 to 100 rpm. By setting the speed relatively low in this way, the applied viscous material95is not disturbed, and the viscous material95can be stirred while maintaining a state in which the viscous material95is applied to the joining part93. In this case, if the moving speed v is too low, the movement locus T will be like a plurality of ellipses overlapping one another, and the viscous material95will be disturbed. If the moving speed v is too high, a plurality of ellipses will be arranged at a large interval in the coating direction, and an unstirred region will be created. Therefore, the moving speed v is set so that a plurality of ellipses constituting the movement locus T circumscribes each other, overlaps with a small amount of overlap, or is arranged with a small clearance. As an example, the moving speed v is set in a range of 0.1 to 15 m/min (1.7 to 250 mm/s). Thereby, the air96can be uniformly discharged without disturbing the viscous material95regardless of the position in the coating direction. As described above, in the present embodiment, the air bleeding work that has been performed manually until now can be automated. For this reason, it contributes to labor saving of work accompanying the viscous material coating work. Embodiment 2 FIG.7is a perspective view showing a holding member107of a stirring apparatus101according to Embodiment 2. In the present embodiment, the stirring head10(unit including the stirring member2, the rotary actuator3, and the holding unit11of the holding member7) according to Embodiment 1 is mounted on a base113of the holding member107. A discharge head180is mounted on the base113adjacent to the stirring head10. The discharge head180has a housing181, a discharge actuator182, and a nozzle183. Although not shown in detail, the housing181has a storage unit that stores a viscous material, a plunger that pushes the viscous material stored in the storage unit to the nozzle183, and the like. The nozzle183discharges the viscous material supplied from the storage unit. The discharge actuator182is a power source of the plunger. When the discharge actuator182operates, the viscous material is discharged from the nozzle183. The discharge actuator182is configured by, for example, an electric motor. A mounting unit112of the holding member107is integrated with the base113, and is detachably attached to a moving mechanism (for example, a tip of a robot arm of a vertical articulated robot) in the same manner as in Embodiment 1. In the stirring apparatus101according to the present embodiment, the stirring head10for performing air bleeding work and the discharge head180for discharging the viscous material are unitized. Therefore, coating work and the air bleeding work can be performed in parallel. Although not shown in detail, the stirring apparatus101according to Embodiment 2 also includes a control device8and an operation panel9(seeFIG.3) in the same manner as in Embodiment 1. When a work start command is input on the operation panel9, the control device8performs the viscous material coating work and the air bleeding work. In other words, the control device8drives the moving mechanism to move the holding member107so that the discharge head180is on a front side in a moving direction of the holding member107and the stirring member2is on a rear side in the moving direction of the holding member107. In a process of moving the holding member107, the control device8drives the discharge head180(discharge actuator182) to apply the viscous material to workpieces, and drives the rotary actuator3to rotate the stirring member2around a rotation axis A. This allows the viscous material to be stirred in the same manner as in Embodiment 1 by immersing a tip of the stirring member2in the viscous material immediately after being applied while performing the work of applying the viscous material to a joining part of the workpieces. Since the coating work and the air bleeding work can be performed in parallel, production efficiency at a manufacturing site is improved. Modifications The embodiments have been described above, but the above configurations can be appropriately changed, added, and/or deleted within the scope of the present invention. The stirring member2only needs to have its tip radially away from the rotation axis A, and a shape of the stirring body22is not limited to a rod shape. As an example, the stirring body22may have a crank shape. In the steps of turning and moving the stirring member2, the rotation speed n and the moving speed v may be changed. The holding member7can be omitted. When the moving mechanism4is a vertical articulated robot and a joint closest to the tip side is a torsion shaft (so-called T shaft), the stirring member2may be detachably attached to the tip of the robot arm5. In this case, of the plurality of actuators that drives the joints of the vertical articulated robot, the actuator corresponding to the joint closest to the tip side functions as the rotary actuator3that drives the stirring member2to rotate, and the remaining actuators function as the moving actuators6that move the stirring member2. Note that the moving mechanism4is not limited to the vertical articulated robot. REFERENCE SIGNS LIST 1,101viscous material stirring apparatus2stirring member3rotary actuator4moving mechanism7,107holding member138control device25eccentric amount adjusting mechanism80,180discharge head91,92workpiece95viscous materialA rotation axise eccentric amount
25,293
11857935
DETAILED DESCRIPTION The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomers. “Ethylene-based polymer” shall mean polymers comprising greater than 50% by weight of units which have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene-based polymer known in the art include Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE). As used herein, the “solution polymerization reactor” is a vessel, which performs solution polymerization, wherein ethylene monomer, optionally with a comonomer, polymerizes or copolymerizes after being dissolved in a non-reactive solvent that contains a catalyst. Heat may be removed or added to the solution polymerization reactors and after typically by coupling the reactor to one or more heat exchangers. In the solution polymerization process, hydrogen may be utilized; however, it is not required in all solution polymerization processes. Ziegler-Natta catalysts are commonly used to produce ethylene-based polymers in copolymerization processes for copolymerizing ethylene and one or more alpha-olefin comonomers. In these copolymerization processes using typical Ziegler-Natta catalysts, polymer average molecular weight decreases rapidly as polymerization temperature increases. However, high polymerization temperatures in solution polymerization processes increase production throughput and produce ethylene-based polymers with desired polymer properties, such as superior optics and dart/tear balance. Increasing the molecular weight capability of a Ziegler-Natta catalyst may expand its ability to make new products and make it possible to operate at higher polymerization temperatures. The present disclosure is directed to a Ziegler-Natta-type heterogeneous procatalyst and catalyst system that exhibit increased molecular weight capabilities compared to existing Ziegler-Natta catalysts. The catalyst system disclosed herein includes a heterogeneous procatalyst and a cocatalyst. The heterogeneous procatalyst includes a titanium species, a thermally-treated magnesium chloride component, and a chlorinating agent. In embodiments, the thermally treated magnesium chloride component may be a product of thermally treating a magnesium chloride slurry at a temperature of at least 100° C. for at least 30 minutes, the magnesium chloride slurry comprising at least magnesium chloride dispersed in a solvent, as will be described subsequently in greater detail. The thermal treatment may change the morphology of the magnesium chloride. The magnesium chloride may be thermally treated before or after addition of the chlorinating agent and titanium compound to the magnesium chloride. The changes in the morphology of the magnesium chloride may increase the molecular weight capability of the heterogeneous procatalyst. A polymerization process is also disclosed that includes contacting ethylene and optionally one or more α-olefin comonomers with a catalyst system that includes the heterogeneous procatalyst disclosed herein and optionally a cocatalyst to form an ethylene-based polymer. The ethylene-based polymers produced using the heterogeneous procatalysts with the thermally treated magnesium chloride, as disclosed herein, may exhibit greater weight average molecular weight (Mw), greater high density fraction (HDF), and lesser content of the optional comonomer compared to comparable polymers made with comparative Ziegler-Natta catalysts, for which the magnesium chloride has not been thermally treated. Preparation of the heterogeneous procatalyst may include preparing the magnesium chloride (MgCl2). In some embodiments, preparing the MgCl2may include reacting an organomagnesium compound, or a complex including an organomagnesium compound, with a chloride compound, such as a metallic or non-metallic chloride, to form a reaction product, then thermally treating the reaction product to form a thermally-treated magnesium chloride (MgCl2) component. Examples of organomagnesium compounds and/or complexes may include, but are not limited to, magnesium C2-C8alkyls and aryls, magnesium alkoxides and aryloxides, carboxylated magnesium alkoxides, and carboxylated magnesium aryloxides, or combinations of these. In some embodiments, the organomagnesium compound may include a magnesium C2-C8alkyl, a magnesium C1-C8alkoxide, or combinations of these. In some embodiments, the organomagnesium compound may be butyl ethyl magnesium. The organomagnesium compound or complex may be soluble in a hydrocarbon diluent, such as an inert hydrocarbon diluent. Examples of hydrocarbon diluents may include, but are not limited to, liquefied ethane, propane, isobutane, n-butane, n-hexane, individual hexane isomers or mixtures thereof, isooctane, paraffinic mixtures of alkanes having from 5 to 20 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, industrial solvents composed of saturated or aromatic hydrocarbons such as kerosene and/or naphthas, and combinations thereof. In some embodiments, the hydrocarbon diluent may be substantially free of any olefinic compounds and other impurities. As used herein, the term “substantially free” of a constituent means that a composition includes less than 0.1 wt. % of the constituent (e.g., impurity, compound, element, etc.). In some embodiments, the hydrocarbon diluent may have a boiling point in the range from about −50° C. to about 200° C. In some embodiments, the hydrocarbon diluent may include an isoparaffinic solvent. Examples of ispoaraffinic solvents may include, but are not limited to, ISOPAR™ synthetic paraffin solvents available from ExxonMobile (e.g., ISOPAR™ E paraffinic solvent) and special boiling point (SBP) solvents available from Shell Chemicals (e.g., SBP 100/140 high purity de-aromatised hydrocarbon solvent). Other examples of hydrocarbon diluents may include ethylbenzene, cumene, decalin, and combinations thereof. In some embodiments, the process of preparing the MgCl2may include dispersing the organomagnesium compound in the hydrocarbon diluent to form a solution or a slurry. The concentration of the organomagnesium compound in the hydrocarbon diluent may be sufficient to provide for efficient production of the magnesium chloride without using an excessive amount of solvent. The concentration of the organomagnesium compound should not be so great that the solution or slurry cannot be properly mixed/agitated or fluidly transported during and after synthesis. The solution or slurry of the organomagnesium compound dispersed in the hydrocarbon diluent may be contacted with the chloride compound to produce the MgCl2. The chloride compound may be a metallic or non-metallic chloride. For example, in some embodiments, the chloride compound may be hydrochloride gas. In some embodiments, the solution or slurry of organomagnesium compound and chloride compound may be contacted at a temperature of from −25° C. to 100° C., or from 0° C. to 50° C. In some embodiments, the solution or slurry of organomagnesium compound and metallic or non-metallic chloride may be contacted for a time of from 1 hour to 12 hours, or from 4 hours to 6 hours. The reaction of the chloride compound with the organomagesium compound may produce an untreated MgCl2. The untreated MgCl2may be in the form of a MgCl2slurry that includes a plurality of MgCl2particles dispersed in the hydrocarbon diluent. In some embodiments, the untreated MgCl2slurry may consist of or consist essentially of the plurality of MgCl2particles dispersed in the hydrocarbon diluent. In some embodiments, the MgCl2slurry may have a concentration of MgCl2of from 0.05 mol/L to 10.0 mol/L, from 0.1 to 5.0 mol/L, or about 0.2 mol/L. The untreated MgCl2slurry may be further processed by thermally treating the untreated MgCl2slurry at a temperature of at least 100° C. and for a time of at least 30 minutes to produce a thermally-treated MgCl2component dispersed in the hydrocarbon diluent. The thermal treatment of the MgCl2slurry may be conducted before or after addition of the chlorinating agent and titanium species to the MgCl2slurry. For example, in some embodiments, the MgCl2slurry including the MgCl2particles dispersed in the hydrocarbon diluent may be thermally treated at a temperature of greater than or equal to 100° C., greater than or equal to 120° C., greater than or equal to 130° C., greater than or equal to 150° C., or even greater than or equal to 190° C. before addition of the chlorinating agent and titanium species. In some embodiments, the MgCl2slurry may be thermally treated at a temperature of from 100° C. to 500° C., from 100° C. to 300° C., from 100° C. to 200° C., from 120° C. to 500° C., from 120° C. to 300° C., from 120° C. to 200° C., from 130° C. to 500° C., from 130° C. to 300° C., from 130° C. to 200° C., from 150° C. to 500° C., from 150° C. to 300° C., from 150° C. to 200° C., from 190° C. to 500° C., or from 190° C. to 300° C. In some embodiments, the MgCl2slurry may be thermally treated at two or more different temperatures during the thermal treatment. The MgCl2slurry may be thermally treated for a time greater than or equal to 30 minutes (0.5 hours), greater than or equal to 1 hour, greater than or equal to 2 hours, greater than or equal to 3 hours, greater than or equal to 6 hours, or greater than or equal to 10 hours to produce the thermally treated MgCl2component. For example, in some embodiments, the MgCl2slurry may be thermally treated for a time of from 0.5 hours to 240 hours, from 0.5 hours to 120 hours, from 0.5 hours to 48 hours, from 0.5 hours to 24 hours, from 1 hour to 240 hours, from 1 hour to 120 hours, from 1 hour to 48 hours, from 1 hour to 24 hours, from 2 hours to 240 hours, from 2 hours to 120 hours, from 2 hours to 48 hours, from 2 hours to 24 hours, from 3 hours to 240 hours, from 3 hours to 120 hours, from 3 hours to 48 hours, from 3 hours to 24 hours, from 6 hours to 240 hours, from 6 hours to 120 hours, from 6 hours to 48 hours, from 6 hours to 24 hours, from 10 hours to 240 hours, from 10 hours to 120 hours, from 10 hours to 48 hours, or from 10 hours to 24 hours to produce the thermally treated MgCl2component. In some embodiments, thermally treating the MgCl2slurry may include agitating the MgCl2slurry. Agitating the MgCl2slurry may be performed simultaneously with thermally treating the MgCl2slurry at a temperature of at least 100° C. and for at least 30 minutes. In some embodiments, the MgCl2slurry may be agitated at a speed of up to 1000 rotations per minute (rpm), up to 100 rpm, from 1 rpm to 1000 rpm, or from 1 rpm to 100 rpm. In some embodiments, thermally treating the MgCl2may include thermally treating the MgCl2in an inert atmosphere. Inert atmosphere refers to an atmosphere that consists essentially of compounds and/or gases that do not react with the MgCl2or any other constituent of the heterogeneous procatalyst. For example, thermally treating the MgCl2may be conducted in the presence of an inert gas, such as nitrogen or argon for example, that does not react with the MgCl2. In some embodiments, thermally treating the MgCl2may include thermally treating a MgCl2slurry consisting of MgCl2particles dispersed in the hydrocarbon diluent at a temperatures of at least 100° C. and for at least 30 minutes. The phrases “consisting of” and “consists of” are used as closed transitional phrases limiting a composition or method to the recited components or method steps and any naturally occurring impurities. In other embodiments, thermally treating the MgCl2may include thermally treating a MgCl2slurry consisting essentially of MgCl2particles dispersed in the hydrocarbon diluent at a temperature of at least 100° C. and for at least 30 minutes. The phrases “consisting essentially of” and “consists essentially of” are intended to be partially closed transitional phrases that limit a composition or method to the recited constituents or method steps as well as any non-recited constituents or method steps that do not materially affect the novel characteristics of the claimed subject matter. In some embodiments, the thermally-treated MgCl2component may be a product of thermally treating a MgCl2slurry prepared as previously described. The thermally-treated MgCl2component may include MgCl2particles dispersed in the hydrocarbon diluent and having morphologies altered from the thermal treatment. Not intending to be bound by theory, it is believed that thermally treating the MgCl2component may modify the surface morphology and surface area of the MgCl2particles. The resultant change in surface morphology of the thermally treated MgCl2may modify the activity of the heterogeneous procatalyst for polymerizing olefins and change the polymerization behaviors of the heterogeneous procatalyst as well as the molecular weight of the resultant polymer. In some embodiments, following thermal treatment, the thermally treated MgCl2may have an average surface area of from 50 meters squared per gram (m2/g) to 1000 m2/g, from 100 m2/g to 1000 m2/g, from 200 m2/g to 1000 m2/g, or from 400 m2/g to 1000 m2/g. In some embodiments, the thermally treated MgCl2may have an average surface area of from 150 m2/g to 400 m2/g, or about 200 m2/g. Preparing the heterogeneous protcatalyst may further include contacting the thermally-treated MgCl2component with a chlorinating agent. The chlorinating agent may have a structural formula A(Cl)X(R1)3-x, where A is an element selected from the group consisting of boron, aluminum, gallium, indium, silicon, and tellurium, R1is a (C1-C30) hydrocarbyl, and x is 1, 2, or 3. In some embodiments, A may be aluminum or boron. In some embodiments, the chlorinating agent may be chosen from aluminum trichloride, methylaluminum dichloride, dimethylaluminum chloride, ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum dichloride, diisobutylaluminum chloride, hexylaluminum dichloride, di-n-hexylaluminum chloride, n-octylaluminum dichloride, di-n-octylalumnium chloride, boron trichloride, phenylboron dichloride, dicyclohexylboron chloride, silicon tetrachloride, methyltrichlorosilane, dimethylchlorosilane, chlorotrimethylsilane, ethyltrichlorosilane, dichlorodiethylsilane, chlorotriethylsilane, n-propyltrichlorosilane, dichlorodi(n-propyl)silane, chlorotri(n-propyl)silane, isopropyltrichlorosilane, dichloro-diisopropylsilane, chlorotriisopropylsilane, n-butyltrichlorosilane, dichlorodi(n-butyl)silane, chlorotri(n-butyl)silane, isobutyl-trichlorosilane, dichlorodiisobutylsilane, chlorotriisobutyl-silane, cyclopentyltrichlorosilane, dichlorodicyclopentylsilane, n-hexyltrichlorosilane, cyclohexyltrichlorosilane, dichlorodicyclohexylsilane, or combinations of these. The thermally-treated MgCl2component may be contacted with the chlorinating agent under conditions sufficient to condition the thermally-treated MgCl2component. The thermally-treated MgCl2component may be contacted with the chlorinating agent at a temperature of from 0° C. to 50° C., from 0° C. to 35° C., from 25° C. to 50° C., or from 25° C. to 35° C. The thermally-treated MgCl2component may be contacted with the chlorinating agent for a time of from 1 hour to 144 hours, from 1 hour to 72 hours, from 1 hour to 24 hours, from 1 hour to 12 hours, from 4 hours to 144 hours, from 4 hours to 72 hours, from 4 hours to 24 hours, from 4 hours to 12 hours, from 6 hours to 144 hours, from 6 hours to 72 hours, from 6 hours to 24 hours, or from 6 hours to 12 hours. Not intending to be bound by any theory, it is believed that conditioning the thermally-treated MgCl2component by contacting the thermally-treated MgCl2component with the chlorinating agent may facilitate or enhance adsorption of additional metals, such as the titanium species for example, onto the thermally-treated MgCl2component. In some embodiments, the a molar ratio of the chlorinating agent to the thermally-treated MgCl2component in the heterogeneous procatalyst may be from 3:40 to 14:40, from 3:40 to 12:40, from 6:40 to 14:40, or from 6:40 to 12:40. The thermally-treated MgCl2component conditioned by the chlorinating agent may then be contacted with a titanium species to produce the heterogeneous procatalyst. The titanium species may be any titanium compound or titanium complex having catalytic activity after being incorporated in the procatalyst upon activation with a cocatalyst. For example, in some embodiments, the titanium species may include a titanium halide, a titanium alkoxide, or combinations thereof. In some embodiments, titanium species is TiCl4-c(OR)cor TiCl3-d(OR)d, wherein R is (C1-C20)hydrocarbyl, c is 0, 1, 2, 3, or 4, and d is 0, 1, 2, or 3. For example, in some embodiments, the titanium species may include, but is not limited to, titanium (IV) tetrachloride, titanium (III) trichloride, diethoxytitanium(IV) dichloride, diisopropoxytitanium(IV) dichloride, di-n-butoxytitanium(IV) dichloride, diisobutoxytitanium(IV) dichloride, triisopropoxytitanium(IV) chloride, tri-n-butoxytitanium(IV) chloride, triisobutoxytitanium(IV) chloride, titanium(IV) tetraisopropoxide (Ti(OiPr)4), titanium(IV) ethoxide, titanium(IV) n-butoxide, titanium(IV) isobutoxide, titanium(IV) 2-ethylhexoxide, dichlorobis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium(IV), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium(III), tetrachlorobis(tetrahydrofuran)titanium(IV), trichlorotris(tetrahydrofuran)titanium(III), methyltitanium (IV) trichloride, or combinations of these. In some embodiments, the titanium species may be titanium (IV) tetrachloride or titanium(IV) tetraisopropoxide (Ti(OiPr)4). The thermally-treated MgCl2component conditioned by the chlorinating agent may be contacted with the titanium species under conditions sufficient to adsorb at least a portion of the titanium species onto the MgCl2component. For example, in some embodiments, the thermally-treated MgCl2component may be contacted with the titanium species at a temperature of from 0° C. to 50° C., from 0° C. to 35° C., from 25° C. to 50° C., or from 25° C. to 35° C. In some embodiments, the thermally-treated MgCl2component may be contacted with the titanium species for a time of from 0.5 hour to 72 hours, from 0.5 hour to 24 hours, from 0.5 hour to 12 hours, from 0.5 hour to 6 hours, from 3 hours to 72 hours, from 3 hours to 24 hours, from 3 hours to 12 hours, from 6 hours to 72 hours, from 6 hours to 24 hours, or from 6 hours to 12 hours. In some embodiments, the heterogeneous procatalyst may include a molar ratio of the titanium species to the thermally-treated MgCl2component in the heterogeneous procatalyst of from 0.5:40 to 5:40, from 0.5:40 to 3:40, from 1.5:40 to 5:40, or from 1.5:40 to 3:40. As previously described, in some embodiments, the untreated MgCl2slurry may be thermally treated after addition of the chlorinating agent and the titanium species to the MgCl2slurry to produce the thermally-treated MgCl2component. For example, in some embodiments, preparing the heterogeneous procatalyst may include preparing the untreated MgCl2slurry, contacting the untreated MgCl2slurry with the chlorinating agent to produce an untreated MgCl2slurry conditioned by the chlorinating agent, contacting the untreated MgCl2slurry conditioned by the chlorinating agent with the titanium species to produce a pretreated heterogeneous procatalyst, and thermally treating the pretreated heterogeneous procatalyst to produce the heterogeneous procatalyst comprising the thermally treated MgCl2component, chlorinating agent, and titanium species. The pretreated heterogeneous procatalyst refers to the mixture of the titanium species and the untreated MgCl2slurry conditioned by the chlorinating agent. The pretreated heterogeneous procatalyst may then be thermally treated at a temperature of at least 100° C. and for a time of at least 30 minutes to produce the heterogeneous procatalyst having the thermally treated MgCl2component. In some embodiments, the pretreated heterogeneous procatalyst may be thermally treated at a temperature of greater than or equal to 100° C., greater than or equal to 120° C., greater than or equal to 130° C., greater than or equal to 150° C., or even greater than or equal to 190° C. In some embodiments, the pretreated heterogeneous procatalyst may be thermally treated at a temperature of from 100° C. to 500° C., from 100° C. to 300° C., from 100° C. to 200° C., from 120° C. to 500° C., from 120° C. to 300° C., from 120° C. to 200° C., from 130° C. to 500° C., from 130° C. to 300° C., from 130° C. to 200° C., from 150° C. to 500° C., from 150° C. to 300° C., from 150° C. to 200° C., from 190° C. to 500° C., or from 190° C. to 300° C. The pretreated heterogeneous procatalyst may be thermally treated for a time greater than or equal to 30 minutes (0.5 hours), greater than or equal to 1 hour, greater than or equal to 2 hours, greater than or equal to 3 hours, greater than or equal to 6 hours, or greater than or equal to 10 hours to produce the heterogeneous procatalyst having the thermally treated MgCl2component. For example, in some embodiments, the pretreated heterogeneous procatalyst may be thermally treated for a time of from 0.5 hours to 240 hours, from 0.5 hours to 120 hours, from 0.5 hours to 48 hours, from 0.5 hours to 24 hours, from 1 hour to 240 hours, from 1 hour to 120 hours, from 1 hour to 48 hours, from 1 hour to 24 hours, from 2 hours to 240 hours, from 2 hours to 120 hours, from 2 hours to 48 hours, from 2 hours to 24 hours, from 3 hours to 240 hours, from 3 hours to 120 hours, from 3 hours to 48 hours, from 3 hours to 24 hours, from 6 hours to 240 hours, from 6 hours to 120 hours, from 6 hours to 48 hours, from 6 hours to 24 hours, from 10 hours to 240 hours, from 10 hours to 120 hours, from 10 hours to 48 hours, or from 10 hours to 24 hours. In some embodiments, thermally treating the pretreated heterogeneous procatalyst after addition of the chlorinating agent and titanium species to the MgCl2slurry may include agitating the pretreated heterogeneous procatalyst during the thermal treatment, as previously described. In some embodiments, thermally treating the pretreated heterogeneous procatalyst may be conducted in an inert atmosphere to produce the heterogeneous procatalyst that includes the thermally-treated MgCl2component, the chlorinating agent, and the titanium species. In some embodiments, the heterogeneous procatalyst may include a vanadium compound. Incorporation of a vanadium compound into the heterogeneous procatalyst may enable the heterogeneous procatalyst to produce an ethylene-based polymer having narrowed molecular weight distribution (MWD), which may be reflected in a reduced polydispersity index (PDI) and a reduced melt flow ratio I10/I2of less than or equal to 7, or even less than or equal to 6.5 compared to a polymer produced using a comparative catalyst without the vanadium compound under the same reaction conditions. Including the vanadium species into the heterogeneous procatalyst may also enable the high density fraction of the ethylene-based polymers produced by the heterogeneous procatalysts to be tuned by modifying the type and/or amount of the vanadium species. The vanadium species may be a vanadium species having catalytic activity. For example, in some embodiments, the vanadium species may include, but may not be limited to, a vanadium halide, a vanadium oxohalide, a vanadium oxoalkoxide, or combinations thereof. For example, in some embodiments, the vanadium species may be chosen from VX4, VOX3, or VO(OR2)3, where each X is independently a halogen atom or (C1-C40heterohydrocarbyl) and R2is (C1-C20)hydrocarbyl or —C(O)R3in which R3is (C1-C30) hydrocarbyl. In one or more embodiments, R2and R3may be chosen from methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, iso-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl, nonyl, or decyl. In some embodiments, when R2is —C(O)R3, R3is 3-heptyl. In some embodiments, the vanadium species may may be chosen from vanadium(IV) chloride, vanadium(V) oxytrichloride (VOCl3), vanadium(V) oxytrimethoxide, vanadium(V) oxytriethoxide, vanadium(V) oxytriisopropoxide, vanadium(V) oxytributoxide, vanadium(V) oxytriisobutoxide, vanadium(V) oxypropoxide (VO(OnPr)3), vanadyl acetate, vanadium(IV) oxide stearate, vanadium octanoate, and combinations of these. In some embodiments, the vanadium species may be added to the heterogeneous procatalyst. In some embodiments, the vanadium species may be added to the pretreated heterogeneous procatalyst or to the MgCl2slurry conditioned by the chlorinating agent. In some embodiments, the heterogeneous procatalyst may have a molar ratio of the vanadium species to the MgCl2in the heterogeneous procatalyst of from 0.1:40 to 8:40, from 0.1:40 to 4:40, from 0.2:40 to 5:40, or from 0.2:40 to 4:40. The heterogeneous procatalyst prepared by any of the previously described processes may be combined with a cocatalyst to produce the catalyst system. The cocatalyst may include at least one organometallic compound such as an alkyl or haloalkyl of aluminum, aluminoxane, alkylaluminum alkoxide, an alkylaluminum halide, a Grignard reagent, an alkali metal aluminum hydride, a metal alkyl, an alkali metal borohydride, an alkali metal hydride, an alkaline earth metal hydride, or the like. In some embodiments, the cocatalyst may be an organoaluminum compound. In some embodiments, the cocatalyst may be chosen from an alkyl of aluminum, a haloalkyl of aluminum, an alkylaluminum halide, and mixtures thereof. In some embodiments, the cocatalyst may be chosen from triethylalumnium, trimethylalumnium, tri-n-butylalumnium, triisobutylalumnium, tri-n-hexylalumnium, tri-n-octylalumnium, diethylalumnum chloride, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), diethylaluminum ethoxide, and mixtures thereof. As previously discussed, the catalyst system may include the heterogeneous procatalyst and the cocatalyst. Preparing the catalyst system may include contacting the heterogeneous procatalyst with the cocatalyst. The formation of the catalyst system from reaction of the heterogeneous procatalyst and the cocatalyst may be carried out in situ (e.g., in place in the reactor), just prior to entering the polymerization reactor, or before polymerization. Thus, the combination of the heterogeneous procatalyst and the cocatalyst may occur under a wide variety of conditions. Such conditions may include, for example, contacting the heterogeneous procatalyst and cocatalyst under an inert atmosphere such as nitrogen, argon or other inert gas at temperatures of from 0° C. to 250° C., from 0° C. to 200° C., from 15° C. to 250° C., from 15° to 200° C., from 15° C. to 50° C., or from 150° C. to 250° C. In the preparation of the catalytic reaction product (i.e., catalyst system), it is not necessary to separate hydrocarbon soluble components from hydrocarbon insoluble components. Time for contact between the heterogeneous procatalyst and the cocatalyst prior to the polymerization reaction may be from greater than 0 minutes to 10 days, from greater than 0 minutes to 60 minutes, from greater than 0 minutes to 5 minutes, from 0.1 minutes to 5 minutes, from 0.1 minutes to 2 minutes, or from 1 minute to 24 hours. Various combinations of these conditions may be employed. In some embodiments, the catalyst system may have a molar ratio of the cocatalyst to the titanium species in the heterogeneous procatalyst of from 0.5:1 to 50:1, 3:1 to 20:1, from 3:1 to 15:1, from 3:1 to 10:1, from 3:1 to 8:1, from 5:1 to 20:1, from 5:1 to 15:1, from 5:1 to 10:1, from 8:1 to 20:1, or from 8:1 to 15:1. The catalyst system including the heterogeneous procatalyst and cocatalyst may be used in a polymerization or copolymerization process for polymerizing olefins. For example, in some embodiments, the catalyst system may be utilized in a polymerization or copolymerization process to make ethylene-based polymers, such as linear low density polyethylene (LLDPE) and/or other ethylene-based polymers. In some embodiments, the polymerization or copolymerization process may include contacting ethylene and optionally one or more α-olefin comonomers with the catalyst system comprising the heterogeneous procatalyst and optionally a cocatalyst to form an ethylene-based polymer. The olefin polymerization/copolymerization reaction may be conducted in a reaction medium. The reaction medium may be a hydrocarbon diluent, such as an isoparaffinic solvent, an aliphatic hydrocarbon, or any of the other hydrocarbon diluents previously described in this disclosure. The olefin polymerization/copolymerization process may include contacting the olefin or a combination of olefins with the reaction medium in the presence of the catalyst system, which includes the heterogeneous procatalyst and the cocatalyst. Conditions may be any that are suitable to initiate and maintain a polymerization reaction. In some embodiments, a molecular weight regulator, such as hydrogen for example, may also be present in the reaction vessel to suppress formation of polymer molecules with undesirably high molecular weight. Any ethylene polymerization or copolymerization reaction system may be employed to produce the ethylene-based polymers using the catalyst systems disclosed herein. Such reaction systems may include, but are not limited to, slurry phase polymerization processes, solution phase polymerization processes, gas-phase polymerization processes, and combinations thereof. The polymerization or copolymerization processes may be performed using one or more conventional reactors, examples of which may include, but are not limited to, loop reactors, stirred tank reactors, fluidized-bed reactors, batch reactors in parallel or in series, and/or any combinations thereof. In some embodiments, the polymerization process may be performed in two or more reactors in series, parallel, or combinations thereof. In other embodiments, the polymerization process may be conducted in a single reactor. The polymerization process may be a batch polymerization process or a continuous polymerization process. For example, in some embodiments, the polymerization process may be a batch polymerization process, which may be conducted in a stirred tank reactor. In some embodiments, the polymerization process may be continuous, such as a polymerization reaction conducted in a continuous solution polymerization reactor. In other embodiments, the polymerization process may include two or more polymerization steps. In these embodiments, the catalyst system including the heterogeneous procatalyst disclosed herein may be used for any one or a plurality of the polymerization steps. The polymers produced from polymerization/copolymerization processes utilizing the heterogeneous procatalyst disclosed herein may be homopolymers of C2-C20alpha-olefins, such as ethylene, propylene, or 4-methyl-1-pentene. In some embodiments, the polymers from polymerization processes using the heterogeneous procatalyst disclosed herein may include copolymers of ethylene or propylene with at least one or more alpha-olefins comonomers. In some embodiments, the polymers may be ethylene-based polymers, such as copolymers of ethylene with at least one of the above C3-C20alpha-olefins, diolefins. In some embodiments, the comonomer may be an α-olefin comonomer having no more than 20 carbon atoms. For example, in some embodiments, the α-olefin comonomer may have from 3 to 20 carbon atoms, from 3 to 10 carbon atoms, or from 3 to 8 carbon atoms. Exemplary α-olefin comonomers may include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, or combinations of these. In some embodiments, the ethylene-based polymers may include an α-olefin comonomer selected from the group consisting of 1-butene, 1-hexene, and 1-octene. In some embodiments, the ethylene-based polymers produced using the catalyst systems disclosed herein may be copolymers of ethylene monomer units and comonomer units chosen from 1-butene, 1-hexene, 1-octene, or combinations of these. In the polymerization/copolymerization process utilizing the catalyst system disclosed herein, polymerization is effected by adding a catalytic amount of the catalyst system including the heterogeneous procatalyst to a polymerization reactor containing the selected α-olefin monomers (e.g., ethylene and/or one or more than one α-olefin comonomers), or vice versa. The polymerization reactor may be maintained at a temperature of from 50° C. to 300° C. For example, in some embodiments, the polymerization reactor may be maintained at temperatures of from 50° C. to 230° C., from 50° C. to 200° C., from 100° C. to 300° C., from 100° C. to 230° C., from 100° C. to 200° C., or from 60° C. to 120° C. In some non-limiting embodiments, the reactants, catalyst system, or both may have a residence time in the polymerization reactor of from 5 minutes to 4 hours, from 5 minutes to 20 minutes, or from 0.5 hours to 4 hours. Longer or shorter residence times may alternatively be employed. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen and in the presence of the catalyst system. The amount of the catalyst system may be sufficient to provide a desired productivity (e.g., yield) of the ethylene-based polymers but not so great that amount of the catalyst system is cost prohibitive. It is understood, however, that the most advantageous catalyst concentration will depend upon polymerization conditions such as temperature, pressure, solvent, and the presence of catalyst poisons. In some embodiments, the polymerization/copolymerization process may be conducted at pressures that are relatively low, such as pressures of from 150 to 3,000 psig (1.0 to 20.7 MPa), from 250 to 1,000 psig (1.7 to 6.9 MPa), or from 450 to 800 psig (3.1 to 5.5 MPa). However, polymerization/copolymerization using the catalyst system described herein may be conducted at pressures from atmospheric pressure to pressures determined by the capabilities (e.g., pressure rating) of the polymerization equipment. In some embodiments, the polymerization/copolymerization process may include a carrier, which may be an inert organic diluent, excess monomer, or both. Oversaturation of the carrier with the polymer may be generally avoided during the polymerization/copolymerization process. If such saturation of the carrier with the polymer occurs before the catalyst system becomes depleted, the full efficiency of the catalyst system may not be realized. In some embodiments, the polymerization/copolymerization process may be operated at conditions sufficient to maintain the amount of polymer in the carrier/diluent at a concentration less than an oversaturation concentration of the polymer. For example in some embodiments, the polymerization/copolymerization process may be operated under conditions sufficient to maintain the amount of the polymer in the carrier/diluent less than 30 weight percent (wt. %), based on the total weight of the reaction mixture. In some embodiments, the polymerization/copolymerization process may include mixing or stirring the reaction mixture to maintain temperature control and enhance the uniformity of the polymerization reaction throughout the polymerization zone. In some embodiments, such as with more rapid reactions with relatively active catalysts, the polymerization/copolymerization process may include refluxing monomer and diluent, if diluent is included, thereby removing at least some of the heat of reaction. In some embodiments, heat transfer equipment (e.g., heat exchangers, cooling jackets, or other heat transfer means) may be provided for removing at least a portion of the exothermic heat of polymerization. In some embodiments, the reaction mixture added to the polymerization/copolymerization process may include an amount of ethylene monomer sufficient to maintain reactor stability and increase catalyst efficiency. In some embodiments, the reaction mixture may have a molar ratio of diluent to ethylene monomer of from 1:2 to 1:8, from 1:2 to 1:5, from 1:3 to 1:8, or from 1:3 to 1:5. In some embodiments, a portion of excess ethylene monomer may be vented from the polymerization process to maintain the concentration of ethylene monomer in the reactor. In some embodiments, the polymerization/copolymerization process may include contacting hydrogen gas with the reaction mixture during the reaction. The hydrogen gas may be operable to reduce molecular weight of the ethylene-based polymer as well as to reduce formation of ultra-high molecular weight molecules of the ethylene-based polymer. In some embodiments in which hydrogen gas is introduced, a concentration of the hydrogen gas in the reaction mixture may be maintained at from 0.001 mole to 1 mole of hydrogen per mole of monomer, where the monomer includes the ethylene monomer and any optional α-olefin comonomers. The hydrogen may be added to the polymerization reactor with a monomer stream, as a separate hydrogen feed stream, or both. The hydrogen may be added to the polymerization reactor before, during, and/or after addition of the monomer to the polymerization reactor. In some embodiments, the hydrogen may be added either before or during addition of the catalyst system. In some embodiments, the polymerization/copolymerization process may be conducted without introducing hydrogen gas. The resulting ethylene-based polymer may be recovered from the polymerization mixture by driving off unreacted monomer, comonomer, diluent, or both. In some embodiments, no further removal of impurities may be required. The resultant ethylene-based polymer may contain small amounts of catalyst residue. The resulting ethylene-based polymer may further be melt screened. For example, the ethylene-based polymer may be melted with an extruder and then passed through one or more active screens, positioned in series of more than one, with each active screen having a micron retention size of from 2 m to about 400 m. During melt screening, the mass flux of the ethylene-based polymer may be from 5 lb/hr/in2to about 100 lb/hr/in2. The increased molecular weight capability of the heterogeneous procatalysts and catalyst systems disclosed herein may enable the polymerization/copolymerization processes to be conducted at greater process temperatures, which may enable the polymerization/copolymerization processes to produce ethylene-based polymers at greater production throughput rates and having improved properties, such as optical properties and/or dart impact/tear balance (i.e., balance between the dart impact performance and the tear performance of the ethylene-based polymer), compared to polymers made at lesser process temperatures. Additionally, the catalyst systems disclosed herein can be used together with molecular catalyst systems for production of bimodal polymers, where the catalyst systems disclosed herein generate a polymer component with high molecular weight and low comonomer content. The ethylene-based polymers may include less than 50 percent by weight of units derived from one or more α-olefin comonomers. All individual values and subranges from less than 50 wt. % are included herein and disclosed herein. For example, in some embodiments, the ethylene-based polymers may include less than or equal to 30 wt. %, less than or equal to 20 wt. %, less than or equal to 15 wt. %, less than or equal to 10 wt. %, less than or equal to 8 wt. %, less than or equal to 5 wt. %, or less than or equal to 3 wt. % units derived from one or more α-olefin comonomers. The ethylene-based polymers may include at least 50 percent by weight (wt. %) units derived from ethylene. All individual values and subranges from at least 50 wt. % to 100 wt. % are included herein and disclosed herein. For example, in some embodiments, the ethylene-based polymers may comprise from 70 wt. % to 100 wt. %, from 80 wt. % to 100 wt. %, from 85 wt. % to 100 wt. %, from 90 wt. % to 100 wt. %, from 95 wt. % to 100 wt. %, or even from 97 wt. % to 100 wt. % units derived from ethylene. The ethylene-based polymers produced using the catalyst systems disclosed herein may further include additional components such as other polymers and/or additives. Examples of additives may include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. In some embodiments, antioxidants, such as IRGAFOS™ 168 and IRGANOX™ 1010 antioxidants available from Ciba Geigy, may be used to protect the ethylene-based polymer compositions from thermal and/or oxidative degradation. The ethylene-based polymers may contain any amount of the additives. For example, in some embodiments, the ethylene-based polymers may include from 0.0 wt. % to 10.0 wt. %, from 0.0 wt. % to 7.0 wt. %, from 0.0 wt. % to 5.0 wt. %, from 0.0 wt. % to 3.0 wt. %, from 0.0 wt. % to 2.0 wt. %, from 0.0 wt. % to 1.0 wt. %, or even from 0.0 wt. % to 0.5 wt. % additives based on the total weight of the ethylene-based polymer compositions including such additives. The ethylene-based polymers produced using the catalyst systems disclosed herein may be included in a wide variety of products including, in particular embodiments, LLDPE, but also high density polyethylenes (HDPE), plastomers, medium density polyethylenes, and polypropylene copolymers. For these and other applications, articles may be prepared showing enhanced overall quality due to the increased average molecular weight and high-density fraction of the ethylene-based polymer. Useful forming operations for the polymers may include, but are not limited to, film, sheet, pipe, and fiber extrusion and co-extrusion as well as blow molding, injection molding, and rotary molding may be pursued. Films may include blown or cast films formed by co-extrusion or by lamination and may be useful as shrink film, cling film, stretch film, sealing film, oriented film, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, agricultural film applications, and membranes, for example, in food-contact and non-food-contact applications. Fibers may include melt spinning, solution spinning, and melt blown fiber operations for use in woven and non-woven form to make filters, diaper fabrics, medical garments, and geotextiles. Extruded articles may include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles may include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers, and toys. TEST METHODS Specific Surface Area Specific surface area of MgCl2support was measured by Brunauer, Emmett, Teller (BET) Surface Area Method. A Tristar 3020 Surface Area Analyzer by Micromeritics was used. 30 mL of MgCl2slurry was filtered to remove solvent and then re-slurried in 30 mL of hexane. The resulting slurry was filtered again under inert atmosphere and washed with additional hexane. This process was repeated once to yield a filtercake of MgCl2. Residual solvent was removed from the filtercake under vacuum. The filtercake was further dried on a Vac Prep 061 by Micromeritics using a 0.5 inch (1.27 cm) sample tube and a Transeal stopper designed for inert sample protection by loading a 0.2 g sample of the vacuum-dried MgCl2into the tube under inert atmosphere with a Transeal stopper. The sample tube was connected to the Vac Prep 061 unit with nitrogen purging. The sample tube was treated with vacuum by opening the Transeal stopper and the evacuated tube was placed in a heating block with an aluminum tube protector. The sample was dried under the vacuum on the Vac Prep 061 unit at 110° C. for 3 hours. Afterward, nitrogen was introduced into the sample tube. The dried sample was allowed to cool to room temperature before disconnecting the sample tube from the Vac Prep 061 unit to give a fully dried sample. Under inert atmosphere, 0.1500 to 0.2000 g of the fully dried sample was transferred into a clean sample tube with a tube filler rod. The sample tube was then sealed with a Transeal stopper and connected to the Tristar 3020 instrument for surface area measurement. QUICKSTART method was used for acquiring data. Melt Index Melt index (I2), is measured in accordance with ASTM D1238, under conditions of 190° C. and 2.16 kg of load. Melt Flow Index (I2) was obtained using a CEAST 7026 or an Instron MF20 instrument. The instruments followed ASTM D1238, Methods E and N. The above methods were also used to determine the melt index (I10) at conditions of 190° C. and 10 kg of load. The melt index (I2) is reported in grams eluted per 10 minutes (g/10 min). The melt index I2was used for polymer characterization. A higher I2value may generally correlates to a lower Mw. Additionally, the melt index ratio I10/I2was also used for polymer characterization. A lower I10/I2may generally correlate to a narrower molecular weight distribution (MWD). Gel Permeation Chromatography (GPC) The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) coupled to a Precision Detectors (Now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040. For all Light scattering measurements, the 15 degree angle is used for measurement purposes. The autosampler oven compartment was set at 160° C. and the column compartment was set at 150° C. The columns used were 3 Agilent “Mixed B” 30 cm 20-micron linear mixed-bed columns. The chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters (μL) and the flow rate was 1.0 milliliters/minute (mL/min). Calibration of the GPC column set was performed with at least 20 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80 degrees Celsius (° C.) with gentle agitation for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (EQU. 1)(as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).: Mpolyethylene=A×(Mpolystyrene)BEQU. 1 where M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0. A fifth order polynomial was used to fit the respective polyethylene-equivalent calibration points. A small adjustment to A (from approximately 0.415 to 0.44) was made to correct for column resolution and band-broadening effects such that NIST standard NBS 1475 is obtained at 52,000 Mw. The total plate count of the GPC column set was performed with Eicosane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation.) The plate count (Equation 2 (EQU. 2)) and symmetry (Equation 3 (EUQ. 3)) were measured on a 200 microliter injection according to the following equations: Plate⁢Count=5.54*((R⁢VPeak⁢MaxPeak⁢Width⁢at⁢12⁢height)2EQU.2 where RV is the retention volume in milliliters, the peak width is in milliliters, the peak max is the maximum height of the peak, and ½ height is ½ height of the peak maximum. Symmetry=(Rear⁢Peak⁢⁢RVone⁢tenth⁢height-R⁢VPeak⁢max)(R⁢VPeak⁢max-Front⁢Peak⁢RVone⁢tenth⁢height) where RV is the retention volume in milliliters and the peak width is in milliliters, Peak max is the maximum position of the peak, one tenth height is 1/10 height of the peak maximum, and where rear peak refers to the peak tail at later retention volumes than the peak max and where front peak refers to the peak front at earlier retention volumes than the peak max. The plate count for the chromatographic system should be greater than 24,000 and symmetry should be between 0.98 and 1.22. Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 2 mg/mL, and the solvent (contained 200 ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 2 hours at 160° C. under “low speed” shaking. The calculations of Mn(GPC), Mw(GPC), and MZ(GPC)were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4-6 (EQU. 4, EQU. 5, and EQU. 6) below, using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1. M⁢n(G⁢P⁢C)=∑i⁢IRi∑i⁢(IRi/Mpolyethylenei)EQU.4M⁢w(G⁢P⁢C)=∑i⁢(IRi×Mpolyethylenei)∑i⁢IRiEQU.5M⁢z(G⁢P⁢C)=∑i⁢(IRi×Mpolyethylenei2)∑i⁢(IRi×Mpolyethylenei)EQU.6 In order to monitor the deviations over time, a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. To facilitate the highest accuracy of a RV measurement of the flow marker peak, a least-squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 7 (EQU. 7). Processing of the flow marker peak was done via the PolymerChar GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within +/−2% of the nominal flowrate. Flow⁢rate(effective)=F⁢l⁢o⁢w⁢r⁢a⁢t⁢e(nominal)×RV(FM⁢Calibrated)RV(FM⁢Sample)EQU.7 A calibration for the IR5 detector rationing was performed using at least ten ethylene-based polymer standards (polyethylene homopolymer and ethylene/octene copolymers) of known short chain branching (SCB) frequency (measured by the13C NMR Method), ranging from homopolymer (0 SCB/1000 total C) to approximately 50 SCB/1000 total C, where total C=carbons in backbone+carbons in branches. Each standard had a weight-average molecular weight (Mw) of 36,000 g/mole to 126,000 g/mole, as determined by the GPC-LALLS. Each standard had a molecular weight distribution (Mw/Mn) from 2.0 to 2.5, as determined by GPC. Example polymer properties for the Copolymer standards are shown in Table A. TABLE A“Copolymer” StandardsWt %IR5 AreaSCB/1000ComonomerRatioTotal CMwMw/Mn23.10.241128.937,3002.2214.00.215217.536,0002.190.00.18090.038,4002.2035.90.270844.942,2002.185.40.19596.837,4002.168.60.204310.836,8002.2039.20.277049.0125,6002.221.10.18101.4107,0002.0914.30.216117.9103,6002.209.40.203111.8103,2002.26 The “IR5 Area Ratio (or “IR5Methyl Channel Area/IR5Measurement Channel Area”)” of “the baseline-subtracted area response of the IR5 methyl channel sensor” to “the baseline-subtracted area response of IR5 measurement channel sensor” (standard filters and filter wheel as supplied by PolymerChar: Part Number IR5_FWM01 included as part of the GPC-IR instrument) was calculated for each of the “Copolymer” standards. A linear fit of the Wt % Comonomer frequency versus the “IR5 Area Ratio” was constructed in the form of the following Equation 8 (EQU. 8): (Wt.%⁢Comonomer)=A0+[A1×(IR⁢5Methyl⁢Channel⁢AreaIR⁢5Measurement⁢Channel⁢Area)]EQU.8 End-Group Correction of the wt % Comonomer data can be made via knowledge of the termination mechanism if there is significant spectral overlap with the comonomer termination (methyls) via the molecular weight determined at each chromatographic slice. Measurement of HDF (High Density Fraction) Improved comonomer content distribution (iCCD) analysis was performed with Crystallization Elution Fractionation instrumentation (CEF) (PolymerChar, Spain) equipped with IR-5 detector (PolymerChar, Spain) and two angle light scattering detector Model 2040 (Precision Detectors, currently Agilent Technologies). A guard column packed with 20-27 micron glass (MoSCi Corporation, USA) in a 10 cm (length) by ¼″ (ID) (0.635 cm ID) stainless was installed just before IR-5 detector in the detector oven. Ortho-dichlorobenzene (ODCB, 99% anhydrous grade or technical grade) was used. Silica gel 40 (particle size 0.2˜0.5 mm, catalogue number 10181-3) from EMD Chemicals was obtained (can be used to dry ODCB solvent before). The CEF instrument is equipped with an autosampler with N2purging capability. ODCB is sparged with dried nitrogen (N2) for one hour before use. Sample preparation was done with autosampler at 4 mg/mL (unless otherwise specified) under shaking at 160° C. for 1 hour. The injection volume was 300 μL. The temperature profile of iCCD was: crystallization at 3° C./min from 105° C. to 30° C., the thermal equilibrium at 30° C. for 2 minute (including Soluble Fraction Elution Time being set as 2 minutes), elution at 3° C./min from 30° C. to 140° C. The flow rate during crystallization is 0.0 ml/min. The flow rate during elution is 0.50 ml/min. The data was collected at one data point/second. The iCCD column was packed with gold coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15 cm (length) by ¼″ (ID) (0.635 cm) stainless tubing. The column packing and conditioning were with a slurry method according to the reference (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017/040127A1). The final pressure with TCB slurry packing was 150 Bars. Column temperature calibration was performed by using a mixture of the Reference Material Linear homopolymer polyethylene (having zero comonomer content, Melt index (I2) of 1.0, polydispersity Mw/Mnapproximately 2.6 by conventional gel permeation chromatography, 1.0 mg/mL) and Eicosane (2 mg/mL) in ODCB. The iCCD temperature calibration consisted of four steps: (1) Calculating the delay volume defined as the temperature offset between the measured peak elution temperature of Eicosane minus 30.00° C.; (2) Subtracting the temperature offset of the elution temperature from iCCD raw temperature data. It is noted that this temperature offset is a function of experimental conditions, such as elution temperature, elution flow rate, etc.; (3) Creating a linear calibration line transforming the elution temperature across a range of 30.00° C. and 140.00° C. so that the linear homopolymer polyethylene reference had a peak temperature at 101.0° C., and Eicosane had a peak temperature of 30.0° C.; (4) For the soluble fraction measured isothermally at 30° C., the elution temperature below 30.0° C. is extrapolated linearly by using the elution heating rate of 3° C./min according to the reference (Cerk and Cong et al., U.S. Pat. No. 9,688,795). The comonomer content versus elution temperature of iCCD was constructed by using 12 reference materials (ethylene homopolymer and ethylene-octene random copolymer made with single site metallocene catalyst, having ethylene equivalent weight average molecular weight ranging from 35,000 to 128,000). All of these reference materials were analyzed same way as specified previously at 4 mg/mL. The modeling of the reported elution peak temperatures as a function of octene mole % using linear regression resulting in the model of Equation 9 (EQU. 9) for which R2 was 0.978. (Elution Temperature)=−6.3515(Octene Mol %)+101.000  EQU. 9 For the whole resin, integration windows are set to integrate all the chromatograms in the elution temperature (temperature calibration is specified above) range from 23.0° C. to 115° C. The weight percentage of the high density fraction of the resin (HDF) is defined by the following Equation 10 (EQU. 10): HDF=(inte⁢g⁢rated⁢area⁢of⁢elution⁢window⁢95-115⁢°⁢C.)(i⁢n⁢t⁢e⁢g⁢rated⁢area⁢of⁢entire⁢elution⁢window⁢23-115⁢°⁢C.)×1⁢00⁢%EQU.10 EXAMPLES Embodiments of the present disclosure will be further clarified by the following examples. Examples 1A-1F: Batch Copolymerization of Ethylene-Based Polymer Using Heterogeneous Procatalyst with Thermally Treated MgCl2 In Examples 1A-1F (1A, 1B, 1C, 1D, 1E, and 1F), batch copolymerizations of ethylene and 1-octene were performed using the heterogeneous procatalyst including the thermally treated MgCl2. The heterogeneous procatalyst incorporating the thermally treated MgCl2component was prepared by first synthesizing the MgCl2particles via reacting butyl ethyl magnesium in ISOPAR™ E paraffinic solvent solution with hydrochloride gas to produce a slurry of MgCl2particles. The MgCl2slurry was stored and handled in a nitrogen purged glovebox to avoid contamination from moisture and oxygen. To thermally treat the MgCl2slurry, 2 L of the MgCl2slurry was loaded into a 5.9 liter (L) reactor via an air-tight designed transferring container, such that the MgCl2was not exposed to air or moisture. N2atmosphere was used for reactor line purging and isolation. The reactor was then heated with a heating jacket to 190° C. for 1 hour. The heating of the reactor was controlled by a step controller, with the ramping time of about one hour (from room temperature to 190° C.). After the designated heating time, the reactor was allowed to cool to room temperature in about 3 hours. During the heating process, the contents of the reactor were agitated at 100 rpm. Variations in temperature were controlled to within +/−2° C. After the reactor was cooled to room temperature, the slurry comprising the thermally treated MgCl2was transferred back into the glovebox using the air-tight transferring container to prevent exposure to air and/or moisture. The thermally treated MgCl2was then used to produce heterogeneous procatalysts of Examples 1A-1F. In the N2-purged glovebox, the heterogeneous procatalysts of Examples 1A-1F were produced via sequential addition of ethyl aluminum dichloride (EADC, Aldrich, 1.0 M in hexane) (chlorinating agent) and titanium tetraisopropoxide (TiPT, Aldrich, 0.125 M in ISOPAR™ E solvent) (titanium species) to the slurry containing the thermally treated MgCl2according to the following process. For each heterogeneous procatalyst, 10 mL of the thermally treated MgCl2slurry was maintained under constant stirring in a capped glass vial. On the first day, a designated amount of the 1.0 M EADC solution was added to the thermally treated MgCl2slurry, and the resulting slurry was left stirring overnight. On the second day, a designated amount of the 0.125 M TiPT solution was added, and the resulting slurry was left stirring overnight. The heterogeneous procatalyst was ready for use on the third day. The designated amounts of EADC solution and TiPT solution as well as the molar ratios of the MgCl2to the EADC to the TiPt (MgCl2/EADC/TiPT) for each of the heterogeneous procatalysts of Examples 1A-1F are provided below in Table 1. For Examples 1A-1F, the batch copolymerization reactions were conducted in a 2 L Parr batch reactor. The reactor was heated by an electrical heating mantle and cooled by an internal serpentine cooling coil using water. The bottom of the reactor was fitted with a dump valve for emptying the reactor contents into a stainless steel dump pot pre-filled with a catalyst kill solution (typically 5 mL mixture of IRGAFOS® organophosphite processing stabilizer from BASF, IRGANOX® antioxidant from BASF, and toluene). The dump pot was vented to a blow down tank under continuous N2purge. All solvents used for the copolymerization and catalyst makeup were passed through purification columns, to remove impurities. The solvents were passed through 2 columns: the first containing A2 alumina and the second containing reduced copper on alumina (Q5 reactant). The ethylene was passed through 2 columns: the first containing A204 alumina and 4 Angstrom (Å) molecular sieves, the second containing Q5 reactant. The N2was passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5 reactant. The reactor was loaded first with 664 grams (g) ISOPAR™ E solvent and 134±2 g 1-octene from a separate tank, which was filled to the load set points using an Ashcroft differential pressure cell. 14.8±0.3 mmol hydrogen was added after solvent addition and the reactor was heated to 190° C. 56±1 g ethylene was then added to the reactor when at the reaction temperature to reach reaction pressure (i.e., 475 psi). Further ethylene addition amounts during the polymerization reaction were monitored by a micro-motion flow meter. For each of Examples 1A-1F, an amount of the heterogeneous procatalyst slurry was pipetted into a 5 mL vial and then taken up in a 20 mL syringe with an 18 gauge needle. The vial was rinsed with solvent and the rinses were also taken into the syringe. A double-ended septa sealed vial was used to cap the syringe for transportation outside the glovebox to the batch reactor. Additionally, an amount of a cocatalyst solution of triethyl aluminum in a solvent (TEA, 1.00-0.05 M solution in ISOPAR™ E solvent) was pipetted into a separate 5 mL vial and then taken up in a separate 20 mL syringe with an 18 gauge needle. For each of Examples 1A to 1D, the amount of the heterogeneous procatalyst slurry contained 1.5 μmol of Ti, and the amount of the cocatalyst solution contained 12.0 μmol of TEA. For Examples 1E and 1F, the amount of heterogeneous procatalyst contained 2.2 μmol of Ti, and the amount of cocatalyst solution contained 17.6 μmol of TEA. The heterogeneous procatalyst and TEA cocatalyst solution were taken up in separate syringes and were injected within several minutes of being prepared. The heterogeneous procatalyst slurry and cocatalyst solution were each injected into a shot tank attached to the reactor under the flow of N2. The heterogeneous procatalyst slurry was prepared second but injected first, and the TEA solution was rinsed three times (2.5, 2.5, 5 mL). The mixture of the two solutions was maintained in the shot tank for 5 minutes, and then introduced to the reactor under a 150 psi differential pressure after the reactor set points were achieved. After injection of the catalyst system (heterogeneous procatalyst and cocatalyst solution), the copolymerization reaction was initiated to produce the ethylene-based polymers. The reaction mixture was collected for analysis in a stainless steel pan for solvent removal. The reactor was washed twice with 850 g of ISOPAR™ E solvent at a temperature between 140° C. and 160° C. The first wash was collected and combined with the reaction mixture. The ethylene-based polymer samples collected for each of Examples 1A-1F were air dried overnight to remove the majority of solvent and then placed in a vacuum oven under N2to further remove trapped solvent. The vacuum oven was designed to do the following: cycle three times between 5 minutes nitrogen flow and vacuum to 40 Torr, ramp temperature 1° C./min to 80° C. and hold for three hours under vacuum, then ramp to 140° C. and hold for 4 hours. The cooled ethylene-based polymers of Examples 1A-1F were then analyzed for Mw, melt index (I2), HDF wt. %, according to the test methods described herein. The results are provided below in Table 2. Examples 2A-2B: Batch Copolymerization of Ethylene-Based Polymer Using Heterogeneous Procatalyst with Thermally Treated MgCl2 In Examples 2A and 2B, batch copolymerization reactions of ethylene and 1-octene were performed using a heterogeneous procatalyst that included MgCl2thermally treated at 190° C. for 24 hours. The MgCl2slurry was first produced by reacting butyl ethyl magnesium in ISOPAR™ E solvent with hydrochloride gas to produce a slurry of MgCl2particles in the solution (diluent). The MgCl2slurry was stored and handled in a nitrogen purged glovebox to avoid contamination from moisture and oxygen. For Examples 2A and 2B, 150 mL of the MgCl2slurry was loaded into a 300 mL stainless steel Parr reactor within the N2purgebox and the reactor was sealed. The Parr reactor was then taken out of the N2purgebox and heated with a heating jacket to a temperature of 190° C. and maintained at 190° C. for 24 hours. The heating of the reactor was controlled by a step controller, with the ramping time of about 30 minutes (from room temperature to 190° C.). After the designated heating time, the reactor was allowed to cool to room temperature in about 1.5 hours. During the heating process, the contents of the reactor kept static without agitation. Variations in temperature were controlled to within +/−2° C. After cooling the reactor to room temperature, the reactor was transferred back into the purgebox, and the thermally treated MgCl2was collected without exposure to air and/or moisture. The thermally treated MgCl2was then used to produce heterogeneous procatalysts of Examples 2A and 2B via sequential addition of EADC and TiPT to the slurry containing the thermally treated MgCl2, according to the process described in Examples 1A-1F. The designated amounts of the EADC solution and the TiPT solution and the molar ratios of the MgCl2to the EADC to the TiPt (MgCl2/EADC/TiPT) for the heterogeneous procatalysts of Examples 2A and 2B are provided below in Table 1. For Examples 2A and 2B, the batch copolymerizations were conducted in a 2 L Parr batch reactor according to the copolymerization process described in Examples 1A-1F. The reaction conditions and reactor parameters were the same as described in Examples 1A-1F except for the amounts of the heterogeneous procatalyst and TEA solution charged to the reactor. For Examples 2A and 2B, the charged amount of the heterogeneous procatalyst slurry contained 1.4 μmol Ti, and the charged amount of the cocatalyst solution contained 11.2 μmol TEA. The ethylene-based polymers of Examples 2A and 2B were collected and analyzed for Mw, melt index (I2), and HDF wt. %, according to the test methods described herein. The results are provided below in Table 2. Comparative Examples CE1 and CE2: Batch Copolymerization of Ethylene-Based Polymer Using Heterogeneous Procatalyst with Non-Thermally Treated MgCl2 In Comparative Examples CE1 and CE2, batch copolymerization reactions of ethylene and 1-octene were conducted using a heterogeneous procatalyst that included MgCl2that was not subjected to thermal treatment. The MgCl2for Comparative Examples CE1 and CE2 was prepared by synthesizing the MgCl2particles via reacting butyl ethyl magnesium in ISOPAR™ E solvent with hydrochloride gas to produce a slurry of MgCl2particles in the solution (diluent). The MgCl2slurry was stored and handled in a nitrogen purged glovebox to avoid contamination from moisture and oxygen. For Comparative Examples CE1 and CE2, the MgCl2was not thermally treated. The non-thermally treated MgCl2slurry was used to produce the heterogeneous procatalysts of CE1 and CE2 via sequential addition of EADC and TiPT to the MgCl2slurry, according to the process of Examples 1A-1F. The designated amounts of the EADC solution and the TiPT solution and the molar ratios of the MgCl2to the EADC to the TiPT (MgCl2/EADC/TiPT) for the procatalysts of CE1 and CE2 are provided below in Table 1. For CE1 and CE2, the batch copolymerizations were conducted in a 2 L Parr batch reactor according to the copolymerization process described in Examples 1A-1F. The reaction conditions and reactor parameters for CE1 and CE2 were the same as described in Examples 1A-1F except for the amounts of the heterogeneous procatalyst and TEA solution charged to the reactor. For CE1 and CE2, the charged amount of the heterogeneous procatalyst slurry (110 μL) contained 1.4 μmol Ti, and the charged amount of the cocatalyst solution contained 11.2 μmol TEA. The ethylene-based polymers produced in CE1 and CE2 were collected and analyzed for Mw, melt index (I2), and HDF wt. %, according to the test methods described herein. The results are provided below in Table 2. Example 3: Comparison of Examples 1A-1F and Examples 2A and 2B with Comparative Examples CE1 and CE2 The following Table 1 provides the composition parameters for each of the heterogeneous procatalysts of Examples 1A-1F, 2A, and 2B and Comparative Examples CE1 and CE2. Table 1 also provides the temperature and treatment time of the thermal treatment of the MgCl2for Examples 1A-1F and Examples 2A and 2B. TABLE 1Heat treatment parameters and heterogeneousprocatalyst compositions for Examples 1A-1F, 2A,and 2B and Comparative Examples CE1 and CE2.MgCl2HeatHeterogeneousTreatmentProcatalyst CompositionTempTimeEADCTiPTMgCL2/EADC/TiPT(° C.)(hrs)(μL)(μL)(mol/mol/mol)1A1901.033767340.0/6.8/1.71B1901.0600120040.0/12.0/3.01C1901.0863172640.0/17.2/4.31D1901.01151230240.0/23.2/5.81E1901.01438287740.0/28.8/7.21F1901.01726345240.0/32.4/8.62A19024.020941840.0/4.0/1.02B19024.0607121540.0/12.0/3.0CE1——599119940.0/12.0/3.0CE2——599119940.0/12.0/3.0 The following Table 2 includes the Mw, melt index (I2), and HDF wt. % measurements for the ethylene-based polymers of Examples 1A-1F, 2A, and 2B and Comparative Examples CE1 and CE2. In Table 2, the change in Mw (ΔMw), change in I2(ΔI2), and change in HDF wt. % (ΔHDF wt. %) for Examples 1A-1F, 2A and 2B are calculated as a comparison of these properties to the average of Comparative Examples CE1 and CE2. TABLE 2Mw, I2, and HDF wt. % Test Data for Examples 1A-1F, 2A,and 2B and Comparative Examples CE1 and CE2MwΔMwI2ΔI2HDFΔHDF(Dalton)(%)(g/10 min)(%)(wt. %)(%)1A106,3626.021.4121.2323.8078.681B113,11612.751.2430.7330.73130.711C115,82015.451.1137.9937.05178.151D118,82318.441.3822.9138.12186.191E118,36817.991.2729.0538.36187.991F116,36015.991.0143.5841.97215.092A131,16430.740.8453.0722.2667.122B134,27233.841.5115.6436.29172.45CE1100,660N/A1.77N/A12.66N/ACE299,984N/A1.80N/A13.98N/A Comparison of the ethylene-based polymers produced in Examples 1A-1F, 2A, and 2B with those produced in Comparative Examples CE1 and CE2 demonstrates that including the thermally treated MgCl2in the heterogeneous procatalyst increases the Mw and HDF wt. % and decreases the I2of the ethylene-based polymers compared to the comparative ethylene-based polymers of CE1 and CE2 produced with procatalysts that included non-thermally treated MgCl2. Thus, it is shown that a heterogeneous procatalyst that includes MgCl2that has been thermally treated before adding the EADC (chlorinating agent) and titanium species may produce an ethylene-based polymer having increased Mw and HDF and decreased I2compared to comparative polymers made with procatalysts having non-thermally treated MgCl2. Examples 4A-4D: Batch Copolymerization Using Heterogeneous Procatalyst Prepared by Thermally Treating the MgCl2after Addition of the Chlorinating Agent and Ti Species For Examples 4A-4D (4A, 4B, 4C, and 4D), batch copolymerizations of ethylene and 1-octene were performed using a heterogeneous procatalyst prepared by thermally treating the MgCl2after adding the chlorinating agent and titanium species to the MgCl2. Before the copolymerization processes were performed, the heterogeneous procatalyst was synthesized. The MgCl2was first produced by synthesizing the MgCl2particles via reacting butyl ethyl magnesium in ISOPAR™ E paraffinic solvent solution with hydrochloride gas to produce a slurry of MgCl2particles in the solution (diluent). The MgCl2slurry was stored and handled in an inert atmosphere to avoid contamination from moisture and oxygen. The MgCl2slurry was then used to produce the heterogeneous procatalysts of Examples 4A-4D by sequential addition of EADC (Aldrich, 1.0 M EADC in hexane) (chlorinating agent) and TiPT (Aldrich, 0.125 M TiPT in ISOPAR™ E solvent) (titanium species) to the MgCl2slurry. For each heterogeneous procatalyst, the MgCl2slurry was maintained under constant stirring, and a designated amount of the 1.0 M EADC solution was added to the MgCl2slurry and mixed for a period of time. A designated amount of the 0.125 M TiPT solution was then added, and the resulting heterogeneous procatalyst slurry was mixed for another period of time. The heterogeneous procatalysts of Examples 4A-4D each had a molar ratio of MgCl2to EADC to TiPT (MgCl2/EADC/TiPT) of 40/12/3. A 5.9 liter (L) reactor was used to thermally treat the heterogeneous procatalyst slurry comprising the MgCl2, EADC and TiPT added. 2 L of the heterogeneous procatalyst slurry was loaded into the reactor via an air-tight designed transferring container, such that the MgCl2was not exposed to air or moisture. N2atmosphere was used for reactor line purging and isolation. The reactor was then heated with a heating jacket to 190° C. The heating of the reactor was controlled by a step controller, with the ramping time of about one hour (from room temperature to 190° C.). During the heating process, the contents of the reactor were agitated at 100 rpm. Variations in temperature were controlled to within +/−2° C. Each heterogeneous procatalysts of Examples 4A-4D was subjected to a different thermal treatment time. After the designated thermal treatment time elapsed for one of Examples 4A-4D, an aliquot of the heterogenous procatalyst was collected from the reactor using a sampling system under N2protection using pressure transferring to prevent contact of the catalyst with air or moisture. Samples of the thermally treated heterogeneous procatalyst were collected after 1 hour (Ex. 4A), 3 hours (Ex. 4B), 6 hours (Ex. 4C), and 10 hours (Ex. 4D). The thermally treated heterogeneous procatalysts of Examples 4A-4B were then utilized to conduct copolymerizations of ethylene and 1-octene to produce ethylene-based polymers. For Examples 4A-4D, the batch copolymerizations were conducted in a 2 L Parr batch reactor. The reactor was heated by an electrical heating mantle and cooled by an internal serpentine cooling coil using water. The bottom of the reactor was fitted with a dump valve for emptying the reactor contents into a stainless steel dump pot pre-filled with a catalyst kill solution (typically 5 mL mixture of IRGAFOS® organophosphite processing stabilizer from BASF, IRGANOX® antioxidant from BASF, and toluene). The dump pot was vented to a blow down tank under continuous N2purge. All solvents used for the copolymerization and catalyst makeup were passed through purification columns, to remove impurities. The solvents were passed through 2 columns: the first containing A2 alumina and the second containing reduced copper on alumina (Q5 reactant). The ethylene was passed through 2 columns: the first containing A204 alumina and 4 Angstrom (Å) molecular sieves, the second containing Q5 reactant. The N2was passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5 reactant. The reactor was loaded first with 662±1 grams (g) ISOPAR™ E solvent and 131 g 1-octene from a separate tank, which was filled to the load set points using an Ashcroft differential pressure cell. 11.2 mmol hydrogen was added after solvent addition and the reactor was heated to 190° C. 56±1 g ethylene was then added to the reactor when at the reaction temperature to reach reaction pressure (i.e., 475 psi). Further ethylene addition amounts during the polymerization reaction were monitored by a micro-motion flow meter. For each of Examples 4A-4D, 110 μL of the thermally treated heterogeneous procatalyst was pipetted into a 5 ml vial and then taken up in a 20 mL syringe with an 18 gauge needle. The vial was rinsed with solvent and the rinses were also taken into the syringe. A double-ended septa sealed vial was used to cap the syringe for transportation outside the glovebox to the batch reactor. Additionally, 11.2 μmol TEA (1.00-0.05 M solution in ISOPAR™ E solvent) was pipetted into a separate 5 mL vial and then taken up in a separate 20 mL syringe with an 18 gauge needle. The thermally treated heterogeneous procatalyst and TEA solution were added to the reaction system and the reaction was conducted according to the process described previously in Examples 1A-1F. The ethylene-based polymers collected from the reactor system for Examples 4A-4D were then analyzed for Mw, melt index (I2), comonomer weight percent (C8 wt. %), and HDF wt. %, according to the test methods described herein. The results are provided below in Table 3. Comparative Example CE3: Batch Copolymerization of Ethylene-Based Polymer Using Non-Thermally Treated Heterogeneous Procatalyst For Comparative Example CE3, batch copolymerization of ethylene and 1-octene was performed using a heterogeneous procatalyst without thermally treating the heterogeneous procatalyst. Before the copolymerization process was performed, the heterogeneous procatalyst was synthesized via reacting butyl ethyl magnesium in ISOPAR™ E solvent solution with hydrochloride gas to produce a slurry of MgCl2particles in the solution (diluent). The MgCl2slurry was stored and handled in a nitrogen purged glovebox to avoid contamination from moisture and oxygen. The MgCl2slurry was then used to produce the heterogeneous procatalysts of CE3 via sequential addition of EADC and TiPT as previous described in Examples 4A-4D. The heterogeneous procatalyst of CE3 was not subsequently subjected to a thermal treatment. The heterogeneous procatalysts of CE3 had a molar ratio of MgCl2to EADC to TiPT (MgCl2/EADC/TiPT) of 40/12/3. Example 5: Comparison of Examples 4A-4D and Comparative Example CE3 The following Table 3 provides the Mw, melt index (I2), C8 wt. %, and HDF wt. % measurements for the ethylene-based polymers of Examples 4A-4D and Comparative Example CE3. In Table 3, the change in Mw (ΔMw) and change in HDF wt. % (ΔHDF wt. %) for Examples 4A-4D are calculated as a comparison to Comparative Examples CE3. Table 3 also provides the thermal treatment conditions for the heterogeneous procatalysts of Examples 4A-4D. TABLE 3Mw, I2, C8 wt. %, and HDF wt. % Test Data for Examples 4A-4D andComparative Example CE3ThermalTreatmentProperties of Ethylene-Based PolymerTTimeMwΔMwI2ΔI2C8ΔC8HDFΔHDF(° C.)(hrs)(Dalton)(%)(g/10 min)(%)wt. %(%)(wt. %)(%)4A1901119454281.39−172.30−6334.63734B1903129942391.29−234.43−2837.17864C1906113529221.23−264.89−2137.20864D19010114163231.23−264.46−2837.7389CE3——93158—1.67—6.16—20.01— Comparison of the ethylene-based polymers of Examples 4A-4D to those of Comparative Example CE3 demonstrates that thermally treating the MgCl2after addition of the chlorinating agent (EADC) and titanium species (TiPT) can produce a heterogeneous procatalyst capable of producing an ethylene-based polymer exhibiting increased Mw and HDF and decreased C8 wt. % and I2compared to procatalysts that include non-thermally treated MgCl2. Example 6: Batch Copolymerization Utilizing the Heterogeneous Procatalyst of Example 4B with Decreased Ethylene and Increased Hydrogen For Example 6, a batch copolymerization of ethylene and 1-octene was performed using the heterogeneous procatalyst of Example 4B. The batch copolymerization was conducted in accordance with the copolymerization process previously described in Examples 4A-4D, except that the amount of ethylene added to the reactor was reduced to 53±1 g and the amount of hydrogen charged to the reactor was increased to 44.9±0.1 mmol hydrogen. All other reactor conditions were the same as described in Examples 4A-4D. Comparative Example CE4: Batch Copolymerization Utilizing the Procatalyst of CE3 with Decreased Ethylene and Increased Hydrogen For Comparative Example CE4, a batch copolymerization of ethylene and 1-octene was performed using the heterogeneous procatalyst of Comparative Example CE3, which was not subjected to thermal treatment. The batch copolymerization was conducted in accordance with the copolymerization process previously described in Example 6, which included the process described in Examples 4A-4D with decreased ethylene and increased hydrogen. Example 7: Comparison of Example 6 to Comparative Example CE4 The ethylene-based polymers collected from the copolymerization reactors for Example 6 and Comparative Example CE4 were analyzed for Mw, melt index (I2), and comonomer weight percent (C8 wt. %), according to the test methods described herein. The results are provided below in Table 4. TABLE 4Mw, I2, and C8 wt. % Test Data for Example 6 and ComparativeExample CE4ThermalTreatmentProperties of Ethylene-Based PolymerTTimeMwΔMwI2ΔI2C8ΔC8(° C.)(hours)(Dalton)(%)(g/10 min)(%)wt. %(%)61903636175.49.78−2.66.8−22.3CE4——60344—10.04—8.75— Comparison of the ethylene-based polymer of Example 6 with that of Comparative Example CE4 demonstrates that a heterogeneous procatalyst having MgCl2that has been thermally treated after addition of the chlorinating agent (EADC) and the titanium species (TiPT) can produce ethylene-based polymers having increased Mw and decreased C8 wt. % and I2compared to CE4 even when additional hydrogen is introduced to the reactor system, which is expected to limit the formation of high-molecular weight molecules in the reactor. Example 8: Batch Copolymerization Utilizing a Thermally Treated Heterogeneous Procatalyst For Example 8, batch copolymerizations of ethylene and 1-octene were performed using a heterogeneous procatalyst prepared by thermally treating the heterogeneous procatalyst under different thermal treatment conditions. The heterogeneous procatalyst was first synthesized by preparing the MgCl2and sequentially adding EADC and TiPT to the MgCl2slurry as described in Examples 4A-4D. The heterogeneous procatalyst of Example 8 was then thermally treated. For the thermal treatment, 25 mL of the heterogeneous procatalyst of Example 8 and a flea-sized magnetic stir bar were placed in a thick-walled glass tube having a length of 10 inches (25.4 millimeters (mm)) and an inside diameter of 0.75 inch (19.05 mm). The heterogeneous procatalyst in the glass tube exhibited a tan color prior to thermal treatment. The glass tube was sealed tightly with a PTFE threaded cap and placed in a heating block. The heterogeneous procatalyst was then heated to a temperature of 150° C. and maintained at 150° C. for 60 hours. The glass tube was cooled to ambient temperature and the heterogeneous procatalyst was transferred to a scintillation vial for subsequent use. The thermally treated heterogeneous procatalyst was then utilized in batch copolymerizations of ethylene and 1-octene to produce the ethylene-based polymers of Example 8. The batch copolymerization process was conducted according to the process previously described in Examples 4A-4D except that no hydrogen (0.0 mmol H2) was used in the batch copolymerization reaction and 62±1 g of ethylene was initially loaded into the reactor. All other reactor processing conditions and parameters were the same as in Examples 4A-4D. The batch copolymerization of Example 8 was conducted two times. The ethylene-based polymers for the two reaction runs of Example 8 (Samples 8-A and 8-B) were collected for further analysis. Comparative Example CE5: Batch Copolymerization Utilizing the Procatalyst of CE3 with the Reaction Conditions of Example 8. For Comparative Example CE5, a batch copolymerizations of ethylene and 1-octene was performed using the heterogeneous procatalyst of Comparative Example CE3, which was not subjected to thermal treatment. The batch copolymerizations of CE5 was conducted in accordance with the copolymerization process previously described in Example 8, which included the process described in Examples 4A-4D with no hydrogen added to the reactor system and 62±1 g of ethylene. The ethylene-based polymers of CE5 were collected for analysis. Example 9: Comparison of Example 8 to Comparative Example CE5 The ethylene-based polymers collected from the copolymerization reactors for Example 8 and Comparative Example CE5 were analyzed for Mw and C8 wt. %, according to the test methods described herein. Two samples of each ethylene-based polymers were analyzed. The results are provided below in Table 5. The Δ Mw and Δ C8 wt. % were calculated as a comparison to the average Mw and C8 wt. %, respectively, for CE5-A and CE5-B. TABLE 5Mw and C8 wt. % Test Data for Example 8 and ComparativeExample CE5ThermalTreatmentProperties of Ethylene-Based PolymerTTimeMwΔMwC8ΔC8(° C.)(hours)(Dalton)(%)wt. %(%)8-A1506024891318.56.87−29.18-B1506027347730.27.76−19.9CE5-A——216109—8.75—CE5-B——203916—10.63— Comparison of the ethylene-based polymers of Examples 8A and 8B with that of Comparative Examples CE5-A and CE5-B demonstrates that a heterogeneous procatalyst having MgCl2that has been thermally treated after addition of the chlorinating agent (EADC) and the titanium species (TiPT) can produce ethylene-based polymers having increased Mw and decreased C8 wt. % and I2compared to the polymers of CE5-A and CE5-B when no hydrogen is present in the reactor system. Examples 10A-10C: Batch Copolymerizations Using a Heterogeneous Procatalyst Including a Thermally Treated MgCl2Component and VOCl3as a Vanadium Species In Examples 10A-10C (10A, 10B, and 10C), batch copolymerizations of ethylene and 1-octene were performed using a heterogeneous procatalyst that included thermally treated MgCl2and a vanadium species in combination with the EADC chlorinating agent and TiCl4titanium species. Before the copolymerization processes, the heterogeneous procatalysts incorporating the thermally treated MgCl2component and vanadium species were synthesized. The thermally treated MgCl2component was synthesized and thermally treated according to the process previously described in Examples 1A-1F. The thermally treated MgCl2was then used to produce heterogeneous procatalysts of Examples 10A-1C via sequential addition of EADC (Aldrich, 1.0 M in hexane), titanium chloride (TiCl4, Aldrich, 0.125 M in ISOPAR™ E solvent), and a vanadium species to the slurry containing the thermally treated MgCl2according to the following process. For each heterogeneous procatalyst, 10 milliliters (mL) of the thermally treated MgCl2slurry was maintained under constant stirring in a capped glass vial. On the first day, a designated amount of the 1.0 M EADC solution was added to the thermally-treated MgCl2slurry and was left stirring overnight. On the second day, designated amounts of the 0.125 M TiCl4solution and the vanadium species solution were added, and the resulting slurry was left stirring overnight. The heterogeneous procatalyst was ready for use on the third day. For Examples 10A-10C, the vanadium species was vanadium oxytrichloride (VOCl3, 0.125 M solution in ISOPAR™ E solvent). The molar ratios of the MgCl2to the EADC to the TiCl4to the vanadium species (MgCl2/EADC/TiCl2/V) and the temperature and time for the MgCl2thermal treatment for each of the heterogeneous procatalysts of Examples 10A-10C are provided below in Table 6. The heterogeneous procatalysts of Examples 10A-10C were then used in batch copolymerization reactions conducted according to the process previously described in Examples 1A-1F. In Examples 10A-10C, the reactant charges to the reactor were 660 g ISOPAR™ E solvent, 132 g of 1-octene, 14.5 mmol hydrogen, and 56 g ethylene. For the catalyst systems of Examples 10A-10C, 16 mole equivalents of TEA (an amount of TEA to produce a molar ratio of TEA to Ti in the catalyst system of 16:1) was combined with the heterogeneous procatalyst in the shot tank before injection into the reactor. The ethylene-based polymers of Examples 10A-10C were collected for further analysis. Examples 11A and 11B: Batch Copolymerizations Using a Heterogeneous Procatalyst Including a Thermally Treated MgCl2Component and VO(OnPr)3as the Vanadium Species For Examples 11A and 11B, the batch copolymerizations were conducted using a heterogeneous procatalyst that included the thermally treated MgCl2and vanadium oxypropoxide (VO(OnPr)3) as the vanadium species. The heterogeneous procatalysts of 11A and 11B were prepared in accordance with the process previously described in Examples 10A-10C except that the VO(OnPr)3was used for the vanadium species. The molar ratios of the MgCl2to the EADC to the TiCl4to the vanadium species (MgCl2/EADC/TiCl2/V) and the temperature and time for the MgCl2thermal treatment for each of the heterogeneous procatalysts of Examples 11A-11B are provided below in Table 6. The heterogeneous procatalysts of Examples 11A and 11B were then used in batch copolymerization processes conducted according to the process previously described in Examples 10A-10C to produce ethylene-based polymers, which were collected for further analysis. Examples 12A-12C: Batch Copolymerizations Using a Heterogeneous Procatalyst Including a Thermally Treated MgCl2Component and VO(OnPr)3as the Vanadium Species For Examples 12A-12C (12A, 12B, and 12C), the batch copolymerizations were conducted using a heterogeneous procatalyst that included the thermally treated MgCl2and VO(OnPr)3as the vanadium species. The heterogeneous procatalysts of 12A-12C were prepared by the process previously described in Examples 11A and 11B except that the conditions for thermal treatment of the MgCl2were varied. The molar ratios of the MgCl2to the EADC to the TiCl4to the vanadium species (MgCl2/EADC/TiCl2/V) and the temperature and time for the MgCl2thermal treatment for each of the heterogeneous procatalysts of Examples 12A-12C are provided below in Table 6. The heterogeneous procatalysts of Examples 12A-12C were then used in batch copolymerization processes conducted according to the process previously described in Examples 10A-10C to produce ethylene-based polymers, which were collected for further analysis. Example 13: Batch Copolymerizations Using a Heterogeneous Procatalyst Including a Thermally Treated MgCl2Component and VOCl3as the Vanadium Species For Example 13, the batch copolymerization was conducted using a heterogeneous procatalyst that included the thermally treated MgCl2and VOCl3as the vanadium species. The heterogeneous procatalyst Example 13 was prepared by the process previously described in Examples 10A-10C except that the MgCl2 was thermally treated at 190° C. for 1 hour. The molar ratios of MgCl2to EADC to Ti to V were also modified. Additionally, 0.5 mole equivalent (to TiCl4) of zirconium tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate) (Zr(TMHD)4) was added to the formulation together with the VOCl3during the formulation process. 0.125 mole/L of Zr(TMHD)4in ISOPAR™ E solvent solution was prepared by dissolving Zr(TMHD)4solid in the ISOPAR™ E solvent. The heterogeneous procatalyst of Example 13 had a molar ratio of Ti to V to Zr of 1:2:0.5. The molar ratios of the MgCl2to the EADC to the TiCl4to the vanadium species (MgCl2/EADC/TiCl2/V) and the temperature and time for the MgCl2thermal treatment for Example 13 are provided below in Table 6. The heterogeneous procatalyst of Examples 13 was then used in a batch copolymerization process conducted according to the process previously described in Examples 10A-10C to produce ethylene-based polymers, which were collected for further analysis. Examples 14A-14C: Batch Copolymerization with Heterogeneous Procatalysts Including Thermally Treated MgCl2with No Vanadium Species For Examples 14A-14C, batch copolymerizations were conducted using a heterogeneous procatalyst having thermally treated MgCl2. The heterogeneous procatalysts of 14A-14C were prepared by the process previously described in Examples 10A-10C except that no vanadium species was included in the synthesis. The molar ratios of the MgCl2to the EADC to the TiCl4(MgCl2/EADC/TiCl2) and the temperature and time for the MgCl2thermal treatment for each of the heterogeneous procatalysts of Examples 14A-14C are provided below in Table 6. The heterogeneous procatalysts of Examples 14A-14C were then used in batch copolymerization processes conducted according to the process previously described in Examples 10A-10C to produce ethylene-based polymers, which were collected for further analysis. Comparative Examples CE6A-CE6C: Batch Copolymerization Utilizing Heterogeneous Procatalysts with Non-Thermally Treated MgCl2 For Comparative Examples CE6A-CE6C, batch copolymerizations were conducted using a heterogeneous procatalyst for which the MgCl2was not thermally treated. The heterogeneous procatalysts of CE6A-CE6C were prepared by the process previously described in Examples 10A-10C except that the MgCl2was not thermally treated. For CE6A, VOCl3was added as the vanadium species. For CE6B and CE6C, no vanadium species was added to the heterogeneous procatalyst. Additionally, 0.5 mole equivalent (to TiCl4) of zirconium tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate) (Zr(TMHD)4) was added to the heterogeneous procatalyst of CE6A together with the VOCl3during procatalyst synthesis as previously described in Example 13. The heterogeneous procatalyst of CE6A had a molar ratio of Ti to V to Zr of 1:2:0.5. For CE6B, TiPT was used instead of TiCl4as the Ti species. The molar ratios of the MgCl2to EADC to Ti to V (MgCl2/EADC/TiCl2/V) for each of the heterogeneous procatalysts of CE6A-CE6C are provided below in Table 6. The heterogeneous procatalysts of CE6A-CE6C were then used in batch copolymerization processes conducted according to the process previously described in Examples 10A-10C to produce ethylene-based polymers. For CE6B, 8 mole equivalent of TEA was combined with the heterogeneous procatalyst so that the molar ratio of TEA to Ti in the catalyst system was 8:1 instead of 16:1. The ethylene-based polymers were collected for further analysis. Example 15: Comparison The following Table 6 provides the synthesis information for the heterogeneous procatalysts produced in Examples 10A-10C, 11A-11B, 12A-12C, 13, and 14A-14C and Comparative Examples CE6A-CE6B. TABLE 6Composition and Thermal Treatment Conditions for Examples 10A-10C, 11A, 11B, 12A-12C,13, and 14A-14C and Comparative Examples CE6A-CE6CThermalTreatmentHeterogeneous Procatalyst CompositionTTimeTEA/TiMgCl2/EADC/Ti/V/ZrSample(° C.)(hours)Ti SpeciesV Species(mol/mol)(mol/mol/mol/mol/mol)10A19024TiCl4VOCl31640/2.3/0.23/0.46/010B19024TiCl4VOCl31640/4.6/0.46/0.93/010C19024TiCl4VOCl31640/4.6/0.46/1.88/011A19024TiCl4VO(OnPr)31640/12/1/2/011B19024TiCl4VO(OnPr)31640/12/1/1/012A19024TiCl4VO(OnPr)31640/12/1/2/012B19072TiCl4VO(OnPr)31640/12/1/2/012C20024TiCl4VO(OnPr)31640/12/1/2/0131901TiCl4VOCl31640/10/1/2/0.514A19024TiCl4—1640/2.3/0.23/0/014B19024TiCl4—1640/4.7/0.47/0/014C19024TiCl4—1640/12/1/0/0CE6A——TiCl4VOCl31640/10/1/2/0.5CE6B——TiPT—840/12/3/0/0CE6C——TiCl4—1640/12/1/0/0 The ethylene-based polymers collected from the copolymerization reactors for Examples 10A-10C, 11A-11B, 12A-12C, 13, and 14A-14C and Comparative Examples CE6A-CE6B were analyzed for Mw, polydispersity index (PDI), C8 wt. %, HDF wt. %, melt index (I2), and melt flow ratio I10/I2, according to the test methods described herein. The results are provided below in Table 7. TABLE 7Mw, PDI, C8 wt. %, HDF, I2, and I10/I2Test Data for Examples10A-10C, 11A, 11B, 12A-12C, 13, and 14A-14C and ComparativeExamples CE6A-CE6CC8MwPDIContentHDFI2Sample(Dalton)(Mw/Mn)(wt. %)(wt. %)(g/10 min)I10/I210A959043.808.4013.851.906.6610B946243.458.2413.622.036.7710C1055193.647.3619.181.366.6711A1110743.387.9316.271.206.4611B925073.678.7010.613.086.6012A961033.368.3714.791.976.7612B1086413.527.9417.691.236.6612C968443.408.5412.751.916.51131166383.698.7820.751.026.6014A838063.998.9310.143.147.2914B878553.808.4910.253.817.4914C834284.189.0710.803.288.39CE6A1034094.268.3916.311.437.01CE6B965374.488.3218.172.057.51CE6C846494.249.957.883.088.17 The heterogeneous procatalysts of CE6A-CE6C were all produced with MgCl2that was not thermally treated. CE6A procatalyst included the VOCl3vanadium species, and the procatalysts for CE6B and CE6C did not include a vanadium species. Additionally, the CE6B procatalyst had a molar ratio of Ti to MgCl2of 3:40, and the CE6C procatalyst had a molar ratio of Ti to MgCl2of 1:40. Under the same batch reactor conditions, the ethylene-based polymer of CE6A exhibited the low I10/I2(around 7). In contrast, the ethylene-based polymer of CE6B had a greater I10/I2of around 7.5, and the ethylene-based polymer of CE6C had an I10/I2of greatre than 8. The ethylene-based polymer of CE6A also exhibited a lower PDI (4.26) compared to the ethylene-based polymer of CE6B (4.48). The ethylene-based polymer of CE6C had the lowest Mw and HDF among the three comparative procatalysts. Although the procatalyst of CE6C produced an ethylene-based polymer with low HDF, the CE6C procatalyst may not be practically applicable due to its too low Mw build. The heterogeneous procatalyst of Example 13 had the same composition as the comparative procatalyst of CE6A except that Example 13 included the thermally treated MgCl2. The comparison of Example 13 to CE6A demonstrates that incorporating the thermally treated MgCl2into the heterogeneous procatalyst can produce an ethylene-based polymer having a narrowed molecular weight distribution (MWD), which is shown by the reduction of I10/I2by 0.4 unit and the reduction of PDI by at least 0.50 unit for the ethylene-based polymer of Example 13 compared to CE6A. Under the same reactor process conditions, the use of the thermally treated MgCl2also increases the Mw and HDF of the ethylene-based polymer, while keeping a similar comonomer content (C8 wt. %). The heterogeneous procatalyst of Example 13 outperformed the comparative procatalysts of CE6A and CE6B in terms of the MWD of the resulting ethylene-based polymers and produces ethylene-based polymers with greater Mw and C8 wt. % compared to the ethylene-based polymers made with the procatalysts of CE6A and CE6B. Comparison of Examples 10A-10C to Example 13 demonstrates that a heterogeneous procatalyst that includes the combination of the thermally treated MgCl2and the VOCl3species (10A-10C) can produce ethylene-based polymers having the narrowed MWD without incorporating the Zr compound into the heterogeneous procatalyst (Example 13). Comparison of Example 10A to Example 14A and comparison of Example 10B to Example 14B demonstrate that the addition of VOCl3to the heterogeneous procatalyst having the thermally treated MgCl2(e.g., Examples 10A and 10B) may produce ethylene-based polymers with decreased PDI and I10/I2if no other vanadium compounds are used. Additionally, the addition of VOCl3to the heterogeneous procatalyst having the thermally treated MgCl2may significantly increase the Mw and HDF and slightly decrease the C8 wt. % of the ethylene-based polymers compared the heterogeneous procatalysts that do not include the VOCl3. Comparison of Example 10B to Example 10C demonstrates that increasing the amount of VOCl3in the heterogeneous procatalyst may increase the Mw and HDF and slightly decrease the C8 wt. % of the ethylene-based polymers produced. Thus, it is shown that controlling the amount of the vanadium species in the heterogeneous procatalyst may enable fine tuning and control of the HDF of the ethylene-based polymers to achieve a desired optical/tear property balance of the final LLDPE film product. Comparison of Example 10A to Example 10B demonstrates that an ethylene-based polymer having a narrowed MWD (i.e., low PDI and I10/I2) can be obtained with a heterogeneous procatalyst having an EADC/Ti/V loading as low as 2.3/0.23/0.46 per 40 equivalent moles of the thermally treated MgCl2. Comparison of Example 11B to Example 14C demonstrates that if VOCl3is not used, an ethylene-based polymer having a narrowed MWD can be produced by incorporating VO(OnPr)3into the heterogeneous procatalyst having the thermally treated MgCl2(Example 11B). In addition to narrowing the MWD (i.e., reducing the PDI and I10/I2) of the ethylene-based polymers, including VO(OnPr)3in the heterogeneous procatalyst may also increase the Mw of the ethylene-based polymers. The use of VO(OnPr)3instead of VOCl3in the heterogeneous procatalyst may also reduce the concentration of free chlorine in the catalyst, which reduces the free chlorine concentration in the ethylene-based polymer produced. Comparison of Example 11A to 11B demonstrates that, under the same reaction conditions with all other concentrations fixed, increasing the amount of VO(OnPr)3in the heterogeneous procatalyst may increase the Mw and HDF and decrease the C8 wt. % of the ethylene-based polymers produced. The PDI and I10/I2of the ethylene-based polymers of Examples 11A and 11B were maintained at low levels even though the amount of the VO(OnPr)3heterogeneous procatalyst was changed. The performance of the heterogeneous procatalyst of Example 13 demonstrates that the length of the process time of the thermal treatment of the MgCl2can be as short as 1 hour or less at 190° C. Comparison of Examples 12A and 12C demonstrates that as long as the thermal treatment is performed on the MgCl2, the process temperature at which the thermal treatment is conducted does not have a significant impact on the properties of the ethylene-based polymers produced using the heterogeneous procatalyst. Comparison of Examples 10A-10C, 11A, 11B, and 12A-12C to Example 13 demonstrates that including the thermally treated MgCl2in the heterogeneous procatalyst enables production of ethylene-based polymers with narrowed MWD without including Zr in the heterogeneous procatalyst, as long as a vanadium species is included in the heterogeneous procatalyst. Comparison of Examples 10A-10C, 11A, 11B, and 12A-12C to Comparative Examples CE6A and CE6B demonstrates that the heterogeneous procatalyst that includes the thermally treated MgCl2and a vanadium species (e.g., Examples 10A-10C, 11A, 11B, and 12A-12C) can produce ethylene-based polymers (e.g., LLDPE) with significantly narrowed MWD (i.e., a PDI of less than 4 and an I10/I2of less than 7) compared to ethylene-based polymers produced with the procatalyst of CE6A (vanadium species and non-thermally treated MgCl2) and ethylene-based polymers produced with the procatalyst of CE6B (no vanadium species and non-thermally treated MgCl2. Additionally, by utilizing the heterogeneous procatalyst having the termally treated MgCl2and the vanadium species, the HDF of the ethylene-based polymer can be tuned and controlled over a relatively large range (e.g., 10-20 wt. %) with the same reactor process conditions to control the optical/tear property balance of the final LLDPE film. In a first aspect of the present disclosure, a heterogeneous procatalyst may include a titanium species, a chlorinating agent, and a thermally-treated magnesium chloride component. The chlorinating agent may have a structure A(Cl)x(R1)3-x, where A is aluminum or boron, R1is a (C1-C30) hydrocarbyl, and x is 1, 2, or 3. A second aspect of the present disclosure may include the first aspect, wherein the thermally treated magnesium chloride component comprises a product of thermally treating a magnesium chloride slurry at a temperature of at least 100° C. for at least 30 minutes. The magnesium chloride slurry may include at least magnesium chloride dispersed in a solvent. A third aspect of the present disclosure may include the second aspect, wherein the magnesium chloride slurry comprises the titanium species and the chlorinating agent. A fourth aspect of the present disclosure may include the first aspect, wherein the heterogeneous procatalyst may include the product of thermally treating a slurry of magnesium chloride dispersed in a solvent at a temperature of at least 100° C. for at least 30 minutes and combining the titanium species and the chlorinating agent with the thermally treated magnesium chloride. A fifth aspect of the present disclosure may include the first aspect, wherein the heterogeneous procatalyst comprises the product of combining the titanium species and the chlorinating agent with a slurry of magnesium chloride dispersed in a solvent to produce a procatalyst slurry and thermally treating the procatalyst slurry at a temperature of at least 100° C. for at least 30 minutes. A sixth aspect of the present disclosure may include any of the first through fifth aspects, wherein the titanium species comprises a titanium species having catalytic activity. A seventh aspect of the present disclosure may include any of the first through sixth aspects, wherein a molar ratio of titanium to magnesium chloride in the heterogeneous procatalyst is from 0.0050 to 0.075 (mole/mole). An eighth aspect of the present disclosure may include any of the first through seventh aspects, further comprising a vanadium species. A ninth aspect of the present disclosure may include the eighth aspect, wherein the vanadium species is chosen from VX4, VOX3, or VO(OR2)3, where each X is independently a halogen atom or (C1-C40) heterohydrocarbyl anion; and R2is (C1-C20) hydrocarbyl or —C(O) R11, where R11is (C1-C30) hydrocarbyl. A tenth aspect of the present disclosure may include either of the eighth or ninth aspects, wherein the ratio of vanadium to titanium in the heterogeneous procatalyst is from 0.0 to 20 (mole/mole). An eleventh aspect of the present disclosure may include any of the eighth through tenth aspects, wherein the molar ratio of vanadium to magnesium chloride in the heterogeneous procatalyst is from 0.0 to 0.10 (mole/mole). A twelfth aspect of the present disclosure may include any of the first through eleventh aspects, in which a process for polymerizing ethylene-based polymers may include contacting ethylene and optionally one or more α-olefins in the presence of a catalyst system, wherein the catalyst system comprises the heterogeneous procatalyst according to any of the first through eleventh aspects of the present disclosure to produce an ethylene-based polymer. A thirteenth aspect of the present disclosure may include the twelfth aspect, wherein the catalyst system further comprises a co-catalyst. A fourteenth aspect of the present disclosure may include the thirteenth aspect, wherein the co-catalyst is chosen from an alkyl of aluminum, a haloalkyl of aluminum, an alkylaluminum halide, a Grignard reagent, an alkali metal aluminum hydride, an alkali metal borohydride, an alkali metal hydride, or an alkaline earth metal hydride. A fifteenth aspect of the present disclosure may include an ethylene-based polymer prepared by the process in any of the twelfth through fourteenth aspects. In a sixteenth aspect of the present disclosure, a process for making a procatalyst may include thermally treating a magnesium chloride slurry at a treatment temperature of at least 100° C. and for at least 30 minutes, the magnesium chloride slurry comprising at least magnesium chloride (MgCl2) dispersed in a solvent. The process may further include combining a chlorinating agent and a titanium species with the magnesium chloride slurry. The chlorinating agent may have a structure A(Cl)x(R1)3-x, where A is aluminum or boron, R1is (C1-C30)hydrocarbyl, and x is 1, 2, or 3. A seventeenth aspect of the present disclosure may include the sixteenth aspect, comprising thermally treating the magnesium chloride slurry before combining the chlorinating agent and the titanium species with the magnesium chloride slurry. An eighteenth aspect of the present disclosure may include the sixteenth aspect, comprising thermally treating the magnesium chloride slurry after combining the chlorinating agent and the titanium species with the magnesium chloride slurry. A nineteenth aspect of the present disclosure may include any of the sixteenth through eighteenth aspects, wherein thermally treating the magnesium chloride slurry comprises agitating the magnesium chloride slurry. A twentieth aspect of the present disclosure may include any of the sixteenth through nineteenth aspects, further comprising combining a vanadium species with the magnesium chloride, titanium species, and the chlorinating agent. It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.
109,957
11857936
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS The present disclosure may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures and examples, which form a part of this disclosure. It is to be understood that this technology is not limited to the specific devices, methods, applications, conditions or parameters described and/or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claimed technology. Also, as used in the specification including the appended claims, the singular forms “a,” “an,” and “the” include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. The term “plurality”, as used herein, means more than one. When a range of values is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. All ranges are inclusive and combinable, and it should be understood that steps may be performed in any order. It is to be appreciated that certain features of the technology which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the technology that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. All documents cited herein are incorporated herein in their entireties for any and all purposes. Further, reference to values stated in ranges include each and every value within that range. In addition, the term “comprising” should be understood as having its standard, open-ended meaning, but also as encompassing “consisting” as well. For example, a device that comprises Part A and Part B may include parts in addition to Part A and Part B, but may also be formed only from Part A and Part B. Provided here are new methods for producing chemically and mechanically robust “sintered” bijels for continuous and simultaneous phase-transfer catalysis and separation. Also provided are new methods for functionalizing “sintered” bijels to allow for not only homogeneous phase-transfer catalysis and separation, but also heterogeneous phase-transfer catalysis and separation. In particular, it has been discovered that bijels can be stabilized and functionalized for a wide variety of chemical processes involving simultaneous catalyzed reaction and separation, which bijels can be tailored to various chemical and industrial processes. Provided are robust “sintered” bijels that have chemical, thermal, and mechanical stability to accommodate a broad range of conditions involved in simultaneous catalytic reactions and separations. Examples of the robust bijels allow for interphase mass transfer with little resistance and remain intact after drying. The robust bijels withstand capillary stresses without damage to the bijel structure when subjected to shear and agitation. Therefore, these sintered bijels can be used to create bijel reactors that allow continuous and scalable catalytic reactive separation impossible in conventional emulsion systems with batch processes. By placing the bijel at an aqueous-oil interface, the bijel's internal hydrophobic/oil channels will be in contact with the external oil phase. Similarly, the internal hydrophilic/aqueous channels will be in contact with the external aqueous phase. Reagents can be continuously supplied, products harvested, and unwanted by-products removed by mass transfer to the outer fluids, allowing the interfacial catalyzed processes previously driven only in the “batch reactors” of emulsion drops to be driven continuously. As used herein, “sintering” is the formation of bridges between interfacially jammed nanoparticles of a bijel by inducing the hydrolysis and condensation of metal oxide precursors dispersed in at least one of the phases of the bijel via sol-gel reaction chemistry. The metal oxide precursors form the bridges between the nanoparticles such that the interfacially jammed nanoparticles are stabilized in their configuration, and the resulting bijels are resistant to changes in pH, temperature, the chemical environment, and the introduction of mechanical perturbation. As used herein, surface-active nanoparticles are nanoparticles (e.g., silica nanoparticles, zinc oxide nanoparticles) capable of congregation at an interface between immiscible phases. The surface-active nanoparticles can, but need not, be produced by treating nanoparticles with an oppositely-charged ionic surfactant, whereby the surfactant imparts surface activity to the nanoparticles by interacting electrostatically with the surface of the nanoparticles. Examples of the technology can include methods of mixing nanoparticles with ionic surfactant to provide the surface-active nanoparticles. Other examples of the technology do not use surfactant to produce surface-active nanoparticles or the resulting bijels. Provided is a new class of robust bijels that feature sintered bridges. The bridges can be formed from sintered metal oxides (e.g., silica, titania, alumina, zirconia, copper oxide, tin oxide, and nickel oxide) between the particles, or from functionalized nanoparticles exposed to a secondary agent (e.g., amine-functionalized silica nanoparticles linked using di-carboxylic acid). These robust bijels are bijel analogues of colloidosomes—they are remarkably strong and withstand high shear, but can continue to sequester hydrophobic/oil—hydrophilic/water bicontinuous phases and to allow interphase mass transfer between the two phases. One can use these sintered bijels to create bijel reactors with soluble catalysts dissolved in one or both phases of the bijel, and with nanocatalysts arranged at the nanoparticle surface; the bicontinuous structure features internal, interconnected oil/hydrophobic channels entwined with internal, interconnected aqueous/hydrophilic channels. The oil/hydrophobic channels are sequestered from the aqueous/hydrophilic channels by the interfacially jammed, sintered nanoparticles of the bijel. The sintered bijel reactors can be connected to external aqueous/hydrophilic and oil/hydrophobic phases wherein reagents in the interconnected channels can be continuously replenished from external aqueous/hydrophilic phase or oil/hydrophobic phase (as appropriate), and products in the interconnected channels can be continuously removed, allowing continuous catalytic reactive separation impossible in conventional emulsion systems. The catalytic reactions of such functionalized sintered bijels can be homogeneous (with soluble catalysts dispersed in one or both bijel domains) or heterogeneous (with nanocatalysts arranged at the surface of the sintered nanoparticles). Physically and chemically robust bijels incorporating catalytic nanoparticles, for instance, could function as microscale crossflow reaction media for biofuel upgrade reactions, enabling continuous mass transfer of reagents in and out of the structure and simultaneously allowing for interfacial catalysis and interphase mass transfer of reactants and products. According to particular examples, a robust sintered bijel is produced by (step101) first dispersing metal oxide precursors into one or both of the oil/hydrophobic phase or aqueous/hydrophilic phase of the bijel (FIG.1). Then, (step102) the metal oxide precursors (MO) are hydrolyzed and condensed in a sol-gel reaction to form sintered bridges between the interfacially jammed nanoparticles. FIG.2provides an illustration of the process carried out according toFIG.1. Metal oxide precursors (MO) are dispersed into the hydrophobic phase10at step101. The MO in the hydrophobic phase10are hydrolyzed and condensed amongst the interfacially jammed nanoparticles25at step102to “sinter” the nanoparticles25together. After sintering, metal oxide bridges15between the nanoparticles25stabilize and connect the nanoparticles25, and maintain the separation of the hydrophobic phase10from the hydrophilic phase20at the interface of the bijel. The sintered bridges15impart chemical, thermal, and mechanical robustness to the bijels (FIG.2). It should be understood that nanoparticles can also bear one or more moieties (e.g., metal oxide precursors) that are reacted to bind adjacent nanoparticles to one another. Robust sintered bijels can be produced by, e.g., using the solvent transfer-induced phase separation (STRIPS) method (FIG.3). Using the STRIPS method allows for the production of bijels using a wide range of combinations of hydrophobic/oil phase and hydrophilic/aqueous phase pairs and nanoparticle types. First, (step301) nanoparticles are dispersed into a liquid mixture including at least one hydrophobic liquid/oil phase, at least one hydrophilic liquid/aqueous phase, and at least one solvent to mediate miscibility between the hydrophobic liquid/oil phase and hydrophilic liquid/aqueous phase (e.g., a ternary liquid mixture). At step303, metal oxide precursors are then dispersed into one or both of the oil/hydrophobic phase or aqueous/hydrophilic phase of the liquid mixture. The liquid mixture having dispersed nanoparticles and metal oxide precursors is then contacted with water at step305to induce a phase separation and a jamming (e.g., close packing) of the surface-active nanoparticles at the interface between the hydrophobic liquid/oil phase and hydrophilic liquid/aqueous phase. Finally, at step307, the metal oxide precursors are hydrolyzed and condensed in a sol-gel reaction to form sintered bridges between the interfacially jammed nanoparticles. The resulting robust bijels can be used for homogeneous catalysis and phase transfer separation. In further examples, robust sintered bijels can be functionalized for heterogeneous catalysis by in situ synthesis of nanocatalysts (FIG.4). First, at step401, metal salts (MX) added to at least one phase of the bijel are adsorbed to the surface of the sintered, bridged interfacially jammed nanoparticles. Adsorption can occur via electrostatic interactions in which the pH is controlled such that the surface of the sintered nanoparticles are charged, and oppositely charged metal ions are attracted to the nanoparticles (e.g., pH is controlled within the bijel to be greater than 3.0, wherein silica nanoparticles have a negative charge; this induces adsorption of positively charged metal ions such as Ag+). Another method of inducing adsorption of noble metal ions is by chemical adsorption via complexation with functional groups on the nanoparticle surface (e.g., amine or thiol groups on the surface of silica nanoparticles interact with noble metal ions). The adsorbed the metal salts (MX) are then exposed at step403to a reducing agent (e.g., ascorbic acid) to form a metal nanocatalyst. Without being bound to any particular theory, this exposure process leads to the in situ formation of nanoparticle-supported metal nanocatalysts and functionalized, catalytic bijels. FIG.5depicts an illustration of the process carried out according toFIG.4. Metal salts (MX) in the hydrophilic/aqueous phase20of the bijel are adsorbed to the sintered nanoparticles25connected by metal oxide bridges15at step401. The adsorbed MX are then exposed to a reducing agent at step403to form metal nanocatalysts50on the surface of the sintered nanoparticles25and/or the metal oxide bridges15on the hydrophilic/aqueous side of the bijel. In certain examples, a metal oxide from a precursor can serve a dual role of providing the mechanical and chemical reinforcement through the formation of sintered bridges between the nanoparticles and of providing catalytic functions after deposition. For example, titania, zirconia, alumina, tin oxide, copper oxide, and nickel oxide metal oxide bridges can also serve as nanocatalysts that can engage in heterogeneous catalysis within the bijel domains. Thus, metal oxide precursors including titanium tetrachloride, titanium isopropoxide, aluminum nitrate, copper methoxide, nickel 2-methoxyethoxide, and iron (III) chloride can be used to produce robust bijels (e.g., by being loaded into a STRIPS ternary mixture) having heterogeneous catalytic properties via sol-gel sintering, without requiring additional steps of adsorption and reduction. The formation of the metal oxide nanocatalysts can be accomplished by, e.g., a pH change or the addition of a reactant to the bijel with the metal oxide precursors, as opposed to the addition of a reducing agent for metal nanocatalysts formed from metal salts (MX). In other examples, certain metal oxide precursors (e.g., aluminum nitrate) can be added to an already sintered, robust bijel. A reactant (e.g., ammonium carbonate) can be added to trigger the formation of catalyst (e.g., alumina) soluble in one or both of the bijel domains. The resulting soluble catalyst in the domain(s) participates in homogeneous catalysis. Example 1—STRIPS Method of Forming Robust Bijels with Silica Bridges Silica (SiO2) nanoparticles were added to and dispersed within a ternary liquid mixture of hydrophilic/aqueous phase, hydrophobic/oil phase, and a miscibility-mediating solvent. The silica nanoparticles can already be surface-activated, or an opposite-charged ionic surfactant can be added to the ternary liquid mixture to adsorb to and impart surface activity to the silica nanoparticles. Tetraethyl orthosilicate (TEOS), a metal oxide precursor, was added to the ternary liquid mixture and dispersed within at least one of the phases (in this example, within the hydrophobic/oil phase). The ternary mixture was kept at 0° C. to avoid unwanted reaction before the bijel formation. The hydrophilic/aqueous phase contains around 10% of ethanol, which facilitated the dissolution of TEOS and enhanced the reaction kinetics. Ethanol, however, is optional as an additive to the hydrophilic/aqueous phase. (It should be understood that TEOS is only one example of a metal oxide precursor, and other metal oxide precursors can be used.) The ternary liquid mixture was contacted with water, causing a spinodal phase separation inducing mass-transfer, which was arrested by the interfacial jamming of the silica nanoparticles. This resulted in a bijel. The TEOS dispersed within the hydrophobic/oil phase of the bijel were then hydrolyzed and condensed in a sol-gel reaction to form sintered silica bridges between the silica nanoparticles. The resulting sintered bijel was suitable for both homogeneous catalysis and mass transfer between the bicontinuous phases. Example 2—STRIPS Method of Forming Sintered Bijels with Dual-Purpose Metal Oxide Precursors Silica (SiO2) nanoparticles were added to and dispersed within a ternary liquid mixture. An oil phase selected for its low reactivity and relatively high boiling point was used (e.g., decalin, a mixture of bromobenzene/cyclohexanone). A miscibility-mediating solvent was used. Such solvents can be, e.g., acids and alcohols, such as ethanol, isopropanol, methanol, acetic acid, and the like. The silica nanoparticles were added as an aqueous suspension of silica. An ionic surfactant (e.g., cetyltrimethylammonium bromide surfactant) was added to facilitate the dispersion of the nanoparticles in the ternary mixture and, without being bound to any particular theory, render the nanoparticles partially hydrophobic via electrostatic adsorption, making them more interface active. Other surfactants besides ionic surfacants can be used, although ionic surfactants are considered especially suitable. Titanium alkoxide or titania precursor was added to the ternary liquid mixture and dispersed. The ternary liquid mixture was contacted with water, causing a spinodal phase separation inducing mass-transfer, which was arrested by the interfacial jamming of the silica nanoparticles. This resulted in a bijel. The titanium alkoxide or titania precursor dispersed within the bijel was then hydrolyzed and condensed in a sol-gel reaction to form sintered TiO2bridges between the silica nanoparticles. The TiO2of the sintered bridges between the interfacially jammed silica nanoparticles can also serve as a metal oxide nanocatalyst for aldol condensation reactions. Thus, the titanium alkoxide or titania precursor can serve a dual purpose as both the precursor for imparting mechanical robustness to the nanoparticles of the bijel, and as a metal oxide nanocatalyst after formation of the sintered bridges. The resulting sintered bijel having the metal nanocatalyst was suitable for both heterogeneous catalysis and mass transfer between the bicontinuous phases. To sinter using TiO2, it is known that the sol-gel reaction rate of titania is very fast and more difficult to control than it is for silica. To alleviate this issue, precursors with different pendant groups (titanium-isopropoxide, -butoxide, -2-ethylhexyloxide etc.) can be used under varying pH and temperature conditions. Example 3—STRIPS Formation of Sintered Bijels Silica (SiO2) nanoparticles were added to and dispersed within a ternary liquid mixture. An oil phase selected for its low reactivity and relatively high boiling point was used (e.g., decalin, a mixture of bromobenzene/cyclohexanone). A miscibility-mediating solvent (e.g., ethanol, isopropanol, methanol, acetic acid) was used. The silica nanoparticles were added as an aqueous suspension of silica. An ionic surfactant (e.g., cetyltrimethylammonium bromide surfactant) was added to facilitate the dispersion of the nanoparticles in the ternary mixture and, more importantly, render the nanoparticles partially hydrophobic via electrostatic adsorption, making them more interface active. TEOS was also added to the mixture to enable the sol-gel sintering. The ternary liquid mixture was contacted with water using a device comprising two concentrically aligned cylindrical capillaries, causing a spinodal phase separation inducing mass-transfer, which was arrested by the interfacial jamming of the silica nanoparticles. This resulted in a bijel fiber. The concentration of TEOS and SiO2nanoparticles in the bijel can be varied. Sintering was performed by increasing the temperature and modulating the pH condition as a function of TEOS concentration. Example 4—In Situ Synthesis of Ag, Pd, and Pt Catalysts in Sintered Bijels Ag nanoparticles using AgNO3as the metal precursors were deposited on the sintered SiO2 network via electrostatic interaction. When the silica nanoparticle surface is held at a pH above 3, the silica surface is negatively charged and attracts positively charged Ag+ metal ions. The adsorbed Ag+ ions were then reduced to form the Ag catalysts. To suppress leaching of the metal catalyst from silica, strong anchoring must be achieved between the reduced metal and silica. Addition of H2O2also produced gas bubbles from these Ag-incorporated sintered bijels, strongly indicating the presence of catalytic nanoparticles. A complexation reaction method can be used to deposit noble metals such as Pd and Pt on the sintered SiO2network. PdCl2or K2PtCl4can be used as the metal precursor, and deposition on a sintered silica network of a bijel can be adjusted as a function of solution pH and Cl− concentrations. Speciation of palladium chloride or K2PtCl4in water is known to depend on the solution pH and Cl− concentration, and the charge of silica also can be varied by the solution pH; these conditions can be varied. If deposition of Pd or Pt onto bare silica surface is challenging, amine and/or thiol groups can be incorporated into the sol-gel process using 3-aminotriethoxysilane, 3-mercaptopropyl trimethoxysilane, and TEOS to facilitate strong anchoring via complexation interactions. Reduction of Pd/Pt ions on the silica surface can be achieved using NaBH4 or ascorbic acid. Example 5—Testing of Robustness and Physical Integrity of Sintered Bijels Sintered bijels produced in Example 1 were subjected to immersion in ethanol for one hour, which is typically sufficient to cause the hydrophobic/oil phase and hydrophilic/aqueous phase to be miscible. Such miscibility would be capable of destroying an unsintered silica layer at the interface. However, the sintered bijels demonstrated excellent resistance to miscibility. The sintered silica nanoparticle network also remained porous, and interphase mass transfer occurred with little resistance as demonstrated by extraction of hydrophobic dye from the oil phase of the bijel upon the addition of ethanol. Additionally, the sintered bijels are resistant to mechanical perturbation and drying. When subjected to shear by action of a magnetic stirrer in a cylindrical vessel, the stirrer generated a flow field of Reynolds number of 5×104at the center of the container based on stirrer tip velocity (0.5 m/s) and length (1 cm) without evidence of damage to the bijel (the bijel fibers experience a lower Reynolds number outside the center). A doubling of this stirring rate did disrupt the bijel by removing small pieces, although it was not clear whether this is due to local weak spots made in placing the bijel into the vessel. As an alternative estimate of bijel strength, the bijel remained intact after drying, and thus withstood capillary stresses without damage to the sintered bijel structure. Estimating the stresses owing to capillarity as (interfacial tension)/(characteristic pore size) with interfacial tension of magnitude 30 mN/m and pores of typical radius of 1 μm suggested that the bijel is indeed very robust. In contrast, as-prepared, unsintered bijels lose their integrity upon drying. EXEMPLARY EMBODIMENTS The following embodiments are exemplary only and do not limit the scope of the present disclosure or the appended claims. Embodiment 1. A method of making a stabilized bijel, comprising: dispersing surface-active nanoparticles into a liquid mixture, the liquid mixture comprising a hydrophilic liquid, a hydrophobic liquid, and a solvent configured to mediate miscibility between the hydrophilic liquid and the hydrophobic liquid; dispersing one or more metal oxide precursors into the liquid mixture; contacting the liquid mixture with water, wherein the surface-active nanoparticles jam at an interface between the hydrophilic liquid and the hydrophobic liquid; and hydrolyzing and condensing the metal oxide precursors in a sol-gel reaction to form metal oxide bridges between the interfacially jammed surface-active nanoparticles, wherein the interfacially jammed surface-active nanoparticles are characterized as sintered. Embodiment 2. The method of Embodiment 1, further comprising: adding one or more metal salts to the stabilized bijel after hydrolyzing and condensing in the sol-gel reaction; adsorbing the one or more metal salts to a surface of the sintered interfacially jammed nanoparticles; and synthesizing nanocatalysts on the surface of the sintered interfacially jammed surface-active particles by exposing the metal salts to a reducing agent. Embodiment 3. A stabilized bijel, comprising: stable mixture of two immiscible liquids separated at an interface by one or more layers of jammed surface-active nanoparticles, and bridges between the interfacially jammed surface-active nanoparticles, wherein the interfacially jammed surface-active nanoparticles are sintered. Embodiment 4. The stabilized bijel of Embodiment 3, further comprising catalytically active metal nanocatalysts and/or metal oxide nanocatalysts on a surface of the sintered interfacially jammed surface-active nanoparticles. Embodiment 5. A method of making a stabilized bijel, the method comprising: dispersing metal oxide precursors into at least one phase of a bicontinuous interfacially jammed emulsion (bijel); and hydrolyzing and condensing the metal oxide precursors in a sol-gel reaction to form metal oxide bridges between interfacially jammed surface-active nanoparticles of the bijel, wherein the interfacially jammed surface-active nanoparticles are sintered. Embodiment 6. The method of Embodiment 5, further comprising: adding metal salts to the stabilized bijel after hydrolyzing and condensing in the sol-gel reaction; adsorbing the metal salts to a surface of the sintered interfacially jammed nanoparticles; and synthesizing nanocatalysts on the surface of the sintered interfacially jammed surface-active particles by exposing the metal salts to a reducing agent. Embodiment 7. The stabilized bijel of Embodiment 3, wherein the stabilized bijel is disposed at an interface between two immiscible fluids. As an example, the stabilized bijel can be disposed such that internal hydrophobic/oil channels of the bijel are in fluid communication with an external oil phase and the internal hydrophilic/aqueous channels of the bijel are in fluid communication with an external aqueous phase. Embodiment 8. A method, comprising: with a mixture of two immiscible liquids separated at an interface by one or more layers of jammed surface-active nanoparticles, the mixture further comprising metal oxide bridges between the interfacially jammed surface-active nanoparticles; reacting a first species with the jammed surface-active nanoparticles so as to give rise to a reactive species on a surface of the jammed surface-active nanoparticles. Embodiment 9. The method of Embodiment 8, wherein the species comprises a metal salt. Embodiment 10. The method of any one of Embodiments 8-9, wherein the first species comprises a reducing agent. Embodiment 11. The method of any one of Embodiments 8-9, wherein the reactive species comprises a catalyst. Embodiment 12. A reactor system, comprising: an aqueous external phase; an organic external phase; a bijel portion that comprises a mixture of an aqueous liquid and an organic liquid separated at an interface by one or more layers of jammed surface-active nanoparticles, at least some of the jammed surface-active nanoparticles comprising bridges therebetween, the bijel portion defining a first plurality of channels comprising the aqueous liquid disposed therein and a second plurality of channels comprising the organic liquid disposed therein, and the first plurality of channels being in fluid communication with the aqueous external phase and the second plurality of channels being in fluid communication with the organic external phase. Embodiment 13. The reactor system of Embodiment 12, wherein at least some of the plurality of jammed surface-active nanoparticles comprise a reactive species thereon. A reactive species can be a catalyst or other species that is not consumed. This is not a requirement, however, and the reactive species can include species that are consumed. Embodiment 14. A method, comprising: with a reactor system according to Embodiment 13, effecting synthesis of one or more products, the synthesis being at least partially mediated by the reactive species. Embodiment 15. The method of Embodiment 14, wherein the synthesis is effected within the aqueous liquid, within the aqueous external phase, or both. Embodiment 16. The method of Embodiment 14, wherein the synthesis is effected within the organic liquid, within the organic external phase, or both. Embodiment 17. The method of any one of Embodiments 14-16, wherein the one or more products are synthesized in a phase and are transported to another phase. Embodiment 18. The method of Embodiment 17, wherein the one or more products are synthesized in at least one of the aqueous liquid and the aqueous external phase. Embodiment 19. The method of Embodiment 17, wherein the one or more products are synthesized in at least one of the organic liquid and the organic external phase. Embodiment 20. The method of any one of Embodiments 14-19, wherein the reactive species is characterized as a catalyst. Although the technology is illustrated and described herein with reference to specific examples, the technology is not intended to be limited to the details shown. Rather, numerous variations, changes and substitutions will occur to those skilled in the art without departing from the spirit of the technology. Accordingly, it is intended that the appended claims cover all such variations as fall within the spirit and scope of the disclosure.
28,533
11857937
DETAILED DESCRIPTION Embodiments of the present disclosure are described in detail below. The embodiments described herein with reference to drawings are explanatory, and used to generally understand the present disclosure. The embodiments shall not be construed to limit the present disclosure. The specific techniques and conditions in the following embodiments which do not indicate are usually in accordance with the conventional techniques and conditions in this field, or the product instructions. The reagents or instruments used without the manufacturers' indication are all conventional products that are commercially available. According to one aspect of the present disclosure, a method for preparing an anisotropic lamellar inorganic fiber aerogel material (herein also referred to in brief as inorganic fiber aerogel material) is provided. According to embodiments of the present disclosure with reference toFIG.1, the method for preparing the anisotropic lamellar inorganic fiber aerogel material includes steps100to300as follows. In step100, a polymer solution, an inorganic precursor and a chloride are mixed to obtain a spinning precursor solution. In this process, the inorganic precursor is hydrolyzed to obtain an inorganic oxide, thus subsequently obtaining an inorganic fiber aerogel material. According to embodiments of the present disclosure, the polymer solution includes a polymer material and a solvent, in which the mass ratio of the polymer material to the solvent is in a range of 2:100 to 30:100, e.g., 2:100, 5:100, 8:100, 10:100, 15:100, 20:100, 25:100, or 30:100. Therefore, a homogeneous polymer solution can be obtained, and the polymer solution at the above concentration is beneficial to the subsequent blow spinning to obtain an inorganic fiber aerogel material with excellent compressibility and flexibility. If the mass ratio of the polymer material to the solvent is less than 2:100, the concentration of the polymer solution is too low to form fibers. If the mass ratio of the polymer material to the solvent is higher than 30:100, the polymer material is not easy to dissolve completely, and the viscosity of the polymer solution is too high, such that it is difficult to blow the polymer solution from a spinneret of a blow spinning device to form fibers. According to embodiments of the present disclosure, in order to obtain a sufficiently dissolved polymer solution, the procedure for preparing the polymer solution includes: adding a certain amount of polymer material to a certain amount of solvent, followed by stirring and dissolving at room temperature (25° C.) to 100° C. at a stirring speed of 50 to 1000 rpm for 0.1 to 10 h, such that a polymer solution with a suitable concentration can be obtained. Herein, the specific amount of the polymer material and the solvent as well as specific process conditions can be determined by those skilled in the art based on the specific polymer material and the selected solvent. There are no limitations here, as long as the polymer material can be fully and quickly dissolved. Herein, the stirring can be performed by mechanical stirring or magnetic stirring. According to embodiments of the present disclosure, the polymer material is selected from at least one of polyvinyl alcohol, polyethylene glycol, polyurethane, polyacrylic acid, polyvinyl pyrrolidone, cellulose acetate, methyl cellulose, carboxymethyl cellulose, polyvinylidene fluoride, polymethyl methacrylate, polyacrylamide, polyethylene oxide, polylactic acid, polyamide, polycaprolactone, polyvinyl butyral, polyaniline, polyimide and polycarbonate. Therefore, the polymer material is widely available, easy to spin, and easy to remove in the subsequent calcination. According to embodiments of the present disclosure, the solvent is selected from at least one of water, formic acid, tetrahydrofuran, acetone, butanone, n-hexane, cyclohexane, n-heptane, acetonitrile, N-methylpyrrolidone, 1,2-propanediol, chloroform, dichloromethane, 1,2-dichloroethane, methanol, ethanol, isopropanol, tert-butanol, n-butanol, toluene, xylene, ethylenediamine, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide and carbon tetrachloride. Therefore, those skilled in the art can select suitable solvents according to different polymer materials to dissolve the polymer materials quickly and effectively. According to embodiments of the present disclosure, the inorganic precursor is selected from at least one of zirconium oxychloride, zirconium acetate, aluminum isopropoxide, zirconium n-propoxide, tetraethyl orthosilicate, and tetramethyl orthosilicate. Therefore, the above-mentioned inorganic precursors can be hydrolyzed to obtain oxides (such as zirconia, alumina and silica), followed by blow spinning to obtain inorganic fiber aerogel materials. According to embodiments of the present disclosure, in order to obtain the inorganic fiber aerogel materials with a lamellar structure, the chloride is selected from at least one of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, radium chloride, zinc chloride, copper chloride, nickel chloride, cobalt chloride, iron chloride, ferrous chloride, manganese chloride, chromic chloride, vanadium chloride, titanium tetrachloride, scandium chloride, aluminum chloride, gallium chloride, indium chloride, thallium chloride, tin chloride, lead chloride, cadmium chloride, palladium chloride, rhodium chloride, ruthenium chloride, zirconium chloride, hafnium chloride, osmium trichloride, platinum chloride, gold chloride and mercuric chloride. Therefore, in blow spinning, under the action of the chloride, the inorganic fiber aerogel materials with a lamellar structure can be obtained, which greatly improves the compressibility of the inorganic fiber aerogel materials. According to embodiments of the present disclosure, in order to promote the hydrolysis of the inorganic precursor, the spinning precursor solution further comprises a catalyst. In an embodiment of the present disclosure, the catalyst is selected from at least one of phosphoric acid, sulphuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid, hydrofluoric acid, perchloric acid, trifluoroacetic acid, citric acid, oxalic acid and maleic acid. Therefore, under the action of the above-mentioned catalyst, the inorganic precursor can be hydrolyzed into an inorganic oxide quickly, effectively, and more fully, such that the inorganic fiber aerogel materials with excellent properties can be obtained in subsequent steps. According to embodiments of the present disclosure, the specific process of mixing above-mentioned reagents and components can be flexibly determined by those skilled in the art according to actual needs. In some embodiments of the present disclosure, the inorganic precursor, the catalyst and the chloride are respectively added to the polymer solution, followed by stirring to obtain a spinning precursor solution with a certain viscosity. In other embodiments of the present disclosure, the inorganic precursor, the catalyst and the chloride are mixed, and then the resulting mixture is added to the polymer solution, followed by stirring to obtain a spinning precursor solution with a certain viscosity. Herein, the specific process of stirring is not particularly limited, and the stirring can be performed by mechanical stirring or magnetic stirring. According to embodiments of the present disclosure, in order to obtain an inorganic fiber aerogel material with better properties, the spinning precursor solution includes 2 to 30 parts by weight of the polymer material, 100 parts by weight of the solvent, 0.5 to 100 parts by weight of the inorganic precursor, 0.001 to 1 part by weight of the catalyst, and 1 to 100 parts by weight of the chloride. Therefore, the inorganic fiber aerogel materials prepared with the above component ratios have good compressibility and flexibility, as well as an anisotropic lamellar structure. The addition of chloride can effectively ensure the lamellar structure of the inorganic fiber aerogel materials. If the amount of the chloride is too low, the lamellar structure of the inorganic fiber aerogel materials is not obvious, which leads to a relatively poor compressibility. If the amount of the chloride is too high, the compressibility of the inorganic fiber aerogel materials is also deteriorated. In step200, the spinning precursor solution is blow spun to obtain a composite fiber aerogel. In this process, under the action of the chloride, the obtained composite fiber aerogels have a multi-layer stacked lamellar structure, and thus has anisotropy, such that the finally obtained inorganic fiber aerogel materials can be cut into any desired shape, and stacked to any desired thickness. Herein, “anisotropy” means that the compressibility and recovery performance of the inorganic fiber aerogel materials are different, when the inorganic fiber aerogel materials are compressed from different directions relative to the inorganic fiber layer in the inorganic fiber aerogel materials. For example, the inorganic fiber aerogel materials can completely return to their original shape when they are compressed from a direction perpendicular to the inorganic fiber layer (refer toFIG.2). However, the inorganic fiber aerogel materials cannot recover to their original shape when they are compressed from a direction parallel to the inorganic fiber layer (refer toFIG.3). According to embodiments of the present disclosure, by blow spinning, the spinning precursor solution is spun, and compressed air is used to blow the spinning precursor solution from a spinneret of a blow spinning device. Specifically, blow spinning is performed using a pair of coaxial nozzles, i.e. inner and outer nozzles, particularly, the spinning precursor solution is ejected from the inner nozzle by using compressed air, and a high-speed airflow is ejected through the outer nozzle, and then the spinning precursor solution forms a polymer jet under the shear effect of the high-speed airflow. The polymer jet is further split, stretched, and refined before reaching a receiving device. At the same time, the solvent continuously volatilizes, such that fibers are formed, solidified and collected on the receiving device (also called receiver). Compared with electrospinning, the blow spinning device is simple, uses the high-speed airflow as a driving force without a high-voltage electrostatic field, and has higher spinning efficiency, and the composite fiber aerogels can be deposited on any substrate. Therefore, it is of great significance to use a blow spinning technology to prepare inorganic fiber aerogel materials with high compressibility and excellent high temperature resistance on a large scale. According to embodiments of the present disclosure, the specific type of the receiving device can be flexibly selected by those skilled in the art according to actual needs. In some embodiments of the present disclosure, the receiving device includes, but is not limited to a metal mesh, a plastic mesh and a non-woven fabric. According to embodiments of the present disclosure, in order to obtain an inorganic fiber aerogel material with excellent compressibility and flexibility, in blow spinning, the extrusion speed of the spinning precursor solution is in a range of 0.1 to 15 mL/h (e.g., 0.1 mL/h, 0.5 mL/h, 1 mL/h, 2 mL/h, 3 mL/h, 4 mL/h, 5 mL/h, 6 mL/h, 7 mL/h, 8 mL/h, 9 mL/h, 10 mL/h, 11 mL/h, 12 mL/h, 13 mL/h, 14 mL/h, or 15 mL/h), the distance between the spinneret and a receiver is in a range of 20 to 100 cm (e.g., 20 cm, 30 cm, 40 cm, 50 cm, 60 cm, 70 cm, 80 cm, 90 cm, or 100 cm), and the flow rate of the compressed air is in a range of 1 to 50 m/s (e.g., 1 m/s, 5 m/s, 10 m/s, 15 m/s, 20 m/s, 25 m/s, 30 m/s, 35 m/s, 40 m/s, 45 m/s, or 50 m/s). Therefore, an inorganic fiber aerogel material with excellent properties can be prepared. In step300, the composite fiber aerogel is calcinated to obtain the anisotropic lamellar inorganic fiber aerogel material. In this process, by calcination, the polymer material is decomposed into small molecules such as carbon dioxide and water, and is removed to obtain the inorganic fiber aerogel materials, such that the lamellar inorganic fiber aerogel materials have excellent fire resistance, good high and low temperature resistance (the inorganic fiber aerogel materials can maintain good compressibility after treatment at −196° C. and 1000° C. for 24 h, respectively), and excellent thermal insulation properties (the thermal conductivity of the inorganic fiber aerogel materials is as low as 0.034 W/m K). According to embodiments of the present disclosure, in order to fully decompose the polymer material, the calcination temperature is in a range of 500° C. to 2000° C. (e.g., 500° C., 800° C., 1000° C., 1300° C., 1500° C., 1800° C. or 2000° C.) at a heating rate of 0.1 to 10° C./min, maintained for a time period of 0 to 24 h (e.g., 1 h, 5 h, 8 h, 10 h, 14 h, 18 h, 20 h or 24 h), and then cooled down to room temperature. The specific parameters in the calcination process can be flexibly set by those skilled in the art according to actual needs. According to embodiments of the present disclosure, the above-mentioned method for preparing inorganic fiber aerogel materials has advantages of simplicity, easy operation, low cost, high efficiency and easy industrialized production. The inorganic fiber aerogel materials prepared by the above-mentioned method are composed of multi-layer stacked fibers and have an anisotropic lamellar structure, and they can be cut into any desired shape, and stacked to any desired thickness. Moreover, the inorganic fiber aerogel materials have good flexibility and compressibility. In addition, the lamellar structure and inorganic components of the inorganic fiber aerogel materials endow them with excellent fire resistance, good high and low temperature resistance and superior thermal insulation, and thus their application field is greatly expanded. In some embodiments of the present disclosure, the prepared inorganic fiber aerogel materials are shown inFIG.2,FIG.3,FIG.4andFIG.5, and a scanning electron micrograph (SEM) of the inorganic fiber aerogel material is shown inFIG.6. The inorganic fiber aerogel materials have good compressibility and flexibility (FIG.2andFIG.5). The inorganic fiber aerogel materials have excellent fire resistance, good high and low temperature resistance (the inorganic fiber aerogel materials can maintain good compressibility after treatment at −196° C. and 1000° C. for 24 h, respectively), and superior thermal insulation properties (the thermal conductivity of the inorganic fiber aerogel materials is as low as 0.034 W/m K). According to another aspect of the present disclosure, an anisotropic lamellar inorganic fiber aerogel material is provided. According to embodiments of the present disclosure, the anisotropic lamellar inorganic fiber aerogel materials are prepared by the above-mentioned method. Therefore, the inorganic fiber aerogel materials are composed of multi-layer stacked fibers and have an anisotropic lamellar structure, which can be cut into any desired shape, and stacked to any desired thickness. In addition, the inorganic fiber aerogel materials have good flexibility and compressibility. Furthermore, the lamellar structure and inorganic components of the inorganic fiber aerogel materials endow them with excellent fire resistance, good high and low temperature resistance and superior thermal insulation, and thus their application field is greatly expanded. According to embodiments of the present disclosure, the bulk density of the inorganic fiber aerogel materials is in a range of 5 to 200 mg/cm3(e.g., 5 mg/cm3, 25 mg/cm3, 50 mg/cm3, 75 mg/cm3, 100 mg/cm3, 125 mg/cm3, 150 mg/cm3, 175 mg/cm3, or 200 mg/cm3), and the average diameter of inorganic fibers in the inorganic fiber aerogel materials is in a range of 0.2 to 10 μm (e.g., 0.2 μm, 0.5 μm, 1 μm, 2 μm, 4 μm, 6 μm, 8 μm or 10 μm). Therefore, the bulk density of the inorganic fiber aerogel materials and the diameter of inorganic fibers are in wide range, such that the inorganic fiber aerogel materials with different bulk densities and fiber diameters can be prepared by those skilled in the art according to different needs and applications, thus meeting different market requirements. EXAMPLES Example 1 A method for preparing an anisotropic lamellar inorganic fiber aerogel material includes the following procedures: (1) Preparation of Polymer Solution 20 g of polyvinyl alcohol was added to 100 g of deionized water, followed by stirring and dissolving at a stirring speed of 800 rpm at 90° C. for 1 h to obtain a polyvinyl alcohol solution with a mass ratio of the polymer material to the solvent of 20:100. (2) Preparation of Spinning Precursor Solution 50 g of zirconium oxychloride, 0.2 g of hydrochloric acid and 40 g of iron chloride were added to the above-mentioned polyvinyl alcohol solution, followed by stirring to obtain a spinning precursor solution with a certain viscosity. (3) Blow Spinning The spinning precursor solution was ejected from a spinneret at a speed of 5 mL/h using compressed air with a flow rate of 5 m/s. The resulting fibers were deposited on a metal mesh receiver at a distance of 60 cm from the spinneret, and the composite fiber aerogel was obtained. (4) Calcination The obtained composite fiber aerogel was heated from room temperature to 1000° C. at a heating rate of 5° C./min and maintained for 1 h, and then cooled down to room temperature to obtain an anisotropic lamellar inorganic fiber aerogel material. The obtained anisotropic lamellar inorganic fiber aerogel material has a bulk density of 15 mg/cm3, a thermal conductivity of 0.037 W/m K at room temperature and an average fiber diameter of 2.5 μm. Example 2 A method for preparing an anisotropic lamellar inorganic fiber aerogel material includes the following procedures: (1) Preparation of Polymer Solution 5 g of polyethylene oxide was added to 100 g of deionized water, followed by stirring and dissolving at a stirring speed of 800 rpm at 60° C. for 1 h to obtain a polyethylene oxide solution with a mass ratio of the polymer material to the solvent of 5:100. (2) Preparation of Spinning Precursor Solution 40 g of tetraethyl orthosilicate, 0.2 g of phosphoric acid and 30 g of manganese chloride were added to the above-mentioned polyethylene oxide solution, followed by stirring to obtain a spinning precursor solution with a certain viscosity. (3) Blow Spinning The spinning precursor solution was ejected from a spinneret at a speed of 5 mL/h using compressed air with a flow rate of 3 m/s. The resulting fibers were deposited on a metal mesh receiver at a distance of 60 cm from the spinneret, and the composite fiber aerogel was obtained. (4) Calcination The obtained composite fiber aerogel was heated from room temperature to 1100° C. at a heating rate of 5° C./min and maintained for 1 h, and then cooled down to room temperature to obtain an anisotropic lamellar inorganic fiber aerogel material. The obtained anisotropic lamellar inorganic fiber aerogel material has a bulk density of 19 mg/cm3, a thermal conductivity of 0.038 W/m K at room temperature and an average fiber diameter of 2.4 μm. Example 3 A method for preparing an anisotropic lamellar inorganic fiber aerogel material includes the following procedures: (1) Preparation of Polymer Solution 12 g of polyvinyl alcohol was added to 100 g of deionized water, followed by stirring and dissolving at a stirring speed of 800 rpm at 80° C. for 1 h to obtain a polyvinyl alcohol solution with a mass ratio of the polymer material to the solvent of 12:100. (2) Preparation of Spinning Precursor Solution 40 g of tetraethyl orthosilicate, 0.1 g of phosphoric acid and 35 g of aluminum chloride were added to the above-mentioned polyvinyl alcohol solution, followed by stirring to obtain a spinning precursor solution with a certain viscosity. (3) Blow Spinning The spinning precursor solution was ejected from a spinneret at a speed of 5 mL/h using compressed air with a flow rate of 5 m/s. The resulting fibers were deposited on a metal mesh receiver at a distance of 60 cm from the spinneret, and the composite fiber aerogel was obtained. (4) Calcination The obtained composite fiber aerogel was heated from room temperature to 1000° C. at a heating rate of 5° C./min and maintained for 1 h, and then cooled down to room temperature to obtain an anisotropic lamellar inorganic fiber aerogel material. The obtained anisotropic lamellar inorganic fiber aerogel material has a bulk density of 21 mg/cm3, a thermal conductivity of 0.035 W/m K at room temperature and an average fiber diameter of 2.7 μm. Example 4 A method for preparing an anisotropic lamellar inorganic fiber aerogel material includes the following procedures: (1) Preparation of Polymer Solution 4 g of carboxymethyl cellulose was added to 100 g of deionized water, followed by stirring and dissolving at a stirring speed of 900 rpm at 40° C. for 2 h to obtain a carboxymethyl cellulose solution with a mass ratio of the polymer material to the solvent of 4:100. (2) Preparation of Spinning Precursor Solution 40 g of zirconium acetate, 0.01 g of phosphoric acid and 30 g of magnesium chloride were added to the above-mentioned carboxymethyl cellulose solution, followed by stirring to obtain a spinning precursor solution with a certain viscosity. (3) Blow Spinning The spinning precursor solution was ejected from a spinneret at a speed of 5 mL/h using compressed air with a flow rate of 5 m/s. The resulting fibers were deposited on a metal mesh receiver at a distance of 60 cm from the spinneret, and the composite fiber aerogel was obtained. (4) Calcination The obtained composite fiber aerogel was heated from room temperature to 1100° C. at a heating rate of 5° C./min and maintained for 1 h, and then cooled down to room temperature to obtain an anisotropic lamellar inorganic fiber aerogel material. The obtained anisotropic lamellar inorganic fiber aerogel material has a bulk density of 20 mg/cm3, a thermal conductivity of 0.034 W/m K at room temperature and an average fiber diameter of 2.6 μm. Example 5 A method for preparing an anisotropic lamellar inorganic fiber aerogel material includes the following procedures: (1) Preparation of Polymer Solution 15 g of polyvinyl pyrrolidone was added to 100 g of deionized water, followed by stirring and dissolving at a stirring speed of 800 rpm at 70° C. for 1 h to obtain a polyvinyl pyrrolidone solution with a mass ratio of the polymer material to the solvent of 15:100. (2) Preparation of Spinning Precursor Solution 50 g of zirconium oxychloride, 0.01 g of sulphuric acid and 30 g of tin chloride were added to the above-mentioned polyvinyl pyrrolidone solution, followed by stirring to obtain a spinning precursor solution with a certain viscosity. (3) Blow Spinning The spinning precursor solution was ejected from a spinneret at a speed of 5 mL/h using compressed air with a flow rate of 5 m/s. The resulting fibers were deposited on a metal mesh receiver at a distance of 60 cm from the spinneret, and the composite fiber aerogel was obtained. (4) Calcination The obtained composite fiber aerogel was heated from room temperature to 1000° C. at a heating rate of 5° C./min and maintained for 1 h, and then cooled down to room temperature to obtain an anisotropic lamellar inorganic fiber aerogel material. The obtained anisotropic lamellar inorganic fiber aerogel material has a bulk density of 25 mg/cm3, a thermal conductivity of 0.037 W/m K at room temperature and an average fiber diameter of 2.1 μm. Reference throughout this specification to “an embodiment”, “some embodiments”, “an example”, “a specific example”, or “some examples” means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. Thus, the appearances of the phrases in different places throughout this specification are not necessarily referring to the same embodiment or example of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples. In addition, those skilled in the art can combine the different embodiments or examples and the features described in this specification without being mutually inconsistent. Although explanatory embodiments have been shown and described, it would be appreciated by those skilled in the art that the above embodiments cannot be construed to limit the present disclosure, and changes, alternatives, and modifications can be made in the embodiments without departing from the spirit, principles and scope of the present disclosure.
25,149
11857938
DETAILED DESCRIPTION OF THE INVENTION As renewable power becomes more economical and more widely deployed, chemical processes that store solar power in chemical bonds (i.e., e-fuels and electro chemicals) such as the ones described herein become more attractive. One advantage of renewable power (e.g., wind and solar) is that they do not consume a limited feedstock and can have a low unit cost of production compared to power derived from fossil fuels. However, one disadvantage can be that sunshine and wind are not constant throughout the year or even within a single day (i.e., are variable). Therefore, without storage of power, supplement of non-renewable power, or other design considerations as described herein, the e-fuel or electrochemical process can occasionally need to be turned down. As used herein, the term “turn down” or “turned down” generally refers to a voluntary reduction in the output of a manufacturing process. However, continuous industrial processes (e.g., those that produce fuels and chemicals) are typically difficult and time-consuming to turn down. Those processes that are better able to reduce their power consumption intermittently, often on short notice, can enjoy significant economic advantages over those that cannot (e.g., by having a lower average cost of power input). One such advantageous process for producing fuels and chemicals is described herein and depicted schematically inFIG.1. Overall, this process converts power, CO2and water into fuels and chemicals. Here, an electrolyzer100can use power102to convert water104into hydrogen106and oxygen108. The hydrogen can be fed to a reverse water-gas-shift module110to be combined with CO2112to produce synthesis gas (syngas)114comprising carbon monoxide (CO) and hydrogen. The syngas can be reacted in a liquid fuel production module116to produce liquid hydrocarbons118, which can be separated into fuel and chemical products120in a fractionation module122. The productivity of the process can be improved by taking the tail gas124from the liquid fuel production module to an autothermal reforming module126to be reacted with oxygen108produce additional feedstock128for the liquid fuel production module. The system depicted inFIG.1can be more readily turned down than competing processes for producing liquid fuels and chemicals because a large fraction of the overall power consumption of the process goes to102the electrolyzer100. Additional power130can go to utilities132or modules other than the electrolyzer (e.g., reverse water-gas-shift, liquid fuel production, fractionation, autothermal reformer). However, these are typically much smaller than the amount of power that is dedicated to electrolysis. In some cases, an amount between 75% and 100% of the total power consumed by the process is consumed by the electrolyzer. In some cases, the output of the process is kept as high as possible given a decrease (i.e., turn down) of an amount of an input to the process (e.g., power). The process can be turned down in a manner that maintains the ability to turn the process back up quickly with minimal disruption. For example, reactors can be kept at or near production temperatures and pressures. Such is the case here, with reference toFIG.1, power can be maintained to most or all of the process130except for the electrolyzer102. Overall, with respect to power consumption, the process can be turned down by 10% to 100%. The process can be improved or modified to maintain as much productivity as possible at a given level of turn down with respect to power consumption. For example,FIG.2shows a hydrogen recovery module200which takes the syngas product114from the reverse water-gas-shift module110and separates hydrogen. The hydrogen202can be returned to the reverse water-gas-shift module to supplement hydrogen that is provided directly from the electrolyzer106. The hydrogen recovery module200can be operated in a turndown case to maintain a suitable amount of hydrogen being fed to the reverse water-gas-shift module, which operates with a stoichiometric excess of excess hydrogen. The process can be turned down in response to a stimulus. The system can include a controller capable of controlling the hydrogen recovery module in response to the stimulus. The hydrogen recovery module is capable of recovering H2from the synthesis gas mixture to produce (i) a H2stream202which is directed to the reverse water gas shift module110and (ii) a synthesis gas mixture that is depleted in H2204, which can be sent to liquid fuel production116. Operation of the hydrogen recovery module200can change the products120produced by the process. In some cases, the distribution of molecular weights of the product molecules is increased. This can be because less hydrogen and more relative CO being fed to the liquid fuel production module116can promote carbon chain extension rather than termination. This change in the product can be an acceptable trade-off for higher overall productivity during the turndown in response to the stimulus, but may be undesirable longer term (i.e., when the stimulus isn't present). The stimulus can be any suitable signal. In some instances, the stimulus is associated with an availability of electrical power and/or a price of electrical power and/or the price of transmission or distribution (T&D) of the electrical power. The price and availability of renewable power can vary, sometimes substantially, throughout the year, or even within a single day. The price and availability of T&D of the electrical power can vary, sometimes substantially, throughout of the year, or even within a single day. For example, various portions of the year (e.g., summer vs winter) or day (e.g., day vs night) can produce more or less average solar power respectively. Variations in the weather (e.g., clouds or wind) is another source of variability. The demand for power is also variable and not always predictable far in advance. These demand fluctuations can be driven e.g., by the need for additional power when more people are active during the day, or by additional air conditioning when the weather is hot. These factors and more can contribute to variability in the availability or price of power. In addition, utility companies try to incentivize power consumers to use less power during periods of peak demand and/or low production in order to manage the power grid, particularly as more of the grid is powered by variable renewable resources. This management might be best achieved by incentivizing the largest (industrial) consumers of power to avoid or reduce their usage during peak times. For example, a program might charge a large industrial consumer less for power even in non-peak times if that consumer can avoid or reduce power consumption during peaks. These peaks can be any relevant period of time. In addition, the utility might inform the power consumer about these peak times any relevant period of time in advance. In some cases, the stimulus is associated with an availability of CO2or other feedstocks such as nitrogen to an e-fuels plant. For example, the process described herein can be coupled to a process that would otherwise emit CO2and that process could be operated intermittently or itself need to be turned down in response to an event. In such case, additional CO2could be supplemented from another source such as a pipeline, or the process can be turned down as described herein. The stimulus can also be associated with a price of CO2. In some cases, the stimulus is a ratio of H2to CO2in the input to the reverse water gas shift module. In normal operation, this ratio is between 2.0 and 4.0. The process can be turned back up following the stimulus. In some cases, following the stimulus, the first amount of electrical power is again provided to the electrolysis module. Hydrogen can be recovered and recycled to the reverse water-gas-shift module in any suitable way. In some cases, hydrogen is recovered with the assistance of a selective membrane. The hydrogen recovery module can comprise a pressure swing adsorber (PSA). In some cases, the hydrogen recovery module is not operated in the absence of the stimulus. In some instances, compared with the hydrogen recovery module not being operated, operation of the hydrogen recovery module increases a ratio of CO to H2being fed to the hydrocarbon synthesis module. Compared with the hydrogen recovery module not being operated, operation of the hydrogen recovery module can increase an average molecular weight of the liquid hydrocarbon that is produced by the hydrocarbon synthesis module. The stimulus can be temporary. The stimulus can last for any relevant period of time. Periods of turndown with respect to power consumption can also be managed by supplementing hydrogen from another source (i.e., to make up for the reduced hydrogen being produced by the electrolyzer). For instance, hydrogen could be temporarily purchased from another, external, source such as a pipeline. Excess hydrogen can also be produced and stored by the electrolyzer during periods of excess power for use later during a turn down scenario in response to a stimulus. FIG.3shows another system for managing hydrogen (e.g., during a process turn-down). In an aspect, a system is provided for producing an e-fuel. The system can include an electrolysis module that is capable of using electrical power to convert water into an electrolysis product stream comprising H2. The system can further include a reverse water gas shift module that is capable of reacting CO2with the electrolysis product stream to produce a synthesis gas mixture comprising CO and H2. The system can further include a hydrocarbon synthesis module capable of converting the synthesis gas mixture into a liquid hydrocarbon. The system can further include a hydrogen recovery module capable of recovering H2from the hydrocarbon synthesis module and feeding said H2to the reverse water gas shift module. The system can further include an auto-thermal reforming (ATR) module capable of reacting O2from the electrolysis module with (i) unreacted reactants from the hydrocarbon synthesis module and/or the hydrogen recovery module and (ii) hydrocarbons having fewer than 5 carbon atoms from the hydrocarbon synthesis module and/or the hydrogen recovery module to produce an ATR product stream capable of being fed to the hydrocarbon synthesis module. With reference toFIG.3, hydrogen in the tail gas124can be recovered in a hydrogen recovery module300to produce (i) a H2stream302which is directed to the reverse water gas shift module110and (ii) a tail gas mixture that is depleted in H2304, which can be sent to the autothermal reformer126. Hydrogen can be recovered and recycled to the reverse water-gas-shift module in any suitable way. In some cases, hydrogen is recovered with the assistance of a selective membrane. The hydrogen recovery module can comprise a pressure swing adsorber (PSA). In another aspect, provided herein is a method for controlling a process that produces e-fuels. The method can include providing a first amount of electrical power to an electrolysis module to produce Hz, mixing the H2with CO2to provide a gas mixture having a first ratio of H2to CO2, performing a reverse water gas shift reaction on the gas mixture to produce synthesis gas, and reacting the synthesis gas to produce a liquid hydrocarbon. The method can further include, in response to a stimulus, providing a second amount of electrical power to the electrolysis module to produce H2, mixing the H2with CO2to provide a gas mixture having a second ratio of H2to CO2, performing a reverse water gas shift reaction on the gas mixture to produce synthesis gas, and reacting the synthesis gas to produce a liquid hydrocarbon. The second amount of electrical power is between zero and the value of the first amount of electrical power. The second ratio of H2to CO2is substantially similar to the first ratio of H2to CO2. The second amount of power can be any suitable fraction of the first amount of power (i.e., amount of turn down with respect to power consumption). The second amount of electrical power can be an amount between 0% and 70% of the first amount of electrical power. Following the stimulus, the first amount of electrical power can be provided to the electrolysis module (i.e., the process can be turned back up). In some embodiments, the flowrate of the gas mixture (i.e., of H2with CO2) is reduced (i.e., amount of turn down with respect to reactant consumption). The flowrate of the gas mixture can be an amount between 0% and 70% of the flowrate of the gas mixture at full capacity of the process. In some cases, the flowrate of the gas mixture is between 0% and 70% of the flowrate of the gas mixture at full capacity of the process. The first ratio and/or the second ratio of H2to CO2can be between 2.0 and 4.0; preferably between 2.5 and 3.5; and even more preferably between 2.8 and 3.2. The second ratio of H2to CO2is substantially similar to the first ratio of H2to CO2. In some instances, the first and second ratio differ by no more than 40%; preferably no more than 15%; and even more preferably no more than 3%. In some embodiments, H2is drawn from a pipeline in response to the stimulus. In some embodiments, the H2is produced by the electrolysis module and stored. In some embodiments, H2is drawn from storage in response to the stimulus. In some embodiments, H2is recovered from a product stream of the reaction of synthesis gas to the liquid hydrocarbon. In some embodiments, the H2is recovered using pressure swing adsorption. In some embodiments, an amount of electrical power delivered to a reactor performing the reverse water gas shift reaction is reduced by an amount which is a value between zero and the value of the ratio of the second to the first amounts of electrical power. Carbon dioxide can be obtained from several sources. Industrial manufacturing plants that produce ammonia for fertilizer produce large amounts of carbon dioxide. Ethanol plants that convert corn or wheat into ethanol produce large amounts of carbon dioxide. Power plants that generate electricity from various resources (for example natural gas, coal, other resources) produce large amounts of carbon dioxide. Chemical plants such as nylon production plants, ethylene production plants, other chemical plants produce large amounts of carbon dioxide. Some natural gas processing plants produce CO2as part of the process of purifying the natural gas to meet pipeline specifications. Capturing CO2for utilization as described here often involves separating the carbon dioxide from a flue gas stream or another stream where the carbon dioxide is not the major component. Some CO2sources are already relatively pure and can be used with only minor treatment (which may include gas compression) in the processes described herein. Some processes may require an alkylamine or other method that would be used to remove the carbon dioxide from the flue gas steam. Alkylamines used in the process include monoethanolamine, diethanolamine, methydiethanolamine, disopropylamine, aminoethoxyethnol, or combinations thereof. Metal Organic Framework (MOF) materials have also been used as a means of separating carbon dioxide from a dilute stream using chemisorption or physisorption to capture the carbon dioxide from the stream. Other methods to get concentrated carbon dioxide include chemical looping combustion where a circulating metal oxide material captures the carbon dioxide produced during the combustion process. Carbon dioxide can also be captured from the atmosphere in what is called direct air capture (DAC) of carbon dioxide. Renewable sources of Hydrogen (H2) can be produced from water via electrolysis. H2⁢O=H2+12⁢O2 This reaction uses electricity to split water into hydrogen and oxygen. Electrolyzers consist of an anode and a cathode separated by an electrolyte. Different electrolyzers function in slightly different ways, mainly due to the different type of electrolyte material involved. However, each electrolysis technology has a theoretical minimum electrical energy input of 39.4 kWh/kgH2(HHV of hydrogen) if water is fed at ambient pressure and temperature to the system and all energy input is provided in the form of electricity. The required electrical energy input may be reduced below 39.4 kWh/kgH2if suitable heat energy is provided to the system. Besides electrolysis, significant current research is examining ways to split water into hydrogen and oxygen using light energy and a photocatalyst. Different electrolyzer designs that use different electrolysis technology can be used including alkaline electrolysis, membrane electrolysis, polymer electrolyte membrane (PEM), solid oxide electrolysis (SOE), and high temperature electrolysis. Alkaline electrolysis is commercially capable of the larger >1 MW scale operation. Different electrolytes can be used including liquids KOH and NaOH with or without activating compounds can be used. Activating compounds can be added to the electrolyte to improve the stability of the electrolyte. Most ionic activators for hydrogen evolution reaction are composed of ethylenediamine (en)-based metal chloride complex ([M(en)3]Clx,M¼Co, Ni, et al.) and Na2MoO4or Na2WO4. Different electrocatalysts can be used on the electrodes including many different combinations of metals and oxides like Raney-Nickel-Aluminum, which can be enhanced by adding cobalt or molybdenum to the alloy. Several combinations of transition metals, such as Pt2Mo, Hf2Fe, and TiPt, have been used as cathode materials and have shown significantly higher electrocatalytic activity than state-of-the-art electrodes. Water at the cathode combines with electrons from the external circuit to form hydrogen gas and negatively charged oxygen ions. The oxygen ions pass through the solid ceramic membrane and react at the anode to form oxygen gas and generate electrons for the external circuit. In this way, both hydrogen gas and oxygen gas are produced in the electrolyzer. In one embodiment, multiple electrolyzers are operated in parallel. No electrolyzer operates with 100% energy efficiency and energy usage is critical to the economic operation of the facility. The energy usage in the electrolyzer should be between 0 and 200 mega-watthours (MWh)/metric ton (MT) of H2produced; preferably between 0 and 120 MWh/MT H2produced; and even more preferably between 0 and 60 MWh/MT H2produced. For the alkaline electrolyzer embodiment, the electricity usage will be greater than 39.4 MWh/MT H2produced. However, for the high temperature electrolyzer embodiment, the electricity usage can potentially be between 0 and 39.4 MWh/MT H2produced if waste heat is used to heat the electrolyzer above ambient temperature. As described herein, the reverse water-gas-shift (RWGS) reaction can be used to produce syngas according to the formula: CO2+H2=CO+H2O This reaction converts carbon dioxide and hydrogen to carbon monoxide and water. This reaction is endothermic at room temperature and requires heat to proceed and elevated temperature and a good catalyst is required for significant carbon dioxide conversion. Hydrogen and carbon dioxide are mixed. The ratio of H2/CO2can be between 2.0 mol/mol to 4.0 mol/mol, in some cases between 3.0 to 4.0 mol/mol. The mixed RWGS feedstock can be heated by indirect heat exchange to a temperature of greater than 900° F. This initial temperature rise can be done without the use of direct combustion of a carbon containing gas to provide the heat. This would mean that carbon dioxide was being produced and could possibly negate the impact of converting carbon dioxide to useful fuels and chemicals. The RWGS feed gas, comprising a mixture of hydrogen and carbon dioxide, can be heated to an inlet temperature. The inlet temperature can be any suitable temperature for performing the RWGS reaction. In some cases, the inlet temperature of the RWGS feed is between 900° F. and 1800° F. The RWGS feed gas can be heated at least partially in a preheater outside the main reactor vessel to produce a heated feed gas. The preheater can be electrically heated and raises the temperature of the feed gas through indirect heat exchange. There can be numerous ways that the electrical heating of the feed gas can be done. One way is through electrical heating in an electrically heated radiant furnace. In some embodiments, at least a portion of the feed gas passes through a heating coil in a furnace. In the furnace, the heating coil is surrounded by radiant electric heating elements or the gas is passed directly over the heating elements whereby the gas is heated by some convective heat transfer. The electric heating elements can be made from numerous materials. The heating elements may be nickel chromium alloys. These elements may be in rolled strips or wires or cast as zig zag patterns. The elements are typically backed by an insulated steel shell, and ceramic fiber is generally used for insulation. The radiant elements may be divided into zones to give a controlled pattern of heating. Multiple coils and multiple zones may be needed to provide the heat to the feed gas and produce a heated feed gas. Radiant furnaces require proper design of the heating elements and fluid coils to ensure good view factors and good heat transfer. The electricity usage by the radiant furnace should be as low as possible. The electricity usage by the radiant furnace is between 0 and 0.5 MWh (megawatt-hour) electricity/metric ton (MT) of CO2in the feed gas; preferably between 0 and 0.40 MWh/MT CO2; and even more preferably between 0 and 0.20 MWh/MT CO2. The heated RWGS feed gas stream can then be fed into the main RWGS reactor vessel. There are at least two possible embodiments of the main RWGS reactor vessel. In some embodiments, the main RWGS reactor vessel is adiabatic or nearly adiabatic and is designed to minimize heat loss, but no added heat is added to the main reactor vessel and the temperature in the main reactor vessel will decline from the inlet to the outlet of the reactor. In some embodiment, the main RWGS reactor vessel is similarly designed but additional heat is added to the vessel to maintain an isothermal or nearly isothermal temperature profile in the vessel. The main RWGS reactor vessel can be a reactor with a length longer than diameter. The entrance to the main reactor vessel can be smaller than the overall diameter of the vessel. The main reactor vessel can be a steel vessel. The steel vessel can be insulated internally to limit heat loss. Various insulations including poured or castable refractory lining or insulating bricks may be used to limit the heat losses to the environment. A bed of catalyst can be inside the main RWGS reactor vessel. The catalyst can be in the form of granules, pellets, spheres, trilobes, quadra-lobes, monoliths, or any other engineered shape to minimize pressure drop across the reactor. In some cases, the shape and particle size of the catalyst particles is managed such that pressure drop across the reactor is between 0 and 100 pounds per square inch (psi) (345 kPa) and preferably between 0 and 20 psi. The size of the catalyst form can have a characteristic dimension of between 1 mm and 10 mm. The catalyst particle can be a structured material that is porous material with an internal surface area greater than 40 m2/g, in some cases greater than 80 m2/g with some cases having a surface area of 100 m2/g. The RWGS catalyst can be a high-performance solid solution catalyst that is highly versatile, and which efficiently performs the RWGS reaction. The robust, solid solution transition metal catalyst can have a high thermal stability up to 1,100° C., does not form carbon (coking), and has good resistance to contaminants that may be present in captured CO2streams. This catalyst can exhibit high activity at low transition metal concentrations (5-20 wt. %), compared to other catalysts that require at least 30 wt. % transition metals. Furthermore, the use of expensive precious metals to enhance catalyst performance is not necessary. The manufacturing process for the RWGS catalyst can produce a catalyst that forms a solid solution phase, bi-metallic crystalline phase that leads to little or no segregation of the metal phases. This chemical structure can lead to enhanced resistance to coking, when compared to conventional metal supported catalysts. This can also lead to enhanced resistance to poisons such as sulfur and ammonia. In addition, this catalyst can have enhanced catalytic activity at lower surface area compared to monometallic segregated catalyst phase for example Ni on alumina. In some instances, this catalyst requires no alkali promotion needed to curb the carbon deposition. In some cases, the pressure of the RWGS step and the pressure of the hydrocarbon synthesis or Liquid Fuel Production (LFP) step are within 200 psi of each other, in some cases within 100 psi of each other, and in some cases within 50 psi of each other. Operating the two processes at pressures close to each other limit the required compression of the syngas stream. The per pass conversion of carbon dioxide to carbon monoxide in the main RWGS reactor vessel can be between 60 and 90 mole % and in some cases between 70 and 85 mole %. If an adiabatic reactor is used, the temperature in the main RWGS reactor vessel can decline from the inlet to the outlet. The main RWGS reactor vessel outlet temperature can be 100° F. to 200° F. less than the main reactor vessel inlet temperature and in some cases between 105 and 160° F. lower than the main reactor inlet temperature. The RWGS Weight Hourly Space Velocity (WHSV) which is the mass flow rate of RWGS reactants (H2+CO2) per hour divided by the mass of the catalyst in the main RWGS reactor bed can be between 1,000 and 50,000 hr−1and in some cases between 5,000 and 30,000 hr−1. The gas leaving the main RWGS reactor vessel is the RWGS product gas stream. The RWGS product gas comprises carbon monoxide (CO), hydrogen (H2), unreacted carbon dioxide (CO2), and water (H2O). Additionally, the RWGS product gas may also comprise a small quantity of methane (CH4) that was produced in the main reactor vessel by a side reaction. The RWGS product gas can be used in a variety of ways at this point in the process. The product gas can be cooled and compressed and used in downstream process to produce fuels and chemicals. The RWGS product gas can also be cooled, compressed, and sent back to the preheater and fed back to the main reactor vessel. The RWGS product gas can also be reheated in second electric preheater and sent to a second reactor vessel where additional conversion of CO2to CO can occur. With the CO (carbon monoxide) from the RWGS reaction and hydrogen from the electrolysis of water, the potential exists for useful products through the catalyst hydrogenation of carbon monoxide to hydrocarbons. Mixtures of H2and CO are called synthesis gas or syngas. Syngas may be used as a feedstock for producing a wide range of chemical products, including liquid fuels, alcohols, acetic acid, dimethyl ether, methanol, ammonia, and many other chemical products. The catalytic hydrogenation of carbon monoxide to produce light gases, liquids and waxes, ranging from methane to heavy hydrocarbons (C100 and higher) in addition to oxygenated hydrocarbons, is typically referred to Fischer-Tropsch (or F-T) synthesis. Traditional low temperature (<250° C.) F-T processes primarily produce a high weight (or wt. %) F-T wax (C25 and higher) from the catalytic conversion process. These F-T waxes are then hydrocracked and/or further processed to produce diesel, naphtha, and other fractions. During this hydrocracking process, light hydrocarbons are also produced, which may require additional upgrading to produce viable products. The catalysts that are commonly used for F-T are either Cobalt (Co) based, or Iron (Fe) based catalysts are also active for the water gas shift (WGS) reaction that results in the conversion of feed carbon monoxide to carbon dioxide. In addition to F-T, the Liquid Fuel Production (LFP) module described herein can be used. The LFP reactor converts CO and H2into long chain hydrocarbons that can be used as liquid fuels and chemicals. This reactor can use a catalyst for production of liquid fuel range hydrocarbons from syngas. Syngas from syngas cooling and condensing can be blended with tail gas to produce an LFP reactor feed. The LFP reactor feed comprises hydrogen and carbon monoxide. Ideally the hydrogen to carbon monoxide ratio in the stream is between 1.9 and 2.2 mol/mol. The LFP reactor can be a multi-tubular fixed bed reactor system. Each LFP reactor tube can be between 13 mm and 26 mm in diameter. The length of the reactor tube is generally greater than 6 meters in length and in some cases greater than 10 meters in length. The LFP reactors are generally vertically oriented with LFP reactor feed entering at the top of the LFP reactor. However, horizontal reactor orientation is possible in some circumstances and setting the reactor at an angle may also be advantageous in some circumstances where there are height limitations. Most of the length of the LFP reactor tube can be filled with LFP catalyst. The LFP catalyst may also be blended with diluent such as silica or alumina to aid in the distribution of the LFP reactor feed into and through the LFP reactor tube. The chemical reaction that takes place in the LFP reactor produces an LFP product gas that comprises most hydrocarbon products from five to twenty-four carbons in length (C5-C24hydrocarbons) as well as water, although some hydrocarbons are outside this range. The LFP reactor does not typically produce any significant amount of carbon dioxide. An amount between 0% and 2% of the carbon monoxide in the LFP reactor feed is typically converted to carbon dioxide in the LFP reactor. Only a limited amount of the carbon monoxide in the LFP reactor feed is typically converted to hydrocarbons with a carbon number greater than 24. An amount between 0% and 25% of the hydrocarbon fraction of the LFP product has a carbon number greater than 24. In some cases, between 0 and 10 wgt % of the hydrocarbon fraction of the LFP product has a carbon number greater than 24; and preferably between 0 and 4 wgt % of the hydrocarbon fraction of the LFP product has a carbon number greater than 24; and even more preferably between 0 and 1 wgt % of the hydrocarbon fraction of the LFP product has a carbon number greater than 24. As discussed above, Fischer-Tropsch (F-T) processes generally make hydrocarbon products that are from 1 to 125 carbon atoms in length. The LFP catalyst described herein does not produce heavy hydrocarbons with the same yield as other catalysts used in the F-T process. In some embodiments, the LFP catalyst has insignificant activity for the conversion of conversion of carbon monoxide to carbon dioxide via the water-gas-shift reaction. In some embodiments, the water gas shift conversion of carbon monoxide to carbon dioxide is between 0% and 5% of the carbon monoxide in the feed. In some embodiments, the LFP catalyst comprises cobalt as the active metal. In some embodiments, the LFP catalyst comprises iron as the active metal. In some embodiments, the LFP catalyst comprises combinations of iron and cobalt as the active metal. The LFP catalyst can be supported on a metal oxide support that chosen from a group of alumina, silica, titania, activated carbon, carbon nanotubes, zeolites or other support materials with sufficient size, shape, pore diameter, surface area, crush strength, effective pellet radius, or mixtures thereof. The catalyst can have various shapes of various lobed supports with either three, four, or five lobes with two or more of the lobes being longer than the other two shorter lobes, with both the longer lobes being symmetric. The distance from the mid-point of the support or the mid-point of each lobe is called the effective pellet radius which can contribute to achieving the desired selectivity to the C5to C24hydrocarbons. The LFP catalyst promoters may include one of the following: nickel, cerium, lanthanum, platinum, ruthenium, rhenium, gold, or rhodium. The LFP catalyst promoters are between 0 and 1 wt. % of the total catalyst and preferably between 0 and 0.5 wt. % and even more preferably between 0 and 0.1 wt. %. The LFP catalyst support can have a pore diameter greater than 8 nanometers (nm), a mean effective pellet radius between 0 and 600 microns, a crush strength greater than 3 lbs/mm and a BET surface area of greater than 100 m2/g. The catalyst after metal impregnation can have a metal dispersion of 4%. Several types of supports have can maximize the C5-C24hydrocarbon yield. These can include alumina/silica combinations, activated carbon, alumina, carbon nanotubes, and/or zeolite-based supports. The LFP fixed bed reactor can be operated in a manner to maximize the C5-C24hydrocarbon yield. The LIT reactor can be operated at pressures between 150 to 450 psi. The reactor can be operated over a temperature range from 350 to 460° F. and more typically at around 410° F. The reaction is exothermic. The temperature of the reactor can be maintained inside the LFP reactor tubes by the reactor tube bundle being placed into a heat exchanger where boiling steam is present on the outside of the LFP reactor tubes. The steam temperature is at a lower temperature than the LFP reaction temperature so that heat flows from the LFP reactor tube to the lower temperature steam. The steam temperature can be maintained by maintaining the pressure of the steam. The steam is generally saturated steam. In some embodiments, the catalytic reactor can be a slurry reactor, microchannel reactor, fluidized bed reactor, or other reactor types known in the art. The CO conversion in the LFP reactor can be maintained at between 30 to 80 mole % CO conversion per pass. CO can be recycled for extra conversion or sent to a downstream additional LFP reactor. The carbon selectivity to CO2can be minimized to an amount between 0% and 4% of the converted CO and in more preferably between 0% and 1%. The carbon selectivity for C5-C24 hydrocarbons can be between 60 and 90%. The LFP reactor product gas contains the desired C5-C24 hydrocarbons, which are condensed as liquid fuels and water, as well as unreacted carbon monoxide, hydrogen, a small amount of C1-C4 hydrocarbons, and a small amount of C24+ hydrocarbons. The desired product can be separated from the stream by cooling, condensing the product and/or distillation or any other acceptable means. The unreacted carbon monoxide, hydrogen, and C1-C4 hydrocarbons can be part of the feed to the auto-thermal reformer (ATR). In the auto-thermal reformer (ATR), the ATR hydrocarbon feed comprises carbon monoxide, hydrogen, and C1-C4 hydrocarbons. The auto-thermal reforming of natural gas that is predominately methane (C1) to carbon monoxide and hydrogen. In some embodiments, the ATR hydrocarbon feed comprises the unreacted carbon monoxide, hydrogen, and C1-C4 hydrocarbons. In some cases, the feed also comprises natural gas. The natural gas comprises methane and may contain light hydrocarbons as well as carbon dioxide. In some embodiments, the fuel and chemicals produced may not be zero carbon fuels but will still have an improved carbon intensity over traditional fuels and chemicals. The ATR feed can be converted to syngas (including a large percentage of hydrogen). This can reduce the amount of water that needs to be electrolyzed to produce hydrogen and reduces the size of the electrolyzer. This may be more economical when producing low carbon fuels and chemicals. In the ATR hydrocarbon feed, the ratio of natural gas to LFP unreacted carbon monoxide, hydrogen, and C1-C4 hydrocarbons can be an amount between 0 kg/kg and 2.0 kg/kg, and more preferably an amount between 0 kg/kg and 1.25 kg/kg. The ATR can produce a product that is high in carbon monoxide. The carbon dioxide in the product gas can be an amount between 0 mol % and 10 mol %. The ATR oxidant feed can comprise steam and oxygen where the oxygen is produced by the electrolysis of water. The ATR oxidant feed and the ATR hydrocarbon feed can be preheated and then reacted in an ATR burner where the oxidant and the hydrocarbon are partially oxidized at temperatures in the burner of greater than 2000° C. The ATR reactor can be divided into a plurality of zones. The combustion zone (or burner) is where at least portion of the ATR hydrocarbon feedstock is fully combusted to water and carbon dioxide. The thermal zone is where thermal reactions occur. In the thermal zone, further conversion occurs by homogeneous gas-phase-reactions. These reactions can be slower reactions than the combustion reactions like CO oxidation and pyrolysis reactions involving higher hydrocarbons. The main overall reactions in the thermal zone can include the homogeneous gas-phase steam hydrocarbon reforming and the shift reaction. In the catalytic zone, the final conversion of hydrocarbons takes place through heterogeneous catalytic reactions including steam methane reforming and water gas shift reaction. The resulting ATR product gas can have a composition that is close to the predicted thermodynamic equilibrium composition. The actual ATR product gas composition can be the same as the thermodynamic equilibrium composition within a difference of an amount between 0° C. and 70° C. This is the so-called equilibrium approach temperature. To keep the amount of CO2produced in the ATR to a minimum, the amount of steam in the ATR oxidant feed can be kept as low as possible. This can still result in a low soot ATR product gas that is close to the equilibrium predicted composition. Typically, the total steam to carbon ratio (mol/mol) in the combined ATR feed (oxidant+hydrocarbon) can be between 0.4 to 1.0, with the optimum being around 0.6. As the steam to carbon ratio in the ATR feed increases, the H2/CO ratio in the syngas increases. The amount of carbon dioxide also increases. In some embodiments, changing or adjusting the steam to carbon ratio can be beneficial to control the amount of overall hydrogen production in the facility. The ATR product can leave the ATR catalytic zone at temperatures more than 800° C. The ATR product can be cooled to lower temperatures through a waste heat boiler where the heat is transferred to generate steam. This steam, as well as the lower pressure steam produced by the LFP reactor, can be used to generate electricity. Suitable ATR catalysts for the catalytic zone reactions are typically nickel based. The novel solid solution catalyst described herein can be used as an ATR catalyst. Other suitable ATR catalysts are nickel on alpha phase alumina or magnesium alumina spinel (MgAl2O4) with or without precious metal promoters. The precious metal promoter can comprise gold, platinum, rhenium, or ruthenium. Spinels can have a higher melting point and a higher thermal strength and stability than the alumina-based catalysts. The ATR product can be blended with the RWGS product and be used as LFP reactor feed. This can result in a high utilization of the original carbon dioxide to C5 to C24 hydrocarbon products. In some embodiments, the LFP product gas is not suitable as a direct feed to the ATR and must be pre-reformed. In those cases, the LFP product gas comprising the unreacted carbon monoxide, hydrogen, C1-C4 hydrocarbons and CO2 comprise the pre-reformer hydrocarbon feed gas. The higher the higher hydrocarbons and carbon oxides in the stream may require the use of a pre-reformer instead of directly being used in as ATR hydrocarbon feed. The pre-reformer is generally an adiabatic reactor. The adiabatic pre-reformer converts higher hydrocarbons in the pre-reformer feed into a mixture of methane, steam, carbon oxides and hydrogen that are then suitable as ATR hydrocarbon feed. One benefit of using a pre-reformer is that it enables higher ATR hydrocarbon feed pre-heating that can reduce the oxygen used in the ATR. The resulting integrated process as described above results in high conversion of carbon dioxide to C5-C24 hydrocarbon products that are suitable as fuels or chemicals. In some embodiments, an autothermal reforming (ATR) process that converts the tail gas (and potentially other hydrocarbon feedstocks) from the fuel/chemical production stage and oxygen from the electrolysis processes into additional syngas. In some embodiments, the use of heat energy from the ATR process for operation of the (CO2) RWGS (hydrogenation) catalyst. In some embodiments, the separation and conversion of the CO2from the ATR process into additional syngas using the CO2 hydrogenation catalyst. In some embodiments, a RWGS catalyst, reactor, and process converts CO2and hydrogen into syngas and operating this RWGS operation at a pressure that is close to the pressure of the fuel/chemical production process, which converts the syngas into fuels or chemicals. In some cases, these fuels or chemicals are paraffinic or olefinic hydrocarbon liquids with a majority being in the C5-C24 range. The systems and methods described herein can utilize a sensor. The sensor can be a flowrate sensor, a sensor that detects the chemical composition of a process stream, a temperature sensor, a pressure sensor, or a sensor coupled to the price or availability of a process input, such as CO2or electrical power. In an aspect, the systems and methods described herein efficiently capture and utilize carbon dioxide and convert it into useful products such as fuels (e.g., diesel fuel, gasoline, gasoline blendstocks, jet fuel, kerosene, other) and chemicals (e.g., solvents, olefins, alcohols, aromatics, lubes, waxes, ammonia, methanol, other) that can displace fuels and chemicals produced from fossil sources such as petroleum and natural gas. This can lower the total net emissions of carbon dioxide into the atmosphere. Zero carbon, low carbon, or ultra-low carbon fuels and chemicals have minimal fossil fuels combusted in the process. In some cases, any heating of the feeds to the integrated process is done by indirect means (e.g., cross exchangers) or via electric heating where the electricity comes from a zero carbon or renewable source such as wind, solar, geothermal, or nuclear. Certain Embodiments The following are certain embodiment of processes for the conversion of carbon dioxide, water, and renewable electricity into low or zero carbon high quality fuels and chemicals: 1. Water is fed into an electrolysis system powered using renewable electricity to produce hydrogen and oxygen. Carbon dioxide is captured from a source. The carbon dioxide is mixed with the hydrogen from the electrolysis system to form a stream (Reverse Water Gas Shift feedstock or “RWGS” feedstock) that is heated and fed into a RWGS reactor vessel that includes a RWGS catalyst. The RWGS reactor converts the feedstock to an RWGS product gas comprising carbon monoxide, hydrogen, unreacted carbon dioxide and water. In response to a stimulus of an increase in the cost of renewable electricity, the amount of power supplied to the electrolysis system is reduced. To compensate for the reduced production of hydrogen, a controller activates a hydrogen recovery module which recovers hydrogen from the RWGS product gas and recycles it to the RWGS reactor. This compensation maintains the ratio of hydrogen and carbon dioxide between 2.0 and 4.0. The RWGS product gas is cooled, compressed, and fed into a Liquid Fuels Production (“LFP”) system. The LFP system converts RWGS product gas into hydrocarbon products, where more than 50 percent of the products are C5 to C24 hydrocarbons. 2. Water is fed into an electrolysis system powered using renewable electricity to produce hydrogen and oxygen. Carbon dioxide is captured from a fermentation exhaust. The carbon dioxide is mixed with the hydrogen from the electrolysis system to form a stream (Reverse Water Gas Shift feedstock or “RWGS” feedstock) that is heated and fed into a RWGS reactor vessel that includes a RWGS catalyst. The RWGS reactor converts the feedstock to an RWGS product gas comprising carbon monoxide, hydrogen, unreacted carbon dioxide and water. In response to a stimulus of an increase in the cost of renewable electricity, the amount of power supplied to the electrolysis system is reduced. To compensate for the reduced production of hydrogen, additional hydrogen is drawn from a pipeline or hydrogen storage vessel. This compensation maintains the ratio of hydrogen and carbon dioxide between 2.0 and 4.0. The RWGS product gas is cooled, compressed, and fed into a Liquid Fuels Production (“LFP”) system. The LFP system converts RWGS product gas into hydrocarbon products, where more than 50 percent of the products are C5 to C24 hydrocarbons. 3. Water is fed into an electrolysis system powered using renewable electricity to produce hydrogen and oxygen. Carbon dioxide is captured from a source. The carbon dioxide is mixed with the hydrogen from the electrolysis system to form a stream (Reverse Water Gas Shift feedstock or “RWGS” feedstock) that is heated and fed into a RWGS reactor vessel that includes a RWGS catalyst. The RWGS reactor converts the feedstock to an RWGS product gas comprising carbon monoxide, hydrogen, unreacted carbon dioxide and water. In response to a stimulus of an increase in the cost of renewable electricity, the amount of power supplied to the electrolysis system is reduced. To compensate for the reduced production of hydrogen, a controller activates a hydrogen recovery module which recovers hydrogen from the RWGS product gas and recycles it to the RWGS reactor. This compensation maintains the ratio of hydrogen and carbon dioxide between 2.0 and 4.0. The RWGS product gas is cooled, compressed, and fed into a Liquid Fuels Production (“LFP”) system. The LFP system converts RWGS product gas into hydrocarbon products, where more than 50 percent of the products are C5 to C24 hydrocarbons. Additionally, one or more C1-C4 hydrocarbons, carbon monoxide and hydrogen are fed into an auto-thermal reformer (“ATR”) that includes a catalyst to provide an ATR product stream. The RWGS product gas is blended with the ATR product stream and fed into a Liquid Fuels Production (“LFP”) system to increase the productivity of the system. 4. Water is fed into an electrolysis system powered using renewable electricity to produce hydrogen and oxygen. Carbon dioxide is captured from a source. The carbon dioxide is mixed with the hydrogen from the electrolysis system to form a stream (Reverse Water Gas Shift feedstock or “RWGS” feedstock) that is heated and fed into a RWGS reactor vessel that includes a RWGS catalyst. The RWGS reactor converts the feedstock to an RWGS product gas comprising carbon monoxide, hydrogen, unreacted carbon dioxide and water. A sensor detects that the ratio of hydrogen to carbon dioxide is below 2.5 and sends a signal to a controller which activates a hydrogen recovery module which recovers hydrogen from the RWGS product gas and recycles it to the RWGS reactor. This compensation maintains the ratio of hydrogen and carbon dioxide between 2.0 and 4.0. The RWGS product gas is cooled, compressed, and fed into a Liquid Fuels Production (“LFP”) system. The LFP system converts RWGS product gas into hydrocarbon products, where more than 50 percent of the products are C5 to C24 hydrocarbons. 5. Water is fed into an electrolysis system powered using renewable electricity to produce hydrogen and oxygen. Carbon dioxide is captured from a source. The carbon dioxide is mixed with the hydrogen from the electrolysis system to form a stream (Reverse Water Gas Shift feedstock or “RWGS” feedstock) that is heated and fed into a RWGS reactor vessel that includes a RWGS catalyst. The RWGS reactor converts the feedstock to an RWGS product gas comprising carbon monoxide, hydrogen, unreacted carbon dioxide and water. In response to a stimulus of an increase in the cost of renewable electricity, the operating temperature of the RWGS reactor is reduced, thereby consuming less power. This modification alters the product composition from the RWGS reactor. The RWGS product gas is cooled, compressed, and fed into a Liquid Fuels Production (“LFP”) system. The LFP system converts RWGS product gas into hydrocarbon products, where more than 50 percent of the products are C5 to C24 hydrocarbons. 6. Water is fed into an electrolysis system powered using renewable electricity to produce hydrogen and oxygen. Carbon dioxide is captured from a source. The carbon dioxide is mixed with the hydrogen from the electrolysis system to form a stream (Reverse Water Gas Shift feedstock or “RWGS” feedstock) that is heated and fed into a RWGS reactor vessel that includes a RWGS catalyst. The RWGS reactor converts the feedstock to an RWGS product gas comprising carbon monoxide, hydrogen, unreacted carbon dioxide and water. In response to a stimulus of a reduced supply of renewable electricity, the amount of power supplied to the electrolysis system is reduced, but the power supplied to other modules of the system is substantially maintained. The RWGS product gas is cooled, compressed, and fed into a Liquid Fuels Production (“LFP”) system. The LFP system converts RWGS product gas into hydrocarbon products, where more than 50 percent of the products are C5 to C24 hydrocarbons. The above-described embodiments can be implemented in any of numerous ways. For example, the embodiments may be implemented using hardware, software or a combination thereof. When implemented in software, the software code can be executed on any suitable processor or collection of processors, whether provided in a single computer or distributed among multiple computers. It should be appreciated that any component or collection of components that perform the functions described above can be generically considered as one or more controllers that control the above-discussed functions. The one or more controllers can be implemented in numerous ways, such as with dedicated hardware or with one or more processors programmed using microcode or software to perform the functions recited above. In this respect, it should be appreciated that one implementation of the embodiments of the present invention comprises at least one non-transitory computer-readable storage medium (e.g., a computer memory, a portable memory, a compact disk, etc.) encoded with a computer program (i.e., a plurality of instructions), which, when executed on a processor, performs the above-discussed functions of the embodiments of the present invention. The computer-readable storage medium can be transportable such that the program stored thereon can be loaded onto any computer resource to implement the aspects of the present invention discussed herein. In addition, it should be appreciated that the reference to a computer program which, when executed, performs the above-discussed functions, is not limited to an application program running on a host computer. Rather, the term computer program is used herein in a generic sense to reference any type of computer code (e.g., software or microcode) that can be employed to program a processor to implement the above-discussed aspects of the present invention. Various aspects of the present invention may be used alone, in combination, or in a variety of arrangements not specifically discussed in the embodiments described in the foregoing and are therefore not limited in their application to the details and arrangement of components set forth in the foregoing description or illustrated in the drawings. For example, aspects described in one embodiment may be combined in any manner with aspects described in other embodiments. Also, embodiments of the invention may be implemented as one or more methods, of which an example has been provided. The acts performed as part of the method(s) may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments. Use of ordinal terms such as “first,” “second,” “third,” etc., in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed. Such terms are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term). The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” “having,” “containing”, “involving”, and variations thereof, is meant to encompass the items listed thereafter and additional items. Having described several embodiments of the invention in detail, various modifications and improvements will readily occur to those skilled in the art. Such modifications and improvements are intended to be within the spirit and scope of the invention. Accordingly, the foregoing description is by way of example only, and is not intended as limiting. The invention is limited only as defined by the following claims and the equivalents thereto. The following Examples are for illustrative purposes and are not in any way meant to limit the scope of the invention. Example 1: This is the base case e-fuels production facility. It is configured as perFIG.1. Electricity is used in an Electrolysis unit to produce hydrogen. Carbon dioxide is supplied from a Carbon Dioxide capture facility. The hydrogen and carbon dioxide are fed to a RWGS reactor with a H2/CO2ratio of 2.0. For this example, if there is a stimulus, this facility responds without the benefit of the invention. The stimulus is a reduction in the amount of electricity available to the e-fuels production facility because of a decrease in wind to the wind turbines. There is a 12-hour period where only 50% of the base electricity is available. The facility electrolysis unit scales back to 50% H2production; to keep the H2/CO2ratio to the RWGS reactor the same, the CO2usage decreases by 50%; syngas from RWGS reactor decreases by 50%; and therefore, the overall LFP fuel production decreases by 50%. Overall plant revenue decreases by 50% for the 12-hour period. This is clearly less than desired. Example 2: For this example, the configuration of the facility is similar to the configuration of Example 1 but with a Hydrogen Recovery Module as shown inFIG.2. In this example, the stimulus is identical to Example 1 where electricity is reduced by 50% for a 12 hour period. The monitor and controller kick in. In this case, the Hydrogen Recovery Module responds to the stimulus by separating H2from the RWGS reactor outlet which also includes syngas from ATR and recycles H2back to RWGS inlet to keep H2/CO2ratio in the feed the same. CO2usage stays the same. Water to the ATR is increased resulting in a higher steam to carbon ratio resulting in a higher H2/CO leaving the ATR. The H2/CO ratio to the LFP decreases from 2.0 to 1.8 (say). The overall LFP reactor conversion declines by 20 relative percent from the pre-stimulus base case of Example 1. The overall decrease in product leaving the facility is declined by 20% instead of the 50% decrease of Example 1 and showing the benefit of the invention. Therefore, the overall plant revenue decreases by 20% for the 12-hour period. This represents a substantial improvement in revenue over the bae case. Example 3: For this example, the configuration is identical to Example 1. The stimulus is a 2 hour cessation of carbon dioxide flow from the carbon capture unit. For this example, in the base configuration, the hydrogen production in the Electrolyzer is ceased. The overall fuel production falls to zero production over that period. The revenue over those two hours falls to zero. The temporary stimulus ceases, and the facility restarts and reaches full production. The facility then receives another stimulus where electricity available falls to zero for 2 hours. The facility then stops production of fuels. The revenue over that two hour period is zero. For this example, over the 4 hours of the two separate stimulus is zero. Example 4: For this example, the configuration is identical to Example 2 with a Hydrogen Recovery Module. The same stimuli of Example 3 are seen by this new facility. During the first stimulus, there is two hours of no carbon dioxide. In this case, in contrast to Example 3, the operation of the electrolyzer continue. The hydrogen recovery module allows for the liquefaction and storage of the hydrogen produced during the outage. During the second stimulus, where electricity is not available to run the electrolyzer, hydrogen is taken from storage and fuel production continues. In this example, during the first stimulus event, the facility revenue is zero but during the second stimulus event, the revenue does not decline. So in this caseover the two stimulus events, the revenue is 50% of the full production revenue. This represents a substantial increase in revenue versus the facility revenue of Example 4. REFERENCES Eichman, J, Koleva, M., Guerra, O. J., McLaughlin, B: Optimizing an integrated renewable-electrolysis system, National Renewable Energy Laboratory Report #NREL/TP-5400-75635, 55 pages (2020).Ince, C., Hagen, S.: Modeling and simulation of Power-to-X systems: a review, Fuel, 304 (2021).Wulf, C., Zapp, P., Schrebier, A.: Review of Power-to-X demonstration projects in Europe, Frontiers in Energy Research (2020).
57,953
11857939
DETAILED DESCRIPTION Referring generally toFIGS.1-5, various exemplary embodiments of an invention may now be described in detail. Where the various figures may describe embodiments sharing various common elements and features with other embodiments, similar elements and features are given the same reference numerals and redundant description thereof may be omitted below. Briefly stated, systems and methods as disclosed herein may be implemented to proactively alert users or implement automated dosing optimization in chemical processes via data analytics. In one particular embodiment as described in more detail below, a system and method may be provided to determine if an acid boil-out to remove mineral scale and/or biological fouling of a chemical feed skid is required, where that chemical feed skid is one that generates an oxidizing biocide solution (monochloramine in a particular instance as referred to throughout the present disclosure, but without limitation on the scope of invention) at an alkaline pH from multiple precursors. The algorithm to determine if a boil-out is required is built using data that comes directly from the feed skid and includes, but is not limited to water conductivity, temperatures, flow rates, pH, run time, etc. In another embodiment as described in more detail below, a system and method (which may be independent, or otherwise part of the same system and further supplement the same method as previously discussed) may be provided to predictively model the true stoichiometric ratio of two chemical precursors used to generate an oxidizing biocide in real time, wherein at least one chemical precursor having an active ingredient that varies in concentration over time is indirectly monitored and/or determined remotely, so that for example volumetric flow adjustments can be made to optimize efficiency and performance of said oxidizing biocide. In another embodiment as described in more detail below, a system and method (which may also be independent, or otherwise part of the same system and further supplement the same method(s) as previously discussed) may relate to controlling the amount of an oxidizing biocide fed to a commercial or industrial process to regulate the amount of microbiological contamination within the process. Such a method may include capturing both online and offline operational and quality data of the process to develop and deploy application specific control logic such that the microbiological contamination is minimized, while optimizing key process performance metrics and oxidizing biocide dosing efficiency. Both streaming and manually entered data may for example be sent to a remote server, where application specific algorithms are developed and pushed back down to an edge device to regulate the biocide feed along one or more points of the process. Referring initially toFIG.1, an embodiment of a hosted system100as disclosed herein may be provided in association with, or even in some cases include, various stages in an industrial plant including an input stage110providing one or more streams of content to a chemical feed stage120, which further provides an output solution such as, e.g., monochloramine (hereinafter “MCA”). In an embodiment, the input stage may include a first precursor including a bleach solution and a second precursor including an amine solution, each of which are fed to a defined area to form a mixture, such as a reaction mixture, from which an MCA product is produced. The MCA product can be applied, for example, to treatment of aqueous end solutions, such as waters, pulps, aqueous containing streams, and the like, and in certain alternative embodiments the supplied oxidant and amine reactants used to make the MCA product can be combined directly in the end solution for in-situ production of the treatment product, or the reactants can be combined onsite and in advance of the end solution. The defined area in which the reactants are shown to be combined may comprise a vessel or line such as, for example, a tank, pipe, conduit, reactor, bath, stream, or container, and the like. Additional supply reactants, not shown in this illustration, can be used depending on the reaction chemistry involved. The term “industrial plant” as used herein may generally connote a facility for production of goods, independently or as part of a group of such facilities, and may for example but without limitation involve an industrial process and chemical business, a manufacturing industry, food and beverage industry, agricultural industry, swimming pool industry, home automation industry, leather treatment industry, paper making process, and the like. A system “host” as referred to herein may generally be independent of a given industrial plant, but this aspect is not necessary within the scope of the present disclosure. The system host may be directly associated with an embodiment of the cloud-based server system100and capable of directly or indirectly implementing predictive analysis and preventative maintenance operations as disclosed herein for each of a group of industrial plants. A data collection stage140may for example include a plurality of sensors142positioned online with various respective components of the chemical feed stage120and/or the input stage110and/or the output solution130. Some or all of the sensors142may preferably be configured to continuously generate signals corresponding to real-time values for conditions and/or states of the respective components. The sensors may be configured to calibrate or otherwise transform raw measurement signals into output data in a form or protocol to be processed by downstream computing devices, or in various embodiments one or more intervening computing devices or controllers (not shown) may be implemented to receive raw signals from some or all of the sensors and provide any requisite calibration or transformation into a desired output data format. The term “sensors” may include, without limitation, physical level sensors, relays, and equivalent monitoring devices as may be provided to directly measure values or variables for associated process components or elements, or to measure appropriate derivative values from which the process components or elements may be measured or calculated. The term “online” as used herein may generally refer to the use of a device, sensor, or corresponding elements proximally located to a container, machine or associated process elements, and generating output signals substantially in real time corresponding to the desired process elements, as distinguished from manual or automated sample collection and “offline” analysis in a laboratory or through visual observation by one or more operators. Individual sensors142may be separately mounted and configured, or the system100may provide a modular housing which includes, e.g., a plurality of sensors or sensing elements142. Sensors or sensor elements may be mounted permanently or portably in a particular location respective to the chemical feed stage120, or may be dynamically adjustable in position so as to collect data from a plurality of locations during operation, for example further including the input stage110, and/or the output solution130from the chemical feed stage. Online sensors142as disclosed herein may provide substantially continuous measurements with respect to various process components and elements, and substantially in real-time. The terms “continuous” and “real-time” as used herein, at least with respect to the disclosed sensor outputs, does not require an explicit degree of continuity, but rather may generally describe a series of measurements corresponding to physical and technological capabilities of the sensors, the physical and technological capabilities of the transmission media, the physical and technological capabilities of any intervening local controller, communications device, and/or interface configured to receive the sensor output signals, etc. For example, measurements may be taken and provided periodically and at a rate slower than the maximum possible rate based on the relevant hardware components or based on a communications network configuration which smooths out input values over time, and still be considered “continuous.” While sensors may be available for directly measuring control parameters such as for example contamination levels in a particular stage or component of the industrial process, or the concentration of halogenated material in a chemical precursor, as previously noted herein such sensors may be prohibitively expensive or unreliable. Accordingly, various embodiments of a system100as disclosed herein implement sensors142in a data collection stage140which directly sense values, levels, states, etc., of variables other than the specified control parameter (e.g., contaminant) at issue, and which are more reliable and readily available for implementation, wherein the process state (e.g., contamination state and/or active ingredient state) is indirectly determined or predicted at the predictive maintenance (cloud-based computing) stage of the system. The data collection stage140may further include a graphical user interface (GUI)144wherein users such as operators, administrators, and the like can provide periodic input with respect to conditions or states of additional components of relevance to the downstream algorithms as further discussed herein. The GUI144may also be in functional communication with a hosted server152and/or local process control units (not shown) to receive and display process-related information, or to provide other forms of feedback with respect to, e.g., cleaning or replenishment processes as further discussed herein. The term “user interface” as used herein may unless otherwise stated include any input-output module with respect to the hosted data server including but not limited to: a stationary operator panel with keyed data entry, touch screen, buttons, dials or the like; web portals, such as individual web pages or those collectively defining a hosted website; mobile device applications, and the like. Accordingly, one example of the user interface may be as generated remotely on a user computing device120and communicatively linked to the remote server110. Alternatively, an example of the GUI144may within the scope of the present disclosure be generated on a stationary display unit in an operator control panel (not shown) associated with a production stage of an industrial plant. The data collection stage140may further include one or more communications devices146configured to receive output signals from the online sensors142and to transmit corresponding output data to a hosted server152via, e.g., a communications network. A communications device may be stand-alone or alternatively be comprised of a local controller configured for example to direct the collection and transmittal of data from the industrial plant to the cloud server, and further to direct output signals from the server to other process controllers at the plant level or more directly to process actuators in the form of control signals to implement automated interventions. In some embodiments the communications device or local controller may be omitted, where for example data collection tools are distributed to directly transmit data streams via the communications network, and a user computing device which also displays and implements the GUI144is implemented to receive the output signals from the server, etc. In some embodiments, the communications device or local controller may be comprised of at least part of an industrial plant's resident control system. In an embodiment (not shown), a conversion stage may be added for the purpose of converting raw signals from one or more of the online sensors142to a signal compatible with data transmission or data processing protocols of the communications network and/or cloud server-based storage and applications. A conversion stage may relate not only to input requirements but also may further be provided for data security between one or more sensors and the cloud-based server152, or between local communications devices146such as a local controller and the server. The term “communications network” as used herein with respect to data communication between two or more system components or otherwise between communications network interfaces associated with two or more system components may refer to any one of, or a combination of any two or more of, telecommunications networks (whether wired, wireless, cellular or the like), a global network such as the Internet, local networks, network links, Internet Service Providers (ISP's), and intermediate communication interfaces. Any one or more conventionally recognized interface standards may be implemented therewith, including but not limited to Bluetooth, RF, Ethernet, and the like. A preventative maintenance stage150as represented inFIG.1may be provided with a hosted server152or network of hosted servers linked to the communications devices146as discussed above. The hosted server152, which may be associated with a third party to the industrial plant or alternatively may be a server associated with the industrial plant or an administrator thereof, further may include or be linked to a data storage device or network154including models and/or algorithms relating to a process state and/or intervention event for the input stage110, chemical feed stage120, and/or solution130from the industrial plant. A cloud-based server152implementation may accordingly be configured to process data provided from the industrial plant, in view of iteratively developed preventative maintenance models residing in the data storage network154, and to generate feedback to respective components in the industrial plant relating to, e.g., automated upstream regulation156at the input stage and/or automated cleaning procedures158at the chemical feed stage. The above-referenced system100may be implemented in an embodiment of a method200as further discussed below with illustrative reference toFIG.2, or in an embodiment of a method300as further discussed below with illustrative reference toFIG.3. Alternative embodiments of a system may be implemented for either method200,300within the scope of the present disclosure unless otherwise stated. Depending on the embodiment, certain acts, events, or functions of any of the algorithms described herein can be performed in a different sequence, can be added, merged, or left out altogether (e.g., not all described acts or events are necessary for the practice of the algorithm) Moreover, in certain embodiments, acts or events can be performed concurrently, e.g., through multi-threaded processing, interrupt processing, or multiple processors or processor cores or on other parallel architectures, rather than sequentially. One of skill in the art may appreciate that numerous steps in the process of generating a desired output solution130via an input stage110and a chemical feed stage120are conventionally known and generally dependent on the type of solution being generated, and detailed discussion of such steps or processes may be omitted herein as being generally outside of the scope of an invention as disclosed herein. More particularly referring toFIGS.1and2, for a given process, e.g., the generation of an MCA mixture, the method200includes online data collection (step210) with respect to a plurality of process components in one or more of the input stage110, the chemical feed stage120, and the output solution130itself. The outputs from the data collection stage140are transmitted via a communications network to a remote (e.g., cloud-based) server network152(step220). The server152may further transmit the outputs from the data collection stage140of the industrial plant to a separate server and/or data storage network154for iterative development and updating of predictive models associated with the present disclosure (step230). As but one illustrative example, a predictive model may be constructed to account for changes in furnish, grade, equipment, and the like, wherein “digital twin” virtual representations in the cloud-based network continuously compare actual performance with expected performance to enable or otherwise facilitate the prediction of future trends and proactive interventions. Such virtual representations may include pairing of digital and physical data and further combining of the same with learning systems such as for example artificial neural networks. Real-time data may be provided throughout a process or the life cycle of a respective asset to generate virtual representations for estimation of a given parameter or performance metric, wherein subsequent comparison of predicted or estimated such parameters or metrics with a corresponding measured or determined parameter or metric may preferably be implemented as feedback for machine learning algorithms executed at the server level. Initial models may for example be constructed based on data collected and optionally aggregated from multiple chemical feed skids distributed across any number of industrial locations. In a particular exemplary embodiment relating to automated cleaning (e.g., acid boilout) or upstream softener replenishment, data may be collected in accordance with each of the following components: An online measurement of pH value of diluted hypochlorite may be one of the driving factors for the model, and would not require manual intervention from anyone in the field. The data may be collected, e.g., every sixty seconds, and a higher system pH will typically correlate with higher scaling rates. An online measurement of pH of the MCA mixture, collected e.g. every sixty seconds, may also be one of the driving factors for the model, and does not require manual intervention from anyone in the field. Low pH is indicative of an excess of chlorine, which causes unintended reactions that depress the pH. Standard pH range may be between 10.5 and 11.5, with higher system pH typically correlating with higher scaling rates. Incoming water conductivity (related to hardness), collected e.g. every sixty seconds, may also be one of the driving factors for the model. Higher water conductivities typically correlate with higher scaling rates. As the softener replaces calcium with sodium ions, the difference in conductivity between a functioning softener and non-functioning softener may not be able to be detected via conductivity alone. A dilution rate of hypochlorite in water may be measured or derived every sixty seconds to adjust for or correlate the dilute hypochlorite pH value. Higher dilutions may result in higher dilute hypochlorite pH readings. A hypochlorite/mcap volume ratio may be measured or derived every sixty seconds to adjust for or correlate the MCA pH value, wherein higher dilutions may result in higher MCA pH readings. One or more relevant pulp flow rates may be measured every sixty seconds to be able to calculate the dilution rate for hypochlorite and the volume ratio for the hypo/mcap, and for calculating the totalized volume for each flow stream. A unit status (e.g., dosing, flushing, idle) may be measured with each process change, for example to filter out flush/idle data. A hypochlorite volume over time may be measured or derived every sixty seconds to determine how much hypochlorite has passed through the unit for a given amount of time. For example, higher ratios of hypochlorite volume with respect to pipe diameter may correlate with a faster scaling rate. An MCA volume over time may be measured or derived every sixty seconds to determine how much MCA has passed through the unit for a given amount of time. For example, higher ratios of MCA volume with respect to pipe diameter may correlate with a faster scaling rate. A water volume over time may be measured or derived every sixty seconds to determine a total flow through the system. For example, a higher total volume for a given pipe diameter may correlate with a faster scaling rate. A system inner pipe diameter, an online mixer size, and/or application line sizes may be one-time measurements provided to the system, as smaller inner diameters may for example require more frequent cleaning when all other variables are held constant. An online antiscalant flow may be measured or otherwise derived every sixty seconds. Whether or not a softener is being utilized may be a one-time measurement provided to the system. In addition, measurement may be provided on process changes with respect to a softener being refilled with salt or cleaned. A visual inspection may be provided daily with respect to a given unit, to provide feedback regarding whether or not an acid clean is required, thereby for example further developing or otherwise providing confirmation of model parameters. As previously noted, once a sufficient dataset is built, models may be developed relating combinations of input variables to a predicted aggregation of contamination in at least one portion of the chemical feed unit, for example to predict when it is necessary to acid clean some or all of the chemical feed unit, or to replenish the brine in a water softener. Various embodiments of models for predicting contamination events (e.g., one or more events identified as requiring acid cleaning) may be constructed for respective system implementations, for example: systems that use a softener; systems that use online antiscalant; systems that use neither a softener nor an antiscalant; systems that use both of a softener and an antiscalant, and the like. In various exemplary embodiments, contamination events may be identified via threshold-based analysis of an indirectly determined contamination state. Alternatively, or in addition, non-threshold based analysis may be used to for example predict timing of a contamination event based on the indirectly determined contamination state. In the context of, for example, an acid cleaning procedure for the chemical feed stage, the system may typically automatically implement such a procedure upon determining the presence of a contamination event, or may schedule such a procedure at a defined time in the future based upon a predicted contamination event. In the context, for example, of brine replenishment in a water softener, the system may implement non-threshold based analysis to regulate brine replenishment based on the determined contamination state and with the objective of at least delaying contamination events in the chemical feed stage, predicted or otherwise. Various models may only require data that is automatically streamed or manually acquired only once (e.g., requiring no “routine” manual data collection). Various embodiments of these models may be deployed in the cloud to provide alerts to users to prompt them to acid clean their systems or replenish their softeners. The users may then be automatically prompted to provide feedback on the accuracy of the models, which would preferably be used to fine tune the models. In an embodiment, upon system prediction of the need for acid cleaning, a message may be generated to a user interface associated with an operator, administrator, representative, or the like for confirmation or approval to initiate an automated cleaning procedure. Such approval may for example be received via user actuation of a dedicated button or other interface tool. Alternatively, and as otherwise noted in the present disclosure, an automated cleaning procedure may be implemented dynamically upon determination of a contamination event, and without manual involvement. With further reference to the flowchart inFIG.2, implementing data from the data collection stage140of the industrial plant, in view of the models residing in the data storage network154, contamination states may be indirectly predicted and/or determined for one or more components of the monitored client system and process (step240). If one or more of the predicted and/or determined contamination states correspond to a determined contamination event (i.e., “yes” in response to the query represented in step250), the method200continues by providing feedback to the industrial plant for triggering an automated cleaning process (step260). An exemplary automated cleaning procedure that is triggered via the model may be performed on the chemical feed skid with limited or no human interaction, and may include some or all of the following operations. First, the method may initiate shut down or disabling of normal unit operation (e.g., MCA production and dosing), after which a water-only system flush is performed to remove any precursors of MCA from the system. System pH may be checked to ensure all precursors and MCA are removed from the system, followed by dosing of acid to the system via a pump connected to an acid clean port. Once filled with acid, the system may be soaked as per user settings/configuration, wherein the dosing/soaking cycle may optionally be repeated per user configuration. An MCAP/water flush may be performed to remove all acid from the system and bring the pH of the system back up to normal levels, along with a water-only flush and checking of pH to ensure the system is fully cleaned and flushed. Finally, an automated restart may be implemented to return the system to normal dosing/operating conditions, or in an embodiment a notification may be generated to a user for approval prior to restart. If none of the predicted and/or determined contamination states correspond to a determined contamination event (i.e., “no” in response to the query represented in step250), or alternatively after or alongside an automated cleaning process260, the method200continues by providing feedback to the industrial plant for regulating upstream conditions relating to potential contamination events (step270). For example, the method may include the ability of the system to determine if (when in use) a softener supplying water to the chemical feed stage requires replenishment, for example to reduce the need to acid clean the chemical feed stage. In various embodiments, a determined event based on the indirectly determined process state may be a prompt for intervention other than automated corrective actions such as cleaning or system regulation, such as for example including a prompt for service or maintenance of one or more system components, or an automated scheduling of such service or maintenance, to prevent future system failures. Examples of system components which may be monitored to determine the need for service or maintenance may include pump failures, valve failures, sensor failures, and the like, as may generally supplement the aforementioned automated cleaning or regulation/control. Certain embodiments of a method200as disclosed herein may be fully automatic in implementation, without requiring or prompting human intervention via, e.g., the graphical user interface. The method may otherwise be selectively implemented for one or more intermediate steps wherein operators or other authorized personnel can approve or modify automated cleaning procedures and/or control adjustments. For example, the hosted server and/or local controller may be configured to determine an amount and direction of recommended amount of brine replenishment or other adjustment to control valve positions in the input stage, and further generate a notification of the same to a designated user interface such as an operator dashboard, mobile app on a phone, etc. The authorized personnel may accordingly be prompted to enact the proposed interventions manually, or to provide feedback, via for example approval or edits to the recommended adjustment, wherein the server/controller resumes automated control of the one or more relevant system components based thereon. Referring now toFIGS.1and3, another embodiment of a method300may be described with respect to the same process, e.g., the generation of an MCA mixture, which still includes online data collection (step310) with respect to a plurality of process components in one or more of the input stage110, the chemical feed stage120, and the output solution130itself. The outputs from the data collection stage140are transmitted via a communications network to a remote (e.g., cloud-based) server network152(step320). The server152may further transmit the outputs from the data collection stage140of the industrial plant to a separate server and/or data storage network154for iterative development and updating of predictive models associated with the present disclosure (step330). As but one illustrative example, a predictive model may be constructed to account for changes in furnish, grade, equipment, and the like, wherein “digital twin” virtual representations in the cloud-based network continuously compare actual performance with expected performance to enable or otherwise facilitate the prediction of future trends and proactive interventions. Such virtual representations may include pairing of digital and physical data and further combining of the same with learning systems such as for example artificial neural networks. Real-time data may be provided throughout a process or the life cycle of a respective asset to generate virtual representations for estimation of a given parameter or performance metric, wherein subsequent comparison of predicted or estimated such parameters or metrics with a corresponding measured or determined parameter or metric may preferably be implemented as feedback for machine learning algorithms executed at the server level. Initial models may for example be constructed based on manual/batch data and on measurable streaming data that is reliably collected and optionally aggregated from multiple chemical feed skids distributed across any number of industrial locations. In a particular exemplary embodiment relating to modeling of the true stoichiometric ratio of two chemical precursors used to generate an oxidizing biocide in real time, wherein at least one chemical precursor has an active ingredient that varies in concentration over time, data may be collected in accordance with several components in common with the embodiment discussed above with respect toFIG.2. For example, an online measurement of the pH value of a diluted precursor solution (e.g., hypochlorite) and an online measurement of pH of the oxidizing biocide solution (e.g., monochloramine mixture) may be driving factors to model the molar ratio. Other measurements also included in the embodiment discussed above, at substantially the same rate of data collection and for substantially the same reasoning, may include a dilution rate of a precursor (e.g., hypochlorite) in water, a hypochlorite/mcap volume ratio, one or more relevant pulp flow rates (e.g., of the water and chemical precursors), a unit status (e.g., dosing, flushing, idle), an inline antiscalant flow (e.g., to determine its concentration in the final solution and its effect thereof), and whether or not a softener is being utilized. Additional measurements relevant to the embodiment represented inFIG.3may include the following components: Inline bleach concentrations (if available), collected e.g. every sixty seconds, may optionally be obtained using hypochlorite sensors to verify model accuracy. Manual measurements of hypochlorite concentration may be taken daily to build and train the model but will typically not be used during actual operation of the process. Larger differences in hypochlorite concentration between the new/incoming hypochlorite and the old/remaining hypochlorite will drive decomposition more quickly. Manual measurements of hypochlorite alkalinity may be taken each time new hypochlorite is delivered, or any time a change is suspected, again to build and train the model but not typically during actual operation of the process. Alkalinity may in many cases be constant for all hypochlorite globally, and any variances in this may be tracked as potentially impacting the pH readings when all other variables are held constant. Bulk hypochlorite temperature and/or ambient temperature may optionally be collected, e.g., every sixty seconds, as temperature is one of the driving factors for hypochlorite degradation. Incoming water conductivity may be measured, e.g., every sixty seconds to adjust or correlate for changes in incoming water conductivity and/or dissolved solids. A temperature of the diluted hypochlorite may be measured, e.g., every sixty seconds to determine a baseline temperature prior to reaction. A temperature of the MCA mixture may be measured, e.g., every sixty seconds to determined exothermic changes based on chemical reaction vigor. One-time data inputs may be provided regarding an antiscalant type to determine which specific chemistry is being used, and also whether or not a softener is being utilized. The bleach manufacturer may optionally be correlated with data as a one-time input, unless the supplier changes of course, to for example determine and attribute differences among hypochlorite manufacturers. Once a sufficient dataset is built, initial models may be developed relating combinations of input variables to a predicted true stoichiometric ratio of the active ingredients in the one or more precursors at issue. The models may be expected to primarily rely on streaming data but may also be augmented with manual data over time to improve the model accuracy. The developed models advantageously enable a real-time prediction and/or estimation of the true stoichiometric ratio of the active ingredients in the chemical precursors, and considers both upstream, downstream, and environmental conditions of the oxidizing biocide generating equipment. There are numerous exemplary results and advantages of such an approach, which include improved accuracy and reliability, as well as a wider range of applicability of the model to include scenarios where one or more conditions (not monitored or included in conventional systems and methods) have an effect on the model and/or the measured controlled parameter. The models may further facilitate reductions in waste consumption of one or more precursors, resulting in improved efficiency and reduced environmental impact, and demonstrable savings of time and money on manual testing of precursor concentration. When a modelled stoichiometric ratio is determined to be outside of optimum conditions, the system may be configured to automatically adjust the precursor volume ratio to optimize the stoichiometric ratio of the active ingredients in the one or more precursors. Alternatively, non-threshold determinations may be made in predicting that the modelled ratio will require correction. In various embodiments, these models may also be deployed remotely to provide alerts to users to prompt them to manually adjust the volume ratio of the active ingredients in the two or more precursors. Users may be automatically prompted to provide feedback on the accuracy of the models, which would preferably be used to fine tune the models. In an embodiment, upon system prediction of the need to adjust the precursor volume ratio to optimize the stoichiometric ratio of the active ingredients in the one or more precursors, a message may be generated to a user interface associated with an operator, administrator, representative, or the like for confirmation or approval to initiate an automated adjustment. Such approval may for example be received via user actuation of a dedicated button or other interface tool. With further reference to the flowchart inFIG.3, implementing data from the data collection stage140of the industrial plant, further in view of the models residing in the data storage network154, active ingredient states may be indirectly predicted and/or determined for one or more precursors of the monitored client system and process (step340). If one or more of the predicted and/or determined active ingredient states correspond to a determined intervention event (i.e., “yes” in response to the query represented in step350), the method300continues by providing feedback to the industrial plant for regulating upstream conditions relating to the composition of at least one chemical precursor (step370). For example, a feed rate of an amine solution can be controlled using an associated valve or pump, or a controller may be configured to regulate a feed rate of either or both of an oxidant solution and the amine solution based on a predicted and/or determined measurement of the active oxidant and further in view of a desired molar ratio, as per specified requirements of the monochloramine production process. The process control operation may be proportional in nature, wherein the controller identifies a directional aspect of the desired correction in order to obtain (or drive the system towards) an optimal molar ratio, and the process control operation may in certain embodiments further include an integral and/or derivative aspect wherein the corrective steps account for a rate of change over time to substantially prevent overshooting. If one or more of the predicted and/or determined active ingredient states do not yet correspond to a determined intervention event (i.e., “no” in response to the query represented in step350), the method300simply continues with online data collection and repeats the aforementioned steps. Referring now toFIGS.1and4, another embodiment of a method400may be described with respect to substantially the same process, e.g., the generation of an oxidizing biocide solution such as an MCA mixture, which still includes online data collection (step410) with respect to a plurality of process components in one or more of the input stage110, the chemical feed stage120, and the output solution130itself. The outputs from the data collection stage140are transmitted via a communications network to a remote (e.g., cloud-based) server network152(step420). The server152may further transmit the outputs from the data collection stage140of the industrial plant to a separate server and/or data storage network154for iterative development and updating of predictive models associated with the present disclosure (step430). As but one illustrative example, a predictive model may be constructed to account for changes in furnish, grade, equipment, and the like, wherein “digital twin” virtual representations in the cloud-based network continuously compare actual performance with expected performance to enable or otherwise facilitate the prediction of future trends and proactive interventions. Such virtual representations may include pairing of digital and physical data and further combining of the same with learning systems such as for example artificial neural networks. Real-time data may be provided throughout a process or the life cycle of a respective asset to generate virtual representations for estimation of a given parameter or performance metric, wherein subsequent comparison of predicted or estimated such parameters or metrics with a corresponding measured or determined parameter or metric may preferably be implemented as feedback for machine learning algorithms executed at the server level. Initial models may for example be constructed based on manual/batch data and on measurable streaming data that is reliably collected and optionally aggregated from multiple process locations such as chemical feed skids distributed across any number of industrial locations. Once a sufficient dataset is built, the initial models may be developed relating combinations of input variables to determine or predict in real time an amount of oxidizing biocide contained within an application or process, to determine or predict in real time the amount of microbiological contamination contained within an application or process, to determine or predict in real time a quality of an end product being produced and/or a key performance metric of a customer process, which through optimization of said determined or predicted data may lead to improvements in operability and performance. Accordingly, and with further reference to the flowchart inFIG.4, implementing data from the data collection stage140of the industrial plant, further in view of the models residing in the data storage network154, end product quality and/or key performance metrics associated with the industrial process may be indirectly predicted and/or determined (step440). If one or more of the predicted and/or determined end product quality and/or key performance metrics correspond to a determined intervention event (i.e., “yes” in response to the query represented in step450), the method400continues by providing feedback to the industrial plant for regulating a feed rate of the oxidizing biocide in at least one point of the process (step470). The process control operation may be proportional in nature, wherein the controller identifies a directional aspect of the desired correction in order to obtain (or drive the system towards) an optimal feed rate, and the process control operation may in certain embodiments further include an integral and/or derivative aspect wherein the corrective steps account for a rate of change over time to substantially prevent overshooting. If one or more of the predicted and/or determined end product quality and/or key performance metrics do not yet correspond to a determined intervention event (i.e., “no” in response to the query represented in step450), the method400simply continues with online data collection and repeats the aforementioned steps. The above-referenced embodiment400may preferably include models and associated control schemes that are refined over time to optimize biocide dosage rates for a given commercial or industrial process. One of skill in the art may appreciate that the prevention of overfeeding of an oxidizing biocide may result in reductions of any one or more of the following: corrosion issues and damage end process equipment; costs of treatment programs; burdens on wastewater treatment systems; impacts on discharge limitations/permissions; and the like. One of skill in the art may further appreciate that the prevention of underfeeding of an oxidizing biocide may result in reductions of any one or more of the following: microbiological outbreaks in an end process which can lead to negative impacts on process operability or end product quality; the spread of airborne illness due to unchecked microbiological growth in commercial and/or industrial processes; and the like. For example, the overfeeding of biocide may result in detrimental exposure-based effects due to vapors that are released from the process, such as lachrymation or other health problems. Referring next toFIG.5, an embodiment of a method500as disclosed herein further illustrates the above-referenced embodiments200,300,400in executable combination for a given commercial and/or industrial process. It may be appreciated that in alternative embodiments any two of the disclosed embodiments may be combined, or that steps associated with the respective embodiments may be executed in an order that differs from the representation inFIG.5, which is merely intended as illustrative. Although embodiments of an invention as disclosed herein may be described for illustrative purposes in the context of certain commercial applications for pulp and paper production (e.g., graphics paper, tissue, packaging), one of skill in the art may appreciate that systems and methods as disclosed herein may foreseeably be provided for other commercial applications including but not limited to water treatment applications (e.g., cooling systems, heating systems, potable water systems, influent systems) and biomass applications (e.g., sugar ethanol, corn ethanol, beet sugar). Throughout the specification and claims, the following terms take at least the meanings explicitly associated herein, unless the context dictates otherwise. The meanings identified below do not necessarily limit the terms, but merely provide illustrative examples for the terms. The meaning of “a,” “an,” and “the” may include plural references, and the meaning of “in” may include “in” and “on.” The phrase “in one embodiment,” as used herein does not necessarily refer to the same embodiment, although it may. As used herein, the phrase “one or more of,” when used with a list of items, means that different combinations of one or more of the items may be used and only one of each item in the list may be needed. For example, “one or more of” item A, item B, and item C may include, for example, without limitation, item A or item A and item B. This example also may include item A, item B, and item C, or item Band item C. The term “coupled” means at least either a direct physical or electrical connection between the connected items or an indirect connection through one or more passive or active intermediary devices. The various illustrative logical blocks, modules, and algorithm steps described in connection with the embodiments disclosed herein can be implemented as electronic hardware, computer software, or combinations of both. To clearly illustrate this interchangeability of hardware and software, various illustrative components, blocks, modules, and steps have been described above generally in terms of their functionality. Whether such functionality is implemented as hardware or software depends upon the particular application and design constraints imposed on the overall system. The described functionality can be implemented in varying ways for each particular application, but such implementation decisions should not be interpreted as causing a departure from the scope of the disclosure. The various illustrative logical blocks and modules described in connection with the embodiments disclosed herein can be implemented or performed by a machine, such as a general purpose processor, a digital signal processor (DSP), an application specific integrated circuit (ASIC), a field programmable gate array (FPGA) or other programmable logic device, discrete gate or transistor logic, discrete hardware components, or any combination thereof designed to perform the functions described herein. A general purpose processor can be a microprocessor, but in the alternative, the processor can be a controller, microcontroller, or state machine, combinations of the same, or the like. A processor can also be implemented as a combination of computing devices, e.g., a combination of a DSP and a microprocessor, a plurality of microprocessors, one or more microprocessors in conjunction with a DSP core, or any other such configuration. The steps of a method, process, or algorithm described in connection with the embodiments disclosed herein can be embodied directly in hardware, in a software module executed by a processor, or in a combination of the two. A software module can reside in RAM memory, flash memory, ROM memory, EPROM memory, EEPROM memory, registers, hard disk, a removable disk, a CD-ROM, or any other form of computer-readable medium known in the art. An exemplary computer-readable medium can be coupled to the processor such that the processor can read information from, and write information to, the memory/storage medium. In the alternative, the medium can be integral to the processor. The processor and the medium can reside in an ASIC. The ASIC can reside in a user terminal. In the alternative, the processor and the medium can reside as discrete components in a user terminal. Conditional language used herein, such as, among others, “can,” “might,” “may,” “e.g.,” and the like, unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or states. Thus, such conditional language is not generally intended to imply that features, elements and/or states are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without author input or prompting, whether these features, elements and/or states are included or are to be performed in any particular embodiment. The previous detailed description has been provided for the purposes of illustration and description. Thus, although there have been described particular embodiments of a new and useful invention, it is not intended that such references be construed as limitations upon the scope of this invention except as set forth in the following claims.
48,750
11857940
DETAILED DESCRIPTION Definitions Terms used in the claims and specification are defined as set forth below unless otherwise specified. These terms are defined specifically for clarity, but all of the definitions are consistent with how a skilled artisan would understand these terms. The term “nucleic acid” refers to a nucleotide polymer, and unless otherwise limited, includes known analogs of natural nucleotides that can function in a similar manner (e.g., hybridize) to naturally occurring nucleotides. The term nucleic acid includes any form of DNA or RNA, including, for example, genomic DNA; complementary DNA (cDNA), which is a DNA representation of mRNA, usually obtained by reverse transcription of messenger RNA (mRNA) or by amplification; DNA molecules produced synthetically or by amplification; mRNA; non-coding RNA; and micro RNA. The term nucleic acid encompasses double- or triple-stranded nucleic acids, as well as single-stranded molecules. In double- or triple-stranded nucleic acids, the nucleic acid strands need not be coextensive (i.e, a double-stranded nucleic acid need not be double-stranded along the entire length of both strands). The term nucleic acid also encompasses any chemical modification thereof, such as by methylation and/or by capping. Nucleic acid modifications can include addition of chemical groups that incorporate additional charge, polarizability, hydrogen bonding, electrostatic interaction, and functionality to the individual nucleic acid bases or to the nucleic acid as a whole. Such modifications may include base modifications such as 2′-position sugar modifications, 5-position pyrimidine modifications, 8-position purine modifications, modifications at cytosine exocyclic amines, substitutions of 5-bromo-uracil, backbone modifications, unusual base pairing combinations such as the isobases isocytidine and isoguanidine, and the like. More particularly, in certain embodiments, nucleic acids, can include polydeoxyribonucleotides (containing 2-deoxy-D-ribose), polyribonucleotides (containing D-ribose), and any other type of nucleic acid that is an N- or C-glycoside of a purine or pyrimidine base, as well as other polymers containing nonnucleotidic backbones, for example, polyamide (e.g., peptide nucleic acids (PNAs)) and polymorpholino (commercially available from the Anti-Virals, Inc., Corvallis, Oregon, as Neugene) polymers, and other synthetic sequence-specific nucleic acid polymers providing that the polymers contain nucleobases in a configuration which allows for base pairing and base stacking, such as is found in DNA and RNA. The term nucleic acid also encompasses linked nucleic acids (LNAs), which are described in U.S. Pat. Nos. 6,794,499, 6,670,461, 6,262,490, and 6,770,748, which are incorporated herein by reference in their entirety for their disclosure of LNAs. The nucleic acid(s) can be derived from a completely chemical synthesis process, such as a solid phase-mediated chemical synthesis, from a biological source, such as through isolation from any species that produces nucleic acid, or from processes that involve the manipulation of nucleic acids by molecular biology tools, such as DNA replication, PCR amplification, reverse transcription, or from a combination of those processes. The term “target nucleic acids” is used herein to refer to specific nucleic acids to be detected in the methods of the invention. Although multiple target nucleic acids can be amplified simultaneously, “target nucleic acids” refers to a subset (i.e., something less than) the full complement of nucleic acids present in the reaction mixture. As used herein the term “target nucleotide sequence” refers to a molecule that includes the nucleotide sequence of a target nucleic acid, such as, for example, the amplification product obtained by amplifying a target nucleic acid or the cDNA produced upon reverse transcription of an RNA target nucleic acid. As used herein, the term “complementary” refers to the capacity for precise pairing between two nucleotides. I.e., if a nucleotide at a given position of a nucleic acid is capable of forming canonical hydrogen bonding with a nucleotide of another nucleic acid, then the two nucleic acids are considered to be complementary to one another at that position. Complementarity between two single-stranded nucleic acid molecules may be “partial,” in which only some of the nucleotides bind, or it may be complete when total complementarity exists between the single-stranded molecules. The degree of complementarity between nucleic acid strands has significant effects on the efficiency and strength of hybridization between nucleic acid strands. A first nucleotide sequence is said to be the “complement” of a second sequence if the first nucleotide sequence is complementary to the second nucleotide sequence. A first nucleotide sequence is said to be the “reverse complement” of a second sequence, if the first nucleotide sequence is complementary to a sequence that is the reverse (i.e., the order of the nucleotides is reversed) of the second sequence. “Specific hybridization” refers to the binding of a nucleic acid to a target nucleotide sequence in the absence of substantial binding to other nucleotide sequences present in the hybridization mixture under defined stringency conditions. Those of skill in the art recognize that relaxing the stringency of the hybridization conditions allows sequence mismatches to be tolerated. In particular embodiments, hybridizations are carried out under stringent hybridization conditions. The phrase “stringent hybridization conditions” generally refers to a temperature in a range from about 5° C. to about 20° C. or 25° C. below than the melting temperature (Tm) for a specific sequence at a defined ionic strength and pH. As used herein, the Tmis the temperature at which a population of double-stranded nucleic acid molecules becomes half-dissociated into single strands. Methods for calculating the Tmof nucleic acids are well known in the art (see, e.g., Berger and Kimmel (1987) METHODS IN ENZYMOLOGY, VOL. 152: GUIDE TO MOLECULAR CLONING TECHNIQUES, San Diego: Academic Press, Inc. and Sambrook et al. (1989) MOLECULAR CLONING: A LABORATORY MANUAL, 2ND ED., VOLS. 1-3, Cold Spring Harbor Laboratory), both incorporated herein by reference). As indicated by standard references, a simple estimate of the Tmvalue may be calculated by the equation: Tm=81.5+0.41(% G+C), when a nucleic acid is in aqueous solution at 1 M NaCl (see, e.g., Anderson and Young, Quantitative Filter Hybridization in NUCLEIC ACID HYBRIDIZATION (1985)). The melting temperature of a hybrid (and thus the conditions for stringent hybridization) is affected by various factors such as the length and nature (DNA, RNA, base composition) of the primer or probe and nature of the target nucleic acid (DNA, RNA, base composition, present in solution or immobilized, and the like), as well as the concentration of salts and other components (e.g., the presence or absence of formamide, dextran sulfate, polyethylene glycol). The effects of these factors are well known and are discussed in standard references in the art. Illustrative stringent conditions suitable for achieving specific hybridization of most sequences are: a temperature of at least about 60° C. and a salt concentration of about 0.2 molar at pH7. The term “oligonucleotide” is used to refer to a nucleic acid that is relatively short, generally shorter than 200 nucleotides, more particularly, shorter than 100 nucleotides, most particularly, shorter than 50 nucleotides. Oligonucleotides may be single-stranded or double-stranded DNA molecules. The term “primer” refers to an oligonucleotide that is capable of hybridizing (also termed “annealing”) with a nucleic acid and serving as an initiation site for nucleotide (RNA or DNA) polymerization under appropriate conditions (i.e., in the presence of four different nucleoside triphosphates and an agent for polymerization, such as DNA or RNA polymerase or reverse transcriptase) in an appropriate buffer and at a suitable temperature. The appropriate length of a primer depends on the intended use of the primer, but primers are typically at least 7 nucleotides long and, more typically range from 10 to 30 nucleotides, or even more typically from 15 to 30 nucleotides, in length. Other primers can be somewhat longer, e.g., 30 to 50 nucleotides long. In this context, “primer length” refers to the portion of an oligonucleotide or nucleic acid that hybridizes to a complementary target sequence and primes nucleotide synthesis. Short primer molecules generally require cooler temperatures to form sufficiently stable hybrid complexes with the template. A primer need not reflect the exact sequence of the template but must be sufficiently complementary to hybridize with a template. The term “primer site” or “primer binding site” refers to the segment of the template to which a primer hybridizes. A primer is said to anneal to another nucleic acid if the primer, or a portion thereof, hybridizes to a nucleotide sequence within the nucleic acid. The statement that a primer hybridizes to a particular nucleotide sequence is not intended to imply that the primer hybridizes either completely or exclusively to that nucleotide sequence. The primer can be perfectly complementary to the target nucleic acid sequence or can be less than perfectly complementary. In certain embodiments, the primer has at least 65% identity to the complement of the target nucleic acid sequence over a sequence of at least 7 nucleotides, more typically over a sequence in the range of 10-30 nucleotides, and often over a sequence of at least 14-25 nucleotides, and more often has at least 75% identity, at least 85% identity, at least 90% identity, or at least 95%, 96%, 97%, 98%, or 99% identity. It will be understood that certain bases (e.g., the 3′ base of a primer) are generally desirably perfectly complementary to corresponding bases of the target nucleic acid sequence. Primers typically anneal to the target sequence under stringent hybridization conditions. The term “primer pair” refers to a set of primers including a 5′ “upstream primer” or “forward primer” that hybridizes with the complement of the 5′ end of the DNA sequence to be amplified and a 3′ “downstream primer” or “reverse primer” that hybridizes with the 3′ end of the sequence to be amplified. As will be recognized by those of skill in the art, the terms “upstream” and “downstream” or “forward” and “reverse” are not intended to be limiting, but rather provide illustrative orientation in particular embodiments. In embodiments in which two primer pairs are used, e.g., in an amplification reaction, the primer pairs may be denoted “inner” and “outer” primer pairs to indicate their relative position; i.e., “inner” primers are incorporated into the reaction product (e.g., an amplicon) at positions in between the positions at which the outer primers are incorporated. As used herein with reference to a portion of a primer, the term “target-specific portion” refers to a sequence that can specifically anneal to a target nucleic acid or a target nucleotide sequence under suitable annealing conditions. As used herein with reference to a primer pair, a “common sequence” refers to a sequence that is present in both primers. The term “tag nucleotide sequence” is used herein to refer to a predetermined nucleotide sequence that is added to a target nucleotide sequence. The nucleotide tag can encode an item of information about the target nucleotide sequence, such the identity of the target nucleotide sequence or the identity of the sample from which the target nucleotide sequence was derived. In certain embodiments, such information may be encoded in one or more nucleotide tags, e.g., a combination of two nucleotide tags, one on either end of a target nucleotide sequence, can encode the identity of the target nucleotide sequence. As used herein with reference to a portion of a primer, the term “tag-specific portion” refers to a sequence that can specifically anneal to a nucleotide tag under suitable annealing conditions. The term “transposon” refers to a nucleic acid molecule that is capable of being incorporated in to a nucleic acid by a transposase enzyme. A transposon includes two transposon ends (also termed “arms”) linked by a sequence that is sufficiently long to form a loop in the presence of a transposase. Transposons can be double-, single-stranded, or mixed, containing single- and double-stranded region(s), depending on the transposase used to insert the transposon. For Mu, Tn3, Tn5, Tn7 or Tn10 transposases, the transposon ends are double-stranded, but the linking sequence need not be double-stranded. In a transposition event, these transposons are inserted into double-stranded DNA. The term “transposon end” refers to the sequence region that interacts with transposase. The transposon ends are double-stranded for transposases Mu, Tn3, Tn5, Tn7, Tn10 etc. The transposon ends are single-stranded for transposases IS200/IS605 and ISrad2, but form a secondary structure, just like a double-stranded region. In a transposition event, single-stranded transposons are inserted into single-stranded DNA by a transposase enzyme. The term “artificial transposon end” refers to a transposon end in which one or more positions in a wildtype transposon end have been substituted with one or more different nucleotides. The term “transposase” refers to an enzyme that binds to transposon ends and catalyzes their linkage to other double- or single-stranded nucleic acids, such as genomic DNA. Transposases usually comprise an even number of subunits and bind two transposon ends. The two transposon ends can be of identical sequence or of different sequences. As used herein, the term “barcode nucleotide sequence” is used to refer to nucleotide sequences that encode information. For example, a barcode nucleotide sequence can identify, e.g., the source of the sample nucleic acids under analysis, such as nucleic acids from a particular sample or a particular reaction. Barcodes can be used to distinguish different cells, different treatments, different time points, different positions in space, etc. The term “stem-loop structure” results from intramolecular base pairing in a single strand of nucleic acid. The structure is also known as a “hairpin” or “hairpin loop” structure. It occurs when two regions of the same strand, usually complementary in nucleotide sequence when read in opposite directions, base-pair to form a double helix with an unpaired loop at one end. “Amplification” according to the present teachings encompasses any means by which at least a part of at least one target nucleic acid is reproduced, typically in a template-dependent manner, including without limitation, a broad range of techniques for amplifying nucleic acid sequences, either linearly or exponentially. Illustrative means for performing an amplifying step include ligase chain reaction (LCR), ligase detection reaction (LDR), ligation followed by Q-replicase amplification, PCR, primer extension, strand displacement amplification (SDA), hyperbranched strand displacement amplification, multiple displacement amplification (MDA), nucleic acid strand-based amplification (NASBA), 2-step multiplexed amplifications, rolling circle amplification (RCA), and the like, including multiplex versions and combinations thereof, for example but not limited to, OLA/PCR, PCR/OLA, LDR/PCR, PCR/PCR/LDR, PCR/LDR, LCR/PCR, PCR/LCR (also known as combined chain reaction—CCR), and the like. Descriptions of such techniques can be found in, among other sources, Ausbel et al.; PCR Primer: A Laboratory Manual, Diffenbach, Ed., Cold Spring Harbor Press (1995); The Electronic Protocol Book, Chang Bioscience (2002); Msuih et al., J. Clin. Micro. 34:501-07 (1996); The Nucleic Acid Protocols Handbook, R. Rapley, ed., Humana Press, Totowa, N.J. (2002); Abramson et al., Curr Opin Biotechnol. 1993 February; 4(1):41-7, U.S. Pat. Nos. 6,027,998; 6,605,451, Barany et al., PCT Publication No. WO 97/31256; Wenz et al., PCT Publication No. WO 01/92579; Day et al., Genomics, 29(1): 152-162 (1995), Ehrlich et al., Science 252:1643-50 (1991); Innis et al., PCR Protocols: A Guide to Methods and Applications, Academic Press (1990); Favis et al., Nature Biotechnology 18:561-64 (2000); and Rabenau et al., Infection 28:97-102 (2000); Belgrader, Barany, and Lubin, Development of a Multiplex Ligation Detection Reaction DNA Typing Assay, Sixth International Symposium on Human Identification, 1995 (available on the world wide web at: promega.com/geneticidproc/ussymp6proc/blegrad.html); LCR Kit Instruction Manual, Cat. #200520, Rev. #050002, Stratagene, 2002; Barany, Proc. Natl. Acad. Sci. USA 88:188-93 (1991); Bi and Sambrook, Nucl. Acids Res. 25:2924-2951 (1997); Zirvi et al., Nucl. Acid Res. 27:e40i-viii (1999); Dean et al., Proc Natl Acad Sci USA 99:5261-66 (2002); Barany and Gelfand, Gene 109:1-11 (1991); Walker et al., Nucl. Acid Res. 20:1691-96 (1992); Polstra et al., BMC Inf. Dis. 2:18- (2002); Lage et al., Genome Res. 2003 February; 13(2):294-307, and Landegren et al., Science 241:1077-80 (1988), Demidov, V., Expert Rev Mol Diagn. 2002 November; 2(6):542-8., Cook et al., J Microbiol Methods. 2003 May; 53(2):165-74, Schweitzer et al., Curr Opin Biotechnol. 2001 February; 12(1):21-7, U.S. Pat. Nos. 5,830,711, 6,027,889, 5,686,243, PCT Publication No. WO0056927A3, and PCT Publication No. WO9803673A1. In some embodiments, amplification comprises at least one cycle of the sequential procedures of: annealing at least one primer with complementary or substantially complementary sequences in at least one target nucleic acid; synthesizing at least one strand of nucleotides in a template-dependent manner using a polymerase; and denaturing the newly-formed nucleic acid duplex to separate the strands. The cycle may or may not be repeated. Amplification can comprise thermocycling or can be performed isothermally. As used herein, the term “amplification cross-hybridization” refers to hybridization of primers to non-target sequences within amplicons. As used herein, a “flow cell attachment site” refers to a nucleotide sequence that can hybridize to a primer immobilized on a substrate, e.g., as in as the bridge amplification (cluster generation) and sequencing method commercialized by Illumina, Inc., San Diego, CA. As used herein, the term “microfluidic device” refers to a device comprising multiple fluid flow paths, wherein each flow path has at least one, and often two, dimensions that are less than 1 millimeter. As used with reference to a reaction, the term “multiplex” refers to the situation in which multiple such reactions are conducted simultaneously in a single reaction mixture. Thus, “multiplex amplification” refers to the simultaneous amplification of multiple target nucleic acids in a single reaction mixture. As used herein with respect to reactions, reaction mixtures, reaction volumes, etc., the term “separate” refers to reactions, reaction mixtures, reaction volumes, etc., where reactions are carried out in isolation from other reactions. Separate reactions, reaction mixtures, reaction volumes, etc. include those carried out in droplets (See, e.g., U.S. Pat. No. 7,294,503, issued Nov. 13, 2007 to Quake et al., entitled “Microfabricated crossflow devices and methods,” which is incorporated herein by reference in its entirety and specifically for its description of devices and methods for forming and analyzing droplets; U.S. Patent Publication No. 20100022414, published Jan. 28, 2010, by Link et al., entitled “Droplet libraries,” which is incorporated herein by reference in its entirety and specifically for its description of devices and methods for forming and analyzing droplets; and U.S. Patent Publication No. 20110000560, published Jan. 6, 2011, by Miller et al., entitled “Manipulation of Microfluidic Droplets,” which is incorporated herein by reference in its entirety and specifically for its description of devices and methods for forming and analyzing droplets.), which may, but need not, be in an emulsion, as well as those wherein reactions, reaction mixtures, reaction volumes, etc. are separated by mechanical barriers, e.g., separate vessels, separate wells of a microtiter plate, or separate chambers of a matrix-type microfluidic device. A “single nucleotide polymorphism” (SNP) occurs at a polymorphic site occupied by a single nucleotide, which is the site of variation between allelic sequences. The site is usually preceded by and followed by highly conserved sequences of the allele (e.g., sequences that vary in less than 1/100 or 1/1000 members of the populations). A SNP usually arises due to substitution of one nucleotide for another at the polymorphic site. A transition is the replacement of one purine by another purine or one pyrimidine by another pyrimidine. A transversion is the replacement of a purine by a pyrimidine or vice versa. SNPs can also arise from a deletion of a nucleotide or an insertion of a nucleotide relative to a reference allele. The designations “first” and “second” with respect to types of nucleotide sequences encompasses embodiments in which these types of nucleotide sequences are the same or different. In typical embodiments, however, these types of nucleotide sequences are different. Amplification Methods—In General Looping Amplification The specificity of nucleic acid amplification can be increased by the use of “looping amplification” to reduce amplicon cross-hybridization. This increased specificity facilitates multiplexing to a much higher degree than was previously possible. In one embodiment, a looping amplification method is used to amplify one or more target nucleic acids. The method entails contacting sample nucleic acids with a novel forward primer pair for each target nucleic acid. The novel primer pair includes forward and reverse primers, wherein each primer comprises a target-specific portion and a common sequence 5′ of the target-specific portion. The target nucleic acid(s) are amplified with the primer pair(s) to produce at least one target amplicon wherein a target nucleotide sequence is flanked by the common sequence on one end and its reverse complement on the other end. This configuration will tend to form a stem-loop structure. SeeFIG.1. During annealing steps, the stem-loop structure will tend to form unless the appropriate target-specific primer is available to prime polymerization, which reduces amplicon cross-hybridization, as compared to when the amplification reaction is carried using standard primers that contain only target-specific sequences. In some embodiments, the average target amplicon size is greater (e.g., closer to the predicted amplicon size) than when amplification is carried out using primers containing only target-specific sequences. This method can be used for high-specificity amplification of a single target nucleic acid in a reaction mixture or a plurality of target nucleic acids (e.g., 2, 3, 4, 5, 6, 7, 8, 9, or 10). The method particularly facilitates high-level multiplex amplification, e.g., wherein more than 10 target nucleic acids are amplified in a single reaction mixture. In various embodiments, at least 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 300, 400, 500, 600, 700, 800, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, or 6000, or more target nucleic acids are amplified in a single reaction mixture. In some embodiments, not more than 25,000, 20,000, 19,000, 18,000, 17,000, 16,000, 15,000, 14,000, 13,000, 12,000, 11,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 450, 400, 350, 300, 250, 200, or 150 target nucleic acids are amplified in a single reaction mixture. The number of target nucleic acids amplified in a single reaction mixture can fall within any range bounded by any of the above values, e.g., 20-170, 40-160, 50-150, 60-140, 70-130, 80-120, 90-110, 100-25,000, 110-20,000, 120-19,000, 130-18,000, 140-17,000, 150-16,000, 160-15,000, 170-14,000, 180-13,000, 190-12,000, 200-1100. In some embodiments, the highest levels of multiplexing results from “overlapped amplicons.” Overlapped amplicons are generated when multiple primer pairs are directed to the same general region of a sample nucleic acid. In this case, a forward primer from a given primer pair can produce an amplicon from the reverse primer in the pair, but can also produce amplicons from other reverse primers. This phenomenon is shown schematically inFIG.8. The common sequence can be any sequence and must be sufficiently long to form a stem, i.e., at least 2 nucleotides, and more typically at least 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 14, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 nucleotides. In some embodiments, the stem is not more than 100, 80, 70, 60, 50, 40, 30, or 20 nucleotides. The length of the stem can fall within any range bounded by any of the above values, e.g., 5-45, 8-40, 10-35, 13-30, 15-25, or 18-20 nucleotides. In particular embodiments, the common sequence is one that facilitates downstream analysis of the target amplicon, such as, for example, by DNA sequencing. In this case, looping amplification can be used to introduce sequences flanking the target nucleotide sequence that facilitate DNA sequencing (e.g., DNA sequencing adaptors). Looping amplification can, for example, by used to prepare DNA sequencing templates that are compatible with Illumina's bridge PCR system. Illumina-compatible libraries are conventionally prepared by tagmentation (NEXTERA™ DNA Sample Prep Kit), which uses transposons to simultaneously fragment and add nucleotide tags which serve as binding sites for DNA sequencing primers and are also used to add flow cell attachment sites. Because the resultant templates contain transposon sequences, the common sequence for looping amplification can be a suitable transposon sequence, e.g., 5′-AGATGTGTNNNAGAGACAG-3′ (SEQ ID NO:1). Table 1 below shows all possible nucleotide sequences for the NNN sequence in SEQ ID NO:1. TABLE 1First NSecond NThird NAAA″″T″″G″″C″TA″″T″″G″″C″GA″″T″″G″″C″CA″″T″″G″″CTAA″″T″″G″″C″TA″″T″″G″″C″GA″″T″″G″″C″CA″″T″″G″″CGAA″″T″″G″″C″TA″″T″″G″″C″GA″″T″″G″″C″CA″″T″″G″″CCAA″″T″″G″″C″TA″″T″″G″″C″GA″″T″″G″″C″CA″″T″″G″″C″ indicates the same nucleotide as above. In a specific embodiment, the common sequence is the transposon sequence used in the NEXTERA™ DNA Sample Prep Kit, which is 5′-AGATGTGTATAAGAGACAG-3′ (SEQ ID NO:2). In certain embodiments, the forward primer and/or the reverse primer for each target nucleic acid include(s) a tag nucleotide sequence 5′ of the common sequence. In particular embodiments, both primers include tag nucleotide sequences, and the tag nucleotide sequence in the forward primer is different from the tag nucleotide sequence in the reverse primer. The different tags can be used to add different sequences to either end of the target amplicon, e.g., the two different flow cell attachment sites used in Illumina's bridge sequencing system. To facilitate sequencing the forward and/or reverse primers can include an additional nucleotide sequence 3′ of the tag sequence, which can be, for example, a binding site for a DNA sequencing primer. In an illustrative embodiment, a forward primer can contain: 5′-first tag nucleotide sequence-first binding site for a first DNA sequencing primer-common sequence-first target-specific sequence-3′, and a reverse primer can contain: 5′-second tag nucleotide sequence-second binding site for a second DNA sequencing primer-common sequence-second target-specific sequence. Illustrative forward and reverse primers of this type are shown inFIG.2, where the DNA sequencing primer binding sites are indicated as “SP,” and their positions relative to “Tag1” and “Tag2” are shown (the target-specific and common sequences are not shown). Looping Amplification with 1-Step Addition of Sequences for DNA Sequencing One approach to using looping amplification for preparing templates for bridge sequencing is a 1-step, 3-primer method. SeeFIG.2. In this method, either the forward or reverse primer described above for use in sequencing additionally includes a first flow cell attachment site 5′ of the tag nucleotide sequence. For sequencing on the Illumina system, this first flow cell attachment site can be PE1, as shown inFIG.2. Amplification can be carried out using a third primer in addition to the forward and reverse primer, to add a second additional nucleotide sequence. All primers are present in one amplification mixture, and all desired sequences are added in one (multi-cycle) amplification step. In this case, the third primer includes a tag-specific portion, with the second additional nucleotide sequence 5′ of the tag-specific portion. For 1-step amplification, the third primer is typically included in the amplification mixture at at least 5-fold the concentration of the forward and reverse primers. The second additional nucleotide sequence can include an optional barcode nucleotide sequence, which, if present, is 5′ of the tag-specific portion. For bridge sequencing, the second additional nucleotide sequence includes a 5′ second flow cell attachment site.FIG.2shows an illustrative third primer having a 5′ P7 sequence as the second flow cell attachment site, which is separated from the tag-specific portion (Tag1) by a barcode nucleotide sequence (“BC”). As shown inFIG.2, if the first flow cell attachment site is part of the forward primer, the third primer is specific for the tag on the reverse primer. Conversely, if the first flow cell attachment site is part of the reverse primer, the third primer is specific for the tag on the forward primer. Looping Amplification with 2-Step Addition of Sequences for DNA Sequencing Another approach to using looping amplification for preparing templates for bridge sequencing is a 2-step method, where the first step employs 3 primers, and the second step employs 2 primers. SeeFIG.3. Typically, these steps are carried out in separate amplification mixtures. In particular embodiments, the first step is carried out using the forward and reverse primers described above for use in sequencing, e.g.: a forward primer containing: 5′-first tag nucleotide sequence-first binding site for a first DNA sequencing primer-common sequence-first target-specific sequence-3′, and a reverse primer containing: 5′-second tag nucleotide sequence-second binding site for a second DNA sequencing primer-common sequence-second target-specific sequence. These forward and reverse primers are shown inFIG.3as “Tag1 SP” and “SP Tag2.” The first step also includes a third primer, wherein the third primer comprises a tag-specific portion, a barcode nucleotide sequence 5′ of the tag-specific portion, and a second flow cell attachment site 5′ of the barcode nucleotide sequence. For sequencing on the Illumina system, this second flow cell attachment site can be PE7, as shown inFIG.3, where this third primer is indicated as “P7 BCx Tag2.” The first amplification step using these three primers produces target amplicons having the structure: 5′-first nucleotide tag-first primer binding site-common sequence-target nucleotide sequence-reverse complement of common sequence-second primer binding site-second nucleotide tag-barcode nucleotide sequence-second flow cell attachment site-3′. In some embodiments, the 1-step method described above or the first step of the 2-step method can be carried out in a plurality of separate reaction mixtures. Each separate reaction mixture can contain one or more primer sets suitable for amplifying one or more target nucleic acids. To increase throughput, amplification is carried in multiplex (i.e., with primers for multiple targets in each reaction mixture). As discussed above, looping amplification permits high-level multiplexing, which is particularly useful, in the DNA sequencing context, for targeted re-sequencing. The reaction mixtures can be formed in any way, for example as droplets (e.g., in an emulsion) or within chambers in a microfluidic device. Microfluidic devices useful in the methods described herein are discussed in greater detail below. For high-throughput analyses, microfluidic devices having a plurality of reaction chambers can be used. Matrix-type microfluidic devices are convenient for this purpose, especially when multiple targets are to be analyzed in different samples in one experiment. Matrix-type devices permit samples to be loaded into the device in one dimension (i.e., columns or rows), while primers can be loaded into the device in the other dimension (i.e., rows or columns, respectively). If different samples are loaded into columns and different primers are loaded into rows, a plurality of target nucleic acids can be amplified in each of a plurality of reaction chambers in the device by loading multiple primer sets into each row. In this case, the number of simultaneous amplifications that can be carried out in the device is the number of reaction chambers×the number of primer sets in each reaction chamber. If, for example, the microfluidic device contains 48 columns for 48 different samples and 48 separate rows, and looping amplification is used to amplify more than 10 target nucleic acids in each chamber, 480 target nucleic acids can be amplified for each sample. If looping amplification is used to amplify at least 100 target nucleic acids in each chamber, at least 4800 target nucleic acids can be amplified for each sample. Where the amplification is carried out to prepare templates for DNA sequencing and the 2-step method described above is used, the reaction products (“target amplicons”) from the first amplification are recovered and subjected to a second amplification step with two different primers. If the first step is performed in a microfluidic device, the target amplicons can be recovered and subjected to the second amplification step outside of a microfluidic device or in a different microfluidic device. Thus,FIG.3refers to “On-chip barcoding” for the first step and “Off-chip Adaptor addition” for the second step. The on-chip portion of this method is conveniently carried out using Fluidigm Corporation's ACCESS ARRAY™ IFC (Integrated Fluidic Circuit), for example. As shown inFIG.3, in some embodiments, it is advantageous to add at least one further nucleotide sequence to each of the target amplicons produced from the first amplification step. When bridge sequencing is to be performed, the further nucleotide sequence can be the first flow cell attachment site, the second flow cell attachment site having been added in the first amplification step. The first flow cell attachment site is added to the end of the amplicon opposite the second flow cell attachment site. In the description above, since the second flow cell attachment site was introduced at the “reverse primer” end of the amplicon, the forward primer for the second amplification step has a portion specific for the first nucleotide tag and a first flow cell attachment site 5′ of said tag-specific portion. This forward primer is shown as “P5 Tag1” inFIG.3. The reverse primer for the second amplification step is specific for the second flow cell attachment site (“P7” inFIG.3). The result of either the 1-step or 2-step methods for adding sequences for DNA sequencing is, in some embodiments, a DNA sequencing library, wherein each member of the library has the structure: 5′-first flow cell attachment site-first nucleotide tag-first primer binding site-common sequence-target nucleotide sequence-reverse complement of common sequence-second primer binding site-second nucleotide tag-barcode nucleotide sequence-second flow cell attachment site-3′. In some embodiments, an additional barcode nucleotide sequence is added to each target amplicon. For example, an additional barcode nucleotide sequence may be introduced at the end of the target amplicon opposite the end bearing the barcode nucleotide sequence discussed above (and shown inFIG.3as BCx). When adding sequences for DNA sequencing, each member of the DNA sequencing library can have the structure: 5′-first flow cell attachment site-first barcode nucleotide sequence-first nucleotide tag-first primer binding site-common sequence-target nucleotide sequence-reverse complement of common sequence-second primer binding site-second nucleotide tag-second barcode nucleotide sequence-second flow cell attachment site-3′. In the scheme ofFIG.3, this structure could be produced, for example, by including a first barcode nucleotide sequence (not shown) in the forward primer is shown as “P5 Tag1” in the Off-chip Adapter addition. The “second” barcode nucleotide sequence (identified as BCx) would have already been incorporated into the target amplicons in the On-chip barcoding step. The primer concentration of the first step of the two-step looping amplification protocol can be adjusted, depending on whether amplicon overlapping, and thus a greater number of possible primer pairs, is desired. This might be the case, for example, when the aim is to sequence a particular region of a sample nucleic acid. Example 4 shows that a primer concentration of 2 nM for the first step gives a major band in the expected amplicon size range for non-overlapped amplicons. Reducing this concentration to 1 nM allows for greater amplicon overlapping, and a further reduction to 0.5 nM allows for even more amplicon overlapping which yields multiple bands over a much boarder range of amplicon sizes. Also, reduction of primer concentration in looping amplification promotes amplification specificity. Sample Nucleic Acids Preparations of nucleic acids (“samples”) can be obtained from biological sources and prepared using conventional methods known in the art. In particular, DNA or RNA useful in the methods described herein can be extracted and/or amplified from any source, including bacteria, protozoa, fungi, viruses, organelles, as well higher organisms such as plants or animals, particularly mammals, and more particularly humans. Suitable nucleic acids can also be obtained from environmental sources (e.g., pond water), from man-made products (e.g., food), from forensic samples, and the like. Nucleic acids can be extracted or amplified from cells, bodily fluids (e.g., blood, a blood fraction, urine, etc.), or tissue samples by any of a variety of standard techniques. Illustrative samples include samples of plasma, serum, spinal fluid, lymph fluid, peritoneal fluid, pleural fluid, oral fluid, and external sections of the skin; samples from the respiratory, intestinal genital, and urinary tracts; samples of tears, saliva, blood cells, stem cells, or tumors. For example, samples of fetal DNA can be obtained from an embryo or from maternal blood. Samples can be obtained from live or dead organisms or from in vitro cultures. Illustrative samples can include single cells, formalin-fixed and/or paraffin-embedded tissue samples, and needle biopsies. Nucleic acids useful in the methods described herein can also be derived from one or more nucleic acid libraries, including cDNA, cosmid, YAC, BAC, P1, PAC libraries, and the like. Nucleic acids of interest can be isolated using methods well known in the art, with the choice of a specific method depending on the source, the nature of nucleic acid, and similar factors. The sample nucleic acids need not be in pure form, but are typically sufficiently pure to allow the reactions of interest to be performed. Where the target nucleic acids are RNA, the RNA can be reversed transcribed into cDNA by standard methods known in the art and as described in Sambrook, J., Fritsch, E. F., and Maniatis, T.,Molecular Cloning: A Laboratory Manual. Cold Spring Harbor Laboratory Press, NY, Vol. 1, 2, 3 (1989), for example. Target Nucleic Acids Target nucleic acids useful in the methods described herein can be derived from any of the sample nucleic acids described above. In typical embodiments, at least some nucleotide sequence information will be known for the target nucleic acids. For example, if PCR is employed as the amplification reaction, sufficient sequence information is generally available for each end of a given target nucleic acid to permit design of suitable amplification primers. In an alternative embodiment, target-specific sequences in primers could be replaced by random or degenerate nucleotide sequences. The targets can include, for example, nucleic acids associated with pathogens, such as viruses, bacteria, protozoa, or fungi; RNAs, e.g., those for which over- or under-expression is indicative of disease, those that are expressed in a tissue- or developmental-specific manner; or those that are induced by particular stimuli; genomic DNA, which can be analyzed for specific polymorphisms (such as SNPs), alleles, or haplotypes, e.g., in genotyping. Of particular interest are genomic DNAs that are altered (e.g., amplified, deleted, rearranged, and/or mutated) in genetic diseases or other pathologies; sequences that are associated with desirable or undesirable traits; and/or sequences that uniquely identify an individual (e.g., in forensic or paternity determinations). When multiple target nucleic acids are employed, these can be on the same or different chromosome(s). In various embodiments, a target nucleic acid to be amplified can be, e.g., 25 bases, 50 bases, 100 bases, 200 bases, 500 bases, or 750 bases. In certain embodiments of the methods described herein, a long-range amplification method, such as long-range PCR can be employed to produce amplicons from the amplification mixtures. Long-range PCR permits the amplification of target nucleic acids ranging from one or a few kilobases (kb) to over 50 kb. In various embodiments, the target nucleic acids that are amplified by long-range PCR are at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, or 50 kb in length. Target nucleic acids can also fall within any range having any of these values as endpoints (e.g., 25 bases to 100 bases or 5-15 kb). Primer Design Primers suitable for nucleic acid amplification are sufficiently long to prime the synthesis of extension products in the presence of the agent for polymerization. The exact length and composition of the primer will depend on many factors, including, for example, temperature of the annealing reaction, source and composition of the primer. For example, depending on the complexity of the target nucleic acid sequence, an oligonucleotide primer typically contains in the range of about 15 to about 30 nucleotides, although it may contain more or fewer nucleotides. The primers should be sufficiently complementary to selectively anneal to their respective strands and form stable duplexes. One skilled in the art knows how to select appropriate primer pairs to amplify the target nucleic acid of interest. For example, PCR primers can be designed by using any commercially available software or open source software, such as Primer3 (see, e.g., Rozen and Skaletsky (2000)Meth. Mol. Biol.,132: 365-386; www.broad.mit.edu/node/1060, and the like) or by accessing the Roche UPL website. Primers may be prepared by any suitable method, including, for example, cloning and restriction of appropriate sequences or direct chemical synthesis by methods such as the phosphotriester method of Narang et al. (1979)Meth. Enzymol.68: 90-99; the phosphodiester method of Brown et al. (1979)Meth. Enzymol.68: 109-151; the diethylphosphoramidite method of Beaucage et al. (1981)Tetra. Lett.,22: 1859-1862; the solid support method of U.S. Pat. No. 4,458,066 and the like, or can be provided from a commercial source. Primers may be purified by using a Sephadex column (Amersham Biosciences, Inc., Piscataway, NJ) or other methods known to those skilled in the art. Primer purification may improve the sensitivity of the methods described herein. Amplification Nucleic acids can be amplified in accordance with the methods described herein for any useful purpose, e.g., to detect and/or quantify and/or sequence one or more target nucleic acids. Amplification can be carried out in droplets, in emulsions, in vessels, in wells of a microtiter plate, in chambers of a matrix-type microfluidic device, etc. In certain embodiments, amplification methods are employed to produce amplicons suitable for automated DNA sequencing. Many current DNA sequencing techniques rely on “sequencing by synthesis.” These techniques entail library creation, massively parallel PCR amplification of library molecules, and sequencing. Conventionally, library creation starts with conversion of sample nucleic acids to appropriately sized fragments, ligation of adaptor sequences onto the ends of the fragments, and selection for molecules properly appended with adaptors. The presence of the adaptor sequences on the ends of the library molecules enables amplification of random-sequence inserts. The above-described methods for tagging target nucleotide sequences can be substituted for ligation, to incorporate adaptor sequences. The above-described methods provide substantially uniform amplification of target nucleotide sequences, which is helpful in preparing DNA sequencing libraries having good coverage. In the context of automated DNA sequencing, the term “coverage” refers to the number of times the sequence is measured upon sequencing. A DNA sequencing library that has substantially uniform coverage can yield sequence data where the coverage is also substantially uniform. Thus, in various embodiments, upon performing automated sequencing of a plurality of target amplicons prepared as described herein, the sequences of at least 50 percent of the target amplicons are present at greater than 50 percent of the average number of copies of target amplicon sequences and less than 2-fold the average number of copies of target amplicon sequences. In various embodiments of this method at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 91, at least 92, at least 93, at least 94, at least 95, at least 96, at least 97, at least 98, or at least 99 percent of the target amplicon sequences are present at greater than 50 percent of the average number of copies of target amplicon sequences and less than 2-fold the average number of copies of target amplicon sequences. The methods described herein can include subjecting at least one target amplicon to DNA sequencing using any available DNA sequencing method. In particular embodiments, a plurality of target amplicons is sequenced using a high throughput sequencing method. Such methods typically use an in vitro cloning step to amplify individual DNA molecules. For example, emulsion PCR (emPCR) isolates individual DNA molecules along with primer-coated beads in aqueous droplets within an oil phase. PCR produces copies of the DNA molecule, which bind to primers on the bead, followed by immobilization for later sequencing. In vitro clonal amplification can also be carried out by “bridge PCR,” where fragments are amplified upon primers attached to a solid surface. DNA molecules that are physically bound to a surface can be sequenced in parallel, for example, by a pyrosequencing or sequencing-by-synthesis method. Microfluidic Devices In certain embodiments, methods described herein can be carried out using a microfluidic device. In illustrative embodiments, the device is a matrix-type microfluidic device that allows the simultaneous combination of a plurality of substrate solutions with reagent solutions in separate isolated reaction chambers. It will be recognized, that a substrate solution can include one or a plurality of substrates (e.g., target nucleic acids) and a reagent solution can include one or a plurality of reagents (e.g., amplification primers). For example, the microfluidic device can allow the simultaneous pair-wise combination of a plurality of different samples and amplification primers. In certain embodiments, the device is configured to contain a different combination of primers and samples in each of the different chambers. In various embodiments, the number of separate reaction chambers can be greater than 50, usually greater than 100, more often greater than 500, even more often greater than 1000, and sometimes greater than 5000, or greater than 10,000. In particular embodiments, the matrix-type microfluidic device is a DYNAMIC ARRAY™ IFC (“DA”) microfluidic device. A DA microfluidic device is a matrix-type microfluidic device designed to isolate pair-wise combinations of samples and reagents (e.g., amplification primers, detection probes, etc.) and suited for carrying out qualitative and quantitative PCR reactions including real-time quantitative PCR analysis. In some embodiments, the DA microfluidic device is fabricated, at least in part, from an elastomer. DA microfluidic devices are described in PCT Publication No. WO05107938A2 (Thermal Reaction Device and Method For Using The Same) and U.S. Patent Publication No. US20050252773A1, both incorporated herein by reference in their entireties for their descriptions of DA microfluidic devices. DA microfluidic devices may incorporate high-density matrix designs that utilize fluid communication vias between layers of the microfluidic device to weave control lines and fluid lines through the device and between layers. By virtue of fluid lines in multiple layers of an elastomeric block, high density reaction cell arrangements are possible. Alternatively DA microfluidic devices may be designed so that all of the reagent and sample channels are in the same elastomeric layer, with control channels in a different layer. In certain embodiments, DA microfluidic devices may be used for reacting M number of different samples with N number of different reagents. Although the DA microfluidic devices described in WO05107938 are well suited for conducting the methods described herein, the invention is not limited to any particular device or design. Any device that partitions a sample and/or allows independent pair-wise combinations of reagents and sample may be used. U.S. Patent Publication No. 20080108063 (which is hereby incorporated by reference it its entirety) includes a diagram illustrating the 48.48 DYNAMIC ARRAY™ IFC, a commercially available device available from Fluidigm Corp. (South San Francisco Calif). It will be understood that other configurations are possible and contemplated such as, for example, 48×96; 96×96; 30×120; etc. In specific embodiments, the microfluidic device can be a DIGITAL ARRAY™ IFC microfluidic device, which is adapted to perform digital amplification. Such devices can have integrated channels and valves that partition mixtures of sample and reagents into nanolitre volume reaction chambers. In some embodiments, the DIGITAL ARRAY™ IFC microfluidic device is fabricated, at least in part, from an elastomer. Illustrative DIGITAL ARRAY™ IFC microfluidic devices are described in copending U.S. Applications owned by Fluidigm Corp. (South San Francisco, CA), such as U.S. application Ser. No. 12/170,414, entitled “Method and Apparatus for Determining Copy Number Variation Using Digital PCR.” One illustrative embodiment has 12 input ports corresponding to 12 separate sample inputs to the device. The device can have 12 panels, and each of the 12 panels can contain 765 6 nL reaction chambers with a total volume of 4.59 μL per panel. Microfluidic channels can connect the various reaction chambers on the panels to fluid sources. Pressure can be applied to an accumulator in order to open and close valves connecting the reaction chambers to fluid sources. In illustrative embodiments, 12 inlets can be provided for loading of the sample reagent mixture. 48 inlets can be used to provide a source for reagents, which are supplied to the chip when pressure is applied to accumulator. Additionally, two or more inlets can be provided to provide hydration to the chip. While the DIGITAL ARRAY™ IFC microfluidic devices are well suited for carrying out certain amplification methods described herein, one of ordinary skill in the art would recognize many variations and alternatives to these devices. The geometry of a given DIGITAL ARRAY™ IFC microfluidic device will depend on the particular application. Additional description related to devices suitable for use in the methods described herein is provided in U.S. Patent Publication No. 20050252773, incorporated herein by reference for its disclosure of DIGITAL ARRAY™ IFC microfluidic devices. In certain embodiments, the methods described herein can be performed using a microfluidic device that provides for recovery of reaction products. Such devices are described in detail in U.S. Pat. No. 8,691,509, (which is hereby incorporated by reference in its entirety and specifically for its description of microfluidic devices that permit reaction product recovery and related methods) and sold by Fluidigm Corp. as ACCESS ARRAY™ IFC (Integrated Fluidic Circuit). In an illustrative device of this type, independent sample inputs are combined with primer inputs in an M×N array configuration. Thus, each reaction is a unique combination of a particular sample and a particular reagent mixture. Samples are loaded into sample chambers in the microfluidic device through sample input lines arranged as columns in one implementation. Assay reagents (e.g., primers) are loaded into assay chambers in the microfluidic device through assay input lines arranged as rows crossing the columns. The sample chambers and the assay chambers are in fluidic isolation during loading. After the loading process is completed, an interface valve operable to obstruct a fluid line passing between pairs of sample and assay chambers is opened to enable free interface diffusion of the pairwise combinations of samples and assays. Precise mixture of the samples and assays enables reactions to occur between the various pairwise combinations, producing one or more reaction product(s) in each chamber. The reaction products are harvested and can then be used for subsequent processes. The terms “assay” and “sample” as used herein are descriptive of particular uses of the devices in some embodiments. However, the uses of the devices are not limited to the use of “sample(s)” and “assay(s)” in all embodiments. For example, in other embodiments, “sample(s)” may refer to “a first reagent” or a plurality of “first reagents” and “assay(s)” may refer to “a second reagent” or a plurality of “second reagents.” The M×N character of the devices enable the combination of any set of first reagents to be combined with any set of second reagents. According to particular embodiments, the reaction products from the M×N pairwise combinations can be recovered from the microfluidic device in discrete pools, e.g., one for each of M samples. Typically, the discrete pools are contained in a sample input port provided on the carrier. In some processes, the reaction products may be harvested on a “per amplicon” basis for purposes of normalization. Utilizing embodiments of the present invention, it is possible to achieve results (for replicate experiments assembled from the same input solutions of samples and assays) for which the copy number of amplification products varies by no more than ±25% within a sample and no more than ±25% between samples. Thus, the amplification products recovered from the microfluidic device will be representative of the input samples as measured by the distribution of specific known genotypes. In certain embodiments, output sample concentration will be greater than 2,000 copies/amplicon/microliter, and recovery of reaction products will be performed in less than two hours. In some embodiments, reaction products are recovered by dilation pumping. Dilation pumping provides benefits not typically available using conventional techniques. For example, dilation pumping enables for a slow removal of the reaction products from the microfluidic device. In an exemplary embodiment, the reaction products are recovered at a fluid flow rate of less than 100 μl per hour. In this example, for 48 reaction products distributed among the reaction chambers in each column, with a volume of each reaction product of about 1.5 μl, removal of the reaction products in a period of about 30 minutes, will result in a fluid flow rate of 72 μl/hour. (i.e., 48×1.5/0.5 hour). In other embodiments, the removal rate of the reaction products is performed at a rate of less than 90 μl/hr, 80 μl/hr, 70 μl/hr, 60 μl/hr, 50 μl/hr, 40 μl/hr, 30 μl/hr, 20 μl/hr, 10 μl/hr, 9 μl/hr, less than 8 μl/hr, less than 7 μl/hr, less than 6 μl/hr, less than 5 μl/hr, less than 4 μl/hr, less than 3 μl/hr, less than 2 μl/hr, less than 1 μl/hr, or less than 0.5 μl/hr. Dilation pumping results in clearing of substantially a high percentage and potentially all the reaction products present in the microfluidic device. Some embodiments remove more than 75% of the reaction products present in the reaction chambers (e.g., sample chambers) of the microfluidic device. As an example, some embodiments remove more than 80%, 85%, 90%, 92%, 95%, 96%, 97%, 98%, or 99% of the reaction products present in the reaction chambers. The methods described herein may use microfluidic devices with a plurality of “unit cells” that generally include a sample chamber and an assay chamber. Such unit cells can have dimensions on the order of several hundred microns, for example unit cells with dimension of 500×500 μm, 525×525 μm, 550×550 μm, 575×575 μm, 600×600 μm, 625×625 μm, 650×650 μm, 675×675 μm, 700×700 μm, or the like. The dimensions of the sample chambers and the assay chambers are selected to provide amounts of materials sufficient for desired processes while reducing sample and assay usage. As examples, sample chambers can have dimensions on the order of 100-400 μm in width×200-600 μm in length×100-500 μm in height. For example, the width can be 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, or the like. For example, the length can be 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, 500 μm, 525 μm, 550 μm, 575 μm, 600 μm, or the like. For example, the height can be 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, 500 μm, 525 μm, 550 μm, 575 μm, 600 μm, or the like. Assay chambers can have similar dimensional ranges, typically providing similar steps sizes over smaller ranges than the smaller chamber volumes. In some embodiments, the ratio of the sample chamber volume to the assay chamber volume is about 5:1, 10:1, 15:1, 20:1, 25:1, or 30:1. Smaller chamber volumes than the listed ranges are included within the scope of the invention and are readily fabricated using microfluidic device fabrication techniques. Higher density microfluidic devices will typically utilize smaller chamber volumes in order to reduce the footprint of the unit cells. In applications for which very small sample sizes are available, reduced chamber volumes will facilitate testing of such small samples. For single-particle analysis, microfluidic devices can be designed to facilitate loading and capture of the particular particles to be analyzed. Each unit cell has a “cell channel” (i.e., sample chamber) and an “assay channel” (i.e., assay chamber). The cell channel is rounded for loading mammalian cells, with dimensions on the order of tens microns in diameter to a hundred of several hundred microns in length. Diameters can be about 15 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, or about 45 μm or more, or can fall within a range having any of these values as endpoints, depending on the size of the cells being analyzed. Lengths can be about 60 μm, about 90 μm, about 120 μm, about 150 μm, about 170 μm, about 200 μm, about 230 μm, about 260 μm, about 290 μm or more, or can fall within a range having any of these values as endpoints, depending on the size of the cells being analyzed. In an illustrative microfluidic device based on the ACCESS ARRAY™ IFC platform (the “MA006”), a unit cell for loading mammalian cells can be about 30 μm×170 μm. Such a device can be equipped to provide, or to facilitate providing, heat to cell channels after loading to lyse the cells. The device can include assay channels separate from cell channels for conducting reactions such as nucleic acid amplification. 170 μm×170 containment valves can be used to close cell channels. U.S. App. No. 61/605,016, filed Feb. 29, 2012, and entitled “Methods, Systems, And Devices For Multiple Single-Particle or Single-Cell Processing Using Microfluidics,” describes methods, systems, and devices for multiple single-particle or single-cell processing utilizing microfluidics. Various embodiments provide for capturing, partitioning, and/or manipulating individual particles or cells from a larger population of particles of cells along with generating genetic information and/or reaction(s) related to each individual particle or cell. Some embodiments may be configured for imaging the individual particles or cells or associated reaction products as part of the processing. This application is incorporated by reference herein it its entirety and, in particular, for its description of microfluidic devices configured for multiple single-particle or single-cell processing and related systems. Fabrication methods using elastomeric materials and methods for design of devices and their components have been described in detail in the scientific and patent literature. See, e.g., Unger et al. (2000) Science 288:113-116; U.S. Pat. Nos. U.S. Pat. No. 6,960,437 (Nucleic acid amplification utilizing microfluidic devices); U.S. Pat. No. 6,899,137 (Microfabricated elastomeric valve and pump systems); U.S. Pat. No. 6,767,706 (Integrated active flux microfluidic devices and methods); U.S. U.S. Pat. No. 6,752,922 (Microfluidic chromatography); U.S. Pat. No. 6,408,878 (Microfabricated elastomeric valve and pump systems); U.S. Pat. No. 6,645,432 (Microfluidic devices including three-dimensionally arrayed channel networks); U.S. Patent Application Publication Nos. 2004/0115838; 2005/0072946; 2005/0000900; 2002/0127736; 2002/0109114; 2004/0115838; 2003/0138829; 2002/0164816; 2002/0127736; and 2002/0109114; PCT Publication Nos. WO 2005/084191; WO 05/030822A2; and WO 01/01025; Quake & Scherer, 2000, “From micro to nanofabrication with soft materials” Science 290: 1536-40; Unger et al., 2000, “Monolithic microfabricated valves and pumps by multilayer soft lithography” Science 288:113-116; Thorsen et al., 2002, “Microfluidic large-scale integration” Science 298:580-584; Chou et al., 2000, “Microfabricated Rotary Pump” Biomedical Microdevices 3:323-330; Liu et al., 2003, “Solving the “world-to-chip” interface problem with a microfluidic matrix” Analytical Chemistry 75, 4718-23, Hong et al, 2004, “A nanoliter-scale nucleic acid processor with parallel architecture” Nature Biotechnology 22:435-39. Applications In particular embodiments, the methods described herein are used in the analysis of one or more nucleic acids, e.g. (in some embodiments). Thus, for example, these methods are applicable to identifying the presence of particular polymorphisms (such as SNPs), alleles, or haplotypes, or chromosomal abnormalities, such as amplifications, deletions, rearrangements, or aneuploidy. The methods may be employed in genotyping or sequencing, which can be carried out in a number of contexts, including diagnosis of genetic diseases or disorders, cancer, pharmacogenomics (personalized medicine), quality control in agriculture (e.g., for seeds or livestock), the study and management of populations of plants or animals (e.g., in aquaculture or fisheries management or in the determination of population diversity), or paternity or forensic identifications. The methods described herein can be applied in the identification of sequences indicative of particular conditions or organisms in biological or environmental samples. For example, the methods can be used in assays to identify pathogens, such as viruses, bacteria, and fungi. The methods can also be used in studies aimed at characterizing environments or microenvironments, e.g., characterizing the microbial species in the human gut. In certain embodiments, these methods can also be employed in determinations of DNA or RNA copy number. Determinations of aberrant DNA copy number in genomic DNA is useful, for example, in the diagnosis and/or prognosis of genetic defects and diseases, such as cancer. Determination of RNA “copy number,” i.e., expression level is useful for expression monitoring of genes of interest, e.g., in different individuals, tissues, or cells under different conditions (e.g., different external stimuli or disease states) and/or at different developmental stages. In addition, the methods can be employed to prepare nucleic acid samples for further analysis, such as, e.g., DNA sequencing. Furthermore, nucleic acid samples can be tagged as a first step, prior subsequent analysis, to reduce the risk that mislabeling or cross-contamination of samples will compromise the results. For example, any physician's office, laboratory, or hospital could tag samples immediately after collection, and the tags could be confirmed at the time of analysis. Similarly, samples containing nucleic acids collected at a crime scene could be tagged as soon as practicable, to ensure that the samples could not be mislabeled or tampered with. Detection of the tag upon each transfer of the sample from one party to another could be used to establish chain of custody of the sample. Kits Kits according to the invention can include one or more reagents useful for practicing one or more of the methods described herein. A kit generally includes a package with one or more containers holding the reagent(s) (e.g., primers), as one or more separate compositions or, optionally, as admixture where the compatibility of the reagents will allow. The kit can also include other material(s) that may be desirable from a user standpoint, such as a buffer(s), a diluent(s), a standard(s), and/or any other material useful in sample processing, washing, or conducting any other step of the method. In specific embodiments, the kit includes one or more matrix-type microfluidic devices discussed above. In particular embodiments, a kit includes a forward primer and a reverse primer, wherein each primer includes a target-specific portion and a common sequence 5′ of the target-specific portion. In certain embodiments, the common sequence includes a transposon sequence, such as, e.g., AGATGTGTNNNAGAGACAG-3′ (SEQ ID NO:1) or, more specifically, 5′-AGATGTGTATAAGAGACAG-3′ (SEQ ID NO:2). In some embodiments, the forward primer and/or the reverse primer for each target nucleic acid include(s) a tag nucleotide sequence 5′ of the common sequence. If both primers include tag sequences, the tag sequences can be the same or different. The forward and/or reverse primer can, in some embodiments, include an additional nucleotide sequence 3′ of the tag nucleotide sequence. Where the target amplicons are to be sequenced, one or both primers can include additional nucleotide sequence(s) that are binding site(s) for DNA sequencing primers. For example a forward primer can include a first binding site for a first DNA sequencing primer, and/or the reverse primer can include a second binding site for a second DNA sequencing primer. The forward or reverse primer can additionally include a flow cell attachment site 5′ of the tag nucleotide sequence to facilitate sequencing on the Illumina platform. In certain embodiments, the forward primer includes a first flow cell attachment site, and a second flow cell attachment site can be added to the amplicon via another primer. A third primer can be included in the kit for the purpose of adding an additional nucleotide sequence of any type. For example, in an embodiment useful for carrying out 1-step addition of sequences for DNA sequencing, a third primer can include a tag-specific portion and a second additional nucleotide sequence 5′ of the tag-specific portion. In various embodiments, the second additional nucleotide sequence comprises a barcode nucleotide sequence and/or a second flow cell attachment site, which can be different from the first flow cell attachment site. In particular embodiments, the second additional nucleotide sequence comprises a barcode nucleotide sequence 5′ of the tag-specific portion, and a second flow cell attachment site 5′ of the barcode nucleotide sequence. In an embodiment useful for carrying out 2-step addition of sequences for DNA sequencing, a third primer can include a tag-specific portion, a barcode nucleotide sequence 3′ of the tag-specific portion, and a second flow cell attachment site 3′ of the barcode nucleotide sequence. Use of this primer after amplification with appropriate forward and reverse primers (described above and illustrated inFIG.3) produces target amplicons having the structure: 5′-first nucleotide tag-first primer binding site-target nucleotide sequence-second primer binding site-second nucleotide tag-barcode nucleotide sequence-second flow cell attachment site-3′. In this case, the kit can include a fourth primer to be used in conjunction with the third primer to generate this amplicon. The fourth primer is typically specific for a sequence at the 3′end of the amplicon, such as the second flow cell attachment site. Kits generally include instructions for carrying out one or more of the methods described herein. Instructions included in kits can be affixed to packaging material or can be included as a package insert. While the instructions are typically written or printed materials they are not limited to such. Any medium capable of storing such instructions and communicating them to an end user is contemplated by this invention. Such media include, but are not limited to, electronic storage media (e.g., magnetic discs, tapes, cartridges, chips), optical media (e.g., CD ROM), RF tags, and the like. As used herein, the term “instructions” can include the address of an internet site that provides the instructions. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. In addition, all other publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes. EXAMPLES Example 1—Looping PCR to Reduce Amplicon Cross-Hybridization For compatibility with Illumina sequencing chemistry, the published tagged transposon sequence was used as a part of tagged specific primers in a common sequence in both forward and reverse primers (the transposon sequence is underlined): Tag used for forward target-specific primer: 5′-TCGTCGGCAGCGTCAGATGTGTATAAGAGACAG-3′ (SEQ ID NO:3) Tag used for reverse target-specific primer: 5′ GTCTCGTGGGCTCGGAGATGTGTATAAGAGACAG-3′ (SEQ ID NO:4) (The transposon sequence is that published for the NEXTERA″ DNA Sample Prep Kit.) A stem loop will form from an amplified amplicon to suppress amplicon cross hybridization (FIG.1). The common sequence in the primers also reduces the probability of primer dimer formation (FIG.4). Example 2—3-Primer Chemistry Facilitates On-Chip Barcoding with Minimal Primer-Dimer Formation The existing ACCESS ARRAY™ multiplex chemistry can provides 10-plex using 4 primers and two PCR steps. In the first step, PCR is conducted on the ACCESS ARRAY™ IFC, and in the second step, harvested samples are barcoded in a PCR plate. This workflow can be used for 10-20-plex, but with less-than-desired sequencing specificity, and is prone to sample cross-contamination. To achieve 1-step sample barcoding with reduced non-specific amplification, a 1-step, 3-primer scheme was proposed.FIG.2shows this 1-step, 3-primer PCR barcoding scheme. The 1-step, 3-primer approach was used in 192-plex and produced specific products that were comparable to a 2-primer reaction (without barcodes), as shown inFIG.5. By contrast, a 1-step, 4-primer assay failed to generate a PCR product in a 192-plex reaction. The sequencing data of the 1-step, 3-primer 192-plex reactions exhibited a >95% mapping rate to targets. However, the cost of the forward primers is very high due to their length. Therefore, a modified 2-step scheme was employed for the super-plex target sequencing library preparation, as shown inFIG.3. The barcoded amplicon libraries were generated in a 3-primer reaction on an ACCESS ARRAY™ IFC, harvested in pools, and then the pooled libraries were further amplified in one tube to add sequencing adaptors. The products of the 2-step scheme exhibited a greater than 95% mapping rate to both genome and targets as shown inFIG.6. Example 3—Addition of 2-Pyrrolidinone or a Mix of 2-Pyrrolidinone with Trehalose to the PCR Reaction to Amplify Amplicons with >65% GC Content Amplification of amplicons with high GC contents has been challenging in PCR field, particularly in multiplex assays. The challenge is to amplify amplicons with high GC contents without sacrificing those with low GC contents. To improve the GC coverage, 2-pyrrolidinone was added to a mixture of 1% 2-pyrrolidine and 150 mM trehalose to the commercial PCR master mix. The optimized concentration of 2-pyrrolidinone is 1-2%. The GC contents of amplicons with average 500 bp are expanded to >70%, with minimal impact on amplicons with <40% GC as shown inFIG.7. Example 4—Thousands-Plex PCR in a Single Reaction Mixture Looping PCR with 2-step addition of sequences for DNA sequencing was carried out essentially as described above and illustrated inFIG.3. 6062 primer pairs were added to a single reaction tube. Multiple tubes were prepared with different PCR master mixes: (1) one with Aptataq DNA polymerase, (2) Thermo's PreAmp Master Mix, (3) 4×TSP Master Mix (used as 2×), and (4) Targeted DNA Seq Library reagent kit (PN101-2511). A 20-cycle PCR was used for the first step with the 6062 primer pairs, followed by 2× cleanups and adapter addition in a 10-cycle PCR for the second step. Similar results were observed with all 4 master mixes. A representative gel image and corresponding Bioanalyzer trace is shown inFIGS.9A-9B. The results show that the 6062-plex amplification worked to produce a major band of amplicons in the expected 320-380 bp size range, when the primer concentration for the first step, 20-cycle PCR was 2 nM. Reducing this primer concentration to 1 nM or 0.5 nM produced greater amplicon overlapping, yielding an amplicon size range of 160-1000 bp, which was the expected size range for overlapped amplicons (seeFIG.9C). The sequencing mapping rate to the genome (determined using the Targeted DNA Seq Library reagent kit) is shown inFIG.9D. This shows that very specific amplification at 6062-plex is achieved at primer concentrations of 0.5-2 nM.
75,723
11857941
DESCRIPTION OF THE PREFERRED EMBODIMENTS First Embodiment First, a microreactor system according to a first embodiment of the invention will be described with reference to the drawings. The same reference numerals are given to the same configurations in the following drawings, and repetitive description thereof will be omitted. FIG.1is a schematic diagram of the microreactor system according to the first embodiment. As shown inFIG.1, a microreactor system1according to the first embodiment includes a first fluid container (a first container)101, a second fluid container (a second container)102, a third fluid container (a third container)103, a fourth fluid container (a fourth container)104, a first fluid pump (a first pump)105, a second fluid pump (a second pump)106, a microreactor107, a collection container108, a tube109, a first fluid sensor (a first measurement unit)110, a second fluid sensor (a second measurement unit)111, a first switch (a first switching unit)112, and a second switch (a second switching unit)113. The microreactor system1mixes fluids in the microreactor107to produce a mixture in which the fluids are mixed with each other or a reaction product (a mixed fluid) generated by a reaction between the fluids. The microreactor107is a flow-type reactor, and has two inflow ports into which individual fluids are introduced, a minute flow path through which the fluids are merged and mixed, and an outflow port through which the merged mixed fluid flows out. In the microreactor system1, while fluids of raw materials prepared in the fluid containers101and102are fed toward the microreactor107by the fluid pumps105and106, amounts of the fluids remaining in the fluid containers101and102are measured by the fluid sensors110and111. Then, when it is measured that there is no fluid in the fluid containers101and102, the fluid or the fluid and the other fluid are switched to another fluid, which is fed toward the microreactor107. In the following description, a case will be exemplified in which a first liquid fluid and a second liquid fluid are used as the fluids of raw materials to be mixed and reacted in the microreactor107. As shown inFIG.1, the first fluid container101and the first fluid pump105are connected to one of the inflow ports of the microreactor107via the tube109. The first fluid container101is connected to the first fluid pump105. The first fluid pump105is connected to the one of the inflow ports of the microreactor107. The first fluid container101is a container in which the first fluid is prepared. The first fluid pump105is a pump that feeds the first fluid toward the one of the inflow ports of the microreactor107. When the first fluid is switched to another fluid, the first fluid pump105feeds the fluid toward the microreactor107. The second fluid container102and the second fluid pump106are connected to the other of the inflow ports of the microreactor107via the tube109. The second fluid container102is connected to the second fluid pump106. The second fluid pump106is connected to the other of the inflow ports of the microreactor107. The second fluid container102is a container in which the second fluid is prepared. The second fluid pump106is a pump that feeds the second fluid toward the other of the inflow ports of the microreactor107. When the second fluid is switched to another fluid, the second fluid pump106feeds the fluid toward the microreactor107. The collection container108is connected to the outflow port of the microreactor107via the tube109. The collection container108is a container that collects a mixture in which fluids are mixed with each other or a reaction product generated by a reaction between the fluids. The tube109is formed of, for example, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), or the like. The tube109is connected to the microreactor107, pumps, containers, and the like via joints (not shown). As the first fluid pump105and the second fluid pump106, for example, an appropriate pump such as a tube pump, a plunger pump, a diaphragm pump, or a screw pump is used. Examples of materials of liquid contact portions such as tubes, syringes, and diaphragms provided in the pumps include resin materials such as polydimethylsiloxane (PDMS), silicone resin, polyethylene (PE), polypropylene (PP), and fluorine-based resin including PTFE. Here, a specific example of the microreactor107that can be used in the microreactor system1will be described. FIG.2is a diagram showing an example of a microreactor. As shown inFIG.2, a microreactor200in which flow path volumes are asymmetrically provided between fluids can be used as the microreactor107in which fluids of raw materials are mixed and reacted. The microreactor200has two inflow ports (210,211) through which fluids are introduced, minute flow paths (220,221,222) through which the individually introduced fluids are merged and mixed, and an outflow port240through which the mixed fluids merged at a junction230flow out to the outside. The microreactor200is formed by overlapping an upper plate201and a lower plate202. The upper plate201is subjected to groove processing, and the lower plate202is overlapped in a manner of covering grooves, so that the minute flow paths (220,221,222) are formed on the same plane. However, the groove processing is not necessarily performed on the upper plate201. The groove processing may be performed on the lower plate202, and the upper plate201may be overlapped in a manner of covering grooves to form the minute flow paths (220,221,222) on the same plane. The lower plate202is formed with through holes at positions overlapping with ends of the minute flow paths (220,221,222). As the through holes, a high flow rate side inflow port210, a low flow rate side inflow port211, and the outflow port240are opened on an opposite surface. The through holes of the lower plate202have a diameter larger than that of the minute flow paths (220,221,222). A screw groove (not shown) is formed in the through hole. The tube109is connected via joints that can be screwed into the screw groove. However, the through hole is not necessarily provided with a diameter larger than that of the minute flow paths (220,221,222). For example, the tube109may be directly connected to the through hole without forming a screw groove in the through hole. The minute flow paths (220,221,222) include a high flow rate side flow path220extending from the high flow rate side inflow port210to the junction230, a low flow rate side flow path221extending from the low flow rate side inflow port211to the junction230, and a discharge flow path222extending from the junction230to the outflow port240. The high flow rate side flow path220, the low flow rate side flow path221, and the discharge flow path222preferably have a flow path width and a flow path depth of 2 mm or less. In particular, the portion immediately before the junction230and the discharge flow path222preferably have the flow path width and the flow path depth in a range of several tens of μm or more and 1 mm or less from the viewpoint of performing rapid mixing. The high flow rate side flow path220is used to flow a fluid that has a high mixing ratio and that is set to a relatively high flow rate among the fluids to be mixed. On the other hand, the low flow rate side flow path221is used to flow a fluid that has a low mixing ratio and that is set to a relatively low flow rate. The high flow rate side flow path220has a total flow path volume larger than that of the low flow rate side flow path221. For example, a flow path length of the high flow rate side flow path220is larger than that of the low flow rate side flow path221having the same flow path width and flow path depth. With such a structure, in a case in which the mixing ratio is biased to one of the fluids and the fluids are controlled to have flow rates greatly different from each other, it is possible to reduce a difference between timings at which the fluids reach the junction230. The high flow rate side flow path220is branched into two symmetrical branch flow paths220aand220bat an intermediate portion, and the branch flow paths merge with each other at the junction230. The low flow rate side flow path221is connected to the junction230from between the two branch flow paths220aand220b. At the junction230, a fluid having a low flow rate and a fluid having a high flow rate flowing in from the same side flow into the discharge flow path222on the opposite side. With such a structure, since the mixing is started in a state in which the fluid having a low flow rate is mixed in the fluid having a high flow rate, it is possible to increase an area of an interface between the fluids and increase the mixing efficiency. The microreactor107is formed of an appropriate material that is chemically stable, that has low reactivity with fluids and low elution properties, and that has processability and mechanical properties. Examples of the material of the microreactor107include stainless steel, silicon, gold, glass, Hastelloy, ceramic, silicone resin, a cycloolefin polymer, a cycloolefin copolymer, polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polydimethylsiloxane (PDMS), acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate (PC), acrylic resin, and various fluorine-based resins. In addition, glass lining, coating of nickel, gold, or the like, or a material obtained by performing an oxidation treatment on silicon or the like may be used. As shown inFIG.1, the microreactor system1includes, as containers in which fluids different from the first fluid and the second fluid are prepared, the third fluid container103connected to a first system extending from the first fluid container101, and the fourth fluid container104connected to a second system extending from the second fluid container102. In the microreactor system1, the tube109of the first system to which the first fluid container101is connected is provided with the first switch112between the first fluid container101and the first fluid pump105. The first switch112is connected to the third fluid container103via the tube109. The third fluid container103is a container in which a third fluid different from the first fluid and the second fluid is prepared. The first switch112is a valve that switches the first fluid to be fed to the microreactor107to another fluid (a third fluid) different from the first fluid and the second fluid. The first switch112is switchable between a state in which a flow path from the first fluid container101to the microreactor107is opened and a flow path from the third fluid container103to the microreactor107is closed and a state in which the flow path from the first fluid container101to the microreactor107is closed and the flow path from the third fluid container103to the microreactor107is opened. In the microreactor system1, the tube109of the second system to which the second fluid container101is connected is provided with the second switch113between the second fluid container102and the second fluid pump106. The second switch113is connected to the fourth fluid container104via the tube109. The fourth fluid container104is a container in which a fourth fluid different from the first fluid and the second fluid is prepared. The second switch113is a valve that switches the second fluid to be fed to the microreactor107to another fluid (a fourth fluid) different from the first fluid and the second fluid. The second switch113is switchable between a state in which a flow path from the second fluid container102to the microreactor107is opened and a flow path from the fourth fluid container104to the microreactor107is closed and a state in which the flow path from the second fluid container102to the microreactor107is closed and the flow path from the fourth fluid container104to the microreactor107is opened. InFIG.1, three-way valves are provided as the switches112and113. However, as the switches112and113, appropriate devices can be provided as long as the devices can switch the fluid to be fed to the microreactor107. For example, a combination of a plurality of two-way valves may be used as the switches112and113. In addition, a detachable sterile connection joint or the like having a valve function may be used. The third fluid and the fourth fluid are fluids that are fed toward the microreactor107instead of the first fluid and the second fluid of raw materials prepared in the fluid containers101and102when the first fluid and the second fluid are exhausted. By feeding the third fluid and the fourth fluid, the fluid inside the microreactor107and inside the tube109is pushed out to a discharge side. Further, by switching the fluid to be fed, the air inside the fluid containers101and102is prevented from flowing into the microreactor107. Unlike the first fluid and the second fluid, fluids that do not contain components of the raw materials are used as the third fluid and the fourth fluid. As the third fluid and the fourth fluid, appropriate fluids can be used as long as the fluids do not significantly react with the first fluid, the second fluid, the components of the raw materials, and the like. The third fluid and the fourth fluid may be the same type of fluids, or may be fluids different from each other. Specific examples of the third fluid and the fourth fluid include a solvent, a cleaning liquid, a buffer solution, physiological saline, ion-exchanged water, and pure water that are used in the first fluid and the second fluid. Examples of the cleaning liquid include alcohols such as ethanol and an aqueous ethanol solution, other organic solvents, and a solution to which a cleaning agent such as a surfactant is added. Examples of the buffer solution include a pH buffer solution such as an acidic buffer solution and an alkaline buffer solution. The third fluid and the fourth fluid are preferably fluids that are unlikely to react with the components of the raw materials and the mixture or the reaction product produced by the mixing and the reaction. The third fluid and the fourth fluid are preferably fluids that are not compatible with the first fluid and the second fluid and that are in a two-phase state. When such fluids are used, even if the switched fluids come into contact with each other at the time of switching the fluids, the reaction and the mixing does not easily proceed. Therefore, the utilization efficiency of the fluids of the raw materials is unlikely to decrease. In the microreactor system1, the first fluid container101is provided with the first fluid sensor110. The second fluid container102is provided with the second fluid sensor111. The first fluid sensor110is a sensor that measures an amount of the first fluid inside the first fluid container101. The second fluid sensor111is a sensor that measures an amount of the second fluid inside the second fluid container102. InFIG.1, electronic balances are provided as the sensors110and111, and the fluid containers101and102are placed on sample dishes. According to the electronic balances, a remaining amount of the fluid in each container can be obtained based on the comparison with an initial weight. However, as the fluid sensors110and111, as long as the amounts of the fluids inside the fluid containers101and102can be obtained, appropriate devices can be provided according to the type of the liquid, the amount of the liquid, and the like. The fluid sensors110and111may be devices that directly measure the amounts of the fluids inside the fluid containers101and102, or may be devices that indirectly obtain the amounts of the fluids based on measurement. For example, after a known amount of fluid is prepared in each of the fluid containers101and102, the amount of the fluid discharged from each of the fluid containers101and102may be measured, and the remaining amount of the fluid may be obtained based on a difference with respect to the known amount. Specific examples of the fluid sensors110and111include, in addition to the electronic balance, a load sensor that measures a change in load, a liquid level detection sensor that measures a liquid level, and a flow rate sensor that measures a flow rate of a liquid fed to the microreactor107. Depending on the specifications of the first fluid pump105and the second fluid pump106, when the insides of the first fluid container101, the second fluid container102, the third fluid container103, and the fourth fluid container104become significantly negative pressure, the first fluid, the second fluid, the third fluid, and the fourth fluid cannot be fed. Therefore, devices that pressurize the first fluid container101, the second fluid container102, the third fluid container103, and the fourth fluid container104may be provided. Specifically, each of the first fluid container101, the second fluid container102, the third fluid container103, and the fourth fluid container104may be placed in a pressure container that can pressurize the fluid containers, or may be pressurized by being physically pressed from the outside. According to such a microreactor system1, since the third fluid container103is connected to the first system to which the first fluid container101is connected, and the fourth fluid container104is connected to the second system to which the second fluid container102is connected, in both of the first system and the second system, the fluid of the raw material prepared in each of the fluid containers101and102can be switched to another fluid. The fluid containers103and104in which other fluids are prepared are individually provided for the first system and the second system. Therefore, the type of the fluid to be switched can be selected in consideration of the compatibility of each fluid of the raw material. In addition, the fluid to be switched can be individually prepared, replaced, discarded, or the like. Next, a specific operation method of the microreactor system1will be described. FIG.3is a flowchart showing an example of the operation method of the microreactor system. In the operation method shown inFIG.3, in the microreactor system1, after the feeding of the first fluid and the second fluid is started, when it is measured that the fluid in one of the first fluid container101and the second fluid container102is exhausted, the fluid on the side where the remaining amount is exhausted is switched to another fluid (the third fluid or the fourth fluid) different from the first fluid and the second fluid, and the feeding of the first fluid and the second fluid is completed without switching the fluid in the other container in which the remaining amount is not exhausted to another fluid (the third fluid or the fourth fluid) different from the first fluid and the second fluid. In the operation method, the first fluid, the second fluid, the third fluid, and the fourth fluid are put into the fluid containers101,102,103, and104, respectively, and the operation of the system is started (step S301). The first switch112is in a state in which the flow path from the first fluid container101is opened and the flow path from the third fluid container103is closed. The second switch113is in a state in which the flow path from the second fluid container102is opened and the flow path from the fourth fluid container104is closed. Subsequently, the feeding of the first fluid performed by the first fluid pump105and the feeding of the second fluid performed by the second fluid pump106are started (step S302). By starting the fluid pumps105and106, the feeding of the fluid from the fluid containers101and102to the microreactor107is started. After the fluid pumps105and106are started, the first fluid and the second fluid are fed to the junction inside the microreactor107through the tube109(step S303). For example, in the case of the microreactor200(seeFIG.2), when the first fluid is controlled to have a relatively high flow rate, the first fluid is introduced into the high flow rate side inflow port210, and the second fluid is introduced into the low flow rate side flow path221. The first fluid flows through the high flow rate side flow path220and reaches the junction230. The second fluid flows through the low flow rate side flow path221and reaches the junction230. When the first fluid and the second fluid are fed to the microreactor107, the first fluid and the second fluid start mixing and reaction inside the microreactor107(step S304). For example, in the case of the microreactor200(seeFIG.2), the mixed fluid in which the mixing and the reaction are started flows downstream of the junction230. Next, the mixed fluid in which the first fluid and the second fluid start mixing and reaction is discharged from the microreactor107(step S305). For example, in the case of the microreactor200(seeFIG.2), the mixed fluid after merging at the junction230flows through the discharge flow path222and is discharged through the outflow port240. The mixed fluid discharged from the microreactor107flows through the tube109while continuing mixing or reaction, and is finally collected in the collection container108. When the feeding of each fluid continues, since the remaining amount of the fluid in any one of the first fluid container101and the second fluid container102is exhausted (step S306), such a state is detected by measuring the amount of the fluid. The amounts of the fluids inside the fluid containers101and102are measured by the fluid sensors110and111at appropriate time intervals during the operation of the system. When it is measured that the fluid in any one of the containers is exhausted, the fluid on the side where the remaining amount is exhausted is switched to another fluid (step S307). When the amount of the fluid in the container is below a threshold close to zero, it is determined that the fluid is exhausted, and fluid switching can be performed. Flow path switching performed by the switches112and113is controlled based on measurement executed by the fluid sensors110and111. In a case in which the remaining amount of the first fluid in the container is first exhausted, the first fluid fed toward the microreactor107is switched to the third fluid. On the other hand, in a case in which the remaining amount of the second fluid in the container is first exhausted, the second fluid fed toward the microreactor107is switched to the fourth fluid. After the fluid fed toward the microreactor107is switched, the feeding performed by the first fluid pump105and the feeding performed by the second fluid pump106are completed at the stage in which the collection of a mixed fluid discharged from the microreactor107is completed (step S308). The feeding of each fluid is stopped by stopping a respective one of the fluid pumps105and106. Thereafter, the operation of the system is completed (step S309). As described above, according to the operation method of switching only the fluid on the side where the remaining amount is first exhausted to another fluid, even if the fluid in the container is exhausted during the operation of the pump, another fluid is fed toward the microreactor. By feeding another fluid, the fluid already fed toward the microreactor is pushed out to the discharge side. In addition, even if the gas in the container is suctioned, the gas can be prevented from flowing into the microreactor by switching the fluid to be fed. Therefore, the fluid of the raw material prepared in the container can be mixed and reacted in the microreactor until the end. That is, the fluid of the raw material can be used for mixing or reaction in the vicinity of a bottom portion of the container without leaving a large amount of fluid in the container. Therefore, according to such an operation method, the fluid of the raw material can be efficiently used. Since a large amount of fluid of the raw material does not remain inside the fluid container, inside the microreactor, or inside the pipe, even if the fluid of the raw material is a toxic substance, a hazardous substance, or the like, a risk due to contact at the time of disposal and costs of post-treatment can be reduced. FIG.4is a flowchart showing an example of the operation method of the microreactor system. In the operation method shown inFIG.4, in the microreactor system1, after the feeding of the first fluid and the second fluid is started, when it is measured that the fluid in one of the first fluid container101and the second fluid container102is exhausted, the fluid on the side where the remaining amount is exhausted is switched to another fluid (the third fluid or the fourth fluid) different from the first fluid and the second fluid, and the other fluid whose remaining amount is not exhausted is switched to another fluid (the third fluid or the fourth fluid) different from the first fluid and the second fluid. In this operation method, similarly to the operation method (seeFIG.3) described above, the start of the operation of the system (step S401), the start of the feeding of the first fluid and the second fluid (step S402), the feeding to the junction of the microreactor107(step S403), the mixing and the reaction inside the microreactor107(step S404), and the discharge of the mixed fluid from the microreactor107(step S405) are proceeded. When the feeding of each fluid continues, since the remaining amount of the fluid in any one of the first fluid container101and the second fluid container102is exhausted (step S406), such a state is detected by measuring the amount of the fluid. The amounts of the fluids inside the fluid containers101and102are measured by the fluid sensors110and111at appropriate time intervals during the operation of the system. When it is measured that the fluid in any one of the containers is exhausted, both the fluid on the side where the remaining amount is exhausted and the other fluid whose remaining amount is not exhausted are switched to another fluid (step S407). When the amount of the fluid in the container is below a threshold close to zero, it is determined that the fluid is exhausted, and fluid switching can be performed. Flow path switching performed by the switches112and113is controlled based on measurement executed by the fluid sensors110and111. In both the case in which the remaining amount of the first fluid in the container is first exhausted and the case in which the remaining amount of the second fluid in the container is first exhausted, the first fluid fed toward the microreactor107is switched to the third fluid, and the second fluid fed toward the microreactor107is switched to the fourth fluid. After the fluid fed to the microreactor107is switched, the feeding performed by the first fluid pump105and the feeding performed by the second fluid pump106are completed at the stage in which the collection of a mixed fluid discharged from the microreactor107is completed (step S408). The feeding of each fluid is stopped by stopping a respective one of the fluid pumps105and106. Thereafter, the operation of the system is completed (step S409). As described above, according to the operation method of switching both the fluid on the side where the remaining amount is exhausted and the other fluid on the side where the remaining amount is not exhausted to another fluid, even if the fluid in the container is exhausted during the operation of the pump, another fluid is fed toward the microreactor. By feeding another fluid, the fluid already fed toward the microreactor is pushed out to the discharge side. In addition, even if the gas in the container is suctioned, the gas can be prevented from flowing into the microreactor by switching the fluid to be fed. Therefore, according to such an operation method, the fluid of the raw material can be efficiently used. At this time, since the other fluid on the side where the remaining amount is not exhausted is also switched to another fluid at the same time, even on the side where the remaining amount is not exhausted, the fluid already fed toward the microreactor can be pushed out to the discharge side by another fluid. That is, in any of the systems, the fluid of the raw material can be removed from the inside of the microreactor or the inside of the pipe by the end of the mixing and the reaction. Therefore, even if the fluid of the raw material is a toxic substance, a hazardous substance, or the like, it is possible to reduce the risk due to contact at the time of disposal and the costs of post-treatment for any of the systems. FIG.5is a flowchart showing an example of the operation method of the microreactor system. In the operation method shown inFIG.5, in the microreactor system1, after the feeding of the first fluid and the second fluid is started, when it is measured that the fluid in one of the first fluid container101and the second fluid container102is exhausted, the fluid on the side where the remaining amount is first exhausted is switched to another fluid (the third fluid or the fourth fluid) different from the first fluid and the second fluid. When it is measured that the fluid in the other container is exhausted after the fluid on the side where the remaining amount is first exhausted is switched, the fluid on the side where the remaining amount is exhausted later is switched to another fluid (the third fluid or the fourth fluid) different from the first fluid and the second fluid. In this operation method, similarly to the operation method (seeFIG.3) described above, the start of the operation of the system (step S501), the start of the feeding of the first fluid and the second fluid (step S502), the feeding to the junction of the microreactor107(step S503), the mixing and the reaction inside the microreactor107(step S504), and the discharge of the mixed fluid from the microreactor107(step S505) are proceeded. When the feeding of each fluid continues, since the remaining amount of the fluid in any one of the first fluid container101and the second fluid container102is exhausted (step S506), such a state is detected by measuring the amount of the fluid. The amounts of the fluids inside the fluid containers101and102are measured by the fluid sensors110and111at appropriate time intervals during the operation of the system. When it is measured that the fluid in any one of the containers is exhausted, the fluid on the side where the remaining amount is first exhausted is switched to another fluid (step S507). When the amount of the fluid in the container is below a threshold close to zero, it is determined that the fluid is exhausted, and fluid switching can be performed. Flow path switching performed by the switches112and113is controlled based on measurement executed by the fluid sensors110and111. In a case in which the remaining amount of the first fluid in the container is first exhausted, the first fluid fed toward the microreactor107is switched to the third fluid. On the other hand, in a case in which the remaining amount of the second fluid in the container is first exhausted, the second fluid fed toward the microreactor107is switched to the fourth fluid. When the feeding of each fluid continues, since the remaining amount of the other fluid in the first fluid container101and the second fluid container102is exhausted (step S508), such a state is detected by measuring the amount of the fluid. When it is measured that the fluid in the container on the side where the fluid remains is exhausted, the fluid on the side where the remaining amount is exhausted later is switched to another fluid (step S509). After the fluid fed toward the microreactor107is switched, the feeding performed by the first fluid pump105and the feeding performed by the second fluid pump106are completed at the stage in which the collection of a mixed fluid discharged from the microreactor107is completed (step S510). The feeding of each fluid is stopped by stopping a respective one of the fluid pumps105and106. Thereafter, the operation of the system is completed (step S511). As described above, according to the operation method of switching the fluid on the side where the remaining amount is first exhausted to another fluid and then switching the fluid on the side where the remaining amount is exhausted later to another fluid, even if the fluid in the container is exhausted during the operation of the pump, another fluid is fed toward the microreactor. By feeding another fluid, the fluid already fed toward the microreactor is pushed out to the discharge side. In addition, even if the gas in the container is suctioned, the gas can be prevented from flowing into the microreactor by switching the fluid to be fed. Therefore, according to such an operation method, the fluid of the raw material can be efficiently used. At this time, since the other fluid on the side where the remaining amount is not exhausted is also switched to another fluid thereafter, even on the side where the remaining amount is not exhausted, the fluid of the raw material prepared in the fluid container can be discharged in the vicinity of the bottom portion of the container. Further, the fluid already fed toward the microreactor can be pushed out to the discharge side by another fluid. That is, in any of the systems as well, the fluid of the raw material can be removed from the inside of the microreactor or the inside of the pipe by the end of the mixing and the reaction. Therefore, even if the fluid of the raw material is a toxic substance, a hazardous substance, or the like, it is possible to reduce the risk due to contact at the time of disposal and the costs of post-treatment for any of the systems. The microreactor107may be a single-use (disposable) type microreactor that is discarded after a single use. Examples of a material of the single-use type microreactor107include PE, PP, PMP, PDMS, PC, acrylic resin, and fluorine-based resin. In addition to the microreactor107, the fluid containers101,102,103, and104, the collection container108, the tube109, the switches112and113, the joints, and other liquid contact portions may be of a single-use type. At least one or more of the first fluid container101, the second fluid container102, the third fluid container103, and the fourth fluid container104, the first switch112, the second switch113, and the tube109connected to the first switch112and the second switch113are preferably of a single-use type. When the at least one or more of the first fluid container101, the second fluid container102, the third fluid container103, and the fourth fluid container104, the first switch112, the second switch113, and the tube109are of a single-use type, even if the fluid of the raw material is a toxic substance, a hazardous substance, or the like, the toxic substance, the hazardous substance, or the like can be post-treated together with the remaining fluid, and thus it is possible to reduce the risk due to contact at the time of disposal and the costs of post-treatment. In addition, by using detachable sterile connection joints as the switches112and113, the switches112and113can be disassembled into a size that is easy to carry at the time of disposal. Second Embodiment Next, a microreactor system according to a second embodiment of the invention will be described with reference to the drawings. FIG.6is a schematic diagram of the microreactor system according to the second embodiment. As shown inFIG.6, similarly to the microreactor system1described above, a microreactor system2according to the second embodiment includes the first fluid container (the first container)101, the second fluid container (the second container)102, the third fluid container (the third container)103, the first fluid pump (the first pump)105, the second fluid pump (the second pump)106, the microreactor107, the collection container108, the tube109, the first fluid sensor (the first measurement unit)110, the second fluid sensor (the second measurement unit)111, the first switch (the first switching unit)112, and the second switch (the second switching unit)113. The microreactor system2is different from the microreactor system1described above in that the microreactor system2includes, as a container in which another fluid different from a first fluid and a second fluid is prepared, the third fluid container103connected to both a first system and a second system. In the microreactor system2, the tube109of the first system to which the first fluid container101is connected is provided with the first switch112between the first fluid container101and the first fluid pump105. The first switch112is connected to the third fluid container103via the tube109. The tube109of the second system to which the second fluid container102is connected is provided with the second switch113between the second fluid container102and the second fluid pump106. The second switch113is connected to the third fluid container103via the tube109. In the microreactor system2, the first switch112is switchable between a state in which a flow path from the first fluid container101to the microreactor107is opened and a flow path from the third fluid container103to the microreactor107is closed and a state in which the flow path from the first fluid container101to the microreactor107is closed and the flow path from the third fluid container103to the microreactor107is opened. The second switch113is switchable between a state in which a flow path from the second fluid container102to the microreactor107is opened and the flow path from the third fluid container103to the microreactor107is closed and a state in which the flow path from the second fluid container102to the microreactor107is closed and the flow path from the third fluid container103to the microreactor107is opened. In the microreactor system2, it is possible to use an operation method (seeFIG.3). In the operation method, after the feeding of the first fluid and the second fluid is started, when it is measured that the fluid in one of the first fluid container101and the second fluid container102is exhausted, the fluid on the side where the remaining amount is exhausted is switched to another fluid (a third fluid) different from the first fluid and the second fluid, and the feeding of the first fluid and the second fluid is completed without switching the fluid in the other container whose remaining amount is not exhausted to another fluid (the third fluid) different from the first fluid and the second fluid. In the microreactor system2, it is also possible to use an operation method (seeFIG.4). In the operation method, after the feeding of the first fluid and the second fluid is started, when it is measured that the fluid in one of the first fluid container101and the second fluid container102is exhausted, the fluid on the side where the remaining amount is exhausted is switched to another fluid (the third fluid) different from the first fluid and the second fluid, and the other fluid whose remaining amount is not exhausted is switched to another fluid (the third fluid) different from the first fluid and the second fluid. Further, in the microreactor system2, it is also possible to use an operation method (seeFIG.5). In the operation method, after the feeding of the first fluid and the second fluid is started, when it is measured that the fluid in one of the first fluid container101and the second fluid container102is exhausted, the fluid on the side where the remaining amount is first exhausted is switched to another fluid (the third fluid) different from the first fluid and the second fluid. When it is measured that the fluid in the other container is exhausted after the fluid on the side where the remaining amount is first exhausted is switched, the fluid on the side where the remaining amount is exhausted later is switched to another fluid (the third fluid) different from the first fluid and the second fluid. According to such a microreactor system2, since the third fluid container103is connected to the first system to which the first fluid container101is connected and the second system to which the second fluid container102is connected, in both of the first system and the second system, the fluid of the raw material prepared in each of the fluid containers101and102can be switched to another fluid. The fluid container103in which another fluid is prepared is integrated as one container and is provided in common for the first system and the second system. Therefore, the overall configuration can be simplified, and the system can be compact. In addition, another fluid can be easily prepared, replaced, disposed of, and the like. Third Embodiment Next, a microreactor system according to a third embodiment of the invention will be described with reference to the drawings. FIG.7is a schematic diagram of the microreactor system according to the third embodiment. As shown inFIG.7, a microreactor system3according to the third embodiment includes a microreactor107ain a first stage and a plurality of microreactors107b,107c, and107din a second and subsequent stages.FIG.7shows a configuration in which a total of four stages of microreactors107a,107b,107c, and107dare arranged in series. The microreactor system3includes a fluid A container (a first-stage first fluid container)701, a fluid B container (a first-stage second fluid container)702, a fluid C container (a container for a fluid to be mixed)703, a fluid D container (a container for a fluid to be mixed)704, a fluid E container (a container for a fluid to be mixed)705, and a fluid F container706. The microreactor system3includes a fluid A pump (a first-stage first fluid pump)707, a fluid B pump (a first-stage second fluid pump)708, a fluid C pump (a pump for a fluid to be mixed)709, a fluid D pump (a pump for a fluid to be mixed)710, and a fluid E pump (a pump for a fluid to be mixed)711. The microreactor system3includes the first microreactor107aconstituting a first stage, the second microreactor107bconstituting a second stage, the third microreactor107cconstituting a third stage, the fourth microreactor107dconstituting a fourth stage, the collection container108, and the tube109. The microreactor system3includes a fluid A sensor (a measurement unit for the first-stage first fluid)712, a fluid B sensor (a measurement unit for the first-stage second fluid)713, a fluid C sensor (a measurement unit for a fluid to be mixed)714, a fluid D sensor (a measurement unit for a fluid to be mixed)715, and a fluid E sensor (a measurement unit for a fluid to be mixed)716. The microreactor system3also includes a fluid A switch (a switching unit for the first-stage first fluid)717, a fluid B switch (a switching unit for the first-stage second fluid)718, a fluid C switch (a switching unit for a fluid to be mixed)719, a fluid D switch (a switching unit for a fluid to be mixed)720, and a fluid E switch (a switching unit for a fluid to be mixed)721. The microreactor system3includes a plurality of microreactors107a,107b,107c, and107dconnected in series to each other. The microreactor system3mixes fluids sequentially introduced into the plurality of microreactors107a,107b,107c, and107dto produce a mixture in which the fluids are mixed or a reaction product (a mixed fluid) generated by a reaction between the fluids. Each of the first microreactor107a, the second microreactor107b, the third microreactor107c, and the fourth microreactor107dincludes two inflow ports into which fluids are introduced, a minute flow path that merges and mixes the individually introduced fluids, and an outflow port that allows the merged mixed fluid to flow out. As the microreactors107a,107b,107c, and107d, the microreactor200shown inFIG.2is preferably used. A fluid A (a first-stage first fluid) is introduced into the first microreactor107afrom one of the inflow ports. A fluid B (a first-stage second fluid) is introduced from the other of the inflow ports. In the first microreactor107a, the fluid A and the fluid B are mixed to produce a primary mixed fluid (a fluid A+B). The second microreactor107bis connected to the outflow port of the first microreactor107avia the tube109. The primary mixed fluid (the fluid A+B) is introduced into the second microreactor107bfrom one of the inflow ports. Further, a fluid C (a fluid to be mixed) is introduced from the other of the inflow ports. In the second microreactor107b, the primary mixed fluid and the fluid C are mixed to produce a secondary mixed fluid (a fluid A+B+C). The third microreactor107cis connected to the outflow port of the second microreactor107bvia the tube109. The secondary mixed fluid (the fluid A+B+C) is introduced into the third microreactor107cfrom one of the inflow ports. A fluid D (a fluid to be mixed) is introduced from the other of the inflow ports. In the third microreactor107c, the secondary mixed fluid and the fluid D are mixed to produce a tertiary mixed fluid (a fluid A+B+C+D). The fourth microreactor107dis connected to the outflow port of the third microreactor107cvia the tube109. The tertiary mixed fluid (the fluid A+B+C+D) is introduced into the fourth microreactor107dfrom one of the inflow ports. A fluid E (a fluid to be mixed) is introduced from the other of the inflow ports. In the fourth microreactor107d, the tertiary mixed fluid and the fluid E are mixed to produce a quaternary mixed fluid (a fluid A+B+C+D+E). The collection container108is connected to the outflow port of the fourth microreactor107dvia the tube109. As shown inFIG.7, the microreactor system3includes, as containers in which a fluid F different from the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E is prepared, the fluid F container706connected to all systems including a fluid A system extending from the fluid A container701, a fluid B system extending from the fluid B container702, a fluid C system extending from the fluid C container703, a fluid D system extending from the fluid D container704, and a fluid E system extending from the fluid E container705. In the microreactor system3, the tube109of the fluid A system to which the fluid A container701is connected is provided with the fluid A switch717between the fluid A container701and the fluid A pump707. The fluid A switch717is connected to the fluid F container706via the tube109. The tube109of the fluid B system to which the fluid B container702is connected is provided with a fluid B switch718between the fluid B container702and the fluid B pump708. The fluid B switch718is connected to the fluid F container706via the tube109. The tube109of the fluid systems to which the fluid containers703,704, and705of the second and subsequent stages are connected is provided with the switches719,720, and721between the fluid containers703,704, and705and the fluid pumps709,710, and711. Each of the switches719,720, and721is connected to the fluid F container706via the tube109. In the microreactor system3, the fluid A switch717is switchable between a state in which a flow path from the fluid A container701to the first microreactor107ais opened and a flow path from the fluid F container706to the first microreactor107ais closed and a state in which the flow path from the fluid A container701to the first microreactor107ais closed and the flow path from the fluid F container706to the first microreactor107ais opened. The fluid B switch718is switchable between a state in which a flow path from the fluid B container702to the first microreactor107ais opened and the flow path from the fluid F container706to the first microreactor107ais closed and a state in which the flow path from the fluid B container702to the first microreactor107ais closed and the flow path from the fluid F container706to the first microreactor107ais opened. The switches719,720, and721of the second and subsequent stages are switchable between a state in which flow paths from the fluid containers703,704, and705to the microreactors107b,107c, and107dare opened and flow paths from the fluid F container706to the microreactors107b,107c, and107dare closed and a state in which the flow paths from the fluid containers703,704, and705to the microreactors107b,107c, and107dare closed and the flow paths from the fluid F container706to the microreactors107b,107c, and107dare opened. The fluid A, the fluid B, the fluid C, the fluid D, and the fluid E are fluids of raw materials to be mixed and reacted in the microreactors107a,107b,107c, and107d. The fluid F is a fluid that is fed toward the microreactors107a,107b,107c, and107dinstead of the fluids of the raw materials prepared in the fluid containers701,702,703,704, and705when the fluids are exhausted. As the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E, appropriate fluids are used depending on the purpose of the mixing and the reaction. Unlike the fluids of the raw materials, a fluid that does not contain the components of the raw material is used as the fluid F, similarly to the third fluid and the fourth fluid described above. In the microreactor system3, the fluid A container701is provided with the fluid A sensor712that measures an amount of the fluid A in the container. The fluid B container702is provided with the fluid B sensor713that measures an amount of the fluid B in the container. The fluid C container703is provided with the fluid C sensor714that measures an amount of the fluid C in the container. The fluid D container704is provided with the fluid D sensor715that measures an amount of the fluid D in the container. The fluid E container705is provided with the fluid E sensor716that measures an amount of the fluid E in the container. As the fluid A sensor712, the fluid B sensor713, the fluid C sensor714, the fluid D sensor715, and the fluid E sensor716, a load sensor, a liquid level detection sensor, a flow rate sensor, or the like may be used in addition to the electronic balance, similarly to the fluid sensors110and111described above. Depending on the specifications of the fluid pumps707,708,709,710, and711, when the insides of the fluid containers701,702,703,704,705, and706become significantly negative pressure, the fluid A, the fluid B, the fluid C, the fluid D, the fluid E, and the fluid F cannot be fed. Therefore, devices that pressurize the fluid containers701,702,703,704,705, and706may be provided. Specifically, each of the fluid containers701,702,703,704,705, and706may be placed in a pressure container that can pressurize the fluid containers, or may be pressurized by being physically pressed from the outside. According to such a microreactor system3, since a plurality of microreactors107a,107b,107c, and107dare provided, it is possible to perform multi-stage mixing and reaction by a flow-type process. Since the fluid F container706is connected to each of the systems to which the fluid containers701,702,703,704, and705are connected, the fluid of the raw material prepared in each of the fluid containers701,702,703,704, and705can be switched to another fluid in any of the systems as well. The fluid F container706for in which another fluid is prepared is integrated as one container and is provided in common for each system. Therefore, the overall configuration can be simplified, and the system can be compact. In addition, another fluid can be easily prepared, replaced, disposed of, and the like. FIG.8is a flowchart showing an example of the operation method of the microreactor system. In the operation method shown inFIG.8, in the microreactor system3, after the feeding of the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E is started, when it is measured that the fluid in any one of the fluid A container701, the fluid B container702, the fluid C container703, the fluid D container704, and the fluid E container705is exhausted, all the fluids of the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E are switched to another fluid (the fluid F) different from the fluid A, the fluid B, the fluid C, the fluid D, the fluid E, and the mixed fluid. In the operation method, the fluid A, the fluid B, the fluid C, the fluid D, the fluid E, and the fluid F are put into the fluid containers701,702,703,704,705, and706, respectively, and the operation of the system is started (step S801). Each of the switches717,718,719,720, and721is in a state in which the flow path from each of the fluid containers701,702,703,704,705in which the fluid of the raw material is prepared is open, and the flow path from the fluid F container706is closed. Subsequently, the feeding of the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E performed by the respective fluid pumps707,708,709,710, and711is started (step S802). By starting the fluid pumps707,708,709,710, and711, the feeding of the fluid from the fluid containers701,702,703,704, and705to the microreactors107a,107b,107c, and107dis started. After the fluid pumps707,708,709,710, and711are started, the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E are fed to the junction inside the microreactors107a,107b,107c, and107dthrough the tube109(step S803). The fluid A, the fluid B, the fluid C, the fluid D, and the fluid E are sequentially introduced into the microreactors107a,107b,107c, and107daccording to a mixing time and a reaction time. When the feeding to the microreactors107a,107b,107c, and107dis performed, the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E start mixing and reaction inside the microreactors107a,107b,107c, and107d(step S804). In each of the microreactors107a,107b,107c, and107d, the mixing and the reaction are sequentially started with the feeding of the fluids. Next, the mixed fluid in which the fluids start mixing and reaction is discharged from the microreactors107a,107b,107c, and107d(step S805). The mixed fluid is sequentially discharged from the microreactors107a,107b,107c, and107daccording to the mixing time and the reaction time. The discharged mixed fluid flows through the tube109while continuing the mixing or the reaction, and is finally collected in the collection container108. When the feeding of each fluid continues, since the remaining amount of the fluid in any one of the fluid A container701, the fluid B container702, the fluid C container703, the fluid D container704, and the fluid E container705is exhausted (step S806), such a state is detected by measuring the amount of the fluid. The amounts of the fluids inside the fluid containers701,702,703,704, and705are measured by the fluid sensors712,713,714,715, and716at appropriate time intervals during the operation of the system. When it is measured that the fluid in any one of the containers is exhausted, all the fluids of the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E are switched to another fluid different from the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E (step S807). When the amount of the fluid in the container is below a threshold close to zero, it is determined that the fluid is exhausted, and fluid switching can be performed. Flow path switching performed by the switches717,718,719,720, and721is controlled based on measurement executed by the fluid sensors712,713,714,715, and716. After the fluids to be fed to the microreactors107a,107b,107c, and107dare switched, the feeding performed by the fluid pumps707,708,709,710, and711is completed at the stage in which the collection of a mixed fluid discharged from the fourth microreactor107dat a final stage is completed (step S808). The feeding of each fluid is stopped by stopping a respective one of the fluid pumps707,708,709,710, and711. Thereafter, the operation of the system is completed (step S809). As described above, according to the operation method in which all the fluids whose remaining amounts are exhausted are switched to another fluid, even if the fluid in the container is exhausted during the operation of the pump, another fluid is fed toward the microreactor. By feeding another fluid, the fluid already fed toward the microreactor is pushed out to the discharge side. In addition, even if the gas in the container is suctioned, the gas can be prevented from flowing into the microreactor by switching the fluid to be fed. Therefore, according to such an operation method, the fluid of the raw material can be efficiently used. At this time, since the remaining fluid at the side where the remaining amount is not exhausted is also switched to another fluid at the same time, for the remaining fluid at the side where the remaining amount is not exhausted as well, the fluid already fed toward the microreactor can be pushed out to the discharge side by another fluid. That is, in any of the systems as well, the fluid of the raw material can be removed from the inside of the microreactor or the inside of the pipe. Therefore, even if the fluid of the raw material is a toxic substance, a hazardous substance, or the like, it is possible to reduce the risk due to contact at the time of disposal and the costs of post-treatment for any of the systems as well. In the microreactor system3, it is also possible to use an operation method (seeFIG.3). In the operation method, after the feeding of the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E is started, when it is measured that the fluid in any one of the fluid A container701, the fluid B container702, the fluid C container703, the fluid D container704, and the fluid E container705is exhausted, a part of the fluids whose remaining amounts are exhausted are switched to another fluid (the fluid F) different from the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E, and the feeding of the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E is completed without switching the remaining fluids in the containers whose remaining amounts are not exhausted to another fluid (the fluid F) different from the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E. In the microreactor system3, it is also possible to use an operation method (seeFIG.5). In the operation method, after the feeding of the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E is started, when it is measured that the fluid in any one of the fluid A container701, the fluid B container702, the fluid C container703, the fluid D container704, and the fluid E container705is exhausted, a part of the fluids whose remaining amounts are first exhausted are switched to another fluid (the fluid F) different from the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E. After the part of the fluids whose remaining amounts are first exhausted are switched, when it is measured that the remaining fluids in the containers are exhausted, the remaining fluids whose remaining amounts are exhausted later are switched to another fluid (the fluid F) different from the fluid A, the fluid B, the fluid C, the fluid D, and the fluid E. Fourth Embodiment Next, a microreactor system according to a fourth embodiment of the invention will be described with reference to the drawings. FIG.9is a schematic diagram of the microreactor system according to the fourth embodiment. As shown inFIG.9, similarly to the microreactor system3described above, a microreactor system4according to the fourth embodiment includes the plurality of microreactors107a,107b,107c, and107d, the collection container108, the tube109, the fluid containers701,702,703,704,705, and706, the fluid pumps707,708,709,710, and711, and the fluid sensors712,713,714,715, and716. The microreactor system4is different from the microreactor system3described above in that a fluid detection sensor901is provided downstream of the fourth microreactor107din the final stage. In the microreactor system4, the tube109of a collection system to which the collection container108is connected is provided with the fluid detection sensor901. The fluid detection sensor901is a sensor capable of measuring components in the mixed fluid to be finally collected. As the fluid detection sensor901, an appropriate detector is used according to the type of the fluid and target components. For example, it is possible to use a detector that detects an image, absorption, refraction, reflection, and scattering of light, electrical conduction, resistance, capacitance, and changes in pressure, temperature, ultrasonic waves, magnetism, and the like. The detector may be a device that executes detection of a specific component according to ultraviolet spectroscopy, infrared spectroscopy, Raman spectroscopy, or the like, or detection according to turbidity or the like. The fluid detection sensor901can transmit a detection signal to a control device (not shown). The control device controls the stop of the operation of each of the fluid pumps707,708,709,710, and711by the input of the detection signal from the fluid detection sensor901. According to such a microreactor system4, the fluid detection sensor901can accurately detect the end of the mixing and the reaction in the microreactor. In general, when a flow-type process is performed in a minute flow path such as a microreactor, the amount of the mixed fluid can be obtained based on the internal volume of the entire flow path. That is, an end time of the process can be determined based on the internal volume of the entire flow path and the flow rate of the mixed fluid. However, in the case of such a determination method, product errors of the internal volume of the flow path of the microreactor and an inner diameter of the tube may have an influence. If the process is not completed at an appropriate time, a collection rate of a target substance decreases, or unreacted impurities are mixed. On the other hand, when the fluid detection sensor901detects the end of the mixing and the reaction, the target components in the mixed fluid can be efficiently collected with high purity. Fifth Embodiment Next, a microreactor system according to a fifth embodiment of the invention will be described with reference to the drawings. FIG.10is a schematic diagram of the microreactor system according to the fifth embodiment. As shown inFIG.10, similarly to the microreactor system4described above, a microreactor system5according to the fifth embodiment includes the plurality of microreactors107a,107b,107c, and107d, the collection container108, the tube109, the fluid containers701,702,703,704,705, and706, the fluid pumps707,708,709,710, and711, the fluid sensors712,713,714,715, and716, and the fluid detection sensor901. The microreactor system5is different from the microreactor system4described above in that a disposal container1001is connected downstream of the fourth microreactor107din the final stage in addition to the collection container108, a collection valve1002is provided in the tube109branched into the collection container108, and a disposal valve1003is provided in the tube109branched into the disposal container1001. The tube109is branched downstream of the fourth microreactor107d, and the collection valve1002is provided in one of the branched flow paths. The collection container108is connected downstream of the collection valve1002. The mixed fluid subjected to multi-stage mixing and reaction in the microreactors107a,107b,107c, and107dis collected in the collection container108. On the other hand, the disposal valve1003is provided in the other branched flow path. The disposal container1001is connected downstream of the disposal valve1003. In the disposal container1001, a fluid or the like that is not mixed at an appropriate mixing ratio in the microreactors107a,107b,107c, and107dis collected for disposal. FIG.11is a flowchart showing an example of the operation method of the microreactor system. In the operation method shown inFIG.11, in the microreactor system5, a desired target substance generated by the multi-stage microreactors107a,107b,107c, and107dis collected in the collection container108, and an unnecessary substance that is not mixed at an appropriate mixing ratio is collected in the disposal container1001. In the operation method, the fluid A, the fluid B, the fluid C, the fluid D, the fluid E, and the fluid F are put into the fluid containers701,702,703,704,705, and706, respectively, and the operation of the system is started (step S1101). The collection valve1002is in a state in which a flow path to the collection container108is open. The disposal valve1003is in a state in which a flow path to the disposal container1001is closed. Subsequently, similarly to the operation method (seeFIG.8) described above, the start of the operation of the system (step S1101), the start of the feeding of each fluid (step S1102), the feeding to the junction of the microreactors107a,107b,107c, and107d(step S1103), the mixing and the reaction inside the microreactors107a,107b,107c, and107d(step S1104), the discharge of the mixed fluid from the microreactors107a,107b,107c, and107d(step S1105), the detection of exhausting of the remaining amount (step S1106), and the switching of the fluid (step S1107) are proceeded. After the fluids to be fed toward the microreactors107a,107b,107c, and107dare switched, when the feeding of each fluid continues, since the desired target substance is not discharged from the fourth microreactor107dat the final stage (step S1108), such a state is detected by measuring the components. An amount of a target component is measured by the fluid detection sensor901at appropriate time intervals during the operation of the system. When it is measured that the desired target substance is not discharged, the container connected downstream of the fourth microreactor107din the final stage is switched from the collection container108to the disposal container1001(step S1109). The collection valve1002is controlled in a state in which the flow path to the collection container108is closed based on the measurement executed by the fluid detection sensor901. The disposal valve1003is controlled in a state in which the flow path to the disposal container1001is opened based on the measurement executed by the fluid detection sensor901. After switching to the disposal container1001, the feeding performed by each of the fluid pumps707,708,709,710, and711is completed (step S1110). The feeding of each fluid is stopped by stopping a respective one of the fluid pumps707,708,709,710, and711. Each of the fluid pumps707,708,709,710, and711may be stopped when it is measured that each fluid of the raw material is not discharged based on the measurement executed by the fluid detection sensor901. Thereafter, the operation of the system is completed (step S1111). According to such a microreactor system5, since the collection container108and the disposal container1001are switched downstream of the fourth microreactor107din the final stage, the target substance mixed at an appropriate mixing ratio can be efficiently collected with high purity, and the fluids of the raw materials such as the unnecessary substance, the toxic substance, and the hazardous substance that are not mixed at an appropriate mixing ratio can be safely collected as disposals. Since the risk due to contact at the time of disposal can be reduced, unnecessary fluids can be safely handled. Sixth Embodiment Next, a microreactor system according to a sixth embodiment of the invention will be described with reference to the drawings. FIG.12is a schematic diagram of the microreactor system according to the sixth embodiment. As shown inFIG.12, similarly to the microreactor system5described above, a microreactor system6according to the sixth embodiment includes the plurality of microreactors107a,107b,107c, and107d, the collection container108, the tube109, the fluid containers701,702,703,704,705, and706, the fluid pumps707,708,709,710, and711, the fluid sensors712,713,714,715, and716, the fluid detection sensor901, the disposal container1001, the collection valve1002, and the disposal valve1003. The microreactor system6is different from the microreactor system5described above in that each of the fluid containers701,702,703,704,705, and706is supported by a rack1201having a shape in which a lower side is opened, and each of the fluid containers discharges a respective one of the fluids in a vertically downward direction. The rack1201is provided in a shape in which the fluid container is supported above a ground contact surface of the rack1201itself and the lower side of the supported fluid container is opened. According to such a rack1201, it is possible to connect a pipe to a discharge port and discharge the fluid in the container in a state in which the fluid container having the discharge port formed in a bottom portion is supported or in a state in which the fluid container having the discharge port formed in a ceiling portion is reversed and supported. Since the fluid including the fluid in the vicinity of the bottom portion of the container can be discharged by gravity, the utilization efficiency of the fluid of the raw material is less likely to decrease. In the rack1201, the support method of the fluid container is not particularly limited as long as the lower side of the fluid container is opened and the pipe such as the tube109can be connected to the discharge port of the fluid container. The fluid container may be supported by being placed on a table-shaped portion, a net-shaped portion, or the like, by being suspended from a bridge portion or the like, by being held on a frame portion or the like, or by being gripped and pinched by a support member. FIGS.13A,13B, and13Care diagrams showing a method for installing a fluid container.FIG.13Ais a diagram showing a method of placing a 3D bag on a table-shaped portion of a rack.FIG.13Bis a diagram showing a method of suspending a 2D bag from the rack.FIG.13Cis a diagram showing a method of holding a 3D bag on a frame portion of the rack. InFIGS.13A,13B, and13C, a reference numeral1301denotes an example of the fluid container, which is a 3D bag provided in a three-dimensional shape, and a reference numeral1302denotes an example of the fluid container, which is a 2D bag provided in a flat two-dimensional shape. A discharge portion1311is provided in the vicinity of the center of a bottom surface of the 3D bag1301. Similarly, a discharge portion1321is provided in the vicinity of the center of a bottom surface of the 2D bag1302. Pipes such as the tube109can be connected to the discharge portions1311and1321. As shown inFIG.13A, the rack1201that supports the fluid container can be provided as a table-shaped rack1201A including a table-shaped portion. The table-shaped rack1201A includes a flat plate-shaped bottom plate portion1211, a pair of left and right flat plate-shaped side plate portions1212, and a flat plate-shaped top plate portion1213. The bottom plate portion1211, the side plate portions1212, and the top plate portion1213form a rectangular parallelepiped rack having an open front surface and an open rear surface. The top plate portion1213is formed with a notch1214from the vicinity of the center of one side to the vicinity of the center of a main surface. The notch1214has a width such that the pipe can be connected. As shown inFIG.13A, the 3D bag1301can be placed on the top plate portion1213of the table-shaped rack1201A such that the discharge portion1311overlaps with the notch1214. The top plate portion1213is supported by the side plate portions1212above the bottom plate portion1211to be grounded. Therefore, a lower side of the 3D bag1301is opened. As shown inFIG.13B, the rack1201that supports the fluid container may be provided as a suspension rack1201B including a bridge portion. The suspension rack1201B includes a frame member1221that forms a skeleton of a rectangular bottom portion and a rectangular ceiling portion, a column member1222that supports a vertex of the rectangular ceiling portion, a bridge member1223that cross-bridges the rectangular ceiling portion, and a hook1224that catches a support object. The frame member1221and the column member1222are assembled in a rectangular parallelepiped shape to form a rack having a skeleton shape. Both ends of the bridge member1223are fixed to the frame member1221, and form a bridge portion that crosses a ceiling surface. The hook1224is attached to the bridge member1223in a manner of being positioned in the vicinity of the center of the bridge portion crossing the ceiling surface. As shown inFIG.13B, the 2D bag1302provided with a locking portion for suspension can be suspended from the hook1224of the suspension rack1201B. A length of the column member1222and a height of the hook1224are larger than those of the 2D bag1302. Therefore, a lower side of the 2D bag1302is opened. As shown inFIG.13C, the rack1201that supports the fluid container may be provided as a frame platform rack1201C including a frame portion. The frame platform rack1201C includes a bottom member1231that forms a skeleton of a rectangular bottom portion, a column member1232that supports a vertex of a rectangular ceiling portion, and a frame member1233that forms a skeleton of the rectangular ceiling portion. The bottom member1231, the column member1232, and the frame member1233are assembled into a rectangular parallelepiped shape to form a rack having a skeleton shape. In order to support an outer edge portion of the 3D bag1301from below, the frame member1233is provided such that an inner size of the skeleton of the rectangular ceiling portion is slightly smaller than a vertical width and a horizontal width of the 3D bag1301. As shown inFIG.13C, the 3D bag1301can be held on the frame member1233of the frame platform rack1201C such that the discharge portion1311faces downward and the periphery of the 3D bag1301is supported. The frame member1233is supported by the column member1232above the bottom member1231to be grounded. Therefore, the lower side of the 3D bag1301is opened. When such a table-shaped rack1201A, a suspension rack1201B, or a frame platform rack1201C is used, the fluid inside the fluid container can be discharged in the vertically downward direction. Therefore, in the microreactor system5or the like, the fluid of the raw material prepared in the fluid container can be used up to the vicinity of the bottom portion of the container without leaving a large amount of fluid in the fluid container. As compared with a case in which a pipe such as a tube is inserted from an upper portion of the fluid container and the fluid in the container is suctioned from the upper portion, the fluid in the container can be used more efficiently. Any of the table-shaped rack1201A, the suspension rack1201B, and the frame platform rack1201C can be mounted on an electronic balance together with the fluid containers such as the 3D bag1301and the 2D bag1302. Since the racks have a skeleton shape or a hollow shape, the racks can be provided in a lightweight manner, and measurement errors due to the weight of the racks themselves can be easily reduced. Although the embodiments and modifications of the invention have been described above, the invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit of the invention. For example, the invention is not necessarily limited to those including all the configurations included in the embodiments described above. A part of a configuration of an embodiment may be replaced with a configuration of another embodiment, may be added to another embodiment, or may be omitted. For example, the microreactor system1described above may have a configuration in which a plurality of microreactors are connected in series. That is, in the microreactor system3described above, a fluid to be switched can be individually prepared for each fluid system. In the microreactor system3described above, the fluid to be switched may be individually prepared for a part of the fluid systems, and a common fluid to be switched may be prepared for the remaining fluid systems. In the microreactor systems1,2,3,4,5, and6described above, the number of stages of the microreactors connected in series may be any number of one or more. In the microreactor of each stage, two or more types of any fluids may be mixed. The fluid detection sensor901, the disposal container1001, the collection valve1002, the disposal valve1003, and the rack1201described above may be provided in the microreactor systems1and2described above. Installation positions of the fluid container, the collection container, the disposal container, the fluid pump, the fluid sensor, the switch, the rack, and the like may be changed or a part of the installation may be omitted as long as the functions thereof are not impaired. As the fluid prepared in the fluid container, a liquid may be used, a gas may be used, a liquid containing a solid may be used, a liquid containing a gas may be used, or a combination of a liquid and a gas may be used, and various fluids that can be treated as a fluid can be used. The microreactor provided in each of the microreactor systems1,2,3,4,5, and6may have an appropriate shape as long as the microreactor has a minute flow path that mixes at least two fluids. For example, the microreactor can be provided in an appropriate shape such as a Y shape or a T shape in a plan view, or can be provided in a shape in which the fluids form a multilayer flow and merge. A volume of the flow path from the inflow of the two fluids to the merging of the two fluids may be biased or may not be biased.
77,662
11857942
DETAILED DESCRIPTION Before the present compositions and methods are described, it is to be understood that this invention is not limited to the particular processes, compositions, or methodologies described, as these may vary. It is also to be understood that the terminology used in the description is for the purpose of describing the particular versions or embodiments only, and is not intended to limit the scope of the present invention, which will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, the preferred methods, devices, and materials are now described. All publications mentioned herein are incorporated by reference in their entirety. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention. It must also be noted that as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to “a combustion chamber” is a reference to “one or more combustion chambers” and equivalents thereof known to those skilled in the art, and so forth. As used herein, the term “about” means plus or minus 10% of the numerical value of the number with which it is being used. Therefore, about 50% means in the range of 45%-55%. Embodiments of the invention are directed to mercury sorbents having enhanced mercury removal capabilities in flue gas streams. Such mercury sorbents have include a mercury adsorptive material having an iodine number of greater than 300 mg/g, and in other embodiments, the mercury adsorptive material may have an iodine number from about 700 mg/g to about 1500 mg/g. In still other embodiments, these mercury sorbents may include one or more additives that may further enhance the effectiveness of the mercury adsorptive material. The mercury adsorptive material of the sorbent composition of various embodiments may include any material having an affinity for mercury. For example, in some embodiments, the mercury adsorptive material may be a porous sorbent having an affinity for mercury including, but not limited to, activated carbon, reactivated carbon, graphite, graphene, zeolite, silica, silica gel, clay, and combinations thereof, and in particular embodiments, the mercury adsorptive material may be activated carbon. The mercury adsorptive material may have any mean particle diameter (MPD). For example, in some embodiments, the MPD of the mercury adsorptive material may be from about 0.1 μm to about 100 μm, and in other embodiments, the MPD may be about 1 μm to about 30 μm. In still other embodiments, the MPD of the mercury adsorptive material may be less than about 15 μm, and in some particular embodiments, the MPD may be about 2 μm to about 10 μm, about 4 μm to about 8 μm, or about 5 μm or about 6 μm. In certain embodiments, the mercury adsorptive materials may have an MPD of less than about 12 μm, or in some embodiments, less than 7 μm, which may provide increased selectivity for mercury oxidation. In certain embodiments, the mercury adsorbent may have high activity as determined by having an iodine number of greater than 300 mg/g. Iodine number is used to characterize the performance of adsorptive materials based on the adsorption of iodine from solution. This provides an indication of the pore volume of the adsorbent material. More specifically, iodine number is defined as the milligrams of iodine adsorbed by one gram of carbon when the iodine concentration in the residual filtrate is 0.02 normal. Greater amounts of adsorbed iodine indicates that the activated carbon has a higher surface area for adsorption and a higher degree of activation activity level. Thus, a higher “iodine number” indicates higher activity. As used herein, the term “iodine number” can refer to either a gravimetric iodine number or a volumetric iodine number. Gravimetric iodine number can be determined using standard test method (ASTM) D-4607, which is hereby incorporated by reference in its entirety, or equivalent thereof. Volumetric iodine number is a product of the gravimetric iodine number (mg of iodine adsorbed/gram of carbon) and the apparent density of the activated carbon (grams of carbon/cc of carbon), which an apparent density can be determined using ASTM D-2854, which is hereby incorporated by reference in its entirety, or an equivalent thereof. In other embodiments, granular or powdered carbon or any other form of carbon where the ASTM apparent density test cannot properly be applied, the apparent density can be determined using mercury porosimetry test ASTM 4284-12 to determine the void volume via mercury intrusion volume at 1 pound per square inch actual pressure. This intrusion volume defines the void volume of the carbon sample to allow calculation of the carbon particle density, and the apparent density is then calculated by correcting this particle density for the void fraction in a dense packed container of the carbon sample. The void fraction is 40% for a typical 3 fold range in particle size for the sample. Thus, Calculated Apparent Density (g.Carbon/cc.Carbon container)=Particle Density (g.carbon/cc.carbon particle volume)*(100%−40% voids)/100%. The result is a volume based activity with the units of mg of iodine adsorbed per cc of carbon. Adsorbent materials typically used for mercury adsorption have an iodine number, based on the gravimetric iodine number, of about 300 mg/g to about 400 mg/g, which is thought to provide equivalent performance in mercury adsorption characteristics to adsorptive materials having higher iodine numbers. Various embodiments of the invention are directed to mercury sorbents that include adsorbent materials having gravimetric iodine number for greater than 400 mg/g, greater than 500 mg/g, greater than 600 mg/g, greater than 700 mg/g, greater than 800 mg/g, greater than 900 mg/g, and so on or any gravimetric iodine number therebetween. In other embodiments, the adsorptive material may have an iodine number of from about 500 mg/g to about 1500 mg/g, about 700 mg/g to about 1200 mg/g, or about 800 mg/g to about 1100 mg/g, or any gravimetric iodine number between these exemplary ranges. In further embodiments, mercury adsorbents exhibiting an iodine number within these exemplary ranges may be an activated carbon or carbonaceous char. As determined using volumetric iodine number methods, adsorbent materials for mercury adsorption may have a volumetric iodine number from about 350 mg/cc to about 800 mg/cc. In embodiments of the invention described herein, the volumetric iodine number may be greater than 400 mg/cc, greater than 500 mg/cc, greater than 600 mg/cc, greater than 700 mg/cc, and so on or any volumetric iodine number therebetween. In other embodiments, the adsorptive material may have a volumetric iodine number of from about 350 mg/cc to about 650 mg/cc, about 400 mg/cc to about 600 mg/cc, about 500 mg/cc to about 600 mg/cc, about 500 mg/cc to about 700 mg/cc, or any volumetric iodine number between these ranges. In further embodiments, mercury adsorbents exhibiting an iodine number within these exemplary ranges may be an activated carbon or carbonaceous char, and in certain embodiments, these activated carbon or carbonaceous chars exhibiting a volumetric iodine number of 400 mg/cc or greater may be combined with activated carbons and carbonaceous chars exhibiting a volumetric iodine number that is less than 400 mg/cc. Without wishing to be bound by theory, adsorbent materials having an iodine number within these exemplary ranges may provide improved adsorption over adsorbent materials having a gravimetric iodine number within the commonly used range of about 300 mg/g to about 400 mg/g. For example, in certain embodiments, about one half as much activated carbon having a gravimetric iodine number between about 700 mg/g to about 1200 mg/g or a volumetric iodine number of about 500 mg/cc to about 2200 mg/cc may be necessary to adsorb the amount of mercury adsorbed by conventional activated carbon. Thus, certain embodiments, are directed to methods in which about 5 lbs/hr to about 10 lbs/hr of activated carbon having an iodine number of from about 700 mg/g to about 1200 mg/g or a volumetric iodine number of about 500 mg/cc to about 2200 mg/cc can adsorb an equivalent amount of mercury as about 15 lbs/hr of an activated carbon having an gravimetric iodine number of about 500 mg/g (see, Example 1). In still other embodiments, any of the adsorptive materials described above may be treated with one or more oxidizing agents that enhance mercury adsorption. For example, in some embodiments, the oxidizing agent may be a halogen salt including inorganic halogen salts, which for bromine may include bromides, bromates, and hypobromites, for iodine may include iodides, iodates, and hypoiodites, and for chlorine may be chlorides, chlorates, and hypochlorites. In certain embodiments, the inorganic halogen salt may be an alkali metal or an alkaline earth element containing halogen salt where the inorganic halogen salt is associated with an alkali metal such as lithium, sodium, and potassium or alkaline earth metal such as magnesium, and calcium counterion. Non-limiting examples of inorganic halogen salts including alkali metal and alkali earth metal counterions include calcium hypochlorite, calcium hypobromite, calcium hypoiodite, calcium chloride, calcium bromide, calcium iodide, magnesium chloride, magnesium bromide, magnesium iodide, sodium chloride, sodium bromide, sodium iodide, potassium tri-chloride, potassium tri-bromide, potassium tri-iodide, and the like. The oxidizing agents may be included in the composition at any concentration, and in some embodiments, no oxidizing agent may be included in the compositions embodied by the invention. In embodiments in which oxidizing agents are included, the amount of oxidizing agent may be from about 5 wt. % or greater, about 10 wt. % or greater, about 15 wt. % or greater, about 20 wt. % or greater, about 25 wt. % or greater, about 30 wt. % or greater, about 40 wt. % or greater of the total sorbent, or about 5 wt. % to about 50 wt. %, about 10 wt. % to about 40 wt. %, about 20 wt. % to about 30 wt. %, or any amount therebetween. In further embodiments, any of the adsorptive materials described above may be treated with one or more nitrogen source. The nitrogen source of such agents may be any nitrogen sources are known in the art and can include, for example, ammonium, ammonia, amines, amides, imines, quaternary ammonium, and the like. In certain embodiments, the agent may be, for example, chlorine, bromine, iodine, ammonium halide, such as, ammonium iodide, ammonium bromide, or ammonium chloride, an amine halide, a quaternary ammonium halide, or an organo-halide and combinations thereof. In some embodiments, the nitrogen containing agent may be ammonium halide, amine halide, or quaternary ammonium halide, and in certain embodiments, the agent may be an ammonium halide such as ammonium bromide. In various embodiments, the nitrogen containing agent may be provided about 5 wt. % or greater, about 10 wt. % or greater, about 15 wt. % or greater, about 20 wt. % or greater, about 25 wt. % or greater, about 30 wt. % or greater, about 40 wt. % or greater of the total sorbent, or about 5 wt. % to about 50 wt. %, about 10 wt. % to about 40 wt. %, about 20 wt. % to about 30 wt. %, or any amount therebetween. The ammonium halide, amine halide, or quaternary ammonium halide may be absent in some embodiments, in other embodiments, the ammonium halide, amine halide, or quaternary ammonium halide may be the only additive included in the sorbent composition, and in still other embodiments, the ammonium halide, amine halide, or quaternary ammonium halide may be combined with other agents such as, for example, halide salts, halide metal salts, alkaline agents, and the like to prepare a composition or sorbent encompassed by the invention. In particular embodiments, sorbent may include at least one of a halogen salt such as sodium bromide (NaBr), potassium bromide (KBr), or ammonium bromide (NH4Br). In some embodiments, the adsorbent material may be combined with an acid gas suppression agent such as, for example, alkaline agent. Numerous alkaline agents are known in the art and currently used to remove sulfur oxide species from flue gas and any such alkaline agent may be used in the invention. For example, in various embodiments, the alkaline additive may be alkali oxides, alkaline earth oxides, hydroxides, carbonates, bicarbonates, phosphates, silicates, aluminates, and combinations thereof, and in certain embodiments, the alkaline agent may be calcium carbonate (CaCO3; limestone), calcium oxide (CaO; lime), calcium hydroxide (Ca(OH)2; slaked lime); magnesium carbonate (MgCO3; dolomite), magnesium hydroxide (Mg(OH)2), magnesium oxide (MgO), sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), trisodium hydrogendicarbonate dihydrate (Na3H(CO3)2.2H2O; trona), and combinations thereof. In various embodiments, the alkaline agent may be provided at a concentration greater than or equal to about 0.15 equivalents per 100 grams of absorptive material, wherein one equivalent of the alkaline agent is defined as the amount required to produce one mole of hydroxyl ions or to react with one mole of hydrogen ions. In particular embodiments, such alkaline agents may have a relatively high surface area such as, for example, above 100 m2/g for neat materials. High surface area materials may provide improved kinetics and capabilities for acid gas or SOxmitigation while complementing halogen compounds and other added oxidants to provide oxidation of elemental mercury. Because alkaline agents are highly polar materials that may associate and bond with water, in various embodiments, alkaline agents may be combined with the primary mercury sorbent as a physical admixture and may not generally be present on the sorbent surface or contained within the sorbent pore structure. In other embodiments, the mercury adsorptive material may be treated to enhance the hydrophobicity of the adsorptive materials with, for example, one or more hydrophobicity enhancement agents that impede the adsorption and transport of water or other treatments of the sorbent that achieve similar results. Embodiments are not limited to the type of treated mercury adsorptive material or the means by which the mercury adsorptive material has been treated with a hydrophobicity enhancement agent. For example, in some embodiments, the mercury adsorptive material may be treated with an amount of one or more elemental halogen that can form a permanent bond with the surface. The elemental halogen may be any halogen such as fluorine (F), chlorine (Cl), or bromine (Br), and in certain embodiments, the elemental halogen may be fluorine (F). In other embodiments, the mercury adsorptive material may be treated with a hydrophobicity enhancement agent such as a fluorine salt, organo-fluorine compound, or fluorinated polymer, such as, TEFLON®. In such embodiments, treatment may be effectuated by grinding the mercury adsorptive material with the organo-fluorine compound or fluorinated polymer. In still other embodiments, carbon sorbents used as the mercury adsorptive material may be treated with mineral acids such as but not limited to, hydrochloric acid, nitric acid, boric acid, and sulfuric acid, under high temperature, e.g., greater than about 400° C. or greater than 600° C. or greater than 800° C. The concentration of the acid is not critical to such treatments and concentrations as low as 1.0 percent by weight or less may be used. Without wishing to be bound by theory, such treatment may enhance hydrophobicity and decreased activity for the catalytic oxidation of sulfur dioxide to sulfuric acid in the presence of oxygen and water. Evidence of such treatments can be found in a high contact pH and a reduced tendency for the carbon alone to decompose hydrogen peroxide when compared to the same carbon without such treatments. The adsorbent material may be combined with an oxidizing agent, nitrogen containing compound, hydrophobicity agent, acid gas suppression agent, or other mercury removal agent (collectively, “additives”) in any way known in the art. For example, in some embodiments, the one or more additive may be introduced onto the surface of the adsorbent material by impregnation in which the adsorbent material is immersed in a liquid mixture of additives or the liquid mixture of additives is sprayed or otherwise applied to the adsorbent material. Such impregnation processes result in an adsorbent material in which the additives are dispersed on the surface of the adsorbent material. In various other embodiments, treatment of the adsorbent material may be combined with one or more additive as a dry admixture in which particles of adsorbent are separated and apart from particles of additive having substantially the same size. For example, in some embodiments, may be provided by co-milling activated carbon with one or more additive to a mean particle diameter (MPD) of less than or equal to about 12 μm, less than or equal to about 10 μm, or less than about 7 μm. Without wishing to be bound by theory, reducing the mean particle diameter of the sorbent and additives by co-milling allows for a close localization of the sorbent and the additives, but the additives are not contained within the sorbent pore structure. These dry admixtures have been found to be surprisingly effective in facilitating rapid and selective mercury adsorption. This effect has been shown particularly effective when all of components of the sorbent are combined and co-milled or otherwise sized to a mean particle diameter of less than or equal to about 12 μm. Co-milling may be carried out by any means. For example, in various embodiments, the co-milling may be carried out using bowl mills, roller mills, ball mills, jet mills or other mills or any grinding device known to those skilled in the art for reducing the particle size of dry solids. Although not wishing to be bound by theory, the small MPD may improve the selectivity of mercury adsorption as the halide effectively oxidizes the mercury. As such, dry admixtures of adsorbent materials and additive may allow for a higher percentage of active halide and alkaline agents to be included in the injected sorbent. Mercury adsorbents that are impregnated with an additive by treating with an aqueous solution of the additive, for example, commercial brominated carbon sorbents, especially those impregnated with elemental bromine, can only retain a small percentage of the additive on the surface of the adsorbent, and impregnation tends to clog the pores of porous mercury adsorbents reducing the surface area available for mercury adsorption. In contrast, the percentage of additive in a dry mixture may be greater than about 10 wt. %, greater than about 15 wt. %, greater than about 20 wt. %, or greater than about 30 wt. % and up to about 50 wt. %, up to about 60 wt. %, or up to about 70 wt. % without exhibiting a reduction in mercury adsorption efficiency. While co-grinding is useful in some embodiments, adsorptive material and additives may be combined by any method. For example, in some embodiments, an adsorptive material and one or more additive may be combined by blending or mixing the materials into a single mercury sorbent that can then be injected into a flue gas stream. In other embodiments, combining may occur during use such that the adsorptive material and the one or more additive are held in different reservoirs and injected simultaneously into a flue gas stream. Further embodiments are directed to methods for removing mercury from flue gas by injecting a mercury adsorbent including a mercury sorbent described above including an adsorbent material and one or more oxidizing agent, nitrogen containing compound, hydrophobicity agent, acid gas suppression agent, or other mercury removal agent into a flue gas stream. The sorbents described herein may be used to adsorb mercury in any flue gas stream. For example, the sorbents of various embodiments may be used in flue gas streams having no or extremely low SO3content or flue gas streams containing high concentrations of other acid gases such as HCl, HF, or NOxspecies. In some embodiments, the mercury adsorptive material and one or more additive may be combined prior to injection into the flue gas stream by, for example, mixing or blending, the mercury adsorptive material with the one or more additives. In other embodiments, the mercury adsorptive material and one or more additives may be injected separately into the flue gas stream and combined in the flue gas stream itself. In still other embodiments, the mercury adsorbent material and the one or more additives may be introduced into a flue gas stream in different portions of the flue gas stream. For example, in some embodiments, all adsorbent materials and additives may be introduced into the flue gas stream simultaneously and at the same portion of the flue gas stream. In other embodiments, an additive such as, for example, a halide salt may be introduced into a boiler or a upstream portion of the flue gas stream and the adsorbent and one or more additional additives may be introduced into the flue gas stream either simultaneously or separately in one or more downstream portions of the flue gas stream. EXAMPLES Although the present invention has been described in considerable detail with reference to certain preferred embodiments thereof, other versions are possible. Therefore the spirit and scope of the appended claims should not be limited to the description and the preferred versions contained within this specification. Various aspects of the present invention will be illustrated with reference to the following non-limiting examples. Example 1 Activated carbons of various activity levels were investigated for their ability to remove mercury from flue gas. Activity was based on the gravimetric iodine number (ASTM D-4607) and volumetric iodine number which the gravimetric iodine number converted to a volumetric basis using the density of the granular material (ASTM D2854). Carbons were all approximately 7 μm in size and were injected into test flue gas upstream of the electrostatic precipitator (ESP) either alone or in a dry admixture with 30% w/w ammonium bromide. Results are reported based on lbs/hr required to remove 90% of the mercury in the flue gas stream. FIGS.1and2shows performance curves for base carbons (no additive) and the base carbon in a dry admixture of 30% w/w ammonium bromide.FIG.1shows the relationship of gravimetric iodine number (mg/g) to the amount of adsorbent required to reach 90% mercury removal, andFIG.2shows the relationship between volumetric iodine number (mg/cc) and the amount of adsorbent required to 90% mercury removal. Table 1 shows the apparent density and gravimetric iodine number used to calculate the volumetric iodine number. TABLE 1ApparentGravimetricVolumetricDensityIodine NumberIodine Number(g/cc)(mg/g)(mg/cc)0.784903820.638505360.531150610 As illustrated inFIGS.1and2, 15.4 lbs/hr of carbon having an gravimetric iodine number of 462 mg/g and a volumetric iodine number of about 382 mg/cc is required to remove 90% of the mercury from the flue gas stream. In contrast, about 8.3 lbs/hr is required to remove 90% of the mercury from the flue gas stream with activated carbon having a gravimetric iodine number of 1150 mg/g and a volumetric iodine number of about 610 mg/cc. This provides an about 45% reduction in the amount of activated carbon required to remove 90% of the mercury from a flue gas stream when the activity as determined by iodine number is increased by 40%. FIGS.1and2also show performance curves for carbons including 30% w/w additive (ammonium bromide) is combined with the activated carbon in a dry admixture before being injected into the flue gas upstream of the ESP. Initially, a 40% reduction in the amount of activated carbon (from 15.4 lbs/hr to 6.2 lbs/hr) necessary to remove 90% of the mercury from the flue gas stream was observed by the addition of ammonium bromide to the activated carbon having an gravimetric iodine number of 462 mg/g. The adsorption of mercury is further enhanced by the introduction of adsorbent having higher activity based on iodine number. Specifically, 1.8 lbs/hr of activated carbon is necessary to remove 90% of the mercury from the flue gas when activated carbon having a gravimetric iodine number of 1150 mg/g and a volumetric iodine number of about 610 mg/cc. This represents a 60% reduction in the amount of activated carbon necessary to reduce the amount of mercury in a full gas stream by 90%. Additionally, the performance curves resulting from activated carbon ammonium bromide mixtures exhibit a non-linear relationship which could be indicative of a synergetic interaction between ammonium bromide addition and both volumetric and gravimetric iodine activity. FIG.2also shows a non-linear decrease in the amount of carbon required when the volumetric iodine number is above about 500 mg/cc when ammonium bromide is present as an admix. Additionally inFIG.2. increasing the volume iodine value of the base carbon does not have a large effect on the performance of this material.
25,774
11857943
EMBODIMENTS OF THE INVENTION Hereinafter, embodiments of the present invention are explained. However, the scope of the present invention are not limited to the embodiments explained below, and various modifications can be made within a range that does not impair the purpose of the present invention. [Activated Carbon] The activated carbon of the present invention has a pore volume at a pore diameter of 10 to 10000 nm measured by the mercury intrusion method of 0.8 to 1.9 mL/g, and a pore volume at a pore diameter of 300 to 1000 nm measured by the mercury intrusion method of 0.19 mL/g or more. The pore at a pore diameter of 10 to 10000 nm serves not only as an adsorbed site, but also as a moving path of a substance to a smaller pore. Therefore, when the pore volume at a pore diameter of 10 to 10000 nm is less than 0.8 mL/g, a movement of an adsorptive substance into the activated carbon inside is prevented, and thus, the desired adsorption performance (for example, the decolorization performance, the equilibrium adsorption amount or the decolorization equilibrium arrival rate) cannot be obtained. In contrast, when the pore volume at a pore diameter of 10 to 10000 nm is more than 1.9 mL/g, a packing density decreases, and the desired adsorption performance cannot be obtained in a case where such activated carbon is packed in an adsorption column or an adsorption tower to be used. In addition, the desired hardness cannot be obtained. The pore volume at a pore diameter of 10 to 10000 nm of the activated carbon of the present invention measured by the mercury intrusion method is preferably 0.9 to 1.7 mL/g, more preferably 1.0 to 1.6 mL/g, especially preferably 1.3 to 1.5 mL/g. When the said pore volume is within the above range, the desired adsorption performance can be obtained more readily and the desired hardness can be obtained more readily. The pore having a pore diameter of 300 to 1000 nm serves as an adsorbed site. In addition, when the pore volume at this pore diameter is large, an adsorptive substance easily diffuses. Therefore, when the pore volume at a pore diameter of 300 to 1000 nm is less than 0.19 mL/g, the desired decolorization performance (in particular, the sugar liquid decolorization performance and the decolorization equilibrium arrival rate) cannot be obtained. The upper limit of the pore volume at a pore diameter of 300 to 1000 nm is not especially limited, but is preferably 0.40 mL/g or less, more preferably 0.38 mL/g or less, further preferably 0.37 mL/g or less since a decrease of an adsorption performance due to a decrease of a packing density and a decrease of hardness (JIS hardness and MS hardness, in particular MS hardness) are concerns. The pore volume at a pore diameter of 300 to 1000 nm of the activated carbon of the present invention measured by the mercury intrusion method is preferably 0.20 mL/g or more, more preferably 0.23 mL/g or more, further preferably 0.25 mL/g or more, especially preferably 0.30 mL/g or more. When the said pore volume is within the above range, the activated carbon having a combination of the desired adsorption performance and the desired hardness can be obtained more readily. The specified pore volumes at the specified pore diameters mentioned above can be adjusted by adjusting a potassium element content of raw material activated carbon to 0.5% by mass or less, adjusting a calcium element content of raw material activated carbon to 0.4 to 4 by mass or less, and activating the raw material activated carbon after the adjustments, as described later. An activation yield should be appropriately selected so as to obtain the specified pore volumes at the specified pore diameters. Hardness of the activated carbon of the present invention measured according to JIS K1474 (hereinafter, it is also referred to as “JIS hardness”) is preferably 70% or more, more preferably 72% or more. When the activated carbon has JIS hardness of the above value or more, a trouble, which is caused by dusts produced from the activated carbon when using the activated carbon for a liquid phase treatment, can be prevented more readily. Micro-strength hardness (hereinafter, it is also referred to as “MS hardness”) of the activated carbon of the present invention is preferably 45% or more, more preferably 50% or more. The MS hardness is an index of resistance to weight load, and can be measured by the method described in the Examples mentioned below. When the activated carbon has MS hardness of the above value or more, dust production due to the self-weight of the activated carbon when packing the activated carbon in an adsorption column or an adsorption tower to be used can be reduced more readily. These specified hardness can be adjusted by adjusting a potassium element content of raw material activated carbon to 0.5% by mass or less, adjusting a calcium element content of raw material activated carbon to 0.4 to 4 by mass or less, and activating the raw material activated carbon after the adjustments while adjusting an activation yield appropriately, as described later. When the pore volume at a pore diameter of 10 to 10000 nm, and especially the pore volume at a pore diameter of 300 to 1000 nm are too large, the hardness (the JIS hardness and the MS hardness, especially the MS hardness) tends to decrease. Therefore, it is important to adjust the pore volumes at the specified pore diameters in order to achieve a good balance between the hardness and the adsorption performance. The activated carbon of the present invention is useful for a liquid phase treatment, since it has the specified pore volumes at the specified pore diameters. Therefore, in one embodiment of the present invention, the activated carbon of the present invention is activated carbon for a liquid phase treatment. In addition, the activated carbon of the present invention is useful for a liquid phase treatment with an adsorption column, an adsorption tower or the like, since it has the high MS hardness. In the present invention, the liquid phase may be any liquid phase as long as it exists as a liquid phase under normal processing conditions. Examples of the liquid phase include a solution, a dispersion, an emulsion, a microemulsion, a suspension, an oil and an alcohol. Examples of the liquid phase treatment include a removal treatment of impurities from a liquid phase and an adjustment of a concentration of a dissolved component in a liquid phase. In one embodiment of the present invention, the above liquid phase treatment is a removal treatment (decolorization treatment) of a coloring component from a liquid phase. A treatment of a liquid phase having a relatively high viscosity in addition to a treatment of a liquid phase having a low viscosity can be performed by use of the activated carbon of the present invention. Therefore, in one embodiment of the present invention, a viscosity of a liquid phase measured at a temperature during the liquid phase treatment by use of DV-I+VISCOMETER manufactured by BROOKFIELD (spindle: LV-1, rotational speed: 20 rpm) is 1 to 50 mPa·s. The liquid phases having such a viscosity may include but are not limited to a sugar liquid, soy sauce and glycerin. The temperature during the liquid phase treatment differs depending on the objective liquid phase. Usually, for example, when the liquid phase is a sugar liquid, the temperature is about 40 to 60° C., when the liquid phase is soy sauce, the temperature is about 15 to 35° C., and the liquid phase is glycerin, the temperature is about 70° C. As to a liquid phase used for evaluating a colorant adsorption amount of activated carbon (for example, an aqueous solution of the dye of Solophenyl RED 3BL (hereinafter, it is also referred to as “SPR”) in an evaluation with SPR, described later), a temperature during the liquid phase treatment is usually a normal temperature (25° C.). A decolorization performance of the activated carbon of the present invention can be evaluated, for example, by use of a sugar liquid or soy sauce by the method described in the Examples mentioned below. The sugar liquid decolorization performance is especially preferably 40% or more, more especially preferably more than 50%. The soy sauce decolorization performance is more preferably 80% or more, especially preferably more than 90%. These decolorization performances can be obtained by adjusting the pore volume at a pore diameter of 10 to 10000 nm and the pore volume at a pore diameter of 300 to 1000 nm to the specified range and the specified value or more, respectively. A colorant adsorption amount of the activated carbon of the present invention can be evaluated, for example, by obtaining an equilibrium adsorption amount and a decolorization equilibrium arrival rate by use of SPR by the method described in the Examples mentioned below. The SPR equilibrium adsorption amount is preferably 90 mg/g or more, more preferably 94 mg/g or more, especially preferably 98 mg/g or more, and the SPR decolorization equilibrium arrival rate is preferably 50% or more, more preferably 55% or more, especially preferably 58% or more. The above equilibrium adsorption amount and decolorization equilibrium arrival rate can be obtained by adjusting the pore volume at a pore diameter of 10 to 10000 nm and the pore volume at a pore diameter of 300 to 1000 nm to the specified range and the specified value or more, respectively. The activated carbon of the present invention is useful for a liquid phase treatment by use of an adsorption column, an adsorption tower or the like, since it can rapidly and efficiently adsorb and remove impurities such as a colorant. The activated carbon used for the liquid phase treatment and thus having the decreased adsorption performance (decolorization performance) can be recycled by the predetermined treatment and can be reused. [Method for Producing Activated Carbon] The activated carbon of the present invention can be obtained by a production method comprising: a step of reducing a potassium element contained in raw material activated carbon (hereinafter, it is also referred to as “a potassium reduction step”), a step of bringing raw material activated carbon into contact with a calcium element supply source (hereinafter, it is also referred to as “a calcium contact step”), a step of activating the raw material activated carbon after adjusting a potassium element content and a calcium element content (hereinafter, it is also referred to as “a second activation step”), and a step of acid-washing the raw material activated carbon after the activation (hereinafter, it is also referred to as “an acid-washing step”). In the present specification, “activated carbon” means activated carbon obtained via the four steps in the above production method, and “raw material activated carbon” means activated carbon obtained by performing an activation treatment (a first activation treatment) of an activated carbon precursor, which is raw material activated carbon for the activated carbon of the present invention and is activated carbon that has not gone through all four of the above steps (that is to say, that is in the middle of the above production process). The activated carbon of the present invention can be produced, for example, by a production method comprising: a step of adjusting a potassium element content of raw material activated carbon to 0.5% by mass or less, a step of adjusting a calcium element content of raw material activated carbon to 0.4 to 4% by mass, and a step of activating the raw material activated carbon after the adjustment steps. Therefore, one embodiment of the present invention relates to activated carbon produced by the production method comprising: a step of adjusting a potassium element content of raw material activated carbon to 0.5% by mass or less, a step of adjusting a calcium element content of raw material activated carbon to 0.4 to 4% by mass, and a step of activating the raw material activated carbon after the adjustment steps. The raw material activated carbon is preferably activated carbon derived from coconut shell. Therefore, in a preferable embodiment of the present invention, a raw material of the activated carbon of the present invention is activated carbon derived from coconut shell. When the raw material activated carbon is derived from coconut shell, each of raw material activated carbon particles has tissue pores inherent in the coconut shell. Therefore, the calcium element supply source can diffuse more readily inside of the particles, and pore development can proceed more readily at the time of the activation step. In addition, coconut shell is commercially advantageous, since it is available in large amounts. Palms for a raw material of the coconut shell are not particularly limited. Examples thereof include palm (oil palm), coconut palm, salak and double coconut and the like. The coconut shell obtained from these palms may be used alone or in combination of two or more. Among them, the coconut shell derived from coconut palm or derived from oil palm which is a biomass waste generated in large amounts as a result of using the palms as foods, detergent raw materials, biodiesel oil raw materials and the like is particularly preferable, since it is readily available and inexpensive. It is also possible to obtain the coconut shell in the form of char prepared by pre-calcining coconut shell (coconut shell char), and it is preferable to use it as the raw material. In addition, char may be prepared from coconut shell, and the prepared char may be used. The method for preparing the char is not particularly limited, and any method well-known in the art may be used. For example, the coconut shell char can be prepared by calcining (carbonizing) coconut shell as a raw material at a temperature of about 400 to 800° C. under an atmosphere of an inert gas such as nitrogen, helium, argon or carbon monoxide, a mixed gas of these inert gases, or a mixed gas with another gas containing at least one of these inert gases as a main component. The raw material activated carbon used in the present invention can be obtained, for example, by the activation treatment (the first activation treatment) of the said activated carbon precursor (coconut shell char). The activation treatment is a treatment of forming pores on the surface of the activated carbon precursor and modifying the activated carbon precursor to a porous carbonaceous material. This treatment can provide the activated carbon (the raw material activated carbon) having a large specific surface area and a large pore volume. In a case where the first activation treatment is not performed and the activated carbon precursor is used as the raw material activated carbon, the specific surface area and pore volumes of the obtained carbonaceous material are not sufficient. Thus, when such a carbonaceous material is used for the liquid phase treatment, it is difficult to achieve a sufficient effect in the liquid phase treatment such as the removal treatment of impurities from the liquid phase and the adjustment of a concentration of the dissolved component in the liquid phase. Therefore, in such a case, the activated carbon of the present invention cannot be obtained. The first activation treatment can be performed by treating the activated carbon precursor at 800° C. or more, preferably 800 to 1000° C., under a mixed gas atmosphere of water vapor, nitrogen and carbon dioxide by use of a fluidized bed, a multi-stage furnace or a rotary furnace. The gas partial pressure at the time is not especially limited, but is preferably a water vapor partial pressure of 7.5 to 40%, a carbon dioxide partial pressure of 10 to 50%, and a nitrogen partial pressure of 30 to 80%. The gas total pressure is usually 1 atm (about 0.1 MPa). A total supplied amount of the mixed gas during the first activation treatment is around 1 to 50 L/minute relative to 100 g of a material to be activated. When the total supplied amount of the activation gas is within the above range, it is easy to make the activation reaction proceed more efficiently. The specific surface area of the raw material activated carbon in the present invention which is calculated by the BET method (hereinafter, it is also referred to as “a BET specific surface area”) is preferably 900 m2/g to 1500 m2/g. When the BET specific surface area of the raw material activated carbon is within the above range, activated carbon having sufficient physical properties for the liquid phase treatment applications can be obtained more readily. <Potassium Reduction Step> In the production method of the present invention, the potassium element in the raw material activated carbon is reduced to 0.5% by mass or less. The reason is that, when the potassium element exists in large amounts, development of volume of micropores is accelerated ahead of that of volumes of mesopores to macropores suitable for the liquid phase treatment in the second activation step after the contact step of the calcium element supply source. Therefore, when the potassium element in the raw material activated carbon exceeds 0.5% by mass, the specified pore volumes of the specified pore diameters cannot be obtained in the activated carbon of the present invention. The potassium element content of the raw material activated carbon is preferably 0.3% by mass or less. When the potassium element content is the above value or less, the desired pore volumes can be obtained more readily. The potassium element content can be measured by the method described in the Examples mentioned below. The lower limit of the potassium element content is 0.0% by mass, which is the detection limit of the measuring method. The method for reducing the potassium element is not particularly limited, and examples thereof include washing with a washing liquid containing an acid, exchanging a potassium component for another component (for example, a calcium component) by an ion-exchanging action, and the like. <Calcium Contact Step> The raw material activated carbon having the potassium element content reduced by the above potassium reduction step is contacted with the calcium element supply source. By this step, the calcium element supply source adheres on the surface of the raw material activated carbon and in the pores of the raw material activated carbon. The calcium element content contained in the raw material activated carbon after the contact step is 0.4 to 4% by mass. When the calcium element content is not within the above range, the specified pore volumes of the specified pore diameters cannot be obtained in the activated carbon of the present invention even when the following second activation step and acid treatment step are performed. The calcium element content contained in the raw material activated carbon after the contact step is preferably 0.5 to 3% by mass. When the calcium element content is within the above range, the desired pore volumes can be obtained more readily. The calcium element content can be measured by the method described in the Examples mentioned below. The calcium element supply source is not particularly limited, and a water-insoluble calcium compound or a water-soluble calcium compound can be used as the calcium element supply source. The calcium compounds may be used alone or in combination of two or more. Examples of the water-insoluble calcium compound include calcium carbonate and calcium hydroxide. From a viewpoint of a handling safety, calcium carbonate is preferably used. From a viewpoint of being able to contact the calcium element supply source in the form of an aqueous solution and thus easily adhering the calcium element supply source uniformly, the water-soluble calcium compound is preferably used. Concrete examples of the water-soluble calcium compound include calcium chloride, calcium nitrate, calcium acetate and the like. Among them, calcium nitrate is preferable, since it is highly soluble, readily available and inexpensive. From a view point of low environmental impact in view of a waste liquid treatment, calcium chloride or calcium acetate is preferably used. The method for contacting the calcium element supply source may be any method as long as the calcium element supply source can adhere to the raw material activated carbon. Examples thereof include, for example, a method in which an aqueous solution of the calcium element supply source is sprayed to the raw material activated carbon, a method in which the raw material activated carbon is immersed in a solution of the calcium element supply source, and a method in which the raw material activated carbon and the powdery calcium element supply source are mixed. Among them, the method in which the calcium element supply source in the form of the aqueous solution is contacted with the raw material activated carbon, such as the spraying method or the immersing method, is preferable, since the calcium element supply source can adhere more readily on the surface of the raw material activated carbon and in the pores of the raw material activated carbon uniformly. In the immersing method which is one of the calcium contact methods, the potassium component in the raw material activated carbon can be exchanged for the calcium component by the ion-exchanging action and discharged into the aqueous solution, and thus, the two steps of the potassium reduction step and the calcium contact step can be simultaneously performed. When the calcium element supply source is used in the form of an aqueous solution in the calcium contact step, the raw material activated carbon after contacting with the calcium element supply source is usually dried before the second activation step, but may be subjected to the second activation treatment without drying after adequately removing liquid from the raw material activated carbon. <Second Activation Step> The raw material activated carbon after subjecting to the potassium reduction step and the calcium contact step is subjected to the second activation treatment. This second activation treatment is performed in the same manner as in the first activation treatment except that the material to be activated is the activated carbon to which calcium is attached. <Acid-Washing Step> The raw material activated carbon after the second activation step is washed with the washing liquid containing an acid, and thereby impurities such as metal components contained in the raw material activated carbon are removed. The acid-washing can be performed, for example, by immersing the raw material activated carbon after the second activation step in the washing liquid containing an acid. In the acid-washing step, the raw material activated carbon may be washed with water after acid-washing, or the acid-washing and the water-washing may be appropriately combined, for example, by repeating the acid-washing and the water-washing. In addition, the acid component may be removed by heating. As the acid contained in the washing liquid, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, or organic acids such as saturated carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid and citric acid or aromatic carboxylic acids such as benzoic acid and terephthalic acid are preferably used. Among them, hydrochloric acid which does not oxidize the raw material activated carbon is more preferably used. When hydrochloric acid is used as the washing liquid containing an acid, a concentration of hydrochloric acid is preferably 0.1 to 10% by mass, more preferably 0.3 to 6% by mass. When the concentration of hydrochloric acid is too low, it is necessary to increase the number of times of acid-washing to remove the impurities. In contrast, when the concentration of hydrochloric acid is too high, residual amount of hydrochloric acid becomes high. Thus, when the concentration is within the above range, the acid-washing step can be efficiently performed, which is preferable in view of productivity. The liquid temperature during the acid-washing step or water-washing step is not particularly limited, but is preferably 0 to 100° C., more preferably 10 to 100° C., further preferably 15 to 95° C. When the temperature of the washing liquid during immersing the raw material activated carbon in the washing liquid is within the above range, it is preferable since washing can be performed in a practical time while suppressing a load on the apparatus. The activated carbon of the present invention can be obtained by drying the activated carbon after the acid-washing step. The method for drying is not particularly limited, and any well-known method for drying may be used. The drying may be performed by use of a natural convection constant-temperature dryer, a forced convection constant-temperature dryer, a vibration fluidized dryer or the like. The drying temperature is preferably 80 to 150° C. A weight loss of the activated carbon after drying is preferably 5% by mass or less. The activated carbon of the present invention produced in this way has the specified developed pore volumes of the pores including mesopores to macropores. Therefore, the activated carbon of the present invention can exhibit the high performances (such as the removal performance of impurities, and the performance for adjusting a concentration of a dissolved component) in the liquid phase treatment, and, in particular, the improved and balanced decolorization performance in a liquid phase having a relatively high viscosity, such as a sugar liquid, in addition to a liquid phase having a low viscosity. EXAMPLES Hereinafter, the present invention will be explained in more detail by the Examples. However, the Examples are not intended to limit the scope of the present invention. A BET specific surface area and a metal element content of the raw material activated carbon, and a pore volume, JIS hardness and MS hardness of the activated carbon were determined by the following methods. <BET Specific Surface Area of Raw Material Activated Carbon> A BET specific surface area of the raw material activated carbon was determined by the high precision surface area/pore distribution measurement device (“BELSORP 28 SA” manufactured by MicrotracBEL Corporation). After degassing the measurement sample at 300° C. for 5 hours under vacuum, a nitrogen adsorption isotherm at 77K was measured. Using the obtained adsorption isotherm, a multipoint analysis by the BET equation was performed. A specific surface area was calculated from a straight line in the range of a relative pressure P/P0 of 0.01 to 0.1 of the obtained curve. <Average Particle Diameter> When a metal element content of the raw material activated carbon and a decolorization performance of the activated carbon are evaluated, the raw material activated carbon or the activated carbon needs to be ground to have a predetermined average particle diameter. Therefore, an average particle diameter of the raw material activated carbon or the activated carbon after grinding was measured by the laser diffraction measurement method in order to confirm whether the raw material activated carbon or the activated carbon has the predetermined average particle diameter. Specifically, the powdery raw material activated carbon or the powdery activated carbon to be measured, the surfactant and ion-exchanged water were mixed to obtain a dispersion, and the average particle diameter in the dispersion was measured by the penetration method by use of the laser scattering⋅laser diffraction/scattering particle diameter distribution analyzer (“MT3000II” manufactured by MicrotracBEL Corporation). A concentration of the powdery activated carbon in the dispersion was adjusted so as to be within the measurement concentration range of the analyzer. Polyoxyethylene (10) octylphenyl ether manufactured by Wako Pure Chemical Corporation was used as the surfactant during preparing the dispersion, and the surfactant was added in an appropriate amount that did not generate bubbles affecting the measurement. The analysis conditions are shown below.Number of measurements: onceMeasurement time: 30 secondsIndication of distribution: volumeParticle diameter classification: standardCalculation mode: MT3000IISolvent name: WATERUpper limit of measurement: 2000 μmLower limit of measurement: 0.021 μmResidue ratio: 0.00Passing material ratio: 0.00Set of residue ratio: disablementPermeability of particle: permeanceRefraction index of particle: 1.81Shape of particle: non-sphericalRefraction index of solvent: 1.333DV value: 0.0150 to 0.0700Permeability rate (TR): 0.700 to 0.950 The D50 value was adopted as the average particle diameter in the measurement result. <Metal Element Content of Raw Material Activated Carbon> First, calibration curves relating to a potassium element content and a calcium element content were prepared by use of the standard solution with known concentrations. Next, after the raw material activated carbon ground so as to have an average particle diameter of 20 μm or less was dried at 115±5° C. for 3 hours, 0.1 g of the raw material activated carbon was added to the specified container. To this container, 10 mL of nitric acid (60.0 to 62.0% by mass) was further added, and then, a pretreatment was performed at a temperature of 210° C. for 1 hour by use of the microwave sample pretreatment device (“MARS 6” manufactured by CEN Japan corporation) to decompose the raw material activated carbon. The obtained solution was taken off, and ion-exchanged water was added to the obtained solution to prepare 200 mL of a measurement solution. The measurement solution was analyzed by use of the multi-type ICP emission analyzer (“ICPE-9820” manufactured by Shimadzu Corporation). A concentration of each of the metal elements was determined by use of the obtained values and the prepared calibration curves, and a potassium element content and a calcium element content were obtained by use of the following mathematical formula. ⁢[Mathematical⁢⁢formula⁢⁢1]Metal⁢⁢element⁢⁢content⁢[%⁢⁢by⁢⁢mass]⁢=Metal⁢⁢element⁢⁢concentration⁢[mg⁢/⁢L]×1⁢0-3×0.2⁡[L]Mass⁢⁢of⁢⁢raw⁢⁢material⁢⁢activated⁢⁢carbon⁢[g]×1⁢0⁢0 <Pore Volume of Activated Carbon> A pore volume per mass of the activated carbon was measured by use of the mercury intrusion method pore volume measurement device (“MicroActive AutoPore V 9600” manufactured by Micromeritics instrument corporation). A mercury pressure of 0.10 psia (about 0.69 kPa) to 61000.00 psia (about 420580.19 kPa) was adopted. <JIS Hardness of Activated Carbon> JIS hardness of the activated carbon was measured according to JIS K1474. <MS Hardness of Activated Carbon> To a steel pot with an inside diameter of 25.4 mm and a length of 304.8 mm, 10 of steel balls with a diameter of 8 mm were added, about 5.0 g (weighed to the order of 0.1 g) of the dried activated carbon was further added, and the steel pot was sealed. The steel pot was attached to a measuring device, and was rotated at a speed of 25 rotations per minute for 40 minutes. Then, the content was taken off, the steel balls were removed from the content, and sieving was performed by use of a 50 mesh sieve (JIS standard). A ratio (unit: %) of mass of the sample left on the sieve to mass of the sample originally added to the steel pot was calculated according to the following mathematical formula, which was adopted as MS hardness. ⁢[Mathematical⁢⁢formula⁢⁢2]MS⁢⁢hardness⁢[%]⁢=Mass⁢⁢of⁢⁢sample⁢⁢left⁢⁢on⁢⁢sieve⁢[g]Mass⁢⁢of⁢⁢sample⁢⁢weighted⁢⁢before⁢⁢measurement⁢[g]×1⁢0⁢0 Example 1 (1) Preparation of Raw Material Activated Carbon Char prepared from coconut shell of the Philippine-grown coconut (a specific surface area: 370 m2/g) was activated at 850° C. by use of propane combustion gas and water vapor (total water vapor partial pressure: 35%) in a rotary kiln, the obtained product was sized by use of a 10 to 30 mesh sieve (JIS standard), and raw material activated carbon having a specific surface area of 1141 m2/g was obtained. (2) Preparation of Activated Carbon The obtained raw material activated carbon (600 g) was added to 2120 mL of hydrochloric acid (0.3 N), washed by boiling for 20 minutes, sufficiently washed with ion-exchanged water so as to obtain a pH of 5 to 7, and dried in a natural convection constant-temperature dryer set at 115±5° C. for 4 hours. The potassium element content of the obtained raw material activated carbon after the acid-washing was 0.0% by mass. Next, an aqueous solution of calcium nitrate (23 g of calcium nitrate tetrahydrate, 117 g of ion-exchanged water) was sprayed to 500 g of the obtained activated carbon, and then, the sprayed activated carbon was dried in the natural convection constant-temperature dryer set at 115±5° C. for 5 to 7 hours. The calcium element content of the obtained activated carbon containing calcium element was 0.8% by mass. Subsequently, 450 g of the obtained activated carbon containing calcium element was put in a fluidized furnace, a mixed gas having a water vapor partial pressure of 16%, a carbon dioxide partial pressure of 12% and a nitrogen partial pressure of 72% was supplied to the fluidized furnace at a gas total pressure of 1 atm and a flow rate of 108.4 L/minute, and activation was performed under a condition of an activation temperature of 920° C. so as to obtain an activation yield of 18.5%. A packing density of the obtained activated product was measured according to JIS K1474, 1800 mL of hydrochloric acid (1 N) was added to 410 mL (in terms of volume) of the activated product, and the activated product was washed with heating for 1 hour, sufficiently washed with ion-exchanged water so as to obtain a pH of 5 to 7, and dried at 115±5° C. for 4 hours to obtain activated carbon. The physical properties of the obtained activated carbon are shown in Table 1. Example 2 Activated carbon was obtained in the same manner as in Example 1 except that an activation yield was 33.0%. The physical properties of the obtained activated carbon were shown in Table 1. Example 3 Activated carbon was obtained in the same manner as in Example 1 except that an activation yield was 39.5%. The physical properties of the obtained activated carbon were shown in Table 1. Example 4 Raw material activated carbon (500 g) obtained in the same manner as in Example 1 was immersed in an aqueous solution of calcium nitrate (55.1 g of calcium nitrate tetrahydrate, 1125 g of ion-exchanged water), stirring was performed at a room temperature for 6 hours, filtering was performed, and then, drying was performed in a natural convection constant-temperature dryer set at 115±5° C. for 5 to 7 hours. The potassium element content and calcium element content of the obtained activated carbon containing calcium element were 0.4% by mass and 0.9% by mass, respectively. Activated carbon was obtained in the same manner as in Example 1 except that the activated carbon containing calcium element was activated so as to obtain an activation yield of 26.0%. The physical properties of the obtained activated carbon were shown in Table 1. Example 5 Raw material activated carbon (500 g) obtained in the same manner as in Example 1 was immersed in an aqueous solution of calcium chloride (26.9 g of calcium chloride, 1125 g of ion-exchanged water), stirring was performed at a room temperature for 6 hours, filtering was performed, and then, drying was performed in a natural convection constant-temperature dryer set at 115±5° C. for 5 to 7 hours. The potassium element content and calcium element content of the obtained activated carbon containing calcium element were 0.3% by mass and 1.1% by mass, respectively. Activated carbon was obtained in the same manner as in Example 1 except that the activated carbon containing calcium element was activated so as to obtain an activation yield of 33.2%. The physical properties of the obtained activated carbon were shown in Table 1. Example 6 Activated carbon was obtained in the same manner as in Example 1 except that an activation yield was 9.1%. The physical properties of the obtained activated carbon were shown in Table 1. Example 7 Activated carbon was obtained in the same manner as in Example 1 except that an activation yield was 45.2%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 1 Bituminous coal having a weak caking property and a button index of 1 measured according to the crucible expansion test method of JIS M 8801 6 and bituminous coal having a slightly caking property and a button index of 0.5 were mixed in a mass ratio of 3:7. Next, to 100 parts by mass of this obtained mixture, 20 parts by mass of a strongly caking coal having a button index of 9 was added, and mixing and grinding were performed by use of a ball mill. The obtained ground product was filled into a container with a diameter of 4 cm and a length of 15 cm by use of a pressure molding machine, and pressure molding was performed at 100° C. under a pressure of 280 kg/cm2. The obtained pressure molded product was crushed with a jaw crusher and sized in a particle diameter of 0.1 to 2.0 mm. This sized product was put in an external heating type rotary kiln, and heated to 300° C. under an oxidizing gas atmosphere, and the temperature was maintained for 2 hours. Then, the obtained product was heated to 650° C. under a reducing gas atmosphere, and cooled to obtain a carbonized product. This carbonized product (75 g) was put in a fluidized furnace, a mixed gas having a water vapor partial pressure of 16%, a carbon dioxide partial pressure of 12% and a nitrogen partial pressure of 72% was supplied at a gas total pressure of 1 atm and a flow rate of 21.7 L/minute to the furnace, and activation was performed under a condition of an activation temperature of 950° C. so as to obtain an activation yield of 50.0%. As to the obtained activated product, a measurement of a packing density, acid-washing, water washing and drying were performed in the same manner as in Example 1 to obtain activated carbon. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 2 Activated carbon was obtained in the same manner as in Example 1 except that an activation yield was 81.9%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 3 Activated carbon was obtained in the same manner as in Example 1 except that an activation yield was 59.5%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 4 An aqueous solution of calcium nitrate (23 g of calcium nitrate tetrahydrate, 117 g of ion-exchanged water) was sprayed to raw material activated carbon and drying was performed in a natural convection constant-temperature dryer set at 115±5° C. for 5 to 7 hours, without performing the adjustment step of the potassium element content of the raw material activated carbon in Example 1. The potassium element content and the calcium element content of the obtained activated carbon containing calcium element were 0.7% by mass and 0.7% by mass, respectively. Activated carbon was obtained in the same manner as in Example 1 except that an activation yield was 80.4%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 5 Activated carbon was obtained in the same manner as in Comparative example 4 except that an activation yield was 57.0%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 6 Activated carbon was obtained in the same manner as in Comparative example 4 except that an activation yield was 36.8%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 7 Activated carbon was obtained in the same manner as in Comparative example 4 except that an activation yield was 30.4%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 8 Activated carbon was obtained in the same manner as in Comparative example 4 except that an activation yield was 18.2%. The physical properties of the obtained activated carbon were shown in Table 1. Comparative Example 9 A temperature of 700 g of a phenol resin was maintained at 300° C. for 2 hours in an external heating type rotary kiln, and the obtained product was heated to 650° C., and then cooled to obtain a carbonized product. This carbonized product (180 g) was put in a rotary kiln set at a temperature of 900° C., and activation was performed at a nitrogen flow amount of 5 L/minute and a water vapor flow amount of 180 g/hour for 6 hours. The physical properties of the obtained activated carbon were shown in Table 1. In order to evaluate decolorization performances of the activated carbon of Examples and Comparative examples, first, each of the activated carbon was ground so as to obtain an average particle diameter of 5 to 20 μm. Next, a sugar liquid decolorization performance and a soy sauce decolorization performance of each of the activated carbon of Examples and Comparative examples were measured by the procedure mentioned below. In addition, in order to evaluate a colorant decolorization performance, a colorant adsorption amount of each of the activated carbon of Examples and Comparative examples was measured by the procedure mentioned below. In this evaluation, the activated carbon before grinding was used. These results are shown in Table 1. <Sugar Liquid Decolorization Performance> A raw sugar (“soft brown sugar” manufactured by Mitsui Sugar Co., Ltd.) (350 g) and 300 mL of ion-exchanged water were mixed at a normal temperature to dissolve the raw sugar. Next, a pH of this aqueous solution of the raw sugar was adjusted to 6.5 to 7.5 with an aqueous solution of sodium hydroxide or hydrochloric acid having a concentration of 0.1 mol/L, and it was confirmed by use of the sugar concentration meter (“Pocket sugar concentration meter PAL-2” manufactured by Atago Co., Ltd.) whether the sugar concentration was 50.0% to obtain a raw sugar liquid. In a case where the sugar concentration was not 50.0%, the raw sugar or ion-exchanged water was added to adjust the sugar concentration to 50.0%, and then, the obtained liquid was used as the raw sugar liquid. Subsequently, 300 g of a granulated sugar (“granulated sugar” manufactured by Mitsui Sugar Co., Ltd.) and 300 mL of ion-exchanged water were stirred at a normal temperature to dissolve the granulated sugar. A pH was adjusted and a sugar concentration was confirmed in the same manner as the raw sugar liquid, thereby a purified sugar liquid was obtained. It was confirmed with a quartz cell (a light path length of 10 mm) by use of the ultraviolet-visible light spectrophotometer (“UV-1800” manufactured by Shimadzu Corporation) whether an absorbance at a wavelength of 420 nm of the raw sugar liquid was 0.75 to 0.78, and the raw sugar liquid was used as a sugar test liquid. Ion-exchanged water was used for zero point correction when the absorbance was measured. In a case where the measured absorbance value was higher than the above specified range (higher than 0.78), the purified sugar liquid was added to adjust the measured absorbance value to the above specified range, and the obtained liquid was used as a sugar test liquid. In contrast, in a case where the measured absorbance value was lower than the above specified range (lower than 0.75), the preparation was performed again by use of a raw sugar with another production lot, and the obtained liquid which had an absorbance falling within the above specified range was used as a sugar test liquid. A viscosity of the sugar test liquid at a temperature during a liquid phase treatment (50° C.) was 7 mPa·s. A powdery activated carbon to be measured was dried at 115±5° C. for 3 hours, and allowed to cool in a desiccator. After cooling, 0.092 g of the powdery activated carbon was weighed, and put in a 100 mL conical flask with a stopper part. To this flask, 50 mL of the sugar test liquid was added, shaking was performed at a shaking amplitude of 140 times/minute for 1 hour in a water bath set at 50±1° C., filtering was performed with a 5C filter paper, the first 15 mL of the filtrate was discarded, and the subsequent filtrate was used as a sample solution. In addition, the above procedure was performed without any powdery activated carbon, and the obtained filtrate was used as a blank liquid. Absorbance values at wavelengths of 420 nm and 750 nm of each liquid were measured, and a sugar liquid decolorization performance was calculated by use of the following formula. The purified sugar liquid was used for zero point correction when the absorbance values were measured. ⁢[Mathematical⁢⁢formula⁢⁢3]Sugar⁢⁢liquid⁢⁢decolorization⁢⁢performance⁢[%]⁢=[1-(absorbance⁢⁢at⁢⁢420⁢⁢nm⁢⁢of⁢⁢sample⁢⁢liquid)-(absorbance⁢⁢at⁢⁢750⁢⁢nm⁢⁢of⁢⁢sample⁢⁢liquid)(absorbance⁢⁢at⁢⁢420⁢⁢nm⁢⁢of⁢⁢blank⁢⁢liquid)-(absorbance⁢⁢at⁢⁢750⁢⁢nm⁢⁢of⁢⁢blank⁢⁢liquid)]×1⁢0⁢0 The sugar liquid decolorization performance was evaluated according to the following criteria.A: more than 50%B: 40% or more, 50% or lessC: 30% or more, less than 40%D: 20% or more, less than 30%E: less than 20% <Soy Sauce Decolorization Performance Measurement> Soy sauce (“Specially selected whole soybean soy sauce” manufactured by Kikkoman Corporation) was diluted about 10 times with ion-exchanged water to adjust an absorbance at a wavelength of 550 nm to 0.47 to 0.55, and the obtained liquid was used as a soy sauce test liquid. A viscosity of the soy sauce test liquid at a temperature during a liquid phase treatment (25° C.) was 2 mPa·s. For an absorbance measurement, a quartz cell (a light path length of 10 mm) was used, and the ultraviolet-visible light spectrophotometer (“UV-1800” manufactured by Shimadzu Corporation) was used. Ion-exchanged water was used for zero point correction when the absorbance values were measured. A powdery activated carbon to be measured was dried at 115±5° C. for 3 hours, and allowed to cool in a desiccator. After cooling, 0.20 g of the powdery activated carbon was weighed, and put in a 100 mL conical flask with a stopper part. To this flask, 40 mL of the soy sauce test liquid was added, shaking was performed at a shaking amplitude of 160 times/minute for 15 minutes in a water bath set at 25±1° C., filtering was performed with a 5C filter paper, the first 15 mL of the filtrate was discarded, and the subsequent filtrate was filtered again to use the obtained filtrate as a sample solution. In addition, the above procedure was performed without any powdery activated carbon, and the obtained filtrate was used as a blank liquid. An absorbance at a wavelength of 550 nm of each liquid was measured, and a soy sauce decolorization performance was calculated by use of the following formula. Ion-exchanged water was used for zero point correction when the absorbance values were measured. ⁢[Mathematical⁢⁢formula⁢⁢4]Soy⁢⁢sauce⁢⁢decolorization⁢⁢performance⁢[%]⁢=[1-(absorbance⁢⁢at⁢⁢550⁢⁢nm⁢⁢of⁢⁢sample⁢⁢liquid)(absorbance⁢⁢at⁢⁢550⁢⁢nm⁢⁢of⁢⁢blank⁢⁢liquid)]×100 The soy sauce decolorization performance was evaluated according to the following criteria.A: more than 90%B: 80% or more, 90% or lessC: 65% or more, less than 80%D: 55% or more, less than 65%E: less than 55% <Colorant Adsorption Amount> An aqueous solution of SPR having a concentration of 0.1% by mass was prepared by use of SPR and ion-exchanged water. A viscosity of the aqueous solution of SPR at a temperature during a liquid phase treatment (25° C.) was 2 mPa·s. The aqueous solution of SPR (20 mL) was added to 0.2 g of activated carbon obtained by sizing with a 10 to 30 mesh sieve (JIS standard) and drying in order to obtain a sample, and two samples were prepared. These samples were shaken at a shaking amplitude of 160 times/minute in a water bath set at 25±1° C. One sample was filtered with Minisart (pore diameter: 0.45 μm) after shaking for 90 minutes, the other sample was filtered with Minisart (pore diameter: 0.45 μm) after shaking for 24 hours, and each filtrate was used as a measurement sample. In addition, the above procedure was performed without any activated carbon, and the obtained filtrate was used as a blank liquid. Each measurement sample and the blank liquid were diluted about 100 times with ion-exchanged water, and absorbance at a wavelength of 520 nm of each liquid was measured. For the absorbance measurements, a quartz cell (a light path length of 10 mm) was used, and the ultraviolet-visible light spectrophotometer (“UV-1800” manufactured by Shimadzu Corporation) was used. A colorant adsorption amount (a SPR adsorption amount) was obtained by use of the following formula. The SPR adsorption amount after shaking for 24 hours was used as a SPR equilibrium adsorption amount. ⁢[Mathematical⁢⁢formula⁢⁢5]SPR⁢⁢adsorption⁢⁢amount⁢[mg⁢/⁢g]={20×0.11⁢0⁢0×[1-(absorbance⁢⁢at⁢⁢520⁢⁢nm⁢⁢of⁢⁢sample⁢⁢liquid)(absorbance⁢⁢at⁢⁢520⁢⁢nm⁢⁢of⁢⁢blank⁢⁢liquid)]×1000}0.2 In addition, from the SPR adsorption amount at a shaking time of 90 minutes and the SPR adsorption amount at a shaking time of 24 hours (the equilibrium adsorption amount), a SPR decolorization equilibrium arrival rate at a shaking time of 90 minutes was calculated by use of the following formula. The higher the decolorization equilibrium arrival rate is, the faster the adsorption rate is. ⁢[Mathematical⁢⁢formula⁢⁢6]SPR⁢⁢decolorization⁢⁢equilibrium⁢⁢arrival⁢⁢rate⁢[%]=SPR⁢⁢absorption⁢⁢amount⁢⁢(90⁢⁢minutes)⁡[mg⁢/⁢g]SPR⁢⁢absorption⁢⁢amount⁢⁢(24⁢⁢hours)⁡[mg⁢/⁢g]×100 TABLE 1SPRSPRequilibriumdecolorization10-10000300-1000adsorptionequilibriumActivationnm porenm poreJISMSSugar liquidSoy sauceamountarrival rateyieldvolumevolumehardnesshardnessdecolorizationdecolorization(24 hours)(90 minutes)[%][mL/g][mL/g][%][%]performanceperformance[mg/g][%]Example 118.51.450.3574.451.4AA98.690.2Example 233.01.130.2678.758.2AA99.660.0Example 339.50.940.2389.464.5BB98.759.8Example 426.01.190.2580.160.5BA99.657.8Example 533.21.120.2574.849.7BA99.658.2Example 69.11.640.4170.749.3AA99.692.4Example 745.20.800.2091.365.5BB99.643.4Comparative example 150.00.360.1296.032.0DE25.340.2Comparative example 281.90.380.0899.574.8DE32.541.6Comparative example 359.50.730.1994.668.9CC91.537.6Comparative example 480.40.270.0599.371.0EE21.743.7Comparative example 557.00.450.0895.567.4DE63.929.4Comparative example 636.80.650.1289.765.0DE91.739.3Comparative example 730.40.720.1382.864.2CD97.151.4Comparative example 818.20.830.1777.061.7CC99.352.9Comparative example 913.30.270.0197.076.4EE48.450.9 As shown in Table 1, in cases where the activated carbon obtained in Examples 1 to 7 was used, high decolorization performances regarding the sugar liquid and soy sauce were exhibited. In contrast, in cases where the activated carbon obtained in Comparative example 1-9 was used, which had a low pore volume at a pore diameter of 10 to 10000 nm and/or 300 to 1000 nm, the sugar liquid decolorization performances and the soy sauce decolorization performances were extremely lower than those of Examples. In addition, in cases where the activated carbon of the present invention obtained in Examples 1 to 7 was used, the SPR equilibrium adsorption amounts were high and the SPR decolorization equilibrium arrival rates in a short time of 90 minutes were high, which exhibit that the activated carbon of the present invention was excellent in the SPR adsorption amount and the SPR adsorption rate. In contrast, as to the activated carbon of Comparative examples 1, 2, 4, 5 and 9, the SPR equilibrium adsorption amounts were extremely lower than those of Examples, and the SPR decolorization equilibrium arrival rates were extremely lower than those of Examples. In addition, as to the activated carbon of Comparative examples 3 and 6, it was exhibited that the SPR equilibrium adsorption amounts were sufficient, but the SPR decolorization equilibrium arrival rates were lower than those of Examples, and that the adsorption rates were lower than those of Examples. Furthermore, the activated carbon obtained in Examples 1 to 7 had the high JIS hardness of 70% or more and the high MS hardness of 45% or more, in addition to the excellent sugar liquid decolorization performances and the excellent soy sauce decolorization performances as well as the excellent SPR equilibrium adsorption amounts and the excellent SPR decolorization equilibrium arrival rates. INDUSTRIAL APPLICABILITY The activated carbon of the present invention is useful for liquid phase treatment applications, since it has the excellent decolorization performances and the excellent decolorization equilibrium arrival rates. In addition, it can be preferably used as activated carbon for treating various liquid phases, since it exhibits the high decolorization performances in a liquid phase having a relatively high viscosity such as the sugar liquid as well as a liquid phase having a low viscosity such as soy sauce. Furthermore, the activated carbon of the present invention having the high hardness can be preferably used for a liquid phase treatment requiring such hardness such as a treatment in an adsorption column or an adsorption tower. In addition, the activated carbon of the present invention can be produced by the simple method of changing a balance of amounts of the two metal elements and performing activation in the production process, which is industrially useful.
53,695
11857944
DETAILED DESCRIPTION Metal organic resins, composite materials composed of the metal organic resins, and anion exchange columns packed with the composite materials are provided. Also provided are methods of using the composite materials to remove metal anions from a sample, methods of using the metal organic resins as fluorescence sensor for detecting metal anions in a sample, and methods of making the composite materials. The metal organic resin (MORs) comprise protonated, amine-functionalized metal organic frameworks with associated counter anions, such as halide anions. In some embodiments of the MORs the halide counter ions are chloride ions. Metal-organic frameworks (MOFs) are a class of hybrid materials comprising inorganic nodes and organic linkers. More specifically, the MOFs have a structure comprising inorganic (e.g., metal) nodes, also referred to as centers, coordinated via organic molecular linkers to form a highly connected porous network. In some embodiments the MORs are Zr4+MORs of the UiO-66 family, comprising hexa-ZrIV(Zr6) nodes with tetratopic linkers. The metal organic frameworks include those having Zr6O4(OH)4nodes and protonated, amine-functionalized 1,4-benzenedicarboxylate (BDC) linkers. Such MORs can be represented by the formula: [Zr6O4(OH)4(NH3+-BDC)6]X−6, where X is a monovalent anion, such as a halide ion and are referred to herein as MOR-1. The structure of these MORs is shown inFIG.1, where the counter anion is Cl−. Alternative formulations of the structure comprise oxo and/or aquo ligands in place of some or all of the hydroxo ligands. Other metal organic frameworks that can be protonated to provide protonated, amine-functionalized metal organic frameworks include [Ti8O8(OH)4(H2N-BDC)6], [Al4(OH)2(OCH3)4(H2N-BDC)3], [Al3OCl(H2O)2(H2N- BDC)3], [AlOH(H2N-BDC)]. The metal organic frameworks also include include those having Zr6O4(OH)8(H2O)4nodes and 2-((pyridin-1-ium-2-ylmethyl)ammonio)teraphthalate (H2PATP) linkers. Such MORs can be represented by the formula: [Zr6O4(OH)8(H2O)4(H2PATP)4]X−6, where X is a monovalent anion, such as a halide ion, and are referred to herein as MOR-2. The structure of these MORs is shown inFIG.23, where the counter anion is Cl−. Alternative formulations of the structure comprise oxo and/or aquo ligands in place of some or all of the hydroxo ligands. The counter anions of the MORs are able to undergo anion exchange with various metal ions, including heavy metal ions, and, therefore, the composite materials have applications in metal anion remediation. (As used herein the term “metal ion” refers to ions composed only of metal elements and anions that include metal elements and other elements, such as oxygen.) The organic polymer that coats the MOR particles provides the composite materials with increased mechanical strength and increases the average particle size and density of the material (relative to a material comprising the MOR particles without the encapsulating coating), making the coated MOR particles less prone to form a fine powder in aqueous solution. As a result, particles of the composite materials can be formed with particle sizes and mechanical strengths that are able to withstand high water pressures and allow for a continuous flow of a liquid sample through an anion exchange column containing the particles of composite materials. Alginic acid polymers are examples of organic polymers that can be used to encapsulate the MOR particles. Other examples include polyvinyl alkyl resins, such as polyvinyl butyl resins, and polyalkylacrylates and polyalkylmethacrylates, such as polymethylmethacrylates. The coating on the MOR particles can be thin, so that it does not substantially affect the sorption capacity of the coated MOR particles relative to the uncoated MOR particles. By way of illustration, some embodiment of the polymer coated MOR particles, the organic polymer coating makes up no greater than 5 weight percent of the coated MOR particles. This includes embodiments of the polymer coated MOR particles that comprise no greater than 3 weight percent polymer coating and further includes embodiments of the polymer coated MOR particles that comprise no greater than 2 weight percent polymer coating. Chromide ions and selenide ions, and other anions (e.g., oxide anions) containing chromium and selenium, are examples of ions that can be removed from a sample via anion exchange using the composite materials. The MORs are able to remove dichromate and chromate ions. The removal of these ions is advantageous because they are toxic. As illustrated in the Examples, both the composite materials and the MORs from which the composite material are made have high sorption capacities for dichromate and/or chromate ions and are able to absorb these species rapidly. For example, sorption capacities of at least 250 mg/g, including at least 300 mg/g can be achieved for dichromate ions and sorption capacities of at least 200 mg/g, including at least 240 mg/g, can be achieved for chromate ions. (Methods for measuring the sorption capacity are described in the Examples.) Other anions that can be removed from a sample using the composite materials include precious metal-containing anions, such as precious metal-containing halide ions, such as PtCl4+and PdCl42−. MnO4−anions, ClO4−anions, and radioactive anions such as TcO4−and ReO4−can also be selectively removed from a sample using the composite materials. Pentavalent arsenic (As(V)) and trivalent arsenic (As(III)) anions can also be removed. Some embodiments of the MORs, including those represented by the formula provided above, have a high selectivity for undergoing anion exchange with chromium and selenium ions, relative to other anions, such as Cl−, NO3−, Br−and SO4−. Therefore, chromium and selenium ions can be effectively remediated from a sample comprising one or more of those other anions, even when these other anions are present in excess. The composite materials can be used to remove anion-exchangeable metal anions (targeted anions) from a sample by contacting the composite materials with a sample, such as an aqueous solution, comprising the targeted metal anions under conditions and for a time sufficient to allow the targeted metal anions to undergo anion exchange with the counter anions of the MORs, and then separating the sample from the composite materials. Because the composite materials are mechanically robust and can be formed as particles with tailored sizes and size distributions, they are well suited for use as packing materials for ion exchange columns. A basic embodiment of an anion exchange column comprises a column characterized by a length, an input opening for introducing a sample into the column at one end, and an output opening for releasing a sample from the column at another end. The column is packed with a packing material that includes the composite material as an anion-exchange material. The packing material may consist of, or consist essentially of, particles of the composite material. However, the particles of composite material may also be mixed with particles of another material, such as sand or other inert granular materials. The composite materials are able to remove metal anions from samples having a wide range of pH values, including pH values in the range from 1-8. This is significant because many industries, such as the mining industry, produce waste water samples that are highly acidic—having pH values of less than 7. For example, the composite materials can be used to remediate samples having pH values in the range from 1 to 4. Even under highly acidic conditions the composite materials are very effective at removing metal anions, such as chromium and selenium anions from a sample. Under less acidic conditions, the effectiveness of the composite materials is even greater. By way of illustration, in some embodiments of the method of removing targeted metal anions (for example, Cr- of Se-containing anions) from a sample, at least 80% of the targeted metal anions are removed. This includes embodiments in which at least 90%, at least 95%, and at least 98% (for example 95 to 99%) of the targeted metal ions are removed. Thus, the composite materials are able to remove metal ions to levels below those required by environmental regulations in the United States and Europe. In addition, the materials are inexpensive to synthesize and can be regenerated after undergoing remediative anion-exchange, allowing the anion-exchange columns to be reused multiple times with only a small—if any—loss in capacity. Industrial wastewaters that can be remediated using the composite materials include those generated by the leather tanning, cement, electroplating, nuclear power, petroleum refining, mining, and dyes industries. In addition, the composite materials can be used to remediate agricultural wastewater (e.g., farm run-off), contaminated drinking water, or contaminated water from natural bodies of water. Because the metal organic resins are so effective at removing target ions, only a small quantity of the composite material need be included in an anion exchange column. Thus, in some embodiments of the anion exchange columns, the packing material in the column comprises no more than 5 percent of the composite material by weight (wt. %), with the remainder comprising another material—typically an inert granular material, such as sand. This includes embodiments in which the packing material in the column comprises no more than 3 wt. % composite material and further includes embodiments in which the packing material in the column comprises no more than 1 wt. % composite material. The composite materials can be made by different methods, as illustrated in the Examples. One method uses a reflux reaction to provide a rapid, high yield, relatively inexpensive, and environmentally friendly synthesis. In this method, a metal halide salt and 2 amino-terephthalic acid (NH2—H2BDC) are refluxed in an acidic aqueous solution at an elevated temperature (that is, a temperature above room temperature) to induce a reflux reaction between the halide salt and the 2 amino-terephthalic acid to form a fine particulate suspension of an amine functionalized metal organic resin. By way of illustration, in order to make MOR-1, or an MOR having the same formula as MOR-1, but with oxo ligands, aquo ligands, or a combination thereof in place of some or all of the hydroxo ligands, ZrCl4salt can be used in the reflux synthesis. Using this procedure, a high yield (e.g., 70% yield) of the metal organic resin can be obtained very quickly; with the maximum yield of the metal organic resin being achieved in an hour or less. Once the metal organic resin particle suspension has been formed, an alkali-metal alginate salt, such as sodium alginate, is added to the suspension where it is converted into alginic acid. The alginic acid forms a water insoluble alginic acid polymer coating on the metal organic resin particles, which then flocculate in the solution. These polymer coated organic resin particles can then be precipitated from the solution and isolated using, for example, filtration or centrifugation. The resulting particulate material can then be treated with an acid, such as a strong inorganic acid (e.g., HCl) to dissolve the remaining NH2—H2BDC ligands and to protonate the amino functional groups of the material. An example of this reflux synthesis-based process is illustrated in detail in Example 2. In another method of making the composite materials, an aqueous solution of an alkali metal alginate salt and the metal organic resin particles is formed. In solution, one or more monolayers of alginate-saturated water form a coating on the metal organic resin particles. An alkali earth metal halide salt is then added to the aqueous solution, whereby a water-insoluble coating of an alkali earth metal alginate forms around the metal organic resin particles. These particles can then be removed from the aqueous solution and reacted with a hydrogen halide to protonate the amine-functionalized metal organic frameworks and convert the alkali earth metal alginate coating into an alginic acid polymer coating. An example of this synthesis process is illustrated in detail in Example 1. In yet another method of making a composite material, an aqueous solution of an alkali metal alginate salt and the metal organic resin particles is formed. In solution, one or more monolayers of alginate-saturated water form a coating on the metal organic resin particles. A hydrogen halide is then added to the solution, whereby the hydrogen halide reacts with the alginate and the metal organic resin particles to protonate the amine-functionalized metal organic frameworks and to form an alginic acid polymer coating around the organic resin particles. An example of this synthesis process is illustrated in detail in Example 1. The polymer coated metal organic resin particles formed by these methods typically have a mean particle size in the range from about 100 nm to about 500 nm, including from about 100 nm to about 300 nm. The particles are microporous, typically having mean pore sizes in the range from about 3 Å to about 12 Å. Although mean particle and pore sizes outside of these ranges can be also be achieved. Another aspect of this invention is a method for making the metal organic resin designated above as MOR-2 and the use of this, and other amine-functionalized metal organic resins, in fluorescence-based sensors for the detection of metal ions. As illustrated in Example 3, MOR-2 can be synthesized via a solvothermal reaction of a zinc halide salt with 2-((pyridine-2-ylmethyl)amino)terephthalic acid (H2PATP) ligand. Different metal halide salts can be used in the solvothermal reaction to form a MOR having the structure of MOR-2, but with different metals, such as Hf4+, at the metal nodes. The metal organic resin can be treated with a halide acid, such as HCl, to protonate its pyridine and amine moieties, thereby providing pyridinium and ammonium functional groups charge balanced by halide anions. Embodiments of the metal organic resins, including MOR-1, MOR-2 and variations of these in which oxo ligands, aquo ligands, or a combination thereof replace some or all of the hydroxo ligands, have absorption bands in the ultraviolet region of the electromagnetic spectrum and produce fluorescence emission upon irradiation with ultraviolet light. This fluorescence emission is quenched by the sorption of metal anions by the metal organic resin. Thus, the photophysical properties of the metal organic resins can be harnessed to detect metal ions, including heavy metal ions, in a sample. In a method of detecting metal ions in a sample, the metal organic resin is contacted with a sample comprising the metal ions and metal ions in the sample undergo anion exchange with the counter anions of the metal organic resin. The metal organic resin is then irradiated with ultraviolet radiation and the resulting fluorescence spectrum is measured. Because the intensity of the fluorescence emission decreases and/or the fluorescence emissions peaks shift with increasing absorbed metal ion concentration, the intensity and/or fluorescence emission profile of the measured fluorescence can be compared to the fluorescence intensity and fluorescence emission profile of a standard sample that includes the metal organic resin without the metal ions to quantify the concentration of metal ions in the sample. The metal organic resin can be contacted with the sample by, for example, adding it into the sample or by passing the sample over the metal organic resin. The latter process can be achieve by providing polymer coated metal organic resin particles, as described in detail herein, in an anion exchange column. Example 3 illustrates the use of an MOR-2 based fluorescence sensor for detecting both chromate and dichromate metal ions in solution. Other metal anions that can be detected with the fluorescence emission sensors base on this and other MORs described herein include, but are not limited to, [PdCl4]2−and [PdCl4]2−. Example 1 This example illustrates an anion exchange composite material based on a protonated amine-functionalized metal organic framework, called Metal Organic Resin-1 (MOR-1), and alginic acid (HA). Additional details regarding the composite material and its use in the capture of hexavalent chromium can be found in Rapti et al.,Chem. Sci.,2016, 7, 2427-2436 and its Supplementary Information, the entire contents of which is incorporated herein by reference. The composite material can be synthesized via a simple and inexpensive method. The sorbent shows an exceptional capability to rapidly and selectively sorb Cr(VI) under a variety of conditions and in the presence of several competitive ions. The composite sorbent can be successfully utilized in an ion-exchange column. Remarkably, an ion exchange column with only 1% wt. MOR-1-HA and 99% wt. sand (an inert and inexpensive material) is capable of reducing moderate and trace Cr(VI) concentrations well below the acceptable limits for water (effluent Cr concentrations ≤1 ppb). Additionally, this column is highly efficient in removing Se (in the form of SeO32−and SeO42−), with the effluent Se concentrations being ≤1 ppb (˜50 times smaller than the USA Environmental Protection Agency (EPA)-defined limit for Se). The anion exchange composite material is based on the [Zr6O4(OH)4(NH3+-BDC)6]Cl6MOR (MOR-1) and alginic acid (HA) polymer (NH2—H2BDC=2-amino-terephthalic acid). The MOR is the analogue of the UiO-66 material containing NH3+functional groups (FIG.1). Through detailed batch studies, the highly efficient and selective anion exchange properties of the composite for Cr2O72−ions are revealed. The successful use of MORs, in the form of MOR-HA composite, in an ion exchange column are demonstrated. The stationary phase in this column is a mixture of MOR-1-HA composite and sand (an inert and inexpensive material). Remarkably, a column with MOR-1-HA/sand stationary phase containing only 1% w/w MOR-1-HA was found to be capable of reducing moderate and trace levels of Cr(VI) well below the allowed safe levels (EU and USA-EPA limits for total Cr in water are 50 and 100 ppb respectively), despite the presence of large excess of competitive ions. Furthermore, the column could be easily regenerated and reused several times with almost no loss of its capacity. The efficiency and relatively low cost of this ion exchange column makes it attractive for use in the decontamination of wide variety of Cr(VI)-containing wastes. Zr4+MORs of the UiO-66 family are useful materials for sorption applications due to their high surface areas, easy incorporation of functional groups and hydrolytic-thermal stability. However, as mentioned above, as-prepared MORs are fine powders and are not suitable for practical ion exchange applications. This is particularly true for UiO-66 type MORs usually isolated as nanoparticles. In fact, as-prepared UiO-66 type MORs form fine suspensions in water and cannot be easily separated from it. The latter is a major drawback for the application of such materials as stationary phases in columns. To this end, a modified alginate encapsulation method was applied to prepare UiO-66 type-composite materials. This encapsulation method involves: a) addition of the sorbent to be encapsulated (i.e. the MOR) into a water solution of sodium alginate (SA), so that one or more monolayers of alginate-saturated water cover each particle of the sorbent (FIG.2, top panel); b) addition of CaCl2) to the SA-sorbent suspension so that the monolayer is immediately converted to calcium alginate (CA), forming a water-insoluble polymer shell around the sorbent particulates (MOR-1-CA) (FIG.2, middle panel); and c) treating the MOR-1-CA composite with hydrochloric acid to produce [Zr6O4(OH)4(NH3+-BDC)6]Cl6-HA (MOR-1-HA) (HA=alginic acid) (FIG.2, bottom panel). Note that only 4% wt. of alginate (i.e., alginate:MOR-1 mass ratio used was ˜0.04) was sufficient for the composite to be formed and thus, the MOR was not encapsulated by thick HA particles that would hinder the diffusion of ions into the MOR pores. Alternatively, the MOR-1-HA composite could be prepared directly by adding HCl into a suspension of MOR-1 in SA water solution. The composite material could be also synthesized by heating a mixture of ZrCl4+NH2—H2BDC in water-acetic acid solution under reflux conditions for a few hours, which results in the formation of a fine MOR suspension. Adding SA+HCl to the suspension produces the MOR-HA composite in high yield. This synthetic method is inexpensive and environmentally friendly, since no organic solvent is used (except for a relatively small quantity of the inexpensive acetic acid). EDS data for the MOR-1-HA sample indicate a Zr:Cl ratio of ˜1, which is in agreement with the protonation of the six amino groups of the Zr6cluster and the presence of six Cl−counter ions. Thermogravimetric analysis (TGA) was used to determine the lattice water molecules (21 water molecules). Powder X-ray diffraction (PXRD) data indicated that the MOR retained its structure in the composite form (FIG.3A). The Brunauer-Emmett-Teller (BET) surface area of the MOR-1-HA was 1004 m2/g (FIG.3B), a value within the range of surface areas found for amino-functionalized UiO-66 materials. Detailed Cr(VI) sorption studies for MOR-1-HA were performed at low pH (pH ˜3), in order to imitate the usual acidic conditions of Cr(VI) industrial waste (for example tannery wastewater). Under such conditions, the predominant Cr(VI) species were Cr2O72−(with some contribution from HCrO4−at dilute solutions). The ion exchange process can be described with the following equation: [Zr6⁢O4⁢(OH)4⁢(NH3⁢BDC)6]⁢Cl6-HA+3⁢Cr2⁢O72-→250⁢C,10⁢minH2⁢O⁡(pH∼3)[Zr6⁢O4⁢(OH)4⁢(NH3⁢BDC)6]⁢(Cr2⁢O7)3-HA+6⁢Cl-(1) EDS data revealed no Cl−anions in the Cr2O72−-loaded material. ICP-MS, EDS and UV-Vis data (see below) indicated a Zr:Cr ratio of 0.9-1.2, close to the expected one (theoretical Zr:Cr=1, considering the insertion of 3 Cr2O72−per Zr6cluster). PXRD data revealed that the MOR structure was retained after the incorporation of the dichromate anions (FIG.3A). There was a drastic decrease, however, in the BET surface area for the Cr2O72−-loaded material, indicating the pores of the structure were filled by Cr2O72−ions. Specifically, after the insertion of Cr2O72−anions, the surface area for MOR-1-HA dropped from ˜1000 to 36 m2/g (FIG.3B). The presence of Cr(VI) species in the exchanged MOR-1-HA material was further shown using infrared (IR) and X-ray photoelectron spectroscopy (XPS). The IR spectrum (FIG.3C) of the exchanged material showed the existence of a peak at ˜924 cm−1(not present in the spectra of pristine MOR1-HA material) assigned to the anti-symmetric CrO3-stretch (for more detailed interpretation of IR data see also below). XPS data revealed the presence of Cr2p1/2and Cr2p3/2peaks, with their main components corresponding to binding energies of 588.1 and 579.3 eV (FIG.3D). These binding energies are consistent with those of Cr(VI). To gain further insight into the Cr2O72−sorption properties of the MOR-1-HA material, batch studies were first performed. By immersing the MOR-1-HA material in a Cr2O72−solution, the removal of Cr2O72−was accomplished very quickly (within a few minutes), something that could be visually observed by the decolorization of the solution and color change of the sorbent. The Cr2O72−ion exchange equilibrium data for MOR-1-HA composite are shown inFIG.4A. The description of the data can be provided by the Langmuir model. The sorption capacity for MOR-1-HA was 242(17) mg Cr2O72−/g of sorbent (or 242/0.96=252 mg/g of MOR-1), which exceeded those reported for other metal organic materials (60-100 mg/g) and most of known inorganic and organic anion exchangers. This sorption capacity was consistent with the absorption of ˜2.7(3) moles of Cr2O72−per formula unit of the MOR, which is close to the expected maximum sorption capacity of the material (3.0 mol per formula unit). The affinity of the MOR-1-HA for dichromate could be expressed in terms of the distribution coefficient Kd, which is given by the equation Kd=V[C0-Cf)/Cf]m, where C0and Cfare the initial and equilibrium concentrations of Cr2O72−(ppm), Vis the volume (ml) of the testing solution, and m is the amount of the ion exchanger (g) used in the experiment. Values for Kdequal to 104L/g and above this value are considered excellent. The maximum KdCr2O7values for the MOR-1-HA material, obtained from the batch equilibrium studies, were in the range 1.2-5.5×104L/g (FIG.4B), which revealed the exceptional affinity of the materials for dichromate ions. It should be noted that MOR-1-HA samples loaded with Cr2O72−could be easily regenerated by treating them with concentrated HCl solutions (1-4 M). The PXRD pattern of the regenerated MOF-1-HA was almost identical with that of the as prepared MOR-1-HA material. The regenerated MOR-1-HA showed similar dichromate exchange capacity (220-230 mg/g) to that of the pristine material (more detailed regeneration studies were performed for the ion exchange columns, see below). The kinetics of the Cr2O72−exchange of the MOR-1-HA composite were also studied. The results indicated that the capture of Cr2O72−by the composite was remarkably fast (FIG.4C). Within only 1 min of solution/composite contact, ˜94.2% of the initial Cr amount (C=10.4 ppm, pH˜3) was removed by the solution. After 3 min of solution/composite contact, the Cr(VI) ion exchange almost reached its equilibrium with 97.5% removal capacity. These kinetic data can be fitted with the first order Lagergren equation (FIG.4C, inset). From these data, it is clear that the ordered highly porous structure of MOR-1-HA facilitating the diffusion of ions in and out of pores, and the presence of protonated amino-functional groups strongly interacting with the Cr2O72−anions, resulted in a sorbent with exceptionally rapid sorption kinetics. Although the Cr(VI) ion exchange studies for MOR-1-HA were performed at pH ˜3 in order to evaluate the capability of the sorbent to operate under acidic conditions usually present in industrial waste, the composite material was found to be capable of absorbing Cr(VI) from solutions of a relatively wide pH range (1-8),FIG.4D. Specifically, it showed 91-98% total Cr removal capacities in pH˜3-8, whereas it retained high Cr removal capability, even under highly acidic conditions (80.5 and 90.2% removal capacities at pH ˜1 and 2 respectively). Cr2O72−-bearing industrial effluent also was found to contain a number of competitive anions, such as Cl−, NO3−, Br−and SO42−, in high concentrations. Thus, competitive Cr2O72−/Cl−, Cr2O72−/Br−, Cr2O72−/NO3−and Cr2O72−/SO42−sorption experiments for MOR-1-HA were performed. An exceptional ability of MOR-1-HA to absorb Cr2O72−(initial concentration=54 ppm, pH ˜3) almost quantitatively (81.6-97.6% dichromate removal capacity) and very high KdCr2O7(4.4×103-4×104L/g) in the presence of tremendous (up to 1000-fold) excess of Cl−, Br−, or NO3−was observed, which indicates very high selectivity of MOR-1-HA for Cr2O72−against these anions. SO42−as a bivalent anion is expected to be a stronger competitor than monovalent anions for dichromate anion exchange. Nevertheless, even with relatively large (20-80-fold) excess of SO42−, MOR-1-HA retained a very good Cr2O72−removal efficiency (40-68%) and relatively high KdCr2O7values (up to 2.1×103mL/g). Comparative Batch Ion-Exchange Studies For comparison, batch Cr2O72−sorption studies (at pH˜3) were performed for: a) protonated MOR-1 [Zr6O4(OH)4(NH3+-BDC)6]Cl6(MOR-1 treated with HCl 4 M); b) non-protonated MOR-1 [Zr6O4(OH)4(NH2-BDC)6] (prepared without adding acid in the reaction mixture); and c) UiO-66 MOF ([Zr6O4(OH)4(BDC)6])-HA composite. The results indicated that the sorption capacities of protonated MOR-1 and non-protonated MOR-1 were similar to each other (247±10 and 267±23 mg/g respectively) and also close to that of the MOR-1-HA composite, whereas the sorption capacity (129±18 mg/g) of UiO-66-HA was almost half of that for MOR-1-HA. The efficiency, however, of protonated MOR-1 and MOR-1-HA for sorption of dichromate in relatively low initial concentrations, as revealed by the KdCr2O7values, was significantly higher than that of non-protonated MOR-1 and UiO-66-HA. Specifically, UiO-66-HA and non-protonated MOR-1 materials showed KdCr2O7values of 2.3 and 6.5×103L/g, respectively, for initial dichromate concentration of ˜21.6 ppm (FIG.9), which were one order of magnitude less than those (˜5.5×104L/g) for MOR-1-HA and protonated MOR-1 samples (FIG.9). As the above results revealed, both protonated and non-protonated MOR-1 materials displayed similar maximum sorption capacities, since at the acidic environment the NH2-groups will be eventually protonated and the inserted Cl−can be exchanged by dichromate anions. However, at low initial Cr(VI) concentrations, the materials pre-treated with acid (i.e., protonated MOR-1 and MOR-1-HA) were much more effective for the sorption of Cr(VI), as revealed by their much higher Kdvalues compared to that of MOR-1 used without any pre-treatment (non-protonated MOR-1). Presumably, the pre-existence of exchangeable Cl−anions in the protonated materials enhances the kinetics of the Cr(VI) sorption, whereas the Cr(VI) sorption by the non-protonated MOR is a slower two-step process involving first protonation of the amine-sites/insertion of Cl— anions and then exchange of Cl−by Cr(VI) species. The enhancement of sorption kinetics was particularly important in the case of low initial Cr(VI) concentrations, which were not as effective as the high Cr(VI) levels at shifting the ion-exchange equilibrium towards the Cr(VI)-containing material. The above explanation was supported by a kinetic study of the Cr2O72−exchange of the non-protonated MOR-1 using a relatively low initial dichromate concentration (21.6 ppm, pH˜3). The results showed that after 1 min of solution/MOR contact only 24% Cr2O72−removal was achieved, whereas even after 60 min of reaction significant amount of dichromate remained in the solution (˜76% Cr2O72−removal). These data are in contrast with the corresponding kinetic results for MOR-1-HA, which indicated almost quantitative sorption of dichromate anions within only 1 min of solution/composite contact (FIG.7). Furthermore, fitting of the kinetic data for the non-protonated MOR-1 with the Lagergren's first order equation revealed a rate constant of 0.55±0.14 min−1, which is six-times smaller than that for the Cr2O72−sorption by MOR-1-HA. This improvement of kinetics via the protonation of the material is key for its substantially higher column sorption efficiency compared to that of non-protonated sorbent. The next step in these investigations was the study of the column Cr(VI) sorption properties of MOR-1-HA material. At this point, it should be mentioned that efforts to use as prepared MOR-1 (even after mixing it with inert materials such as sand) in columns were unsuccessful, since MOR-1 forms fine suspensions in water that pass through the column. Thus, only MOR-1-HA composite could be successfully employed for column sorption studies. The stationary phase in the columns was a mixture of MOR-1-HA and sand, a common inexpensive and inert material typically used in columns. The use of such mixtures instead of the pure composite was found to have several advantages: a) the pieces of the composite material were immobilized (not disturbed and moved by the water flow) and separated by particles of sand, thus ensuring a continuous water flow through the column; b) the pressure exerted by water on the composite was reduced, since part of this pressure was absorbed by the second material (sand); and c) mixing the composite material with a very low cost material such as sand would be economically attractive. It should be noted that no clogging of MOR-1-HA/sand columns was observed after passing several litres of solutions through them. Remarkably, it was found that stationary phases containing only 1% wt. of MOR-1-HA and 99% wt. sand were very effective for the removal of either high or low concentration Cr(VI) from aqueous solutions of various compositions. It could be seen that highly concentrated dichromate solution (C˜1080 ppm, pH˜3) was decolorized after passing it through the MOR-1-HA/sand column. Also, the stationary phase changed color from cream white to orange(red)-brown after the sorption of significant amount of Cr2O72−anions. The sorbent could be easily regenerated by washing it with ˜4 M HCl (FIG.4B). The regeneration could be visually observed by the restoration of the cream white color of the initial MOR-1-HA/sand stationary phase. Detailed column sorption studies were performed with Cr2O72−solutions of low and trace levels, which cannot be treated with common methods such as precipitation. Specifically, column sorption of a solution (pH˜3) of dichromate anions with concentration of 6 ppm resulted in almost no Cr(VI) species (removal capacities ≥98% and total Cr concentrations ≤47 ppb, i.e. below the EU and USA-EPA defined limit for total Cr) for 80 bed volumes (Bed volume=[bed height (cm) cross-sectional area (cm2)] mL) of the effluent (FIG.5A). After regeneration, a breakthrough curve almost identical to that of the first run was obtained, whereas only a small decrease (˜3 bed volumes) of the breakthrough capacity was observed for a third run of the column (FIG.5A). Column sorption studies have been also conducted with dichromate solutions (pH˜3, C=7 ppm) containing 100-fold excess of each of Cl−, Br−and NO3. Still, the ion exchange column showed significant breakthrough capacity (˜43 bed volumes), which was retained exactly the same after its regeneration. Because of the excellent Cr2O72−-column sorption properties described above, it was decided to examine the applicability of MOR-1-HA/sand column for remediation of real world water samples intentionally contaminated by trace concentrations of Cr2O72−. Specifically, the performance of this ion exchange column was tested for the decontamination of natural spring water solutions (with the pH of the solution adjusted to ˜3), to which trace levels of Cr2O72−(total Cr concentration analyzed with ICP-MS ˜450 ppb) were added. Note that the tested water solutions contained 27, 28 and 305-fold excess of SO42−, NO3−and Cl−anions, compared to the initial concentration of dichromate anions. The results indicated that at least 21 samples (bed volumes) collected after running the column three times (with regeneration of the column after each run) contained total Cr in a concentration ≤1 ppb, i.e. well below the allowed total Cr concentration in water,FIG.5B. Finally, it should be mentioned that no Zr was found in the effluent samples, thus excluding MOR leaching from the column. The MOR-1-HA sorbent was also capable of absorbing Se species. Thus, the MOR-1-HA/sand column was very effective for the sorption of SeO32−in trace levels. Specifically, after passing a solution of SeO32−(initial concentration=736 ppb, pH˜3) through the column, at least 7 samples (bed volumes) contained Se in concentrations well below the USA-EPA limit (50 ppb) for Se in water (FIG.6). In addition, batch SeO42−sorption studies were performed. The selenate ion-exchange equilibrium data at two different pH values are shown inFIG.7. These data could be fitted with the Langmuir or Langmuir-Freundlich models. The maximum sorption capacity was found to be 65(3) and 135(22) mg/g at pH˜7.7 and 2.8, respectively. These values correspond to 1.1(1) (pH˜7.7) and 2.3(4) (pH˜2.8) moles of selenate per formula of MOR-1. Thus, the selenate sorption capacity of the material was close to its theoretical maximum value (3 selenate moles per formula of MOR-1) only at pH ˜2.8. Presumably, all amino-groups remain protonated at the low pH value and thus, the material contains more anions (counter ions) to be exchanged by SeO42−. The sorbent was particularly effective for the removal of selenate in moderate and trace concentrations. It could be seen that the % SeO42−removal capacities were 90-98% for initial concentrations of 2.2-35.7 ppm at pH˜7.7 (FIG.8A), whereas the corresponding values at pH˜2.8 were 98-99.9% (FIG.8B). The maximum Kdvalues for selenate removal were 5×104and 6.7×105mL/g at pH ˜7.7 and 2.8, respectively. (FIGS.8(C) and8(D)The above indicate significantly higher affinity of the sorbent for selenate removal at low pH. Thus, the sorbent may be particularly effective for removing Se species from mining wastewater, which is usually acidic. Mechanism of Cr(VI)-Sorption To provide an explanation for the remarkable selectivity of the protonated amino functionalized material for dichromate anions, the interaction energies of Cr2O72−, HOCrO3−, Cl Br, NO3−, HOSO3−and SO42−anions with the [Zr6O4(OH)4(NH3+-BDC)6]Cl6-HA (MOR-1-HA) was calculated, represented by the simple anilinium Ar—NH3+cation, employing DFT methods. The calculated interaction energies along with selected structural parameters of the respective associations are compiled in Table 1. TABLE 1Interaction energies, IE (in kcal/mol) and selected structural parameters(bond lengths in Å, bond angles in degrees) for the Ar—NH3+···A(A = Cl−, Br−, NO3−, HOSO3−, HOCrO3−, Cr2O72−)associations in aqueous solutions calculatedby the wB97XD/Def2-TZVPPD/PCM computational protocol.AnionIER(O···H—N)R(N—H)<O···H—NCl−11.71.9421.070176.1Br−9.92.1391.061176.0NO3−13.31.5971.071175.7HOSO3−12.01.6601.055166.62.4781.020110.3HOCrO3−12.61.6721.052159.42.1421.024127.9Cr2O72−15.51.6371.055163.1 Interestingly, the calculations indicated that SO42−abstracts a NH3+proton from the Ar—NH3+cation yielding HOSO3−anions via an exothermic process (exothermicity of −26.7 kcal/mol). Thus, in Cr2O72−/SO42−competition ion-exchange reactions with MOR-1-HA, the actual competitor for dichromate exchange was HOSO3−. The latter as a monovalent anion is expected to be less competitive than SO42−for Cr(VI) sorption. This can be one of the reasons for the relatively high selectivity of MOR-1-HA for Cr(VI) vs. SO42−, which was experimentally observed. Among the anions studied, the Cr2O72−anion shows the strongest interactions (15.6 kcal/mol). However, the estimated values of the interaction energies for the Ar—NH3+. . . A (A=Cl−, Br−, NO3−, HOSO3−, HOCrO3−, Cr2O72−) associations could not fully explain the high selectivity of the material under study towards Cr2O72−anions and the limited selectivity for the rest of the competitive anions in the series. Therefore, this selectivity could be due to much stronger interactions between the Cr2O72−anions and the Ar—NH3+cation. Experimental IR-data indicated that the amine-deformation band was significantly red-shifted for MOR-1-HA@Cr(VI) (1565 cm−1) compared to that for pristine MOR-1-HA (1590 cm−1) and as prepared MOR-1 (1580 cm−1) samples (FIG.3C). Furthermore, the IR peak at 1620 cm−1(assigned to ring stretching vibration) in the spectrum of MOR-1-HA@Cr(VI), which was also present in the IR spectrum of non-protonated MOR, but it is not shown or is of very weak intensity in the spectrum of MOR-1-HA, is indicative of NH2rather than NH3+-containing phenyl ring. In addition, the solid-state UV-Vis spectrum for MOR-1-HA@Cr(VI) revealed a broad feature (around 500 nm) in the visible region (not shown in the spectrum of as-prepared MOR-1 and MOR-1-HA), which may be due to charge transfer from the electron rich NH2-BDC2−ligand to the Cr(VI) species (LMCT). The above support strong NH2—Cr(VI) interactions in MOR-1-HA@Cr(VI). This suggests the transformation of dichromate to CrVIO3species, which in turn forms the tetrahedral [(Ar—NH2)CrO3] complex. To test this hypothesis, the equilibrium geometry of the [(Ar—NH2)CrO3] complex in aqueous solution was optimized at the wB97XD/Def2-TZVPPD level of theory,FIGS.10A-10B. The formation of such a complex may be promoted by the significant acidity of anilinium ion (the pKa of the anilinium ion is lower than 4.6). Anilinium may interact with the bridging O atom (nucleophilic center) of Cr2O72−, enforcing the rupture of a O—Cr bridging bond with concomitant coordination of aniline to CrO3fragment and formation of HOCrO3−anion. The latter subsequently re-equilibrates to produce Cr2O72−: Ar—NH3++Cr2O72−→(Ar—NH2)CrO3+HOCrO3−(4) 2HOCrO3−→Cr2O72−+H2O  (5) The condensation of the HOCrO3−anion to form Cr2O72−is particularly an enthalpy driven reaction with a dimerization constant K=159 at standard conditions. The formation of the (Ar—NH2)CrO3complex is an almost thermoneutral process, the endothermicity found to be 1.8 kcal/mol. The presence of six NH3+functional groups per Zr6cluster affords six moles of the (Ar—NH2)CrO3complex, thus accounting well for the experimentally observed sorption of ˜3 moles of Cr2O72−per formula unit of the MOR (FIGS.10A-10B). Oxochromium(VI)-amine complexes are well-known compounds and many of them have been used as oxidants in organic synthesis. The brick-red color of the oxochromium(VI)-amine complexes can account well for the change of color from cream white to orange(red)-brown of the MOR-1-HA sorbent observed experimentally. The regeneration of the MOR-1-HA columns by treating them with concentrated HCl solutions (1.2-4 M) can be easily explained by the acidic hydrolysis of the (Ar—NH2)CrO3complex [(Ar—NH2)CrO3]+H2O→Ar-NH3++HOCrO3−with concomitant dimerization of HOCrO3−to Cr2O72−(FIGS.10A-10B). The exothermicity of the hydrolysis is predicted to be 30.5 kcal/mol at the wB97XD/Def2-TZVPPD level. The estimated binding energy of the aniline ligand with the CrO3moiety was 34.4 kcal/mol, while the negative natural atomic charge on the coordinated N donor atom renders the N atom susceptible to electrophilic attack by the H+ions, which is transformed to ammonium NH3+salt, thus regenerating the MOR-1-HA column. Experimental Section Synthesis of MOR-1 ZrCl4(0.625 gr, 2.7 mmol) and NH2—H2BDC (0.679 gr, 3.75 mmol) were dissolved in 75 mL DMF and 5 mL HCl in a jar. The jar was sealed and placed in an oven operated at 120° C., remained undisturbed at this temperature for 20 h, and then was allowed to cool at room temperature. White powder of MOR-1 was isolated by filtration and dried in the air. Yield: 1 g. Synthesis of MOR-1-HA Composite Method A. 0.1 g of sodium alginate was dissolved in 200 mL of warm water, and the solution was allowed to cool. To the alginate solution 0.1 g of MOR-1 was added. 0.1 g of CaCl2was then added into the alginate-MOR-1 suspension with continuous stirring. The composite MOR-1-CA immediately precipitated and was then isolated by filtration, washed with water and acetone and vacuum dried. To isolate the MOR-1-HA material, MOR-1-CA (0.2 g) was treated with 4 M HCl (50 mL) for ˜1 h. Yield: 0.85 g. Method B. This method is similar to Method A, with the difference that HCl solution (final concentration ˜4 M) was added to the alginate-MOR-1 suspension instead of CaCl2). Prior to the batch and column sorption studies, the MOR-1-HA was further treated with 4 M HCl to ensure full protonation of the MOR-1. Method C. ZrCl4(0.625 gr, 2.7 mmol) and NH2—H2BDC (0.679 gr, 3.75 mmol) were dissolved in 40 mL H2O and 10 mL CH3COOH in a round-bottom flask. The solution was heated under reflux conditions for ˜2 h. A fine suspension of the MOR-1 formed and was allowed to cool. Then, SA solution (80 mL of 0.05% SA water solution) was added to the suspension of MOR-1. Precipitation of the MOR-1-HA was immediately observed. To complete the precipitation, HCl was added (final concentration ˜4 M). MOR-1-HA was isolated by filtration, washed with water and acetone and vacuum dried. Yield ˜1 g. Thermal analysis data (in combination with EDS) indicated the formula [Zr6(OH)4O4(NH3C8O4H3)6]Cl6.21H2O-HA. Preparation of the Column 50 mg of MOR-1-HA composite and 5 g of sand (50-70 mesh) was mixed in a mortar and pestle and filled in a glass column. Batch Ion-Exchange Studies A typical ion-exchange experiment of MOR-1-HA with Cr2O72−was the following: In a solution of K2Cr2O7(0.4 mmol, 117 mg) in water (10 mL, pH ˜3), compound MOR-1-HA (0.04 mmol, 100 mg) was added as a solid. The mixture was kept under magnetic stirring for ≈1 h. Then, the polycrystalline material, which had orange(red)-brown color, was isolated by filtration, washed several times with water and acetone and dried in air. The Cr(VI) uptake from solutions of various concentrations was studied by the batch method at V:m ˜1000 mL/g, room temperature and 1 h contact. These data were used to determine Cr(VI) sorption isotherms. UV-Vis was used for analysis of dichromate solutions with concentration ≥1 ppm. The solutions with Cr(VI) content less than 1 ppm were analyzed with ICP-MS. The competitive and variable pH ion exchange experiments were also carried out with the batch method at V:m ratio (1000) mL/g, room temperature and 1 h contact. To determine the sorption kinetics, Cr(VI) ion-exchange experiments of various reaction times (1-60 min) have been performed. For each experiment, a 10 mL sample of Cr2O72−solution (initial dichromate concentration=21.6 ppm, pH˜3) was added to each vial and the mixtures were kept under magnetic stirring for the designated reaction times. The suspensions from the various reactions were filtrated and the resulting solutions were analyzed for their chromium content with ICP-MS. Batch sorption studies for Se-containing solutions were performed similarly as for Cr(VI). Column Ion-Exchange Studies Several bed volumes of the solution were passed through the column and collected at the bottom in glass vials. The solutions with Cr2O72−concentration ≥1 ppm were analyzed with UV-Vis, whereas the Cr content of those with smaller concentration was determined with ICP-MS. Column sorption studies for Se-containing solution were performed similarly as for Cr(VI). Physical Measurements PXRD diffraction patterns were recorded on a Bruker D8 Advance X-ray diffractometer (CuKa radiation, λ=1.5418 Å). Energy Dispersive Spectroscopy (EDS) were performed using a JEOL JSM-6400V scanning electron microscope (SEM) equipped with a Tracor Northern EDS detector. Data acquisition was performed with an accelerating voltage of 25 kV and 40 s accumulation time. Thermogravimetric analysis (TGA) was carried out with a Shimatzu TGA 50. Samples (10±0.5 mg) were placed in a quartz crucible. X-ray photoelectron spectroscopy was performed on a Perkin Elmer Phi 5400 ESCA system equipped with a Mg Kα x-ray source. Samples were analyzed at pressures between 10−9and 10−8Torr with a pass energy of 29.35 eV and a take-off angle of 45°. All peaks were referred to the signature C1speak for adventitious carbon at 284.6 eV. The peaks were fitted by using the software XPSPEAK41. UV/vis Cr(VI) solution spectra were obtained on a Shimadzu 1200 PC in the wavelength range of 200-800 nm. IR spectra were recorded on KBr pellets in the 4000-400 cm−1range using a Perkin-Elmer Spectrum GX spectrometer. Gas sorption isotherms were measured on a Quantachrome NOVA 3200e volumetric analyzer. The solutions with Cr(VI) content less than 1 ppm were analyzed with Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) using a computer-controlled Thermo Fisher X Series II Inductively Coupled Plasma Mass Spectrometer with a quadruple set-up equipped with Collision Cell Technology. Example 2 This example reports a new synthetic method for the isolation of purely microporous and highly crystalline MOR-1 and its composite form MOR-1-HA, which involves acidified water as a solvent and is completed within an hour. (The structure of (protonated) MOR-1 is shown inFIG.11.) The obtained materials show exceptional capability to absorb hexavalent chromium under a diverse range of experimental conditions, including pH of the solution and the presence of competitive ions. Importantly, the composite MOR-1-HA is particularly suitable to be used in an ion-exchange column, showing excellent Cr(VI) absorption properties. In addition, for the first time it is shown that the MOR-1-HA column is efficient for the decontamination of industrial (chrome plating) Cr(VI) wastewater samples. Considering the relatively low cost, and the fast and environmentally friendly synthesis method of the MOR-1-HA reported here, the MOR-1-HA column seems promising for real-world applications in the field of environmental remediation. Results and Discussion Synthesis of MOR-1 and MOR-1-HA Composite In Example 1, MOR-1-HA composite was prepared via a three-step procedure involving: a) synthesis of MOR-1 via a solvothermal reaction in DMF/HCl solution; b) encapsulation of MOR-1 by calcium alginate (CA) resulting in a MOR-1-CA composite; and c) formation of MOR-1-HA material by treatment of MOR-1-CA with HCl acid. Alternatively, the MOR-1-HA could be prepared by addition of HCl acid in a water suspension of MOR-1 and sodium alginate (SA). As mentioned above, the material would be more attractive for applications if it could be synthesized with a fast and inexpensive synthesis method involving minimal quantities of organic solvents. Recently, it was shown that a UiO-66-amino functionalized type metal organic framework could be isolated with a reflux reaction of almost equimolar Zr(NO3)4and NH2—H2BDC (2-amino-terephthalic acid) in water-acetic acid solutions. (Z. Hu, Y. Peng, Z. Kang, Y. Qian, and D. Zhao,Inorg. Chem.,2015, 54, 4862.) However, the reported material showed structural characteristics that differ from those of the compound isolated from the reaction with DMF (J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga and K. P. Lillerud,J. Am. Chem. Soc.,2008, 130, 13850; M. J. Katz, Z. J. Brown, Y. J. Colon, P. W. Siu, K. A. Scheidt, R. Q. Snurr, J. T. Hupp and O. K. Farha,Chem. Commun.,2013, 49, 9449; M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen, U. Olsbye, M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino and K. P. Lillerud,Chem. Mater.,2010, 22, 6632). It was thus challenging to isolate hydrothermally a UiO-66-amino functionalized material (i.e. MOR-1) with the same features as those of the well-known material prepared with solvothermal reaction. This synthesis was attempted by modifying the reported reflux synthesis method (FIG.12). Thus, the same Zr4+source (i.e. ZrCl4) and a ligand to metal salt molar ratio (˜1.4) equal to those used in the solvothermal synthesis of UiO-66-NH2BDC were employed, with the difference that in our synthesis the solvent was a mixture of water and acetic acid (25 v/v % acetic acid). This reaction resulted in a fine suspension of the MOR which was formed in less than 1 h. The product of this reaction, isolated via centrifugation, contained impurities, probably some amount of unreacted organic ligand. Indeed, treating the product with HCl acid solution, which can dissolve the NH2—H2BDC ligand, resulted in the isolation of pure MOR-1 in ˜70% yield. After the method for the isolation of the high quality UiO-66 amino-functionalized material was established, the next step was the preparation of the MOR-1-HA composite. Fortunately, the isolation of the composite did not involve the separation process via centrifugation followed for MOR-1, which is time-consuming and not attractive for large scale synthesis of materials. The isolation of materials forming colloidal solutions requires the use of flocculation agent that causes agglomeration of the particles thus simplifying the separation process. Such a flocculation agent could be sodium alginate, which in an acidic environment is transformed to alginic acid. The latter forms an insoluble polymer shell around MOR particulates, resulting in the precipitation-easy separation of the solid from the solution (FIG.12). Indeed, by adding sodium alginate to the MOR-1 water-acetic acid suspension, the MOR-1-HA was readily precipitated and could be isolated via simple filtration. Only a small amount of sodium alginate was required for the isolation of the composite material, and thus the composite showed almost identical properties to those of the pristine MOR material. Specifically, the composite isolated contained alginic acid in an amount up to 2.1% wt. (see experimental section, supporting information). The obtained product was further treated with HCl acid to dissolve the unreacted NH2—H2BDC ligand and complete the protonation of the amino-functional groups of the material. Studies for the formation of the material vs. the reaction time were also performed. The results indicated that a) a significant amount of MOR-1-HA was formed within only 5 min; and b) an hour of reflux reaction was enough to achieve the maximum possible yield for the isolation of the MOR-1-HA composite material. Characterization of MOR-1 and MOR-HA Materials Field Emission-Scanning electronic microscopy (FE-EM) images showed that both the MOR-1 and MOR-1-HA materials were composed of aggregated polyhedral-shape nanoparticles with size ˜150-300 nm. (FIG.13). High-magnification images revealed that the nanoparticles of MOR-1 were spongy with relatively large voids, whereas those of MOR-1-HA contained significantly smaller pores in their surface. Presumably, this was due to the fact that a thin layer of alginic acid covered the large pores in the surface of MOR-1 nanoparticles, thus creating the denser nanoparticles of the composite. Therefore, MOR-1-HA isolated in a relatively compact form was much less dispersed in water, and thus could be successfully utilized in columns (see below). Note that no clear shape and size of nanoparticles could be observed by SEM studies of MOR-1 isolated from the solvothermal reaction in DMF and the corresponding MOR-1-HA material. Thus, in this case, differences in morphology between MOR-1 and MOR-1-HA particles could not be observed. Here, for the first time, the clear differences between MOR-1 and MOR-1-HA materials could be visualized, which may explain their different capability to form or not fine suspension in water. Powder X-ray diffraction (PXRD) studies indicated that MOR-1 isolated with the 1 h reflux reaction after its purification with HCl acid shows the typical structure of UiO-66 type materials (FIG.14A. Elemental (C,H,N), energy-dispersive spectroscopy (EDS) (indicating Zr:Cl molar ratio ˜1) and thermal analysis (TGA) data indicated the formula [Zr6O4(OH)4(NH3+-BDC)6]Cl6.35H2O for MOR-1. PXRD (FIG.14A) and EDS (revealing Zr:Cl molar ratio-1) data for the composite sample confirmed its close similarity to the pristine MOR-1 solid. TGA data were also used for the determination of the water content of composite material (˜19 water molecules). Nitrogen physisorption measurements recorded at 77 K for the activated MOR-1 and MOR-1-HA revealed type-I adsorption isotherms, characteristic of microporous solids (FIG.14B). The Brunauer-Emmett-Teller (BET) surface areas of the MOR-1 and MOR-1-HA were determined to be 1097 (Langmuir 1638 m2/g) and 1182 (Langmuir 1670 m2/g) m2/g respectively. These values fall within the range of surface areas found for amino-functionalized UiO-66 type materials prepared with solvothermal reactions (J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga and K. P. Lillerud,J. Am. Chem. Soc.,2008, 130, 13850; M. J. Katz, Z. J. Brown, Y. J. Colon, P. W. Siu, K. A. Scheidt, R. Q. Snurr, J. T. Hupp and O. K. Farha,Chem. Commun.,2013, 49, 9449; M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen, U. Olsbye, M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino and K. P. Lillerud,Chem. Mater.,2010, 22, 6632.) CO2adsorption isotherms at 1 bar and 273 K indicated a sorption capacity of ˜4.4 mmol/g for both samples. Analysis of CO2adsorption data with the density function theory (DFT) suggested that both MOR-1 and MOR-1-HA had a microporous network with pore size in the range of 8-9 Å. Interestingly, the MOR-1 and MOR-1-HA polymers presented here showed significantly higher surface area and CO2sorption capacity compared to those (BET=833 m2/g, Langmuir=1073 m2/g; CO2sorption capacity=2.8 mmol/g at 273 K) for the reported UiO-66 amino-functionalized compound prepared by a hydrothermal reaction. (Z. Hu, Y. Peng, Z. Kang, Y. Qian, and D. Zhao,Inorg. Chem.,2015, 54, 4862.) Furthermore, the type-I shape for the isotherms of MOR-1 and MOR-1-HA indicated a predominantly microporous structure, whereas the reported UiO-66-NH2BDC solid isolated hydrothermally showed a combination of type-I and type-IV isotherms revealing the existence of both micro- and mesoporosity. Thus, here is proposed for the first time a hydrothermal synthesis approach that yields amino-functionalized UiO-66-type materials with same characteristics as those found in the UiO-66-NH2BDC compound prepared with typical solvothermal reaction. Isolation and Characterization of Cr(VI)-Containing Material The isolation of the Cr(VI)-loaded composite material [MOR-1-HA@Cr(VI)] was achieved by treating it with a Cr2O72−water solution for ˜1 h. An anion-exchange reaction is taking place represented by the following equation: [Zr6O4(OH)4(NH3+-BDC)6]Cl6-HA+3Cr2O72−→ [Zr6O4(OH)4(NH3+-BDC)6](Cr2O7)3-HA+6Cl−(1) EDS analysis showed no Cl in the Cr(VI)-exchanged material. Furthermore, analytical data from ICP-MS, EDS and UV-Vis spectroscopy indicated a Zr:Cr molar ratio of ˜1, consistent with the replacement of 6 Cl−by 3 Cr2O72−anions. PXRD data of MOR-1-HA@Cr(VI) indicated that the structure of the UiO-66 type framework was preserved after the ion-exchange process (FIG.14A). The presence of Cr(VI) ions was also evidenced by IR, which showed a characteristic peak at 924 cm−1attributed to the anti-symmetric CrVIO3-stretch. Furthermore, XPS data showed the presence of Cr2p1/2and Cr2p3/2core-level signals. The main components of these peaks corresponded to binding energies (588.1 and 579.2 eV), which are characteristic of Cr in the (VI) valence state. The insertion of Cr(VI) species into the pores was also demonstrated by the substantially smaller BET surface area of Cr(VI) exchanged samples compared to that of pristine composite material. Thus, after the Cr(VI) exchange process, the surface area dropped from 1182 m2/g for MOR-1-HA to 298 m2/g for MOR-1-HA@Cr(VI) (FIG.14B). Finally, FE-SEM studies indicated that the nanoparticles of MOR-1-HA@Cr(VI) retained the polyhedral shape of the MOR-1-HA particles (FIG.15). However, the MOR-1-HA@Cr(VI) nanoparticles contained some defects and relatively large pores in their surface, which presumably resulted from the ion-exchange process. Batch Ion Exchange Studies Ion-Exchange Isotherm Data Cr(VI) equilibrium ion-exchange studies for MOR-1-HA were performed at pH˜3, in order to reproduce the usual acidic conditions of Cr(VI)-bearing industrial wastewater. Under such conditions, the main form of Cr(VI) was Cr2O72−, with some contribution from HCrO4−at dilute Cr(VI) acidic solutions. Fitting of the isotherm data with the Langmuir equation (FIG.16) revealed a maximum sorption capacity of 280±19 mg Cr2O72/g of MOR-1-HA, which corresponded to a capacity of 286.0±19.4 Cr2O72−mg/g of MOR-1, considering that the composite contains ˜97.9% MOR-1. This sorption capacity was consistent with the absorption of 3.1±0.2 moles of Cr2O72−per formula unit of the MOR ([Zr6O4(OH)4(NH3+-BDC)6]Cl6·xH2O, x˜19 for the MOR component of the composite), which was close to its maximum sorption capacity (3 moles per formula unit). Fitting of the isotherm data could also be done using the Freundlich model. The high efficiency of the composite for dichromate sorption was also revealed by the values of the distribution coefficient Kdcalculated by the following equation: Kd=V[C0-Cf)/Cf]m(2) where C0and Cfare the initial and equilibrium concentrations of Cr2O72−(ppm) respectively, Vis the volume (ml) of the testing solution and m is the amount of the ion exchanger (g) used in the experiment. The maximum KdCr2O7values obtained from the batch equilibrium studies are in the range 4.5×104-1.2×105mL/g. Such values are considered excellent and indicate the exceptional affinity of the material for Cr(VI). The material could be also regenerated and reused for Cr(VI) sorption, as indicated by the column sorption studies (see below). The ion-exchange studies focused on the composite and not on the pristine MOR, since only the composite form is suitable for column ion-exchange (see below). For comparison, however, the isotherm Cr2O72−sorption data for the MOR-1 material has also been determined). The results revealed a maximum sorption capacity of 321±16 Cr2O72−mg/g of MOR-1, slightly higher than that found for the composite. Thus, the presence of alginic acid in such a small quantity (˜2% wt.) in the composite resulted in a minor differentiation of the ion-exchange properties of the metal organic material. Kinetic studies. The kinetics of the Cr2O72−absorption by MOR-1-HA were also investigated.FIG.17Ashows UV-Vis data from the kinetic experiments (initial dichromate concentration=21.2 ppm, pH˜3).FIG.17Bshows % Total Cr removal by MOR-1-HA vs. time (min). The results indicated that this sorption process was quite fast, with ˜85.5% of the initial Cr2O72−content (C0=21.2 ppm, pH˜3) removed within only 1 min MOR-1-HA/solution contact. After 3 min, the Cr2O72−removal percentage increased to 97.2%, whereas the ion exchange reached its equilibrium within 9 min, and more than 99% Cr2O72−sorption was observed. The kinetic data could be roughly fitted with the Lagergren's first order equation: qt=qe[1−exp(−KLt)]  (3) where qe=the amount (mg/g) of metal ion absorbed in equilibrium and KL=the Lagergren or first-order rate constant (Fitting parameters: qe=20.6±0.4 mg/g, KL=1.9±0.3 min−1). The rapid Cr(VI) sorption kinetics observed for MOR-1-HA resulted from its highly porous structure, allowing fast diffusion of ions within the pores and the strong Cr(VI)-amine groups interactions. Variable pH studies. Although more focus was placed on the Cr(VI) sorption under acidic conditions that are usually observed in industrial waste, also studied was the Cr(VI) ion exchange by MOR-1-HA in a relatively wide pH range (1-8). The results indicated that the material was capable of absorbing Cr(VI) from highly acidic to alkaline solutions (FIG.18). In particular, it showed 97-99.6% Cr(VI) removal capacities in the pH range 2-8 (initial total chromium concentration=10.2 ppm), whereas even at pH˜1, MOR-1-HA displays a high Cr(VI) removal capacity (˜82%). Selectivity Studies Competitive Cr2O72−/Cl−, Cr2O72−/Br−, Cr2O72−/NO3−and Cr2O72−/SO42−sorption experiments were also performed for MOR-1-HA. Cl−, Br−and NO3−ions had no effect on the dichromate (initial concentration 0.25 mM, pH˜3) sorption by MOR-1-HA. Thus, high dichromate removal capacities ˜98-99% and excellent KdCr2O7˜1.0-2.2×105mL/g were observed even in the presence of a large excess of Cl−, Br−and NO3−ions (Cl−, Br−, NO3−concentration=2.5 mM). SO42−, as a divalent cation, was expected to be a stronger competitor for dichromate ion exchange. Still, even in the presence of ten-fold excess of SO42−ions (concentration=2.5 mM), a significant dichromate removal capacity (˜55%) was obtained. The selectivity of MOR-1-HA for dichromate anions was explained on the basis of strong O3CrVI. . . NH2interactions. Column Ion Exchange Studies Initial check of the sorbents. The next step was the study of the column ion-exchange properties of the materials. The stationary phase in the columns prepared was a mixture of the sorbent and sand, an inexpensive and inert material. The use of such a mixture instead of the pure sorbent material ensured a continuous flow of the water through the column, since a) the sorbent particles were immobilized and separated by sand pieces; and b) the pressure exerted by water was absorbed mainly by the sand, thus keeping the sorbent particles intact. Columns containing a sorbent to sand mass ratio of 1:100 proved to be highly effective for Cr(VI) sorption and also showed a stable and relatively fast water flow (see below and reference 3). That columns with high efficiency for Cr(VI) removal contained only a small quantity of the sorbent (˜1% by weight), and the main component (99% by weight) of the stationary phase is sand, an abundant and very low cost material, are both economically attractive features. Prior to the breakthrough sorption experiments, MOR-1 and MOR-1-HA/sand columns (with a sorbent to sand mass ratio of 1:100) were tested to determine the capability of the sorbent to remain fixed in the stationary phase, as well as the flow rate for the column. SEM studies, presented above, indicated that the MOR-1 particles were porous and spongy, and thus it was expected to be easily dispersed in water. Indeed, MOR-1 (even mixed with an inert material as sand) was gradually removed from the column, since it formed a fine water suspension. Thus, clearly MOR-1 was not suitable to be used for column sorption applications. The composite material, however, was composed of relatively compact MOR particles partially coated by the insoluble alginic acid shell (see SEM images above), and thus it had limited capability to form suspensions in water. As a result, the effluents flowing out of the composite/sand columns were clear solutions. Flow rate for the columns should be also taken into account. Sorbents that result in column clogging are not desirable for applications. Thus, the flow rate of a MOR-1-HA/sand column was investigated. The water flow through the MOR-1-HA/sand column was observed to be stable over several runs and relatively fast (1.2-1.4 mL/min). MOR-1-HA particles were of uniform (polyhedral) shape (FIG.14), and thus they could be distributed evenly in the column allowing a continuous and stable water flow. Thus, the MOR-1-HA/sand column seems promising in terms of immobilization of the sorbent in the stationary phase and flow rate. Determination of breakthrough curves and sorption capacity. Sorption experiments with the MOR-1-HA/sand(mass ratio 1:100) column and initial Cr2O72−concentration of 6.4 ppm (pH˜3) revealed that 97 bed volumes (Bed volume=bed height (cm)×cross sectional area (cm2)=3.5 mL) of the effluent samples (bed volumes) showed a total Cr content ≤30 ppb, significantly below the acceptable safety limits defined by the US EPA (100 ppb) and EU (50 ppb) (FIGS.19A and19B). The column could be regenerated by washing it with HCl acid solution (4M). The regeneration process could be visually observed by the decolorization of the (yellow-colored) Cr(VI)-loaded column. After regeneration, the column could be reused, showing only a small decrease (˜4) of bed volumes, with Cr content below the Cr safety limits. Even after a fifth run the column displayed a high number of bed volumes (84) with total Cr concentration ≤30 ppb. The breakthrough capacity Qb(mg) of this ion-exchange column could be determined by the equation: Qb=C0·Vb(4) where C0is the initial concentration of Cr2O72−(mg/L), and Vbis the volume (L) passed until the breakpoint concentration (usually defined as the maximum acceptable concentration of the contaminant). The numbers of bed volumes passed through the column until the break-point concentration (i.e., total Cr concentration ≤50 ppb) were 97, 93, 87, 92 and 84 for the 1st-5thcolumn runs, respectively. Thus, the Qbvalues for the different runs of the specific MOR-1-HA/sand column and Cr2O72−initial concentration of 6.4 ppm were calculated 2.17 (1strun), 2.08 (2ndrun), 1.95 (3rdrun), 2.06(4thrun) and 1.88 (5thrun) mg Cr2O72−(FIG.19). The effect of the initial Cr(VI) concentration on the breakthrough sorption capacity of this MOR-1-HA/sand column was also examined. It was observed that breakthrough capacities of 2.06-2.25 and 2.25-2.34 mg Cr2O72−were obtained for initial dichromate concentrations of 53.5 and 25.7 ppm, respectively. Thus, similar breakthrough capacity was observed independently of the initial Cr(VI) concentration, thus emphasizing the reproducible sorption results obtained with the MOR-1-HA/sand column. In addition, the performance of the MOR-1-HA/sand column was tested for the decontamination of solutions containing low Cr levels. However, these were above the safety limits. Thus, 1.1 L (˜315 bed volumes) of a solution with a total Cr concentration of 394 ppb (pH˜3) was passed through the MOR-1-HA/sand column. ICP-MS analysis for the Cr content of the effluents collected indicated that the Cr concentrations were 7-27 ppb (FIG.20), which was well below the EU and US EPA acceptable limits. These results indicated the exceptional capability of the MOR-1-HA/sand column to remediate water contaminated with extremely low Cr levels. Note that it is not easy to treat wastewater with quite low Cr concentrations (<1000 ppb) with common methods such as precipitation. Thus, the development of new technologies that are effective for such low Cr levels is particularly desirable. The performance of MOR-1-HA/sand column (MOR-1-HA to sand mass ratio=1/100), containing MOR-1-HA prepared with the reflux synthesis/SA addition, may be compared to that of the corresponding column with composite isolated from solvothermally prepared MOR-1. The latter displayed breakthrough capacity of 1.55-1.68 mg Cr2O72−(number of bed volume till the breakpoint concentration=74-80, 1 bed volume=3.5 mL, initial Cr2O72−concentration=6 ppm), lower than that (1.88-2.17 mg Cr2O72−for initial dichromate concentration of 6.4 ppm) of the column with MOR-1-HA isolated from reflux synthesis-SA addition. Thus, high quality MOR-1-HA could be prepared with a fast, low-cost and environmentally-friendly synthesis that, at the same time, showed improved column Cr(VI) sorption properties. Column Sorption of Chrome Plating Wastewater A common type of Cr(VI)-containing industrial waste is chrome plating wastewater. Such Cr(VI)-bearing water is generated by rinsing the plated parts upon their removal from the plating bath. It should be noted that the Cr(VI) concentration in metal plating effluents may vary from very high to moderate or low levels depending on the amount of water used in the rinsing step of the metal plating process. Thus, Cr(VI) concentrations greater than 1000 and lower than 10 ppm have been reported for metal plating waste. Encouraged by the above excellent column sorption results, it was decided to test the performance of the column for the removal of Cr(VI) from chrome plating wastewater. A metal plating company (located in Northern Greece) provided us with two different types of hexavalent chromium waste: Sample (A) contained dichromate ions in very high concentrations (4855 ppm, pH˜1.6); and sample (B) was a neutral pH solution with lower Cr(VI) content (analysis of the Cr(VI) concentration of this solution was done after adjusting its pH to ˜3, see below). Sample A was too concentrated to be treated with our laboratory-scale ion exchange columns. Thus, Cr(VI)-contaminated wastewater was prepared by diluting the original sample A to ˜54 ppm of Cr2O72−(pH˜3.5 after the dilution). The column was very efficient in decontaminating this wastewater, something that could be seen even with the naked eye. The breakthrough curves (FIG.21A) obtained from five column runs (with regeneration of the column after each run) indicated 13-14 bed volumes with total Cr concentration <50 ppb (EU defined acceptable Cr limit), and a breakthrough capacity of 2.44-2.63 mg Cr2O72−(FIG.21B). These breakthrough capacity values were similar to those obtained for the experiments with the laboratory prepared dichromate solutions. Also studied were the column ion-exchange properties with sample B supplied by the metal plating company. Prior the sorption experiments, the pH of sample B was adjusted to ˜3 in order to enable the UV-Vis analysis of Cr(VI) as Cr2O72−anions (at neutral pH there is equilibrium between chromate and dichromate anions) and allow a comparison with the results for the synthetic dichromate solutions. The UV-Vis data for sample B revealed a concentration of Cr2O72−of 108 ppm. The decontamination of the wastewater sample after its treatment with the MOR-1-HA/sand column was apparent even with the naked eye. Five runs of the column with sample B (FIG.22A) revealed breakthrough capacities of 2.268-2.646 mg, relatively close to those observed for the experiments with sample A and the laboratory-prepared solutions. In these column ion-exchange experiments, due to the relatively high initial Cr(VI) concentration of sample B, the sorbent rapidly reached complete saturation with Cr(VI). The MOR-1-HA/sand column performance for the decontamination of sample B could be very well modelled by the Thomas equation: CC0=11+exp⁡(kThQ⁢(qmax⁢m-C0⁢Veff))(5) where C, C0are the concentrations (mg/L) of the ion in the effluent and its initial concentration (mg/L), respectively; kTh(L mg−1min−1) is the Thomas model or sorption rate constant; qmax(mg/g) is the predicted maximum sorption capacity; m (mg) is the mass of the sorbent; and Q (mL min−1) is the volumetric flow and Veffis the effluent volume (mL). (V. J. Inglezakis and S. G Poulopoulos, Adsorption, Ion Exchange and Catalysis. Design of Operations and Environmental Applications, Elsevier, 2006.) The fitting of the data with the Thomas equation (FIG.22B) revealed maximum column sorption capacities of 61-63 mg Cr2O72−/g of the sorbent. These predicted column sorption capacities were close to those experimentally observed (67-70 mg/g). The latter were calculated from the difference between the Cr2O72−content of the initial and effluent solutions. The excellent description of the column ion exchange generated using the Thomas model indicated that the external (fluid-film) and intra-particle mass transfer resistance had negligible effect on the column ion-exchange of the MOR-1-HA sorbent. Finally, another important feature of the breakthrough curve was the degree of column utilization defined as the ratio of breakthrough to total column sorption capacity. For practical applications, it is desirable to achieve a degree of column utilization as close as possible to unity. For the column ion exchange experiments with wastewater sample B, the degree of column utilization (%) lay in the range of 78-89%, thus revealing the highly efficient performance of the MOR-1-HA sand column. Conclusions In conclusion, a new rapid, green and low-cost synthetic method for MOR-1 and composite MOR-1-HA materials was developed, which involved 1 h reflux reaction in water-acetic solvent (yielding MOR-1) and addition of sodium alginate (SA) to the resulted suspension of MOR-1 under reflux conditions (yielding MOR-1-HA). The hydrothermal synthesis approach used, for the first time, afforded UiO-66 type amino-functionalized materials which were purely microporous as the well-known UiO-66-NH2BDC compound prepared with the solvothermal method. It is important that high quality UiO-66 amino-functionalized compounds could be prepared very fast via an inexpensive reflux synthesis in acidified water, since such materials are of great interest not only for their Cr(VI) sorption capacity but also for their gas sorption and photocatalytic properties, post-synthetic chemistry etc. Furthermore, the presented synthetic method revealed the usefulness of sodium alginate (SA), being a) the precursor for the formation of the alginic acid component of the composite; and b) a flocculation agent for the easy separation of MOR-1 from its fine suspension in water. Thus, SA could be useful for the large scale synthesis and facile isolation of a number of metal organic materials forming colloidal water solutions, such as various UiO-66, UiO-67 analogues, MOFs of the MIL-family, etc. Detailed batch Cr(VI) sorption studies for the MOR-1-HA composite isolated with the new method revealed its exceptional capability to absorb Cr(VI) under various conditions. This sorbent was particularly able to be used in ion-exchange columns. It comprised of relatively compact and polyhedral shape nanoparticles that could be uniformly distributed in the column allowing a stable flow rate. In addition, this sorbent, due to the coating of MOR-1 particles by alginic acid, was not easily dispersed in water (in contrast to the pristine MOR-1 material), and thus could be immobilized in the stationary phase of the column. Thus, an ion-exchange column containing MOR-1-HA showed relatively high and reproducible Cr(VI) sorption capacities, as well as excellent regeneration capability and reusability. Compared to columns with composites isolated from solvothermally prepared MOR-1, the column with MOR-1-HA synthesized with the new method exhibited improved performance. Importantly, this column was highly efficient for the removal of Cr(VI) not only from laboratory prepared solutions, but also from industrial wastewater samples. Overall, the results indicated that MOR-1-HA ion-exchange column could be inexpensive, considering the relatively low cost of the new synthetic method for MOR-1-HA, and also promising for the remediation of real-world wastewater. The next step of this research could be thus the development of large scale MOR-1-HA columns and their application in wastewater treatment plants. Example 3 This example reports a new member of the UiO-66 series, namely the MOF [Zr6O4(OH)8(H2O)4(H2PATP)4]Cl8.12H2O (MOR-2) (H2PATP=2-((pyridin-1-ium-2-ylmethyl)ammonio)terephthalate). MOR-2 showed exceptionally high dichromate sorption capacity (˜402 mg/g) and remarkably rapid sorption kinetics (equilibrium is reached within 1 min). MOR-2 also exhibited excellent chromate sorption capacity (˜264 mg/g) and rapid uptake of this Cr(VI) species. MOR-2 was capable of eliminating Cr(VI) from a variety of solutions including industrial and drinking water samples. MOR-2-alginic acid (MOR-2-HA) composite is also described herein. This material was successfully employed in ion-exchange columns that showed very efficient performance for the sorption of both high and trace amounts of Cr(VI) from simulated and industrial waste samples, with noticeable recyclability of the column. Furthermore, the ability of MOR-2 toward selective and real-time luminescence sensing of ppb levels of Cr(VI) in real-world water samples was demonstrated. Results and Discussion Synthesis of MOR-2 and MOR-2-HA MOR-2 was synthesized via a solvothermal reaction of ZrCl4and the new ligand H2PATP (=2-((pyridin-2-ylmethyl)amino)terephthalic acid,FIG.23) in DMF-HCl solution. To introduce positive charge on the framework of MOR-2 and thus unlock its anion exchange properties, the material was treated with relatively concentrated HCl solution (4 M) in order to protonate its pyridine and amine moieties, affording pyridinium and ammonium functional groups charge balanced by Cl−anions. The pyridinium-methyl-ammonium moieties were expected to be particularly capable of strongly binding Cr(VI) via the formation of both covalent and hydrogen bonds (see below). Pristine MOR-2 is not suitable for use as a stationary-phase in ion-exchange columns since it is isolated as a very fine powder which passes through the frits into the eluding fractions (see below). To tackle this problem, the composite of MOR-2 was prepared with alginic acid, MOR-2-HA, by adding HCl into a suspension of MOR-2 in a sodium alginate (SA) solution in water. The composite material could be easily separated from water because a thin HA shell covered the MOR particles, which were now far less prone to form fine suspensions in aqueous solutions. In contrast, as-prepared MOR-2 forms very fine suspension upon its contact with water. Note that the composite can be successfully isolated (and used in ion-exchange columns) using only 1% wt. of alginate. Thus, the particles of MOR-2 were not covered by a thick layer of alginic acid that could slow the sorption kinetics. Characterization of MOR-2 and MOR-2-HA Field-emission scanning electron microscopy (FE-SEM) studies revealed that the MOR-2 was composed of sponge-like aggregates of particles. In contrast, due to the alginic acid coating, the particles of MOR-2-HA were more compact and, as a consequence, were less dispersed in water. Powder X-ray diffraction (PXRD) data indicated the structural similarity of MOR-2 (and MOR-2-HA) with the UiO-66 MOF. Nevertheless, a series of analytical data (C,H,N, EDS, Zr analyses and TGA) were consistent with the formula H16[Zr6O16(H2PATP)4]Cl8.12H2O for the MOR-2 material. Nitrogen physisorption measurements carried out at 77 K for the activated MOR-2 and MOR-2-HA samples showed typical type-I adsorption isotherms, characteristic of microporous solids. The Brunauer-Emmett-Teller (BET) surface areas of the MOR-2 and MOR-2-HA were measured to be 354 and 442 m2g−1respectively. CO2adsorption isotherms recorded at 1 bar and 273 K indicated a sorption capacity of ˜0.94 and 1.66 mmol g−1for MOR-2 and MOR-2-HA respectively. Analysis of CO2adsorption data with the density functional theory (DFT) suggests that both MOR-2 and MOR-2-HA have a microporous network with a pore size of about 5.5 Å. Isolation and Characterization of Cr(VI)-Loaded Materials The porous structure of MOR-2 in combination with the presence of labile Cl−anions and pyridinium-methyl-ammonium functional groups (which are expected to show high affinity for Cr(VI)) motivated the study of the Cr(VI) anion exchange properties of this material. The sorption of dichromate and chromate species by MOR-2 can be visually observed by the change of the color of the pristine compound (from light yellow to orange-brown and yellow-brown after the sorption of Cr2O72−and CrO42−, respectively). EDS analytical data revealed that no existed in the Cr(VI)-exchanged products. Furthermore, various analytical (EDS, ICP-MS and UV-Vis) data indicated the presence of 9 and 6 Cr(VI) per formula unit of dichromate and chromate-loaded MOR-2, respectively. The mechanism of the anion exchange processes is discussed below. PXRD data indicated that the crystal structure of MOR-2 was retained after the Cr(VI) exchange processes. However, both dichromate and chromate loaded materials showed a BET surface area of ˜23 m2/g, substantially lower than that of pristine MOR-2. This result confirmed the incorporation of the Cr(VI) species into the pores of the material. The IR spectra of the Cr(VI)-containing compounds exhibited a characteristic peak at ˜926 cm−1(not existing in the IR spectrum of the pristine material) attributed to the anti-symmetric CrVIO3-stretch. X-ray photoelectron spectroscopy (XPS) data showed Cr2p1/2and Cr2p3/2core-level signals, with their main components corresponding to binding energies of 589 and 580 eV, respectively. These values were consistent with hexavalent chromium species. Batch Ion Exchange Studies Batch ion exchange experiments were performed in order to gain further insight into the Cr(VI) sorption properties of MOR-2. Both dichromate and chromate ion exchange properties of MOR-2 are presented. Cr2O72−Exchange Determination of Isotherm Ion-exchange experiments using relatively low (˜20 ppm) to extremely high (up to 3700 ppm) initial dichromate concentration were carried out. Note that such a wide range of Cr(VI) concentrations is commonly observed in industrial effluents (see below). The isotherm dichromate ion exchange data, obtained at pH˜3, are shown inFIG.24A. These data can be described with the Langmuir model (eq. 1) q=qm⁢bCe1+bCe(1) where q (mg/g) is the amount of the cation sorbed at the equilibrium concentration Ce(ppm), qmis the maximum sorption capacity of the sorbent and b (L/mg) is the Langmuir constant related to the free energy of the sorption. The fitting results indicated a maximum sorption capacity of 402±14 mg Cr2O72−/g, which was the highest sorption capacity reported so far for MOFs (Table 2) and, in general, anion exchange sorbents (LDHs, organic resins and porous organic polymers show dichromate sorption capacities in the range 90-358 mg/g). This sorption capacity corresponded to the insertion of 4.5 Cr2O72−ions per formula unit of MOR-2. The affinity of the sorbent for Cr2O72−can be expressed by the distribution coefficient (Kd) defined by the equation (eq. 2) Kd=V[C0-Ce)/Ce]m(2) where C0and Ceare the initial and equilibrium concentration of Cr2O72−(ppm), respectively; Vis the volume (ml) of the testing solution; and m is the amount of the ion exchanger (g) used in the experiment (Manos, M. J.; Kanatzidis, M. G.Chem. Sci.2016, 7, 4804). The Kdvalues, calculated for a relatively wide range of initial concentrations (21.6-216 ppm), were found to be 1.2×104-1.19×105mL/g, which is particularly high (Kdvalues above 104mL/g are considered excellent). Regeneration of MOR-2 after the Cr2O72−sorption could be achieved by treatment of the Cr(VI)-loaded material with 4M HCl acid. Detailed studies of regeneration/reuse of the sorbent are reported below in the section for the column experiments. The isotherm dichromate exchange data for the MOR-2-HA material was also determined. The fitting of the results with the Langmuir model revealed a maximum sorption capacity of 338±19 mg/g. Although this value was smaller than that for MOR-2, it was still higher than the sorption capacities of reported MOF-based sorbents (Table 2). TABLE 2Selected Cr(VI) sorption characteristics of reported MOFsKineticstudies-Equi-SorptionlibriumcapacitytimeMOF(mg/g)at RTReferenceCrO42−1-ClO462.96hP F. Shi, B. Zhao, G. Xiong, Y. L.Hou and P. Cheng,Chem. Commun.,2012, 48, 8231SLUG-216048hH. H. Fei, M. R. Bresler and S. R. J.Oliver,J. Am. Chem. Soc., 2011, 133,11110.Zn-Co-68.52hH. H. Fei, C. S. Han, J. C. Robins,SLUG-35and S. R. J. Oliver,Chem. Mater.2013, 25, 647.MOR-22641minThis workMOR-2431minThis work2-HACr2O72−ABT ·213-27148hX. X. Li, H. Y. Xu, F. Z. Kong and R.2ClO4H. Wang,Angew. Chem. Int. Ed.,2013, 52, 13769.FIR-537410minH. R. Fu, Z. X. Xu and J. Zhang,Chem. Mater.2015, 27, 205.FIR-5410330minH. R. Fu, Z. X. Xu and J. Zhang,Chem. Mater.2015, 27, 205.ZJU-10124510minQ. Zhang, J. Yu, J. Cai, L. Zhang, Y.Cui, Y Yang, B. Chen and G. Qian,Chem. Commun., 2015, 51, 14732.MOF-86753>12hQ. Zhang, J. Yu, J. Cai, L. Zhang, Y.Cui, Y Yang, B. Chen and G. Qian,Chem. Commun., 2015, 51, 14732.MOR-242-2803-9minS. Rapti, A. Poumara, D. Sarma, I. T.1-HAPapadas, G. S. Armatas, A. C. Tsipis,T. Lazarides, M. G. Kanatzidis andM. J. Manos,Chem. Sci.2016, 7,2467; and Y. S. Hassan, M. H.Alkordi, M. G. Kanatzidis and M. J.Manos,Inorg. Chem. Front.2016, 3,635.1-SO416672hA. V. Desai, B. Manna, A. Karmakar,A. Sahu and S. K. Ghosh,Angew.Chem. Int. Ed.2016, 55, 7811.MOR-24021minThis workMOR-3381minThis work2-HA Kinetics Interestingly, the sorption of dichromate anions by MOR-2 was found to be exceptionally fast. Equilibrium was reached within 1 min (for an initial Cr2O72−concentration of 21.6 ppm) and 99.1% removal capacity was observed (FIG.25). This was the fastest Cr(VI) sorption rate observed for MOFs (Table 2) and other anion-exchange sorbents (e.g., LDHs require several hours to reach the ion exchange equilibrium). This result reflected the rapid diffusion of Cr2O72−ions into the crystalline porous network of MOR-2 and the particularly strong binding of dichromate by the pyridinium-methyl-ammonium functional groups of the material. The sorption kinetics were also studied for the MOR-2-HA composite. The removal of dichromate could be completed within 1 min, as in the case of pristine MOR-2 material. Presumably, the small (1% wt.) content of alginic acid had negligible influence on the dichromate exchange kinetics of the composite. pH Dependence of Sorption The sorption of dichromate was also investigated in solutions of various pH values (in the range 1-8). The results revealed 98.7-99.6% removal in pH˜2-8 (initial dichromate concentration was 21.6 ppm) and highly efficient removal capacity (˜87.8%) even at pH˜1. Selectivity Experiments Common competitive ions for Cr(VI) ion exchange include Cl−, NO3−, Br−and SO42−. Dichromate exchange experiments in the presence of Cl−, NO3−or Br−indicated almost no effect on the Cr(VI) anion exchange process, since very high dichromate removal capacities (93-94%) were obtained even with 1000-fold excess of the competitive anions. This selectivity of MOR-2 for Cr2O72−was not only due to the higher charge of this anionic species (compared to Cl−, NO3−or Br−), but also to its strong interactions with the functional groups of the material (see below). SO42−had a larger effect on the dichromate sorption capacity. Still, high removal capacities (52-96%) could be obtained with 2-4-fold excess of SO42−. It should be noted that in industrial chrome plating solutions, the weight content of SO42−is much lower (80-100 times) than that of Cr(VI) species (N. V. Mandich and D. L. Snyder, Electrodeposition of Chromium, Modern Electroplating, 5thEdition, pg. 205-249; V. Boddu, K. H Abburi, J. L. Talbott and E. Smith,Environ. Sci. Technol.,2003, 37, 4449; L.-Y. Chang, Chrome reduction and heavy metals removal from wastewater—A pollution prevention approach, Proceedings of WM-01 Conference, Feb. 25-Mar. 1, 2001, Tucson, Ariz.). In such a concentration, the SO42−is not a serious competitor for dichromate exchange by MOR-2, as will be shown below in the experiments with industrial wastewater samples. Chromate Ion Exchange The sorption of chromate species by MOR-2 in terms of isotherm determination and kinetic studies were also investigated. Previous to this study no MOF had been investigated for sorption of both dichromate and chromate ions (see Table 2). The isotherm exchange data were obtained at pH˜7 (FIG.24B). Fitting was performed with the Langmuir model, and the results indicated a maximum capacity of 264±10 mg/g. This value indicated exchange of 8 Cl−by 6 Cr(VI) ionic species (4 HCrO4−and 2 CrO42−, see below). This capacity was ˜4 times higher than that of MOF-based chromate exchangers (Table 2). A Pb2+MOF recently reported showed higher chromate capacity (˜324 mg/g) than MOR-2. However, a Pb2+material would be of no practical interest for environmental remediation (L. Aboutorabi, A. Morsali, E. Tahmasebi O. Buyukgungor,Inorg. Chem.2016, 55, 5507). In addition, exceptional high Kdvalues (up to 2.2×105mL/g) were obtained for the chromate exchange by MOR-2. The investigation of the kinetics of CrO42−exchange revealed that the sorption is completed within 1 min (FIG.25), and ≥99.2% removal was observed. This excellent sorption rate, the fastest observed among MOFs (Table 2) and other materials, indicated strong interactions between CrO42−and the functional groups of MOR-2. The selectivity of MOR-2 for chromate vs. various competitive ions (Cl−, NO3−, CO32−etc) was very high, as observed from the results with potable and industrial water samples described below. The isotherm chromate sorption and kinetics data were also obtained for the composite MOR-2-HA. The results revealed that the maximum sorption capacity of the composite (243±15 mg/g) was very close to that of MOR-2. In addition, the chromate sorption rate for MOR-2-HA was as fast as that for MOR-2, with the exchange equilibrium reached within 1 min (≥99.5% removal capacity was observed). Experiments with Potable and Industrial Water Solutions Although a number of MOF materials have been studied for their Cr(VI) exchange properties, there was a lack of data for sorption tests with real-world samples. Thus, the Cr(VI) sorption properties of MOR-2 for industrial wastewater samples and potable water solutions intentionally contaminated with traces of Cr(VI) were investigated. The results are presented in Table 3. The industrial wastewater used in the ion exchange investigations was chrome plating water samples. The chrome plating wastewater was generated by rinsing the plated parts upon their removal from the plating bath. Depending on the amount of water used in the rinsing step, the Cr(VI) concentrations ranged from very high (>1000 ppm) to moderate (<100 ppm) or low (<10 ppm) levels. In addition, the chrome plating wastewater included a small amount of H2SO4(typically the mass ratio of CrO3to H2SO4, used for the preparation of the chrome plating solution, is 50-100). Two different types of chrome plating waste were provided by a metal plating company (located in Thessaloniki, Greece): One acidic sample (A) with dichromate ions in extremely high concentration (5170 ppm, pH˜1.8); and a second alkaline one (B) with chromate ions in moderate concentration (52 ppm, pH˜8). Sample A was too concentrated (5170 ppm) to be treated on a laboratory scale. Thus, Cr(VI)-containing wastewater was prepared by diluting the original sample A to ˜1 ppm of Cr2O72−(pH˜3 after the dilution), and subsequently used in ion-exchange tests with MOR-2. Both original and diluted (˜1 ppm CrO42−) samples B were treated by MOR-2. The results of the ion-exchange experiments with the chrome plating solutions indicated removal capacities in the range 90-96.% (Table 3). For the experiments with the dilute samples, the total Cr content in the final solutions was found <50 ppb, below the acceptable limit in water (100 and 50 ppb for the US EPA and EU, respectively). The potable water samples were natural spring water solutions in which CrO42−traces (total Cr was 31-448 ppb) were added. These samples contained a huge excess of various competitive anions, such as Cl−, HCO3−and SO42−. Specifically, the molar concentrations of Cl−, HCO3−and SO42−were 68-978, 167-2391 and 34-483 times higher respectively than that of Cr(VI). Still, MOR-2 showed a remarkable capability to capture CrO42−from these solutions and the removal capacities were found to be 90-99.6%. The final total Cr content of the potable water solutions, after their treatment with MOR-2, was found to be 2-9 ppb, i.e., well below the acceptable Cr levels (Table 3). These results revealed an exceptional selectivity of MOR-2 for CrO42−anions. TABLE 3Results of ion exchange experimentswith industrial and potable water solutionsSamplepHC0(ppb)aCe(ppb)a% removalChrome platingb823300870c96.3Chrome platingd7448.342.290.6Chrome platinge3481.549.889.7Potable waterf731.43.190.1Potable waterf7107.69.091.6Potable waterf7273.52.099.3Potable waterf7448.31.899.6aTotal Cr measured with ICP-MS;bAs received sample;cThis final concentration was achieved by using V/m ratio of 500 mL/g. In all other experiments, V/m ratio of 1000 mL/g was used;dSample after dilution of the chrome plating waste with initial Cr concentration of 23.3 ppm, pH~8;eSample after dilution of the chrome plating waste with initial Cr concentration of 5170 ppm, pH~2;fNatural spring water with Ca2+:30.5 ppm, Mg2+:12.2 ppm, K+:1.2 ppm, Na+:21.4 ppm, HCO3−:88 ppm, Cl−:21 ppm, SO42−:28 ppm. Column Ion-Exchange Data Initial Check of the Sorbents As reported above, MOR-2 is not suitable for use in ion-exchange columns since it forms very fine suspensions in water. Thus, passing water through a column containing MOR-2 mixed with silica sand (an inert material) resulted in the formation of a fine water suspension flowing out of the column. In contrast, MOR-2-HA remained fixed in the column and the effluents were clear solutions as indicated by testing them with a laser beam. The stationary phases in the columns used for the ion exchange experiments were mixtures of MOR-2-HA and silica sand. The use of such mixtures instead of pure MOR-2-HA provided a stable flow of the solution through the column due to the immobilization of the composite particles in the sand. Furthermore, mixing the composite with an abundant material such as sand was economically attractive. In fact, the columns prepared contained only 1-2 wt. % of MOR-2-HA, so the main component of the stationary phase was sand. Still, the columns were highly efficient for the decontamination of Cr(VI)-containing solutions. Dichromate Ion Exchange Column exchange experiments with a solution of dichromate with an initial concentration of 108 ppm and a stationary phase containing 5 and 0.05 g of sand and MOR-2-HA, respectively, were carried out. The dichromate sorption could be seen even with the naked eye. The results indicated that 11 bed volumes (bed volume=bed height (cm)×cross sectional area (cm2)=3.5 mL) of the effluent samples showed a total Cr content ≤10 ppb, i.e., well below the acceptable safety levels (FIG.26A). The column could be easily regenerated by treating it with 4 M HCl acid. The regeneration process could be visually observed by the decolorization of the (yellow-brown colored) column. A second run showed only a small decrease of the sorption capacity (1 bed volume less) compared with the initial run of the column. Even after 5 runs of the column, the sorption capacity remained high (9 bed volumes till the breakthrough) (FIG.26A). The breakthrough capacity Qb(mg) could be defined by the equation (eq. 3) Q=C0×Vb(3) where C0and Vbare the initial concentration of dichromate (mg/L) and the volume (L) of the effluent passing until the breakpoint concentration (defined as the maximum allowed level of the contaminant). Thus, the breakthrough capacities from the five runs of the column were ˜4.2 (1strun), 3.8 (2ndand 3rdruns) and 3.4 (4thand 5thruns) mg (FIG.26A, inset). In order to calculate the total column sorption capacity, the column was loaded until saturation was reached (the point that the concentration of dichromate in the effluent was identical to the initial dichromate concentration) (FIG.26B). Then, the data were fitted with the Thomas equation (eq. 4): CC0=11+exp⁡(kThQ⁢(qmax⁢m-C0⁢Veff))(4) where C, C0are the concentration (mg/L) of the ion in the effluent and its initial concentration (mg/L), respectively; km (L mg−1min−1) is the Thomas model or sorption rate constant; qmax(mg/g) is the predicted maximum sorption capacity; m (mg) is the mass of the sorbent; Q (mL min′) is the volumetric flow and Veffis the effluent volume (mL). This model assumes that the external (fluid-film) and the intra-particle mass transfer resistance have no effect on the column ion exchange process. The results of the fitting revealed a maximum sorption capacity of ˜100 mg/g, close to the experimentally calculated (98.2 mg/g). The latter was determined by the difference of the dichromate content of the initial and effluent solutions. Another important parameter for an ion-exchange column is the degree of column utilization, which is defined as the ratio of breakthrough to total column sorption capacity. This ratio should be as close as possible to 1 (or 100%). The degree of column utilization in the case of the MOR-2-HA/sand column was calculated to be 84.6%. Such a high value indicated highly efficient performance of the column. Column experiments after doubling the quantity (100 mg) of MOR-2-HA in the column were also performed. Thus, for the same initial dichromate concentration (108 ppm), more than double breakthrough capacity (9.8 mg) was obtained. Even after 5 runs of the column, the breakthrough capacity remained relatively high (6.8 mg). Column ion exchange experiments also have been conducted with a dichromate solution of very low concentration (total Cr content was 0.48 ppm, pH˜3) which, however, was above acceptable levels. The treatment of such dilute solutions is usually challenging, since conventional methods like precipitation are not effective in removing the contaminants in ppb levels. Remarkably, a MOR-2-HA/sand column containing only 50 mg of the composite (and 5 g of sand) was found to be efficient for the decontamination of 3 L (˜857 bed volumes) of the dilute Cr(VI) solution, which showed a total Cr concentration <12 ppb after passing it through the column (FIG.27). Chromate Ion Exchange Chromate ion exchange with a MOR-2-HA/sand column was also investigated (the stationary phase was composed of 0.1 and 5 g of MOR-2-HA and sand, respectively). This was the first study conducted for a MOF-based sorbent. Five column ion exchange runs were performed (initial CrO42−concentration was 52 ppm, pH˜7). Upon sorption of chromate anions, the stationary phase of the column turned yellow. The regeneration of the sorbent was carried out by acid treatment (HCl 4M), and the stationary phase restored its initial color. In the first and second column runs, 11 bed volumes (breakthrough capacity=2 mg of CrO42−) of the effluent solution contained total Cr in a concentration <47 ppb (i.e. below the acceptable limit) (FIG.28). A small decrease (two bed volumes less) of the breakthrough sorption capacity (=1.638 mg of CrO42−) was observed for the third run (FIG.28). However, this breakthrough capacity remained unchanged even after a 5thrun of the column (FIG.28). Column Tests with Industrial (Chrome-Plating) Samples The last part of the column ion exchange studies involved tests with chrome plating wastewater samples. One sample tested was the diluted (total Cr ˜0.48 ppm, pH˜3) chrome plating solution A (see above). The MOR-2-HA/sand column was found particularly capable of decontaminating this wastewater sample. Specifically, 2.5 L (˜714 bed volumes) of the diluted chrome plating solution had a total Cr content <18 ppb, after passing it through the MOR-2-HA/sand column (FIG.29). This result was similar to that obtained with the laboratory prepared dichromate solution (FIG.27). The second industrial sample tested was the original (as received) chrome plating solution B (initial total Cr content ˜23.3 ppm, pH˜8). The MOR-2-HA/sand column was to be found highly efficient for the decontamination of this wastewater sample. This process could even be visually observed. The color of the stationary phase changed to yellow after it was fully loaded by the Cr(VI) species. The regeneration of the column also could be achieved by its treatment with 4 M HCl solution, and the stationary phase restored its original color. Five ion exchange runs were carried out. In the first run, 7 bed volumes of the effluent solution had a total Cr content <10 ppb (Cr removal ˜100%, breakthrough capacity ˜1.27 mg) (FIG.30A). A small decrease in the breakthrough capacity (only 1 bed volume less, or 1.09 mg) was observed in the second and third runs (FIG.30A). Even in the 4thand 5thruns, the column largely retained its initial breakthrough capacity (5 bed volumes, 0.91 mg) (FIG.30A). The column sorption data for the five runs of the column could be well described by the Thomas equation. The total column sorption capacities predicted by the Thomas model were 11-14.6 mg CrO42−/g of MOR-2-HA. Those are close to the experimentally found capacities (10.1-13.8 mg/g) (FIG.30B). In addition, a high degree of column utilization (83.4-92.6%) was found for the column ion exchange tests with the chrome plating solution B, which is another indication of the excellent performance of the MOR-2-HA/sand column. Mechanism of the Cr(VI) Sorption Processes In aqueous solution, hexavalent chromium exists as oxido-forms in a variety of species depending on pH and Cr(VI) concentration. For the oxo species of hexavalent chromium, three main pH regions may be distinguished: (1) H2CrO4(pH<0); (2) HCrO4−and Cr2O72−(pH 2-6); and (3) CrO42−(pH>6). Depending on the concentration and acidity, hexavalent chromium can exist either as chromate CrO42−or dichromate Cr2O72−. The common dissolved chromium species (all hexavalent chromium) are HCrO4−, CrO42−and Cr2O72−. Another species possibly present in aqueous solutions of oxido-Cr(VI) species is chromic anhydride CrO3, which can be formed in the course of the strongly exothermic interactions of CrO42−or Cr2O72−anions with protons from the strongly acidic aqueous solutions, or with the protons of the protonated amine groups of MOR-2, according to the reactions (eq. 5,6): CrO42−+2H+→CrO3+H2O+334.4 kcal/mol  (5) Cr2O72−+2H+→2CrO3+H2O+258.1 kcal/mol  (6) Which entity will dominate in a particular environment depends upon the specific conditions, including, for example, pH, Eh(redox potential), total concentration of chromium, and the overall aqueous chemistry. Therefore, the possible interaction modes of MOR-2@CrO42−, MOR-2@HCrO4−, MOR-2@Cr2O72−and MOR-2@CrO3, and the thermodynamics of possible reactions involved in the oxido-Cr(VI) anion exchange processes taking place in the MOR-2-HA columns by means of DFT computational protocols, were explored. Comparable results were obtained employing the wB97XD/Def2-TZVPP DFT method. The proton affinities of pyridine and methylamine moieties of the PhNHCH2Py ligand used as a model of the PATP ligand predicted to be −157.5 and −151.7 kcal/mol, respectively, at the BP86/6-31G(d,p) level of theory indicate the slightly more basic character of pyridine compared to methylamine moieties. On the other hand, the proton affinities of CrO42−and Cr2O72−are predicted to be −203.0 and −164.5 kcal/mol, respectively. The detachment of the proton either from the pyridinium or methylammonium moieties of the [PhNH2CH2PyH]2+ligand by the CrO42−dianions according to the reactions (eq. 7,8): [PhNH2CH2PyH]2++CrO42−→[PhNH2CH2Py]++HCrO4−(7) [PhNH2CH2PyH]2++CrO42−→[PhNHCH2PyH]++HCrO4−(8) are slightly less exothermic (−45.1 kcal/mol) for the proton detachment process from pyridinium than methylammonium moieties (−51.3 kcal/mol). The deprotonation of the pyridinium or methylammonium moieties by the chromate anions was clearly shown in the structures of the [PhNH2CH2PyH(CrO4)] and [PhNH2(CrO4)CH2PyH] associations optimized at the BP86/6-31G(d,p) level of theory (FIG.31). It could be observed that the CrO42−anions deprotonating either the pyridinium or methylammonium moieties were transformed to HCrO4−species associated with the [PhNHCH2Py] ligand through hydrogen bonds. The HCrO4−species interacting with the [PhNH2CH2Py]+and PhNH2CH2PyH]2+ligands yielded the [PhNH2(HOCrO3)CH2Py] and PhNH2CH2PyH(HOCrO3)]+weak associations, respectively, supported by N—H . . . O—H hydrogen bonds (FIG.31). The interaction energies for the [PhNH2(HOCrO3)CH2Py] and PhNH2CH2PyH(HOCrO3)]+associations are 11.6 and 23.9 kcal·mol respectively at the BP86/6-31G(d,p) level of theory. Similarly, the deprotonation of the pyridinium or methylammonium moieties of the [PhNH2CH2PyH]2+ligand by the Cr2O72−dianions according to the reactions: [PhNH2CH2PyH]2++Cr2O72−→[PhNH2CH2Py]++HCr2O7− [PhNH2CH2PyH]2++Cr2O72−→[PhNHCH2PyH]++HCr2O7− are predicted to be slightly exothermic, the estimated exothermicities being −7.1 and −12.8 kcal/mol, respectively. Therefore, the dichromate anions do not deprotonate the pyridinium or methylammonium moieties of the [PhNH2CH2PyH]2+ligand. Rather, interacting with [PhNH2CH2PyH]′ ligand yields the weak association [PhNH2CH2PyH(Cr2O7)] supported by three hydrogen bonds (FIG.31). The estimated interaction energy was −37.3 kcal/mol. The above calculations indicated that (no protonated) the dichromate anions were capable of strongly interacting with the functional groups of MOR-2. The results from the sorption experiments revealed that 4.5 Cr2O72−anions (per formula unit of the material) could be inserted into the pores of the material at the same time all Cl−anions were removed. Combining the theoretical and experimental findings, it is suggested that 4Cr2O72−exchange 8 Cl−anions. Additional 0.5 Cr2O72−could be incorporated into the structure, presumably with the simultaneous removal of one OH−terminal ligand (which may be replaced by a water molecule). In the case of chromate exchange, the calculations clearly showed the tendency of CrO42−to withdraw one proton from either pyridinium or methylammonium functional groups of MOR-2, thus forming HCrO4−species. The chromate exchange data revealed that ˜6 Cr(VI) species are inserted per formula unit of the material, with the simultaneous removal of 8 Cl−anions. Given the capability of chromate anions to deprotonate the pyridinium or methylammonium moieties, it is suggested that 4 HCrO4−will be incorporated into the pores of the material, removing 4 Cl−anions. The remaining 2 Cr(VI) species, exchanging the rest of Cl−anions, will be thus in the form of no protonated chromate anions. All of the above can be summarized by the following equations (eq. 9,10): H16[Zr6O16(H2PATP)4]Cl8+4.5Cr2O72−+H2O→H17[Zr6O16(H2PATP)4](Cr2O7)4.5+8Cl—+OH−(9) H16[Zr6O16(H2PATP)4]Cl8±6CrO42−→H16[Zr6O16(HPATP)4](HCrO4)4(CrO4)2+8Cl−(10) Importantly, among all oxido-Cr(VI) species participating in the anion exchange processes, only chromic anhydride, CrO3, is attached to the N donor atoms of the HPATP and PATP model ligands yielding tetrahedral [PhNH2CH2Py(CrO3)]+, [PhNHCH2Py(CrO3)], [PhNH(CrO3)CH2PyH]+, [PhNH(CrO3)CH2Py], and [PhNH(CrO3)CH2Py(CrO3)] complexes (FIG.31). The estimated binding energies for the [PhNH2CH2Py(CrO3)]+, [PhNHCH2Py(CrO3)], [PhNH(CrO3)CH2PyH]P, [PhNH(CrO3)CH2Py], and [PhNH(CrO3)CH2Py(CrO3)] complexes were 34.0, 23.2, 39.6, 35.3 and 35.5 kcal/mol, respectively. It should be noted that CrO3formed stronger coordination bonds when coordinated to pyridine N donor atom than to amine N donor atom. The stronger Pyr-CrO3bond, compared to the PhN—CrO3bond, is reflected by the Pyr-CrO3and PhN—CrO3bond lengths, with the former being shorter than the latter. The regeneration of the MOR-2-HA columns by treating them with concentrated HCl solutions (4 M) can be easily explained by the acidic hydrolysis of the weak associations, and the complexes involved in the oxido-Cr(VI) anion exchange processes taking place in the columns. Photophysical Properties and Luminescence Sensing The photophysical properties of MOR-2 were studied by solid state UV-vis diffuse reflectance and steady state emission spectroscopy. The diffuse reflectance spectrum of MOR-2 (FIG.32) showed an absorption band in the UV region (λmax=266 nm) and a lower energy absorption signal which maximized at 380 nm and tailed off in the visible region at ca. 450 nm. These bands were attributed to ligand based singlet π-π* and n-π* transitions with the latter involving the lone pair on the amino group. The high-energy band also included a contribution from Zr cluster-based transitions. In the exchanged materials MOR-2@CrO42−and MOR-2@Cr2O72−(vide supra), absorption extended further in the visible region tailing off at ca. 580 and 720 nm, respectively (FIG.32). In the case of MOR-2@Cr2O72−, a shoulder at approximately 605 nm was also observed. These additional absorption features reflected the presence of the oxido-to-metal-charge-transfer transitions (LMCT) of the chromium species. Upon excitation at 360 nm, MOR-2 exhibited turquoise fluorescence. The emission spectrum of MOR-2 (FIG.33) included a broad band with maximum at ca. 470 nm originating mainly from radiative deactivation of a singlet n-π* excited state. The fluorescence of MOR-2, in combination with its ability to rapidly and efficiently sorb Cr(VI) from water, prompted the testing of MOR-2 as a luminescent sensor for Cr(VI) in aqueous media. A titration experiment in which aliquots of a 10−4M aqueous standard stock solution of K2Cr2O7were added to a suspension of MOR-2 at pH 3 led to strong fluorescence quenching (FIG.33). The fluorescence intensity continually decreased with concentrations of 25 ppm, 51 ppm, 76 ppm, 101 ppm, 126 ppm, 151 ppm, 180 ppm, 210 ppm, 249 ppm, 297 ppm, 345 ppm, 392 ppm, and 485 ppm. At the end of the titration, loss of more than 80% of the initial emission signal was observed, which was also evident to the naked eye. Notably, the MOR-2 was activated overnight in 4 M HCl prior to its use in order to ensure that pyridine and amino moieties were fully protonated. At this pH and at the low concentrations of the fluorescence experiments, Cr(VI) in solution was almost totally in the form of HCrO4−ions. In the theoretical work of the previous section it is shown that HCrO4−may interact via charge-assisted hydrogen bonding with the [ArNH2CH2PyH]2+units of MOR-2. However, it is more possible that once HCrO4−ions enter the pores of MOR-2, the equilibrium 2HCrO4−Cr2O72−+H2O shifts to the right for two reasons: i) the concentration of Cr(VI) within the pores is greater than that in solution; and ii) the dichromate species is able to interact more strongly with the [ArNH2CH2PyH]2+units via the formation of three charge-assisted hydrogen bonds, thereby providing a driving force which renders its formation more favorable. A superposition of the absorption spectrum of MOR-2@Cr2O72−and the emission spectrum of MOR-2 showed that there was a clear overlap between the latter and the absorption features attributable to the dichromate ion. Therefore, the observed emission quenching in the titration experiment may have been a result of energy transfer from the excited n-π* levels of the aromatic bridging ligands to the dichromate LMCT transitions. Additionally, given the great oxidizing ability of dichromates and the electron-donating nature of amino terephthalate derivatives, it is also highly possible that the quenching mechanism involved a bridging ligand to Cr(VI) electron transfer component. Analysis of the calibration curve of the fluorescence titration allowed the limits of detection (LOD) and quantification (LOQ) at 4 and 13 ppb, respectively, to be determined. These values demonstrated the extremely high sensitivity of MOR-2 towards Cr(IV), as both the LOD and LOQ values were well below the EU and US EPA acceptable levels of Cr(VI) in water (50 and 100 ppb respectively). To further assess the sensing ability of MOR-2 towards Cr(IV) in real samples, two additional sensing experiments were performed using the lower concentration chrome plating waste sample B (vide supra) as a stock solution, after adjusting its pH to 3 and diluting it to achieve a Cr(VI) concentration of 10 ppm. In the first experiment, distilled water was used as a solvent both for the dilution of the Cr(VI) sample and as a suspension medium for MOR-2, while in the second experiment distilled water was replaced with potable water containing 10.5 ppm of the main competing anion SO42−(vide supra). As seen inFIG.34A, in the first experiment, the system showed comparable response as in the case of the standard Cr(VI) sample, giving LOD and LOQ values of 6 and 18 ppb, respectively. However, when potable water was used as solvent (FIG.34B), a considerable decrease in sensitivity, with LOD and LOQ values of 35 and 110 ppb, respectively, was observed. These results are agreement with the competition results described above, which showed that in the presence of excess SO42−ions, the selectivity of MOR 2 towards dichromate ions was somewhat hindered. As shown inFIG.34A, in the first experiment, the fluorescence intensity continually decreased with concentrations of 29 ppm, 57 ppm, 85 ppm, 113 ppm, 141 ppm, 169 ppm, 196 ppm, 224 ppm, 279 ppm, 333 ppm, 387 ppm, 440 ppm, 492 ppm, 545 ppm, and 648 ppm. As shown inFIG.34B, in the second experiment, the fluorescence intensity continually decreased with concentrations of 57 ppm, 113 ppm, 169 ppm, 224 ppm, 333 ppm, 440 ppm, 545 ppm, and 645 ppm. Nevertheless, even in the latter case the LOD value was lower than the acceptable levels of Cr(VI) in water. Conclusions In conclusion, MOR-2, a microporous Zr4+MOF with pyridinium-methyl-ammonium functional groups, was described. MOR-2 was synthesized via direct solvothermal reaction of Zr4+salt and a pre-functionalized ligand, a strategy that ensured incorporation of the highest possible number of functional groups. MOR-2 represented a unique sorbent with capability to effectively capture both chromate and dichromate species. In fact, MOR-2 exhibited the highest capacity and the fastest kinetics for Cr(VI) sorption among all known materials. Remarkably, MOR-2 could sorb selectively Cr(VI) not only from synthetic solutions, but also from industrial waste and drinking water. The composite of MOR-2 with alginic acid (MOR-2-HA) was also prepared. Extensive Cr(VI) sorption studies were carried out with an ion exchange column filled mainly with silica sand and only a small quantity of MOR-2-HA (1-2 wt %). Such a simple and relatively inexpensive ion exchange column would be capable of decontaminating a large variety of Cr(VI)-containing solutions, including industrial waste with either high or quite low Cr(VI) content. The column could easily be regenerated by treating it with HCl solution and would be reusable for several cycles, a significant aspect for applications in wastewater treatment. Theoretical studies revealed that MOR-2, through its functional groups, was involved in relatively strong interactions with the Cr(VI) species, with the interaction energies ranging from −11.6 up to −61.3 kcal/mol. These results explained the excellent Cr(VI) sorption property of MOR-2. Besides being an excellent sorbent, MOR-2 was also shown to be a highly efficient sensor for Cr(VI) species, as shown by fluorescence titration experiments in acidic aqueous media. Maximum LOD and LOQ values were 4 and 13 ppb, while the system showed excellent sensitivity when real-world, rather than standard, samples were used. Considerable sensitivity even in the presence of excess competing SO42−anions was observed. Therefore, MOR-2 showed great promise as a fluorescent sensor for Cr(VI) in water. The word “illustrative” is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “illustrative” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Further, for the purposes of this disclosure and unless otherwise specified, “a” or “an” means “one or more”. The foregoing description of illustrative embodiments of the invention has been presented for purposes of illustration and of description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The embodiments were chosen and described in order to explain the principles of the invention and as practical applications of the invention to enable one skilled in the art to utilize the invention in various embodiments and with various modifications as suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
118,646
11857945
DETAILED DESCRIPTION The applicants have started to design components for mercury remediation in order to produce clean potable water. In this work, the applicants have synthesized a cheap environmentally and biologically friendly iron base porous metal-organic framework (MOF), known as Fe-BTC, as shown inFIG.1(detailed process of synthesis at the end of the patent application). The MOFs unique framework architecture allows metal ions to diffuse through while inhibiting large organic molecules (like humic acid) from entering. The Fe-BTC MOF acts as a porous template that catalyzes the in-situ polymerization of a variety of small molecules. For example, the applicants have found that the Fe3+sites of Fe-BTC distributed throughout the framework facilitates the polymerization of the monomer dopamine, to its polymer polydopamine (PDA) and adheres the polymer to the pore surface. During this process PDA is pinned to the internal surface of the pores via attachment to the open metal sites introducing extrinsic porosity to an intrinsically non-porous polymer as illustrated inFIG.2. The result is a highly porous composite. The activity of this porous composite has been studied by the applicants. Firstly, the applicants studied the rate of mercury removal (FIG.4a). In order to do that, a solution of Hg2+has been treated with Fe-BTC/PDA or Fe-BTC over a period of an hour. For each experiment, 20 mL of Millipore water containing 1 ppm of Hg2+were treated with 20 mg of Fe-BTC or 20 mg of Fe-BTC/PDA. Secondly, the applicants studied the mercury removal capacity at low Hg2+concentrations (FIG.4b). To study this, Fe-BTC or Fe-BTC/PDA were soaked in Millipore water spiked with mercury for 24 hours. For the experiment ˜10 mg of Fe-BTC or ˜10 mg Fe-BTC-PDA were added to 20 mL of a 0.9 ppm solution of Hg2+. The results of these experiments show that Fe-BTC/PDA is a highly porous composite that fosters the rapid, selective removal of Hg2+from water samples containing high concentrations of Hg2+. Indeed, the composite component Fe-BTC/PDA binds up to 1634 mg Hg2+per gram of composite, and removes over 99% of these ions from a 1 ppm solution to yield drinkable levels in less than a minute. FIG.5ashows that Fe-BTC/PDA is efficient at different initial Hg concentrations. For each experiment, ˜10 mg of Fe-BTC or ˜10 mg Fe-BTC/PDA were added to 20 mL of Rhone river water containing various amounts of Hg2+. The results of the experiments shown inFIGS.5band5c, clearly indicates that the high removal capacity for Hg from water is achieved via reduction of Hg2+to Hg1+. InFIG.5b,10 mg Fe-BTC/PDA was soaked in 20 mL of 1000 ppm solution of HgCl2for 24 hours. The XPS was used to elucidate the electronic structure of the heavy metal. Two signature peaks fitting the data for HgCl2and Hg2Cl2or HgO were observed. This data confirms that the polymer is reducing the Hg2+to Hg1+. For the experiment presented inFIG.5c,10 mg Fe-BTC/PDA was soaked in 20 mL of 1000 ppm solution of HgCl2for 24 hours. After treating a solution of Hg2+with Fe-BTC/PDA the mercury precipitates as solid Hg2Cl2, evident by PXRD. This data also confirms that the polymer is reducing the Hg2+to Hg1+. Hereunder is the proposed mechanism of the Fe-BTC/PDA composites' enhanced properties for Hg2+remediation from water. Through a reduction mechanism the Fe-BTC/PDA composite is able to remediate large quanitites of mercury. The material Fe-BTC/PDA has also proven to be easily regenerated and cycleable after reduction of mercury as shown inFIG.4c. For this experiment, 0.500 g of Fe-BTC/PDA was added to a 1 L solution of Milipore water spiked with 1000 ppm of Hg2+. The remaining Hg2+concentration in the aqueous media were analyzed to determine the mercury capacity (Qe, mg/g). The Fe-BTC/PDA samples was then added to 0.001 M solutions of ascorbic acid. The samples were filtered, washed with methanol, dried and weighed. The regenerated materials were then added to 1000 ppm solutions of Hg2+again. This procedure was repeated three more times to obtain the capacity Qe(mg/g) for each of the four cycles. Previously described performance results are also maintained using real-world water samples from the Rhone River (which contains other metal ions and organics) and water samples spiked with large amounts of humic acid, illustrating the uptake selectivity of Fe-BTC/PDA. Thus, this material is an excellent, inexpensive candidate for in-home and industrial water treatment. The applicants have discovered the impact of the MOF Fe-BTC on the polymerization of the monomer dopamine to polydopamine (PDA). They have discovered that the polymer, PDA undergoes redox chemistry that fosters the extraordinary heavy metal remediation properties of Fe-BTC/PDA with Hg2+. After these experiments the applicants have tried to apply this composite to other metals with a high reduction potential starting with toxic hexavalent chromium Cr6+. For each experiment associated toFIG.6b, ˜10 mg of Fe-BTC or ˜10 mg Fe-BTC-PDA were added to 20 mL of river water containing various amounts of Cr6+. Results of this experiment show that Fe-BTC/PDA sees a 7-fold increasing in removal capacity compared to Fe-BTC alone. For high resolution-XPS experiment ofFIG.6a,10 mg Fe-BTC/PDA was soaked in 20 mL of 300 ppm solution of Cr6+for 24 hours. Two signature peaks fitting the data for Cr3+and Cr6+species were observed. The data implies that the increase in removal capacity for Fe-BTC/PDA compared to Fe-BTC is the result of the redox active polymer reducing Cr6+to Cr3+. Hereunder is the proposed mechanism of the Fe-BTC/PDA enhanced properties for Cr6+remediation from water. Through a reduction mechanism Fe-BTC/PDA component is able to remediate large quanitites of hexavalent chromium. This result is very interesting as Cr3+is 500 to 1000 times less toxic than Cr6+hexavalent chromium. Previously presented results led the applicants to begin to design a variety of new redox activate MOF/polymer composites with the hope of creating high selectivity in order to design materials for specific analytes. Indeed, since it was possible to remove over 99% of Hg from aqueous medium comprising Hg2+by a reduction reaction with Fe-BTC/PDA and since the standard reduction potentials of precious metals are comparable to Hg2+reduction potential, as shown in table 1 hereafter, it may be possible to recover other precious metals from water. It is to be noted that the standard reduction potential of Cr6+/Cr3+is of about 1.36 as shown in table 1 hereunder. TABLE 1standard reduction potentials E° of various compounds (V)Half-ReactionE° (Volts)Half-ReactionE° (Volts)Li++ e−→ Li−3.040SO42−+ 4H++ 2e−→ H2SO3+ H2O0.158K++ e−→ K−2.942Cu2++ e−→ Cu+0.159Rb++e−→ Rb−2.942HAsO2+ 3H++ 3e−→ As + 2H2O0.248Cs++ e−→ Cs−2.923UO22++ 4H++ 2e−→ U4++ 2H2O0.27Ba2++ 2e−→ Ba−2.92Bi3++ 3e−→ Bi0.3172Sr2++ 2e−→ Sr−2.89Cu2++ 2e−→ Cu0.340Ca2++ 2e−→ Ca−2.84O2+ 2H2O + 4e−→ 4OH−0.401Na++ e−→ Na−2.713Cu++ e−→ Cu0.520La3++ 3e−→ La−2.37I2+ 2e−→ 2I−0.5355Mg2++ 2e−→ Mg−2.356H3AsO4+ 2H++ 2e−→ HAsO2+ 2H2O0.560Ce3++ 3e−→ Ce−2.34O2+ 2H++ 2e−→ H2O20.695Nd3++ 3e−→ Nd−2.32Rh3++ 3e−→ Rh0.7H2+ 2e−→ 2H−−2.25Tl3++ 3e−→ Tl0.72Sc3++ 3e−→ Sc−2.03Fe3++ e−→ Fe2+0.771Be2++ 2e−→ Be−1.97NO3−+ 2H++ e−→ NO2+ H2O0.775Al3++ 3e−→ Al−1.676Hg22++ 2e−→ Hg0.7960U3++ 3e−→ U−1.66Ag++ e−→ Ag0.7991Ti2++ 2e−→ Ti−1.63O2+ 4H+(10−7M) + 4e−→ 2H2O0.815Hf4++ 4e−→ Hf−1.56AmO2++ 4H++ e−→ Am4++ 2H2O0.82No3++ 3e−→ No−1.2NO3−+ 2H++ 2e−→ NO2−+ H2O0.835Mn2++ 2e−→ Mn−1.18OsO4+ 8H++ 8e−→ Os + 4H2O0.84Cr2++ 2e−→ Cr−0.90Hg2++ 2e−→ Hg0.85352H2O + 2e−→ H2+ 2OH−−0.8282Hg++ 2e−→ Hg22+0.9110Zn2++ 2e−→ Zn−0.7626Pd2++ 2e−→ Pd0.915Cr3++ 3e−→ Cr−0.74NO3−+ 4H++ 3e−→ NO(g) + 2H2O0.957Ga3++ 3e−→ Ga−0.529Br2++ 2e−→ 2Br−1.0652U4++ e−> U3+−0.52SeO42−+ 4H++ 2e−→ H2SeO3+ H2O1.1512CO2+ 2H++ 2e−→ H2C2O4−0.475Ir3++ 3e−→ Ir1.156S + 2e−→ S2−−0.447Pt2++ 2e−→ Pt1.188Fe2++ 2e−→ Fe−0.44O2+ 4H++ 4e−→ 2H2O1.229Cr3++ e−→ Cr2+−0.424Tl3++ 2e−→ Tl+1.252H2O + 2e−→ H2+ 2OH−(10−7M)−0.414Pd4++ 2e−→ Pd2+1.263Cd2++ 2e−→ Cd−0.4025Cl2+ 2e−→ 2Cl−1.35828Ti3++ e−→ Ti2+−0.37Au3++ 2e−→ Au+1.36PbI2+ 2e−→ Pb + 2I−−0.365Cr2O72−+ 14H++ 6e−→ 2Cr3++ 7H2O1.36PbSO4+ 2e−→ Pb + SO4−0.3505MnO4−+ 8H++ 5e−→ Mn2++ 4H2O1.51In3++ 3e−→ In−0.3382Au3++ 3e−→ Au1.52Tl++ e−→ Tl−0.3363H5IO6+ H++ 2e−→ IO3−+ 3H2O1.603Co2++ 2e−→ Co−0.2772HBrO + 2H++ 2e−→ Br2+ 2H2O1.604H3PO4+ 2H++ 2e−→ H3PO3+ H2O−0.276PbO2+ 2SO42−+ 4H++ 2e−→ PbSO4+ 2H2O1.698Ni2++ 2e−→ Ni−0.257H2O2+ 2H++ 2e−→ 2H2O1.763Sn2++ 2e−→ Sn−0.136Au++ e−→ Au1.83Pb2++ 2e−→ Pb−0.1251Co3++ e−→ Co2+1.92Hg2I2+ 2e−→ 2Hg + 2I−−0.0405S2O82−+ 2e−→ 2SO42−1.96Fe3++ 3e−→ Fe−0.04O3+ 2H++ 2e−→ O2+ H2O2.0752H++ 2e−→ H20.0000F2+ 2e−→ 2F−2.87Sn4++ 2e−→ Sn2+0.154F2+ 2H++ 2e−→ 2HF3.053 With this in mind, the applicants have synthesized and tested the following composites: Fe-BTC/PBDT, Fe-BTC/PHQ, Fe-BTC/PpPDA, Fe-BTC/PTA and Fe-BTC/PDA. In all polymerization reactions, the porous template retains its structural integrity, as determined by the powder x-ray diffraction patterns ofFIG.7. These new composites are quite porous as illustrated by the results of nitrogen adsorption isotherms (77K) ofFIG.8. Attenuated total reflectance infrared spectroscopy illustrate new peaks from the vibration modes of the functional groups of the polymers of these composites (seeFIG.9). Moreover,FIG.10shows numerous crystal facets hinting at polymerization inside the pores. FIG.11aillustrates that the composites Fe-BTC/PDA and Fe-BTC/PTA are capable of reducing Au3+to Au0. For each experiment, ˜10 mg of Fe-BTC/PTA or ˜10 mg Fe-BTC-PDA were soaked in 20 mL of Milipore water containing 500 ppm of Au3+for 24 hours. Hereunder is the proposed mechanism of the Fe-BTC/PDA composite's enhanced properties for Au3+remediation from water. Such a mechanism is confirmed byFIG.11bthat shows the apparition of solid gold Au0(s) after contacting Fe-BTC/PDA. Similar results are obtained with Fe-BTC/PTA composite. For each experiment ofFIGS.12aand12b,10 mg of Fe-BTC, Fe-BTC/PDA, Fe-BTC/PTA, Fe-BTC/PHQ, Fe-BTC/PpPDA or Fe-BTC/PBDT were soaked in 20 mL of the Millipore water spiked with Au3+for 24 hours. All the studied composites Fe-BTC/PDA, Fe-BTC/PTA, BTC/PHQ, Fe-BTC/PpPDA and BTC/PBDT, in a 1 ppm solution, have the ability to remove over 99% of gold from water compared to the Fe-BTC alone which only retains 74% of the gold as shown inFIG.12a. While the capacities of all composites have not been determined, Fe-BTC/PDA, is able to remove up to 1.3 g of Au per gram of composite. The applicants estimate the cost of the raw materials needed to make the composite, if bought on a ton scale, to be around 2.5 USD per kg of composite. For each experiment ofFIGS.13aand13b,10 mg of Fe-BTC, Fe BTC/PDA, Fe BTC/PTA, Fe BTC/PHQ, Fe BTC/PpPDA or Fe BTC/PBDT were soaked in 20 mL of the Millipore water spiked with Pd2+for 24 hours. Results ofFIG.13ashow that, for palladium, the situation is similar as for gold. Indeed, all composites remove 99% of palladium from water in a 550 ppb Pd aqueous solution compared to 78% for the Fe-BTC template. For each experiment ofFIGS.14aand14b,10 mg of Fe-BTC, Fe BTC/PDA, Fe BTC/PTA, Fe BTC/PHQ, Fe BTC/PpPDA or Fe BTC/PBDT were soaked in 20 mL of the Millipore water spiked with Ag+ for 24 hours. The data reveals over 99% silver removal for one of the composites, which is significantly enhanced compared to Fe-BTC. Results ofFIG.14ashow that, for silver, the situation differs. The bare framework Fe-BTC can remove 86% of Ag ions from water in a 718 ppb Ag aqueous solution. Fe-BTC/PDA, Fe-BTC/PpPDA and Fe-BTC/PHQ can remove over 95% of Ag of the same 718 ppb Ag aqueous solution. In the same 718 ppb Ag aqueous solution, Fe-BTC/PBDT only removes 81.8%, which is less than the bare framework and Fe-BTC/PTA removes only 0.8% of Ag illustrating no activity. From a roughly 100 ppm solution of Au, the bare framework is only able to remove 43% of the gold from water, but all the composites can remove over 99% of the gold, with some composites reaching even 99.9% removal as shown inFIG.12b. For Pd, the bare framework can remove 96% from a 55 ppm solution while all the other composites can remove over 99% of Pd, as shown inFIG.13b. Concerning Ag, at roughly 90 ppm (90.5 ppm), most composites showed removal capabilities less than the bare framework, but interestingly Fe-BTC/PDA is the only composite that is highly active for silver, removing over 99% of Ag from water, as shown inFIG.14b. These results illustrate that the different redox active composites Fe-BTC/PBDT, Fe-BTC/PHQ, Fe-BTC/PpPDA, Fe-BTC/PTA and Fe-BTC/PDA can reduce and/or remove precious metals from aqueous media. It is to be noted that changing the polymer alters the activity and hence the selectivity of the composite towards certain precious metals. Remarkably the composites are highly selective and fast. For the experiment ofFIG.15a, Rhone River water was spiked with 1 ppm of Au3+and then 10 mg of Fe-BTC/PTA were soaked in the 20 mL of water for 24 hours. For the experiment ofFIG.15b, ˜10 mg Fe-BTC/PTA were soaked in 20 mL of Milipore water spiked with 1 ppm of Au3+. Using Fe-BTC/PTA as an example, it as been found that it removes over 99% of gold in a 1 ppm aqueous solution in less than 30 minutes, as shown inFIG.15b. Fe-BTC/PTA illustrate high selectivity for Au over common interferents found in river water, such as Ca and large organics. Further it was discovered that Fe-BTC/PTA can selectively remove over 99% of gold from a 1 ppm Au3+solution obtained from Milipore water (FIG.16). For this experiment Millipore water was spiked with 1000 ppb of Au3+and 200000 ppb of Cu2+and Ni2+. 20 mL of the solutions were treated with 10 mg of Fe-BTC/PTA for 24 hours. The results illustrate that the composite Fe-BTC/PTA exhibits high selectivity over high concentrations of these other common ions, copper and nickel. To stress the selectivity capabilities of the Fe-BTC-redox polymer, the applicants have assessed its Au removal performance in the presence of high concentrations of abundant Cu and Ni seen in electroplating industry for example. To do so, Millipore water was spiked with 190000 ppb of Au3+and 200000 ppb of Cu2+and Ni2+. 20 mL of the solutions were treated with 10 mg of Fe-BTC/PTA for 24 hours. Results are presented inFIG.17. Fe-BTC/PTA removes over 99% of a roughly of 190000 ppb solutions of Au (FIG.17) in the presence of roughly 200000 ppb of Cu and Ni, with little to no removal of Cu or Ni from water, as shown inFIG.18. At lower concentration, 1000 ppb of Au, the results are remarkable: Fe-BTC/PTA is capable of removing 99% of Au in the presence of roughly 200000 ppb concentration of Cu and Ni, as shown inFIG.16. The concentration of Cu and Ni is 200 times the concentration of Au and there is no uptake of Cu or Ni. This implies the selectivities are tremendous. After Fe-BTC/PTA, the ability of Fe-BTC/PpPDA to remove gold from water has also been studied more specifically. The experiments ofFIGS.17ato17eevaluate the capacity of Fe-BTC/PpPDA to extract gold from a simulated e-waste solution. Said solution is obtained by spiking the main components in e-waste including ˜870 ppm of Cu2+and Ni2+and ˜9 ppm of Au3+in a Rhone water solution that already contains many competing ions and organics. In the experiment ofFIGS.17aand17b,10 mg of Fe-BTC/PpPDA were added to a sample of 20 mL of said simulated e-waste solution. Then, they were placed in a thermo scientific maxQ4450 orbital shaker at 420 rpms and held at a constant temperature of 28° C. under shaking for 24 hours. For the experiment ofFIG.17c, a sample of 20 mL of the aforementioned simulated e-waste solution was treated with 10 mg of Fe-BTC/PpPDA. At each time point (1, 2, 5, 10, 15, 20 and 30 minutes), the aqueous samples were isolated and filtered using a 25 mm hydrophilic PTFE membrane syringe filter with 0.22 μm pores. After elemental analysis, the percent removal of gold was calculated. The results of said experiments show that Fe-BTC and Fe-BTC/PpPDA remove 75% and 99.9% of the gold respectively (FIG.17c) from said simulated e-waste solution, with a minimal uptake of the other ions (FIGS.17aand17b). The lack of uptake of the other ions is likely due to gold's higher reduction potential combined with higher polarizability when compared to the other ions present. Further, as shown inFIG.17c, like for Fe-BTC, for Fe-BTC/PpPDA the gold is extracted in less than 2 minutes. This remarkable rapid extraction rate is attributed to the extrinsic porosity of PpPDA introduced by the MOF template. The Fe-BTC/PpPDA composite's extraction efficiency was also investigated at varying pH, within the same e-waste simulated solution. For this experiment, 10 mg of Fe-BTC/PpPDA was added to samples of 20 mL of the aforementioned e-waste solution with varying pH. For each sample the pH was adjusted using 0.02M aqueous solutions of HCl and NaOH and was then remeasured. The vials were placed in a Thermo Scientific MaxQ4450 Orbital Shaker for 24 hours at 420 rpms and held at a constant temperature of 28° C. The samples were then filtered using a mm hydrophilic PTFE membrane syringe filter with 0.22 μm pores to remove any solids for elemental analysis of the aqueous media. The results of this experiment are shown inFIG.17d. Remarkably, more than 99% removal is achieved for solutions between pH 2-10. At pH 11 gold removal is only slightly reduced to ˜98%, indicating that at these concentrations, pH does not hinder the composite's extraction properties. The aforementioned assessments indicate that the composite to Fe-BTC/PpPDA has the unprecedented selectivity and the relevant stability needed for various gold extraction processes. While the material rapidly extracts Au3+(FIG.17c), the quantity of gold compared to the composite mass is about 0.018 weight % which is quite low, due to low starting concentrations. As such, the material must be able to concentrate gold over time or with regeneration for actual implementation into recovery processes. So, the regenerability of Fe-BTC/PpPDA was tested. The results of this experiment are shown inFIG.17e. For this experiment, 50 mg of Fe-BTC/PpPDA was exposed to a sample of 20 mL of previously mentioned simulated e-waste solution for five minutes. After said exposure the composite was removed from the solution and exposed to another sample of 20 mL of previously mentioned simulated e-waste solution for five more minutes, this process was repeated nine times. Then the composite Fe-BTC/PpPDA was soaked in ascorbic acid for four hours to reduce the imine (═NH) generated during Au3+reduction back to the amine (—NH2) and then washed with ethanol. The regenerated Fe-BTC/PpPDA composite was again soaked successively ten more times into samples of the e-waste simulated solution, subsequently regenerated, and then washed. The same process was repeated one more time. The results of this experiment are shown inFIG.17e. In this figure, the grey bars correspond to successive cycles of exposure and every white bar constitutes regeneration with ascorbic acid. They reveal that the removal efficiency remained at 99% removal for four exposures. After cycle five, the removal efficiency decreases to 98% and after ten cycles to 81%. It should be noted that after each regeneration, 99% removal of Au3+is observed. However, there is a decrease in performance with continued exposure. This is likely due to a combination of material loss, decrease in extraction rate, and/or pore clogging as the gold is becoming more concentrated inside the composite. After three regeneration cycles, the composite reclaimed 0.29 mg of Au0per mg of composite, a value that is readily increased with continued cycling. The composite/Au powder resulting from the previously described experiment associated toFIG.17ewas loaded in an MTI OTF-1200X tube furnace and heated to 900° C. at a ramp of 30° C. per minute in air. The temperature was held for two hours and then allowed to cool to room temperature. The brown powder was transferred to a vial and 10 mL of concentrated HCl was added. The vial was loaded into a thermos scientific maxQ4450 orbital shaker at 420 rpms and held at a constant temperature of 28° C. for 24 hours. The Au particles were separated from the obtained yellow acidic solution and soaked in a fresh batch of concentrated HCl. The sample was allowed to shake at 420 rpms at a constant temperature of 28° C. for another 12 hours. The Au particles were then separated from the clear acidic solution and washed with distilled water 3 times. PXRD was performed to confirm neutral state gold. The purified Au was then dissolved in aqua regia and underwent subsequent elemental analysis to determine the purity. It was determined to be 23.9 karat which is very high purity. The gold can also be concentrated over time. In order to demonstrate that, the applicant have placed 10 mg of Fe-BTC/PpPDA in 10 L of a solution containing ppm Au3+. All of the gold was removed over a three-weeks period without regeneration steps. It means that the composite has extracted a weight of gold equal to about 80% of its mass. These results demonstrate that the Fe-BTC/PpPDA can concentrate metals also without regeneration step and that if simply soaked in large quantities of solutions with low concentrations of gold, the composite can still concentrate gold inside. In order to confirm the effectiveness of the Fe-BTC/PpPDA composite for gold extraction from e-waste, gold was extracted from actual solutions obtained from e-waste. For this purpose, metals were mechanically removed from a computer processing unit (CPU), and then leached into an aqueous N-bromosuccinimide (NBS) and pyridine (Py) solution. It should be noted that, like ore extraction, gold extraction from e-waste is currently done using toxic alkali cyanide agents and/or extreme pH conditions. Here, a facile method that utilizes an aqueous solution of N-bromosuccinimide and pyridine at near neutral pH levels has been used (reference is made to the article «Environmentally Benign, Rapid, and Selective Extraction of Gold from Ores and Waste Electronic Materials»Angew. Chem. Int. Ed.56, 9331-9335, (2017), Yue, C. et al.) This oxidative leaching process is more environmentally benign than the aforementioned methods. The resulting solution is a blue solution that had a metal composition of 1470 ppm Cu2+, 95 ppm Ni2+and 7.3 ppm Au3+. After soaking 30 mg of the composite Fe-BTC/PpPDA in a 20 mL sample of said blue solution, 86% gold removal was obtained in less than two minutes, over 90% in 10 minutes, and 95% removal in 30 minutes, as shown inFIGS.18aand18c. The composite Fe-BTC/PpPDA is over 662 times more selective for Au3+than Cu2+and Ni2+based on the calculated distribution coefficient, kd, 1.3×104mL/g, 19.13 mL/g, and 5.38 mL/g, respectively. With continued cycling and subsequent composite removal, it is expected that the extracted gold metal will be free of other competing metals, as previously observed in river water (FIG.17a-17e). Hence, it is concluded that Fe-BTC/PpPDA has great potential for Au recovery from e-waste. The applicants have also studied the rate of gold removal from several matrices including river water, wastewater, electronic waste leaching solution, sea water, and a solution obtained after treating incinerated sewage with NBS/Py. For the experiment in river water, 10 mg of Fe-BTC/PpPDA were soaked in 20 mL of a solution comprising Rhone river water spiked with 120 ppb of Au3+, for various periods of time. After the time point was reached the sample was filtered and elemental analysis was done to calculate the % removal of gold. Such a concentration of 120 ppb of Au approaches the gold concentration in Alaskan river which is usually between 60 and 120 ppb. Indeed, mining operations near the fresh water sources tend to discharge metal ions into the environment. For the experiment in waste water, 10 mg of Fe-BTC/PpPDA were soaked in mL of a solution of waste water that contained 3.7 ppb Au received from a waste water treatment plant in Switzerland, for various periods of time. After the time point was reached the sample was filtered and elemental analysis was done to calculate the % removal of gold. For the experiment in electronic waste leaching solution, 30 mg of Fe-BTC/PpPDA were soaked in 20 mL of a solution of electronic waste water obtained by oxidizing and hence dissolving the metals extracted from a CPU in a NBS/Py solution (same solution as the one studied inFIG.18a), for various periods of time. Said solution of NBS/Py had 1470 ppm Cu2, 95 ppm Ni2+and 7.3 ppm Au3+. After the time point was reached the sample was filtered and elemental analysis was done to calculate the % removal of gold. For the experiment in Mediterranean sea water, 10 mg of Fe-BTC/PpPDA were soaked in 20 mL of Mediterranean sea water spiked with 1 ppm Au3+, for various periods of time. Said Mediterranean sea water had many other complex ions in the solution including Ca, Mg, Na, K, Sr, B and Pb. After the time point was reached the sample was filtered and elemental analysis was done to calculate the % removal of gold. We find that the final concentration of Au3+is below our detectable limit, indicating it is less than 100 ppt. For the experiment in incinerated ash leaching solution, 50 mg of Fe-BTC/PpPDA were soaked in 10 mL of an incinerated ash leaching solution for various periods of time. Said solution comes from a treatment plant in Switzerland and the NBS/Py previously mentioned method was used to extract the metals. The resulting solution contained 5.47 ppm of Au3+and many other species such as Ca2+, Cs+, Mg2+, Na+, Fe3+, Cu2+, K+, B3+, Zn2+and Rb+. After the time point was reached the sample was filtered and elemental analysis was done to calculate the % removal of gold.FIGS.18dand18eshow the identity and concentrations of the metals present in said incinerated ash leaching solution before and after a 24 hours treatment with said Fe-BTE/PpPDA. The percents removal of gold over time resulting from the five experiments mentioned above are illustrated inFIGS.18band18c. Concerning waste water, the results show that, in less than 1 minute 90% removal is achieved, and in under 30 minutes over 99% of Au3+was extracted from the wastewater solution and the final concentration was <10 ppt. This extraction is truly remarkable, particularly considering the high concentrations of organics in wastewater, which often competitively complex metal ions and also often foul mesoporous adsorbents. Concerning the incinerated ash leaching solution, the results show that in less than two minutes, the composite Fe-BTC/PpPDA is able to extract 61% of the Au3+from the solution and then reaches 90% removal in 24 hours. Moreover, it can be observed little to no uptake of most of the other metal interferents present, as shown inFIGS.18dand18e. Although the Cu2+concentration is decreased from 1.76 ppm to 0.16 ppm, the removal capacity is quite low. Further, Cu2+is readily desorbed, and hence will not influence the gold purity. Regarding the river water solution, remarkably, in less than 2 minutes the applicants have observed 90% Au extraction and then 99% removal in less than 30 minutes in the solution indicating that Fe-BTC/PpPDA could be implemented in mining Au from surface water sources. One of the most difficult challenges is gold recovery from the sea. Indeed, it is estimated that the ocean contains gold valued at 720 trillion US dollars. But, unfortunately, gold in seawater has an ultra-low concentration, less than 20 ppt, and is one of the most complex matrices in the world. For example, competing ions, such as Na+can have concentrations that are 2×10 9 times higher than that of Au3+. As such, extraction of the precious metal from the sea is conceptually thought to be nearly impossible. The experiment conducted forFIGS.18band18cin Mediterranean Sea water spiked with 1 ppm Au3+showed that Fe-BTC/PpPDA is able to extract 95% of the gold in 20 minutes and then reached more than 99% removal in 30 minutes. It should be noted that given the complexity of the solution, it was not possible to obtain the remaining concentration of gold in the seawater. However, it is below 100 ppt based on the detection limit of the ICP-MS method. As this value is approaching the gold concentration in the sea, the applicants daringly attempted to concentrate Au directly from the ocean. For this, 0.5 g of Fe-BTC/PpPDA was soaked in the ocean for 1 week off the coast of Jacksonville Florida, USA. The sample was then recovered, dried and digested in aqua regia to determine if any Au was extracted while soaking. The post-treated sample was found to contain 0.01 wt % Au. While this is a small amount, with much longer soak times and subsequent regeneration, composites like Fe-BTC/PpPDA might bring new found optimism towards even mining Au from the sea. Another compound has been made by functionalizing a porous template “Cu-BTC” by in-situ polymerization of bio-derived para-phenylenediamine onto the internal surface of the pores of Cu-BTC, thereby introducing extrinsic porosity to the intrinsically non-porous polymer PpPDA and obtaining Cu-BTC/PpPDA. FIG.22shows powder X-ray diffraction patterns of the porous template HKUST-1 (also known as Cu-BTC). The template was soaked in para-Phenylenediamine (pPDA) leading to polymerized Poly-para-phenylenediamine (PpPDA). Cu-BTC and Cu-BTC/PpPDA were soaked in water for 7 days. The diffraction patterns show that the polymerization process enhances the stability of the Cu-BTC porous template in water. FIG.23CO2adsorption isotherms at 25° C. for Cu-BTC and Cu-BTC/PpPDA. Cu-BTC and Cu-BTC/PpPDA were degassed under vacuum at 125° C. for hours at a ramp rate of 1.0° C. per minute. After activation, adsorption experiments were performed at 25° C. using a water bath. It is observed that Cu-BTC/PpPDA has an enhancement in CO2adsorption at ambient temperatures compared to HKUST-1. The increase in adsorption at low pressures illustrates that the binding energy of CO2increased compared to Cu-BTC. Images ofFIGS.24a,bandcimply the polymer is going inside of the porous template. These results show that the polymerization of para-phenylenediamine onto the surface of the pores of Cu-BTC can also enhance its stability in water. The applicants have also tested Fe-BTC/PDA composite for extraction of Pb from water sample. As the standard reduction potential of Pb is much lower it was not expected to observe a reduction reaction. In a first experiment (seeFIG.3a), the applicants have determined the rate of lead removal. For this experiment, a solution of Pb2+was treated with Fe-BTC or Fe-BTC/PDA over a period of an hour. For each experiment, 20 mL of Millipore water containing 1 ppm of Pb2+were treated with 20 mg of Fe-BTC or 20 mg of Fe-BTC/PDA. In the solution treated with Fe-BTC/PDA, over 99% of lead is removed to reach drinkable limits in less than a minute. In a second experiment (seeFIG.3b), the applicants have determined the lead removal capacity at low Pb concentrations. Fe-BTC or Fe-BTC/PDA were soaked in Millipore water spiked with lead for 24 hours. For the experiment ˜10 mg of Fe-BTC or ˜10 mg Fe-BTC/PDA were added to 20 mL of a 0.9 ppm solution of Pb2+. The results of these experiments are presented inFIGS.3aand3band show the rapid and selective removal of lead from water samples containing high concentration of Pb2+. The composite Fe-BTC/PDA binds up to 394 mg Pb2+per gram of composite, and removes over 99% of Pb2+ions from a 1 ppm solution to yield drinkable levels in less than a minute (seeFIG.3a). Therefore, the applicants have discovered that Fe-BTC/PDA is able to efficiently reduce the concentration of Pb in water. X-ray diffraction experiments have been made and have shown no other lead compound. These results seem to confirm that the mechanism of action of the composite Fe-BTC/DPA for extraction of Pb from water is different from the aforementioned reduction process observed for Hg2+and various precious metals. The composite Fe-BTC/PDA has also proven to be easily regenerated and cycleable in this context, as illustrated by the results ofFIG.3c. For this experiment, g of Fe-BTC/PDA was added to a 1 L solution of Milipore water spiked with 1000 ppm of Pb2+. The remaining Pb2+concentration in the aqueous media were analyzed to determine the lead capacity (Qe, mg/g). The Fe-BTC/PDA sample was then added to 0.001 M solutions of EDTA (ethylenediaminetetracetic acid). The samples were filtered, washed with methanol, dried and weighed. The regenerated composites were then added to 1000 ppm solutions of Pb2+again. This procedure was repeated three more times to obtain the capacity Qe (mg/g) for each of the four cycles. Concerning Pb extraction, other experiments have been made in order to study the selectivity of the porous template Fe-BTC and of the composites Fe-BTC/PDA, Fe-BTC/PTA, Fe-BTC/PHQ, Fe-BTC/PpPDA and Fe-BTC/PBDT, it means their ability to extract Pb from water comprising other common ions such as Na, Mg, Ca, Sr and K and organics. A first experiment has been made in a sample of Rhone river water comprising an initial concentration of Pb around 700 ppb and 39.49 ppm Na, 9.18 ppm Mg, 74.13 ppm Ca and 1.21 ppm Sr (FIGS.20aand20b). ForFIG.20b,10 mg of Fe-BTC or the composites Fe-BTC/PDA, Fe-BTC/PTA, Fe-BTC/PHQ, Fe-BTC/PpPDA or Fe-BTC/PBDT were soaked in 20 mL of Rhone River water spiked with 700 ppb of lead for 24 hours. Results ofFIG.20bshow that Fe-BTC is able to remove 72% of Pb, while Fe-BTC/PDA, Fe-BTC/PTA and Fe-BTC/PpPDA are able to extract over 99% of Pb (below detectable limit) and Fe-BTC/PHQ and Fe-BTC/PBDT are able to remove more than 93% of Pb. It means that almost all the studied composites reduce the concentration of Pb2+to what is deemed drinkable by the Environmental Protection Agency in the presence of other chemical species present in the river water (FIG.20a). A second experiment has been conducted in Mediterranean Sea water. For this experiment (FIG.21b), 10 mg of Fe-BTC or the composites Fe-BTC/PDA, Fe-BTC/PTA, Fe-BTC/PHQ or Fe-BTC/PpPDA were soaked in 20 mL of Mediterranean Sea water spiked with 350 ppb of lead for 24 hours. The results show that Fe-BTC/PDA, Fe-BTC/PTA, Fe-BTC/PHQ, Fe-BTC/PpPDA are able to remove over 99% (below detectable limit) of Pb a roughly of 350 ppb solution of Pb in the presence of 2640 ppm of Na, 407.89 of Cu, 378.86 ppm of Mg, 546.12 ppm of Ca, 8.66 ppm of Sr and 5.22 ppm of B, as shown inFIGS.21aand21b. Fe-BTC/PBDT is able to remove 91.4% of Pb of this same solution. That is to say, almost all the studied composites reduce the concentration of Pb2+to what is deemed drinkable by the Environmental Protection Agency in the presence of other chemical species present in the Mediterranean Sea water, refer toFIG.21a. These experiments show that the studied composites adsorb a significant amount of lead. In most composites it is possible to get below the EPA limit of lead in water in both Rhone river water and sea water. These graphs show high selectivity as there are many other ions in solution that compete with lead. The applicants have also studied the efficiency of the composite according to the invention for extraction of some specific chemical species from a gas medium. FIG.19shows CO2adsorption isotherms at 25° C. for Fe-BTC and Fe-BTC/PpPDA. Fe-BTC and Fe-BTC/PpPDA were degassed under vacuum at 125° C. for 15 hours at a ramp rate of 1.0° C. per minute. After activation, adsorption experiments were performed at 25° C. using a water bath. It is observed that Fe-BTC/PpPDA has an enhancement in CO2adsorption at ambient temperatures compared to Fe-BTC. The increase in adsorption at low pressures illustrates that the binding energy of CO2increased compared to Fe-BTC. Therefore the composites according to the invention show high promise for air purification. It seems possible to change the binding energy of certain small molecules with different polymers. The introduction of porosity to redox active polymers has shown improvements in chemical separation of metals in water but also has shown an enhancement in small molecule gas adsorption and framework stability as well. In view of these results, the applicants believe that the composites according to the invention will be good for adsorption of Cl2gas, ozone, ammonia, and also volatile organics compounds from air. It is to be expected that with the high reduction potential of Cl2or ozone that the composites according to the invention would be very efficient for scrubbing toxic chlorine gas or ozone from air. Moreover, it is known that volatile organic compounds (VOCs) are well absorbed by intrinsically porous polymers (polymers that are naturally porous), as mentioned for example in the publication “Rapid removal of organic micropollutants from water by β-cyclodextrin polymer”, Alsbaiee et al. 2016—doi:10.1038/nature16185. And, as demonstrated by the applicants, it is possible to introduce extrinsic porosity to polymers using a porous template. For these reasons, it is supposed that the composites according to the present invention would also be efficient in extracting VOCs from both air and water. According to the invention, VOCs are typically chosen among ethanol, methanol, butanone, ethylbenzene, acetone, n-hexane, cyclohexane, toluene, benzene, various xylenes, dichloromethane and n-butylamine, benzothiophene, thioanisole, Methyl tert-butyl ether, Dibromochloropropane, Chloroform, Perchloroethane, 1,1,1-Trichloroethane, 1,2-chloropentane, ethylene dibromide, 1,2-Dichloroethene, Vinyl chloride, Dichlorodofluoromethane, Decabromodiphenyl ether, Trichloroethylene (TCE), organochlorine insecticides (DDT). The methods that have been used in order to synthesize Fe-BTC, Fe-BTC/PDA, Fe-BTC/PTA, Fe-BTC/PpPDA, Fe-BTC/PHQ, Fe-BTC/PBDT and Cu-BTC are described in details below. The method to obtain the compound of interest Fe-BTC/PDHAA is also disclosed. As mentioned before other MOFs such as Cu-TDPAT and Al-BDC-NH2can be used in the context of this invention. Methods for obtaining them are also disclosed. Synthesis of Fe-BTC (Porous Template) Iron(III) chloride hexahydrate (FeCl3·6H2O), 97% was bought from Alfa Aesar and 1,3,5-benzenetricarboxylic acid (trimesic acid, BTC), 98% was bought from ABCR GmbH and used without further purification. 19.44 g of iron(III) chloride hexahydrate, 6.72 g of trimesic acid and 240 mL of distilled water were loaded in a 1 L teflon reactor. The reactor was placed in a 1200 watts Milestone SynthWAVE Microwave Single Reaction chamber and pressurized to 5 bars with nitrogen. The reaction was heated to 130° C. over 5 min and remained at the temperature for 60 mins. After the reaction was cooled down to room temperature the orange solid was filtered under vacuum and washed with copious amounts of water and methanol. The resulting powder was loaded into a double thickness whatman cellulose extraction thimble and underwent soxhlet purification with methanol for 24 hours. After purification the sample was dried under vacuum overnight. The material was activated under vacuum at 150° C. for 17 hours before nitrogen adsorption and standard characterization. Free Base Dopamine Synthesis (Monomer for PDA) Dopamine HCl, dry sodium hydride 95% and anhydrous solvents were bought from Sigma Aldrich and used without further purification. In a N2purged, 2-neck round bottom flask, 10 g of Dopamine HCl was mixed with 80 mL of anhydrous tetrahydrofuran (THF) and 80 mL of anhydrous methanol. 1.264 g of dry sodium hydride 95% was added slowly in small quantities over a period of approximately 15 minutes. The reaction mixture was allowed to stir for 48 hours with flowing N2. After the completion of the reaction, the mixture was filtered under vacuum and washed with copious amounts of THF. The white powder was dried and kept under vacuum until further use. 1H NMR (400 MHz, Methanol-d4): δ=6.72 (d, J=8.0 Hz, 1H), 6.67 (d, J. 2.1 Hz, 1H), 6.55 (dd, J. 8.0, 2.1 Hz, 1H), 2.87 (t, J=7.1 Hz, 2H), 2.65 (t, J=7.1 Hz, 2H) Synthesis of Fe-BTC/PDA (Polydopamine) Fe-BTC was activated at 150° C. under vacuum overnight in a 500 mL 2-neck round bottom flask using a schlenk line and an oil pump. After activation of Fe-BTC, the reaction vessel was cooled to room temperature and then N2was flowed over the sample for 10 minutes. After the sample was sealed under an inert atmosphere, 400 mL 0.02 M anhydrous methanol solution containing the as-prepared free base dopamine, was prepared in a glove box purged with N2. Using a steel cannula and N2, the methanol/dopamine solution was transferred to the flask containing the activated Fe-BTC. Over a period of 1 hour, the orange powder turned dark purple indicative of polymerization. The reaction was allowed to stir for 24 hours at room temperature under an inert atmosphere. After completion, the reaction mixture was filtered under vacuum and washed with copious amounts of methanol and water. To remove any excess dopamine, the resulting purple powder was loaded into a double thickness Whatman cellulose extraction thimble, and the composite underwent soxhlet extraction with methanol for 24 hours under N2. Afterwards, the sample was dried under vacuum at room temperature over night, and then the material was activated under vacuum at 125° C. for 17 hours before nitrogen adsorption and standard characterization. Elemental Analysis Fe-BTC/PDA-19: C, 39.553%; N, 1.81%; H, 2.45%; Fe, 17.84% Synthesis of Fe-BTC/PTA (Polytyramine) Tyramine 99% and anhydrous solvents were bought from Sigma Aldrich without further purification. 2 g of Fe-BTC was activated at 150° C. under vacuum overnight in a 500 mL 2-neck round bottom flask using a schlenk line and an oil pump. After activation, the reaction was cooled to room temperature and then N2was flowed over the sample. A 400 mL anhydrous ethanol 0.06 M solution of tyramine was prepared in a nitrogen purged glove box. Using a steel cannula and N2, the ethanol/tyramine solution was transferred to the flask containing the activated Fe-BTC. The orange powder turned dark purple indicative of polymerization. The reaction was allowed to stir for 24 hours at room temperature under an inert atmosphere. After completion, the reaction mixture was filtered under vacuum. Once dry the sample was placed in a vacuum oven and heated at 125° C. over night. The material was activated under vacuum at 125° C. for 17 hours before nitrogen adsorption and standard characterization. Synthesis of Fe-BTC/PpPDA para-phenylenediamine >99% and anhydrous solvents were bought from Sigma Aldrich without further purification. 0.300 g of Fe-BTC was activated at 150° C. under vacuum overnight in a 100 mL 2-neck round bottom flask using a schlenk line and an oil pump. After activation, the sample was cooled to room temperature and then N2was flowed over the sample. 0.384 g of pphenylenediame was added to 50 mL anhydrous methanol in a nitrogen purged glove box. Using a steel cannula and N2, the ethanol/para-phenylenediamine solution was transferred to the flask containing the activated Fe-BTC. The orange powder turned dark purple indicative of polymerization. The reaction was allowed to stir at room temperature under an inert atmosphere for 24 hours. After completion, the powder was recovered using vacuum filtration. The material was activated under vacuum at 125° C. for 17 hours before nitrogen adsorption and standard characterization. Synthesis of Fe-BTC/PHQ Hydroquinone 99.5% and anhydrous solvents were bought from Sigma Aldrich without further purification. 0.2 g of Fe-BTC was activated at 150° C. under vacuum overnight in a 100 mL 2-neck round bottom flask and schlenk line and an oil pump. After activation, the sample was allowed to cool to room temperature and then N2was flowed over the sample. 0.869 g of hydroquinone was added to 50 mL of anhydrous ethanol in nitrogen purged glove box. Using a steel cannula, and N2, the ethanol/hydroquinone solution was transferred to the reaction flask containing Fe-BTC. The reaction was allowed to stir for 1 hour to allow the monomers to diffuse through the porous system. After the diffusion of the monomers equilibrated, 1.5 mL of 25% NH3in water was added to the reaction vessel with a syringe. The orange powder turned dark purple indicative of polymerization. The reaction was allowed to stir at room temperature under an inert atmosphere for 24 hours. After completion, the powder was recovered using vacuum filtration. The material was activated under vacuum at 125° C. for 17 hours before nitrogen adsorption and standard characterization. Synthesis of Fe-BTC/PBDT 1,4-benzenedithiol 99% and anhydrous solvents were bought from Sigma Aldrich without further purification. 0.2 g of Fe-BTC was activated at 150° C. under vacuum overnight in a 100 mL 2-neck round bottom flask and schlenk line and an oil pump. After activation, the sample was allowed to cool to room temperature and then N2was flowed over the sample. 0.056 g of 1,4-benzendithiol was added to 50 mL of ethanol in a nitrogen purged glove box. Using a steel cannula, and N2, the ethanol/1,4-benzenedithiol solution was transferred to the reaction flask containing Fe-BTC. The reaction was allowed to stir for 1 hour to allow the monomers to diffuse through the porous system. After the diffusion of the monomers equilibrated, 0.073 mL of 25% NH3in water was added to the reaction vessel with a syringe. The reaction was allowed to stir at room temperature under an inert atmosphere for 24 hours. After completion, the powder was recovered using vacuum filtration. The material was activated under vacuum at 125° C. for 17 hours before nitrogen adsorption and standard characterization. Synthesis of Fe-BTC/PDHAA 2,5-Dihydroxy-1,4-benzenediacetic acid and anhydrous solvents were bought from Sigma Aldrich without further purification. 0.250 g of Fe-BTC was activated at 150° C. under vacuum overnight in a 100 mL 2-neck round bottom flask and schlenk line and an oil pump. After activation, the sample was allowed to cool to room temperature and then N2 was flowed over the sample. 0.0893 g of 2,5-dihydroxy-1,4-benzenediacetic acid was added to 50 mL of ethanol in a nitrogen purged glove box. Using a steel cannula, and N2, the ethanol/2,5-dihydroxy-1,4-benzenediacetic acid solution was transferred to the reaction flask containing Fe-BTC. The orange powder turned dark purple indicative of polymerization. The reaction was allowed to stir for 24 hours at room temperature under an inert atmosphere. After completion, the reaction mixture was filtered under vacuum. Once dry the sample was placed in a vacuum oven and heated at 125° C. over night. The material was activated under vacuum at 125° C. for 17 hours before nitrogen adsorption and standard characterization. Synthesis of Cu-BTC Cu-BTC can be made using a Cu2+salt and trimesic acid. In order to do that, the two compounds are added together in a water ethanol mixture. The material can precipitate out through the addition of base or by heating the solution. The result is a blue powder and is purified using a soxhlet extractor with ethanol as the solvent. The material is highly crystalline and has a surface area up to 2000 m2/g. Synthesis of Cu-TDPAT Cu-TDPAT is a copper-containing MOF where copper is linked by TDPAT ligands (where TDPAT=deprotonated 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine). Since TDPAT is not commercially available, it has to be synthesized, for example by using the following procedures. In a 250 mL round bottom flask, mix together 7.6 g of 5-aminoisophthalic acid acid, 2.68 g of NaOH, 4.37 g of NaHCO3and 70 mL of H2O.Cool the mixture to 0° C. using an ice bath and add drop wise 1.84 g of cyanuric chloride in 35 mL of 1,4-dioxane with an addition funnel.Heat the mixture to 100° C. under reflux for 24 hours.Once cooled to room temperature, adjust the pH to pH −2 with HCl.Recover the resulting solid by vacuum filtration and wash it with distilled water and hot methanol. The resulting solid is a dried powder. It is pure H6TDPAT ((2,4,6-tris (3,5-dicarboxylphenylamino)-1,3,5-triazine)) which is subsequently used for the synthesis of Cu-TDPAT.In a 100 mL bottle, mix together 30 mL of dimethylamine, 30 mL dimethylsulfoxide, 13.5 mL HBF4and 1.5 mL H2O.After, add 2.46 g of Cu(NO3)2·H2O and 0.45 g of H6TDPAT to the mixture. Place the bottle in a Thermo Scientific Heratherm oven and heat to 85° C. for 72 hours.After completion of the reaction, purify the resulting solid with methanol using a soxhlet apparatus for 24 hours.Dry the sample under vacuum and then heat to 125° C. before standard characterization. Synthesis of Al-BDC-NH2 Al-BDC-NH2is a MOF containing Al3+that are linked together by BDC-NH2ligands (where BDC-NH2is deprotonated 2,amino terepthalic acid). It can be synthesized as follows.In a 250 mL round bottom flask, dissolve completely 544 mg of 2-aminoterephthalic acid in 120 mL of dimethylformamide.Stir the solution at 420 rpm and heat to 110° C.Divide 1.45 g of AlCl3·6H2O into 6 equal portions and add two portions to the heated mixture every 15 minutes.Stir the mixture for 3 hours and then turn off the stirring for another 16 hours.After completion of the reaction, filter the resulting yellow powder was and underwent soxhlet extraction with ethanol for 24 hours.Dry the sample under vacuum and heat at 125° C. before standard characterization. Material and Methods Inductive Coupled Plasma Optical Emission Spectroscopy Precious metal salts and standards were bought from Sigma Aldrich and used without further purification. Precious metals were simulated at different concentrations in water obtained from a millipore purification system and also from the Rhone river (Sion, Switzerland, Latitude: 46.228332, Longitude: 7.369975). The precious metal concentrations were measured using an Agilent 5110 Synchronous Vertical Dual View ICP-OES. Before ICP analysis, all samples, including the standards, controls, and treated water solutions were first filtered using a 25 mm hydrophilic PTFE membrane syringe filter with 0.22 μm pores to remove any solid and then the remaining solutions were treated with HNO3or HCl, to create a 2%, 3% and 5% acidic solutions. Five wavelengths were chosen for analysis and averaged. Batch Precious Metal Removal Experiments Fe-BTC and the composites mentioned above removal capacities were evaluated at low concentrations (1 ppm) and at higher concentrations (>60 ppm). Aqueous solutions of Au3+(AuCl3), Pd2+(Pd(NO3)2and Ag+(Ag(NO3) were prepared using millipore water and water from the Rhone river (Sion, Switzerland, Latitude: 46.228332, Longitude: 7.369975). About 10 mg of Fe-BTC or the composites were added to 20 mL of the solution and the vials were placed in a Thermo Scientific MaxQ4450 Orbital Shaker for 24 hours at 400 rpms and held at a constant temperature of 30° C. The samples were filtered using a 25 mm hydrophilic PTFE membrane syringe filter with 0.22 μm pores to remove any solids and elemental analysis was carried out on the remaining aqueous media after acidification.
51,296
11857946
DETAILED DESCRIPTION OF THE EMBODIMENTS As the present invention can be variously modified and have various forms, specific embodiments thereof are shown by way of examples and will be described in detail. However, it is not intended to limit the present invention to the particular form disclosed and it should be understood that the present invention includes all modifications, equivalents, and replacements within the idea and technical scope of the present invention. Hereinafter, the preparing method of a super absorbent polymer sheet according to one embodiment of the present disclosure and the super absorbent polymer sheet prepared therefrom will be described in more detail. According to one embodiment of the present disclosure, there is provided a preparing method of a super absorbent polymer sheet, including the steps of: preparing a monomer composition including an acrylic acid-based monomer having at least partially neutralized acidic groups, a comonomer containing polyethylene glycol (methyl ether) (meth)acrylate, an internal cross-linking agent containing a polyol, an encapsulated blowing agent, and a polymerization initiator; preparing a hydrogel polymer by thermal polymerization or photopolymerization of the monomer composition; and drying the hydrogel polymer to form a super absorbent polymer sheet. In the present disclosure, the monomer composition which is a raw material of the super absorbent polymer includes an acrylic acid-based monomer having at least partially neutralized acidic groups, a comonomer containing polyethylene glycol (methyl ether) (meth)acrylate, an internal cross-linking agent containing a polyol, an encapsulated blowing agent, and a polymerization initiator. First, the acrylic acid-based monomer is a compound represented by the following Chemical Formula 1: R1—COOM1[Chemical Formula 1]in Chemical Formula 1,R1is a C2 to C5 alkyl group having an unsaturated bond, andM1is a hydrogen atom, a monovalent or divalent metal, an ammonium group, or an organic amine salt. Preferably, the acrylic acid-based monomer includes at least one selected from the group consisting of acrylic acid, methacrylic acid, and a monovalent metal salt, a divalent metal salt, an ammonium salt, and an organic amine salt thereof. Herein, the acrylic acid-based monomers may be those having acidic groups which are at least partially neutralized. Preferably, the acrylic acid-based monomer partially neutralized with an alkali substance such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, or the like may be used. A degree of neutralization of the acrylic acid-based monomer may be 40 to 95 mol %, 40 to 80 mol %, or 45 to 75 mol %. The range of the degree of neutralization can be adjusted according to final properties. An excessively high degree of neutralization causes the neutralized monomers to be precipitated, and thus polymerization may not readily occur, whereas an excessively low degree of neutralization not only deteriorates the absorbency of the polymer, but also endows the polymer with hard-to-handle properties, such as those of an elastic rubber. The concentration of the acrylic acid-based monomer may be about 20 to about 60 wt %, preferably about 40 to about 50 wt %, based on the monomer composition including the raw materials of the super absorbent polymer and the solvent, and it may be appropriately selected in consideration of the reaction time and the reaction conditions. However, when the concentration of the monomer is excessively low, the yield of the super absorbent polymer may become low and there may be a problem in economic efficiency. In contrast, when the concentration is excessively high, it may cause problems in processes that some of the monomer may be extracted or the pulverization efficiency of the prepared hydrogel polymer may be lowered in the pulverizing process, and thus physical properties of the super absorbent polymer may be deteriorated. The monomer composition of the present disclosure includes polyethylene glycol (methyl ether) (meth)acrylate as a comonomer. The polyethylene glycol (methyl ether) (meth)acrylate is copolymerized with the acrylic acid-based monomer in the polymerization process to enable polymerization of a super absorbent polymer having a flexible polymer structure. In order to form an optimized polymer structure, the number of ethylene glycol repeating units in the polyethylene glycol (methyl ether) (meth)acrylate may be 3 to 100, 3 to 80, or 3 to 50. The polyethylene glycol (methyl ether) (meth)acrylate may be included in an amount of 5 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the acrylic acid-based monomer. When the comonomer is included too little, there may be no effect of improving flexibility, and when included too much, there may be a decrease in the absorption rate and absorption ability. Therefore, the comonomer may be included within the above range. The monomer composition of the present disclosure includes a polyol as an internal cross-linking agent. The polyol cross-links with the acrylic acid-based monomer and the comonomer to form a flexible polymer structure, and may also contribute to increase the moisture content of the super absorbent polymer sheet due to its hygroscopicity. Examples of the polyol may include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-hexanediol, 1,3-hexanediol, 2-methyl-1,3-propanediol, 2,5-hexanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, tripropylene glycol and glycerol, and the glycerol is preferable. The polyol may be included in an amount of 10 to 100 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight, based on 100 parts by weight of the acrylic acid-based monomer. When the polyol is included too little, there may be no effect of improving the moisture content, and when included too much, there may be a decrease in the absorption rate and absorption ability. Therefore, the polyol may be included within the above range. The monomer composition of the present disclosure may further include other internal cross-linking agents in addition to the polyol. As the internal cross-linking agent, a poly(meth)acrylate-based compound of polyol, for example, a poly(meth)acrylate-based compound of C2 to C10 polyol may be used. More specifically, trimethylolpropane tri(meth)acrylate, ethyleneglycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, polypropyleneglycol di(meth)acrylate, butanediol di(meth)acrylate, butyleneglycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, hexanediol di(meth)acrylate, triethyleneglycol di(meth)acrylate, tripropyleneglycol di(meth)acrylate, tetraethyleneglycol di(meth)acrylate, dipentaerythritol pentaacrylate, glycerin tri(meth)acrylate or pentaerythol tetraacrylate may be used. And, the polyethyleneglycol diacrylate is preferable. The monomer composition of the present disclosure includes an encapsulated blowing agent. The encapsulated blowing agent is present in an encapsulated state during polymerization of the monomer composition, and is then foamed by the heat applied during a drying process described later. As a result, pores having an appropriate size are formed in the polymer structure of the super absorbent polymer so that the super absorbent polymer sheet can have an open pore channel structure. The encapsulated blowing agent may have a structure including a core containing a hydrocarbon, and a shell surrounding the core and formed of a thermoplastic resin. The encapsulated blowing agent varies in expansion characteristics depending on the components constituting the core and the shell, and the weight and diameter of each component. By controlling them, the blowing agent may expand to a desired size and control porosity of the super absorbent polymer sheet. Meanwhile, it is necessary to first confirm expansion characteristics of the encapsulated blowing agent in order to determine whether pores having a desired size are formed. However, the form in which the blowing agent encapsulated in the super absorbent polymer is foamed may vary depending on manufacturing conditions of the super absorbent polymer, and thus it is difficult to define it. Therefore, it is possible to determine whether the blowing agent is suitable for forming the desired pores, by first foaming the encapsulated blowing agent in air to check an expansion ratio and a size. Specifically, the encapsulated blowing agent is applied on a glass petri dish and then heated at 150° C. for 10 minutes in air to expand the encapsulating blowing agent. When the encapsulated blowing agent exhibits a maximum expansion ratio in air of 3 to 15 times, 5 to 15 times or 8.5 to 10 times, it is suitable for forming an open pore structure in the preparing method of a super absorbent polymer sheet of the present disclosure. The encapsulated blowing agent may have an average diameter of 5 to 50 μm, 5 to 30 μm, 5 to 20 μm, or 7 to 17 μm. It can be determined that the encapsulated blowing agent is suitable to achieve appropriate porosity when exhibiting such an average diameter. In addition, it can be determined that the encapsulated blowing agent is suitable for forming a suitable open pore structure in the preparing method of a super absorbent polymer sheet of the present disclosure, when exhibiting a maximum expanded diameter of 20 to 190 μm, 50 to 190 μm, 70 to 190 μm, or 75 to 190 μm in air. The maximum expansion ratio and the maximum expanded diameter in air of the encapsulated blowing agent will be described in more detail in the Examples below. The hydrocarbon constituting the core of the encapsulated blowing agent may be at least one selected from the group consisting of n-propane, n-butane, iso-butane, cyclobutane, n-pentane, iso-pentane, cyclopentane, n-hexane, iso-hexane, cyclohexane, n-heptane, iso-heptane, cycloheptane, n-octane, iso-octane and cyclooctane. Among these, C3 to C5 hydrocarbons (n-propane, n-butane, iso-butane, cyclobutane, n-pentane, iso-pentane, cyclopentane) are suitable for forming pores having the above-described sizes, and the iso-butane may be most suitable. In addition, the thermoplastic resin constituting the shell of the encapsulated blowing agent may be a polymer formed from at least one monomer selected from the group consisting of (meth)acrylate, (meth)acrylonitrile, aromatic vinyl, vinyl acetate, vinyl halide and vinylidene halide. Among these, a polymer of the (meth)acrylate and (meth)acrylonitrile may be most suitable for forming pores having the above-described sizes. The encapsulated blowing agent may include 10 to 30 wt % of a hydrocarbon based on a total weight of the encapsulated blowing agent. It may be most suitable for forming an open pore structure within this range. The encapsulated blowing agent may be prepared and used, or a commercially available blowing agent satisfying the above conditions may be used. The encapsulated blowing agent may be included in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the acrylic acid-based monomer. When the encapsulated blowing agent is included too little, the open pore structure may not be properly formed, and when included too much, there may be a decrease in strength of the super absorbent polymer due to its high porosity. Therefore, the encapsulated blowing agent may be included within the above range. In the preparing method of a super absorbent polymer sheet of the present disclosure, a polymerization initiator that has been generally used for preparing a super absorbent polymer can be applied without particular limitations. Specifically, the polymerization initiator may be an initiator for thermal polymerization or an initiator for photopolymerization by UV radiation according to the polymerization method. However, even when the photopolymerization method is applied thereto, a certain amount of heat is generated by UV radiation and the like, and some heat occurs as the polymerization reaction, an exothermal reaction, progresses. Therefore, the composition may additionally include the thermal polymerization initiator. Herein, any compound which can form a radical by light such as UV rays may be used as the photopolymerization initiator without limitation. For example, the photopolymerization initiator may be one or more compounds selected from the group consisting of benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, benzyl dimethyl ketal, acyl phosphine, and α-aminoketone. Further, as the specific example of acyl phosphine, commercial Lucirin TPO, namely, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide, may be used. More various photopolymerization initiators are well disclosed in “UV Coatings: Basics, Recent Developments and New Application (Elsevier, 2007)” written by Reinhold Schwalm, p 115, and the present invention is not limited thereto. The concentration of the photopolymerization initiator in the monomer composition may be about 0.01 to about 1.0 wt %. When the concentration of the photopolymerization initiator is excessively low, the polymerization rate may become slow, and when the concentration is excessively high, the molecular weight of the super absorbent polymer may become low and the properties may be uneven. Furthermore, as the thermal polymerization initiator, one or more initiators selected from the group consisting of a persulfate-based initiator, an azo-based initiator, hydrogen peroxide, and ascorbic acid may be used. Specifically, sodium persulfate (Na2S2O8), potassium persulfate (K2S2O8), ammonium persulfate ((NH4)2S2O8), and the like may be used as examples of the persulfate-based initiators; and 2,2-azobis-(2-amidinopropane)dihydrochloride, 2,2-azobis-(N,N-dimethylene)isobutyramidinedihydrochloride, 2-(carbamoylazo)isobutylonitrile, 2,2-azobis-[2-(2-imidazolin-2-yl)propane]dihydrochloride, 4,4-azobis-(4-cyanovaleric acid), and the like may be used as examples of azo-based initiators. More various thermal polymerization initiators are well disclosed in “Principle of Polymerization (Wiley, 1981)” written by Odian, p 203, and the present invention is not limited thereto. The concentration of the thermal polymerization initiator included in the monomer composition may be about 0.001 to about 0.5 wt %. When the concentration of the thermal polymerization initiator is excessively low, additional thermal polymerization hardly occurs and there may be less effect according to the addition of the thermal polymerization initiator. When the concentration of the thermal polymerization initiator is excessively high, the molecular weight of the super absorbent polymer may become low and the properties may be uneven. In the preparing method of the present disclosure, the monomer composition may include an additive such as a thickener, a plasticizer, a preservation stabilizer, an antioxidant, and the like, if necessary. The raw materials such as the acrylic acid-based monomer, the comonomer, the internal cross-linking agent, the polymerization initiator, and the additive may be prepared in the form of a monomer composition solution dissolved in a solvent. The solvent may be included in the monomer composition at a residual quantity except for the above components. At this time, any solvent which can dissolve the components may be used without limitation, and for example, one or more solvents selected from water, ethanol, ethyleneglycol, diethyleneglycol, triethyleneglycol, 1,4-butanediol, propyleneglycol, ethyleneglycol monobutylether, propyleneglycol monomethylether, propyleneglycol monomethylether acetate, methylethylketone, acetone, methylamylketone, cyclohexanone, cyclopentanone, diethyleneglycol monomethylether, diethyleneglycol ethylether, toluene, xylene, butyrolactone, carbitol, methylcellosolve acetate, N,N-dimethylacetamide, and the like may be used alone or in combination. Subsequently, a hydrogel polymer is prepared by thermal polymerization or photopolymerization of the monomer composition. Meanwhile, the method of preparing the hydrogel polymer by thermal polymerization or photopolymerization of the monomer composition is not particularly limited if it is a common polymerization method for preparing a super absorbent polymer. Specifically, the polymerization method is largely divided into the thermal polymerization and the photopolymerization according to the energy source of the polymerization. In the case of thermal polymerization, it is generally carried out in a reactor having a kneading spindle, such as a kneader. In the case of photopolymerization, it may be carried out in a reactor equipped with a movable conveyor belt. However, the polymerization method is just an example, and the present invention is not limited thereto. Generally, the moisture content of the hydrogel polymer obtained by the above method may be about 40 to about 80 wt %. At this time, “moisture content” in the present description is the content of moisture in the entire weight of the hydrogel polymer, and it means a value of which the weight of the dried polymer is subtracted from the weight of the hydrogel polymer. Specifically, the moisture content is defined as a value calculated from the weight loss due to moisture evaporation from the polymer in the process of increasing the temperature of the polymer and drying the same through infrared heating. At this time, the drying condition for measuring the moisture content is that the temperature is increased to about 180° C. and maintained at 180° C., and the total drying time is 20 min including 5 min of a heating step. Subsequently, the hydrogel polymer is formed into a sheet form and dried to form a super absorbent polymer sheet. The drying step may be carried out at a temperature of about 120 to 250° C. When the drying temperature is lower than 120° C., the drying time may become excessively long and the properties of the super absorbent polymer finally prepared may decrease. And when the drying temperature is higher than 250° C., the surface of the polymer is excessively dried, and the properties of the super absorbent polymer finally prepared may decrease. Therefore, the drying step may be preferably carried out at a temperature of 120 to 250° C., more preferably at a temperature of 140 to 200° C. Meanwhile, the drying step may be carried out for about 20 to 90 minutes in consideration of process efficiency, but it is not limited thereto. A drying method in the drying step is not particularly limited if it has been generally used in the drying process of the hydrogel polymer. Specifically, the drying step may be carried out by the method of hot air provision, infrared radiation, microwave radiation, UV ray radiation, and the like. The moisture content of the super absorbent polymer sheet after the drying step may be about 10 wt % or more, for example, about 10 to about 40 wt %, or about 15 to about 30 wt %. When the moisture content of the super absorbent polymer sheet is in the above range, flexibility of the sheet can be ensured. According to one embodiment of the present disclosure, the super absorbent polymer sheet may have a thickness of about 100 μm or more, 1,000 μm or more or 5,000 μm or more, and about 10 cm or less, about 5 cm or less, or about 1 cm or less. When the thickness of the super absorbent polymer sheet is excessively thin, strength may be low to make the sheet torn. When it is excessively thick, drying and processing may be difficult. From this point of view, it may be preferable to make the thickness within the range described above. According to the preparing method of a super absorbent polymer sheet of the present disclosure, since the super absorbent polymer sheet is in a sheet form with an open pore channel structure in which at least a part of pores are connected to each other, absorption of water by capillary pressure is possible, so that absorption rate and permeability are improved. Therefore, the super absorbent polymer sheet can be provided as a pulpless absorber. According to another embodiment of the present disclosure, a super absorbent polymer sheet prepared by the above preparing method is provided. The super absorbent polymer sheet has an open pore channel structure in which at least a part of pores are connected to each other, so that absorption of water by capillary pressure is possible. Accordingly, absorption rate and permeability can be improved as compared with the conventional powdery super absorbent polymer. In addition, the super absorbent polymer sheet may have centrifuge retention capacity (CRC) of about 10 to about 40 g/g, preferably about 15 to about 25 g/g, measured in accordance with EDANA WSP 241.2. Moreover, the super absorbent polymer sheet may have absorbency under pressure (AUP) at 0.7 psi of about 5 to about 20 g/g, preferably about 7 to about 15 g/g, measured in accordance with EDANA WSP 242.2. As described above, the super absorbent polymer sheet of the present disclosure has excellent absorption properties and permeability, and can be used as a pulpless absorber. Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. However, these examples are for illustrative purposes only, and the invention is not intended to be limited by these examples. EXAMPLES Preparation of Super Absorbent Polymer Sheet Example 1 35.3 g of acrylic acid, 43.5 g of sodium hydroxide (NaOH, 30 wt % solution) and 7.7 g of water were mixed to prepare a neutralized solution in which about 70 mol % of the acrylic acid is neutralized (solid content: 56 wt %). 7.1 g of polyethylene glycol (methyl ether) (meth)acrylate (product name: FA-401, manufacturer: Hannong Chemicals) as a comonomer, 10 g of glycerol, 0.06 g of polyethylene glycol diacrylate (MW=330, manufacturer: Aldrich) and 0.51 g of an encapsulated blowing agent (36D grade, manufacturer: Matsumoto) were added to the neutralized solution to prepare a monomer composition. The monomer composition was high-shear blended for about 10 minutes at 500 rpm using a mechanical mixer. Thereafter, the mixture was added through a feeder of a polymerization reactor to carry out polymerization to form a hydrogel polymer. At this time, the temperature of the polymerization reactor was kept at 100° C., the maximum temperature during the polymerization was 110° C., and the polymerization was performed for 10 minutes. Subsequently, the hydrogel polymer was dried in a hot-air drier at 140° C. for 30 minutes, and cut into a sheet form (thickness: 5,000 μm) using a cutter. In the super absorbent polymer sheet, centrifuge retention capacity (CRC) measured in accordance with EDANA WSP 241.2 was 22.7 g/g, and absorbency under pressure (AUP) at 0.7 psi measured in accordance with EDANA WSP 242.2 was 11.0 g/g. Example 2 A super absorbent polymer sheet was prepared in the same manner as in Example 1, except that 20 g of glycerol was used. Example 3 A super absorbent polymer sheet was prepared in the same manner as in Example 1, except that 2.5 g of the encapsulated blowing agent was used. Comparative Example 1 A super absorbent polymer sheet was prepared in the same manner as in Example 1, except that the encapsulated blowing and glycerol were not used. In the super absorbent polymer sheet, centrifuge retention capacity (CRC) measured in accordance with EDANA WSP 241.2 was 26.0 g/g, and absorbency under pressure (AUP) at 0.7 psi measured in accordance with EDANA WSP 242.2 was 12.7 g/g. Comparative Example 2 A super absorbent polymer sheet was prepared in the same manner as in Example 1, except that polyethylene glycol (methyl ether) (meth)acrylate and glycerol were not used. Comparative Example 3 A super absorbent polymer sheet was prepared in the same manner as in Example 1, except that glycerol was not used. Comparative Example 4 A super absorbent polymer sheet was prepared in the same manner as in Example 1, except that the encapsulated blowing was not used. Comparative Example 5 A super absorbent polymer sheet was prepared in the same manner as in Example 1, except that 7.1 g of poly(ethylene oxide) (PEO, manufacturer: Sigma-Aldrich, Mw=300,000 g/mol) was used instead of 7.1 g of polyethylene glycol (methyl ether) (meth)acrylate (product name: FA-401, manufacturer: Hannong Chemicals). EXPERIMENTAL EXAMPLES Evaluation of Characteristics of Super Absorbent Polymer Sheet (1) Cross Section of Super Absorbent Polymer Sheet FIG.1is a scanning electron microscope (SEM) photograph of a cross section of the super absorbent polymer sheet according to Example 1 of the present disclosure. FIG.2is a scanning electron microscope (SEM) photograph of a cross section of the super absorbent polymer sheet according to Comparative Example 1 of the present disclosure. ComparingFIG.1andFIG.2, it was confirmed that an open pore channel structure was formed on the surface of the super absorbent polymer sheet according to Example 1 of the present disclosure, but such a structure could not be observed inFIG.2. (2) Flexibility The super absorbent polymer sheet was folded in half and then unfolded. Thereafter, it was evaluated as ◯ when returning to the original sheet state, and it was evaluated as X when the folded part did not return to the original sheet state due to cracking or breaking. The properties of the super absorbent polymer sheets prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated and shown in Table 1 below. TABLE 1Comp.Comp.Comp.Comp.Comp.Ex. 1Ex. 2Ex. 3Ex. 1Ex. 2Ex. 3Ex. 4Ex. 5Thickness5,000 μm5,000 μm5,000 μm4,000 μm5,000 μm5,000 μm5,000 μm4,000 μm(μm)Moisture24.80%21.10%20.30%27.00%22.30%8.50%25.1%28.5%content (%)SEM○○○x○○xxobservationof porestructureFlexibility○○○○xxxx Referring to Table 1, the super absorbent polymer prepared according to the preparing method of the present disclosure had an open pore channel structure and excellent flexibility. However, the super absorbent polymers prepared according to Comparative Examples 1 to 5 were found to be difficult to use in a sheet form due to a lack of flexibility, or no open pore channel structure was observed.
26,513
11857947
DETAILED DESCRIPTION In an embodiment, the present invention at least partially eliminates the aforementioned disadvantages. In particular, a material is to be provided which has good water absorption and retention. The material should also be capable of reversibly binding water and optionally water vapor. Moreover, it should have controlled swellability and it should be possible to avoid a blocking effect. Finally, it should be able to be used in a low-dust manner. In an embodiment, the present invention provides use of an absorber material comprising a casing and superabsorbent particles arranged therein for absorbing and/or distributing liquids in an actively and/or passively cooled current-carrying system, in particular in an actively and/or passively cooled power storage system, wherein the casing is formed of at least two plies arranged in a planar fashion on one another, wherein regions of the plies are connected to one another by at least one seam such that the casing is segmented in the form of pockets separated from one another, and wherein at least some of the pockets have the superabsorbent particles. According to the invention, it has been found that the absorber material according to the invention is outstandingly suitable for absorbing and distributing liquids in actively and/or passively cooled current-carrying systems, since arranging the superabsorbent particles in a segmented casing prevents or at least reduces a gel blocking effect in use. This can be attributed to the fact that forming segments divides up the amount of superabsorber, which can reduce the maximum possible accumulation of superabsorbent particles in one location and thus reduce the resulting “clumps” in the event of possible gel blocking. Moreover, the at least one seam between the pockets, similarly to a transport channel, allows a further transport of the liquid into the interior of the absorber material during the liquid absorption. As a result, the absorption capacity of the superabsorbent particles can be optimally utilized, which can likewise counteract gel blocking. In addition, the segmentation of the superabsorbent particles can reduce the risk of dust formation, since if the casing is damaged, only the portion of particles contained in the damaged segment is released. Finally, the segmentation makes it possible to use superabsorbers in particle form. Compared to superabsorbent fibers, these have the advantage of having a higher absorption capacity with comparable thermal stability both in the dry and in the swollen state. In a preferred embodiment, the at least one seam is embodied as a welded seam, in particular as a thermally and/or ultrasonically welded seam, glued seam and/or stitched seam. An advantage of welded seams is that they can be produced particularly quickly and easily. According to the invention, the casing is segmented by the formation of pockets separated from one another by at least one seam. By means of the at least one seam, moreover, the plies arranged in a planar fashion on one another can be connected to one another. The regions of the casing which do not have a seam are preferably not compressed, and/or at least less compressed than the seam regions. According to the invention, the term “current-carrying system” is used in the conventional sense as a system through which electric current flows. Current-carrying systems preferred according to the invention are current-carrying systems selected from a power storage system, a current-carrying energy converter, a transformer, a power electronics system, a control electronics system, in particular a processor-controlled system, a charging station, an inverter, a rectifier, an electrolyzer and/or combinations thereof. According to the invention, the term “power storage system” is used in the usual sense. In particular, a power storage system is understood to be a system for storing energy, which is currently available but not required, for later use. This storage is frequently accompanied by a conversion of the energy form, for example from electrical to chemical energy. When needed, the energy is then converted back into the desired electrical form. According to the invention, preferred power storage systems are battery systems, capacitors and/or rechargeable batteries. Battery systems are most particularly preferred. Battery systems are modules connected in series or in parallel, which contain secondary or primary cells connected in series or in parallel. Rechargeable batteries are modules connected in series or in parallel, which contain secondary cells connected in series or in parallel. Capacitors are passive electrical components with the ability to statically store electrical charge and the associated energy in an electric field in a DC circuit. The absorption of liquids is to be understood as meaning that the absorber material absorbs liquids. As a result, the current-carrying system can be protected from damage by the liquids. The distribution of liquids is to be understood as meaning that the absorber material distributes liquids over its surface. Absorption and distribution preferably take place in parallel. The liquids to be absorbed by the system according to the invention are preferably cooling liquids and/or water, since these are usually used or formed in actively or passively cooled current-carrying systems. Preferred cooling liquids are alcohols, in particular glycol and/or alcohol/water mixtures, in particular glycol/water mixtures. In one embodiment of the invention, the liquid to be absorbed by the system according to the invention is not a battery electrolyte. The at least one seam may be continuous or discontinuous. Discontinuous seams are composed of direct seam areas, i.e. those regions of the seam which serve to bond the two plies, and indirect seam areas, i.e. those regions of the seam which lie between the direct seam areas and do not belong to the pockets. In welded seams, the direct seam areas are the welded regions, in sewn seams they are the regions covered by the thread, in glued seams, they are the regions connected by adhesive. Discontinuous seams have the advantage that they have a lower proportion of seam area and thus have higher capillarity and better passage of the liquid to be absorbed. Continuous seams have the advantage that the risk of the superabsorbent particles escaping is reduced. Further, the at least one seam may be designed as a straight or curved line or combinations thereof. In a discontinuous configuration, the at least one seam may be designed in the form of dots and/or dashes arranged linearly and/or regularly. As explained above, those portions of the seam that serve to bond the two plies are the direct seam areas of the seam. The width of the at least one seam is preferably 0.5 to 15 mm, more preferably 0.5 to 10 mm and particularly preferably 1 to 6 mm. Further preferably, the seam area, i.e. the sum of the indirect and direct seam area on the surface of the absorber material, is at least 0.4 to 50 area %, more preferably 2 to 40 area % and particularly preferably 4 to 35 area %. If the seam area is less than 0.4 area %, the strength of the seam is generally too low. If the seam area is above 50%, the area available for swelling is too low. In a particular embodiment, the at least one seam is designed as a welded seam which is perforated, preferably in its center. It is advantageous here that the absorber material can be adapted to the installation situation in a particularly simple manner. For example, recesses can be formed in a targeted manner by detaching partial regions along the perforated welded seam. The shape of the welded seam may vary. In a preferred embodiment, the transition between the welded seam and the unwelded regions of the plies is smooth. Thus, in a preferred embodiment, the thickness of the welded regions of the welded seam increases in the direction of at least one pocket adjacent to the welded seam, preferably in the direction of both pockets adjacent thereto. Accordingly, the density of the welded regions of the welded seam decreases in the direction of at least one pocket, preferably in the direction of both pockets adjacent thereto. The transition between welded seam and pocket is preferably continuous. The region of highest compression is preferably located in the center of the welded seam. This can result in a rounded, in particular semicircular, geometry of the welded seam. This affords the advantage of a higher strength of the welded seam. The pocket geometry may vary. The pockets preferably have, independently of one another, one or more of the following geometries: rectangular, triangular, hexagonal, scalloped, round, oval and/or curved. Particularly preferably, the pockets are at least partially present with a rectangular pocket geometry. This geometry is preferred because it can be technically reproduced in a particularly simple manner. In a further preferred embodiment, the number of pockets per square meter of absorber material is in the range of at least two pockets per square meter, for example 4 to 400 pockets per square meter, more preferably 8 to 300 pockets per square meter and in particular 16 to 200 pockets per square meter. Further preferably, the amount of superabsorbent particles is at least 20 g/m2, for example 20 to 1000 g/m2, preferably 20 to 800 g/m2and particularly preferably 20 to 600 g/m2, based on the area of the absorber material. Furthermore, the amount of superabsorbent particles per pocket is preferably at least 0.5 g per pocket, for example 0.5 g to 500 g per pocket, preferably 20 to 400 g per pocket and in particular 20 to 200 g per pocket. Superabsorbers are wherein they can bind and absorb water exceptionally well, i.e. they have good retention. According to the invention, a superabsorber is understood to mean a polymer which is capable of soaking up or absorbing a multiple—up to 500 times—of its own weight in liquids, preferably water, wherein it increases in volume. Superabsorbers form hydrogels in the swollen state. Suitable superabsorbent particles have in particular crosslinked polymers which are polar, and in particular consist thereof. Particular preference is given to polyacrylamide, polyvinylpyrrolidone, amylopectin, gelatin and/or cellulose. Very particular preference is given to copolymers of acrylic acid (propenoic acid, H2C═CH—COOH) and/or sodium acrylate (sodium salt of acrylic acid, H2C═CH—COONa) on the one hand and acrylamide on the other. The ratio of the two monomers to one another can vary. As a rule, what is referred to as a core cross-linker (CXL) is added to the aforementioned monomers, which connects (crosslinks) the long-chain polymer molecules formed to one another at certain points using chemical bridges. These bridges make the polymer water-insoluble. In addition, what is referred to as a surface cross-linker (SXL) can be used. In this case, a further chemical is applied to the surface of the particles, which, by heating, forms a second network only on the outer layer of the particle. This layer supports the swollen gel in order to hold it together even with external loading (movement, pressure). In a preferred embodiment, at least one pocket comprises, in addition to the superabsorbent particles, a filler material, for example absorbent materials such as cellulose pulp, fibers, guar, silica gel and/or foam. The filler material is preferably present in a proportion by weight (filler material to total amount of filler material plus superabsorbent particles) of at least 5 wt %, for example from 5 to 90 wt %, more preferably from 5 to 75 wt % and in particular from 5 to 50 wt %. In a further preferred embodiment, at least one pocket comprises, in addition to the superabsorbent particles, fire-retardant substances, for example substances which release fire-retardant and/or combustion gas-diluting gases. In a further preferred embodiment, the absorber material has a degree of sound absorption a, measured in accordance with DIN EN ISO 10534-1:2001 in the impedance tube, of at least 0.1 at 1000 Hz, for example from 0.1 to 1, preferably from 0.2 to 1, more preferably from 0.3 to 1. The degree of sound absorption can be adjusted in various ways known to those skilled in the art. A high degree of absorption can be achieved by at least one additional ply, which is preferably arranged on the plies arranged in a planar fashion on one another. The additional ply preferably has a meltblown nonwoven. Thus, in a preferred embodiment, the absorber material according to the invention has at least one additional ply, which is preferably a meltblown nonwoven. Further preferably, the additional ply is arranged on at least one outer side of the casing. It is likewise conceivable for the additional ply to be arranged within the pockets. In a further preferred embodiment, at least one pocket has acoustically active fillers, such as in particular fiber pulp. In a further preferred embodiment, at least one ply of the casing has a textile fabric, for example a nonwoven, a woven, a knitted fabric and/or an open-pored foam. These materials are advantageous because of their good water permeability paired with a high structural integrity, even in the wet state. Preferred nonwovens are spunbond nonwovens, wetlaid nonwovens and/or drylaid nonwovens. The basis weight is preferably 10 g/m2to 500 g/m2. In a further preferred embodiment, the surface energy of the textile fabric, measured in accordance with DIN 55660-2:2011-12, is greater than 30 mN/m, preferably greater than 35 mN/m and particularly preferably greater than 40 mN/m. It is advantageous here that polar media such as water or water/glycol mixtures can be distributed particularly well. In a further preferred embodiment, the air permeability of the textile fabric is more than 10 dm3/(m2s), more preferably 20 to 3000 dm3/(m2s), more preferably 30 to 2000 dm3/(m2s), in particular 30 to 1000 dm3/(m2s). The air permeability is measured in accordance with DIN EN ISO 9237:1995 at a differential pressure of 200 Pa. The measurements of air permeability take place before liquid makes contact with samples of the textile fabric with a thickness of 0.05 to 10 mm, preferably 0.1 to 1 mm, particularly with a sample surface area of 20 cm2, which sample has air flowing through it, at an air pressure differential of 200 Pa. In a further preferred embodiment, the air permeability of the absorber material is more than 10 dm3/(m2s), preferably in the range from 20 to 3000 dm3/(m2s), more preferably from 30 to 2000 dm3/(m2s), particularly preferably in the range from 30 to 1000 dm3/(m2s). The air permeability is measured in accordance with DIN EN ISO 9237:1995 at a differential pressure of 200 Pa. The measurements of air permeability take place before liquid makes contact with samples of the textile fabric with a thickness of 0.1 to 15 mm, preferably 0.25 to 5 mm, particularly with a sample surface area of 20 cm2, which sample has air flowing through it, at an air pressure differential of 200 Pa. In a preferred embodiment of the invention, the textile fabric has an average pore size, measured in accordance with ASTM E 1294-89, of more than 1 μm, for example from 1 μm to 1000 μm, in particular from 10 to 800 μm. In a further preferred embodiment of the invention, the textile fabric has microfibers, preferably with a titer of less than 1 dtex, for example from 0.01 to 1 dtex, more preferably from 0.01 to 0.9 dtex. It is advantageous here that the microfibers enable a particularly high capillarity and thereby a particularly good distribution of liquids. Moreover, because of their fineness, microfibers enable a particularly small pore size and thus a particularly low permeability for dust released by the superabsorbent particles. In a further preferred embodiment of the invention, the absorber material has a liquid absorption capacity (demineralized water) of at least 2 l/m2, for example from 2 l/m2to 300 l/m2, more preferably from 3 l/m2to 300 l/m2, more preferably from 5 l/m2to 300 l/m2, more preferably from 10 l/m2to 300 l/m2and in particular from 20 l/m2to 300 l/m2. The textile fabric preferably contains thermoplastic polymers, in particular having a melting point below 270° C. Particularly preferred polymers are polyesters, copolyesters, polyamides, copolyamides, polyolefins and/or blends thereof. It is advantageous here that these can be used for thermal welding. However, the use of non-thermoplastic polymers is also conceivable. Such textile fabrics can be adhesively bonded to one another if required. In a further preferred embodiment, the absorber material is compressible. As a result, it can be fixed well in actively and/or passively cooled current-carrying systems, in particular in actively and/or passively cooled power storage systems. Moreover, good contact with adjacent components can be ensured thereby. The compressive hardness of the absorber material, measured in accordance with DIN EN ISO 3386-1:2015-10, is preferably at least 0.05 kPa, for example 0.05 to 50 kPa, preferably 0.05 to 25 kPa, and particularly preferably 0.1 to 10 kPa, at 40% compression. In a further preferred embodiment, the casing has at least two different textile fabrics arranged in a planar fashion on one another. In this case, the textile fabrics preferably differ in terms of the polymer materials from which they are constructed. Alternatively or additionally, the textile fabrics may differ in terms of the manner in which they are produced, thickness, maximum tensile strength, maximum tensile elongation, modulus, weight, air permeability and/or porosity. It is therefore conceivable for the casing to have two or more different textile fabrics which differ, for example, in terms of one or more of the aforementioned properties. In order to form the pockets, as explained above, the various textile fabrics can be connected to one another in various ways, for example thermally welded to one another and/or glued to one another and/or sewn to one another. In a further preferred embodiment, the absorber material has a self-adhesive ply on at least one side of the casing. Self-adhesive should be understood here to mean that the self-adhesive ply makes it possible to fix the absorber material on different solid surfaces. The self-adhesive ply can cover the casing over its entire surface or only partially. The self-adhesive ply can be a double-sided adhesive tape, for example. The use of superabsorbent particles is advantageous in that they generally burn poorly and thereby increase the flame resistance of the absorber material. If an even further increased flame resistance is desired, the absorber material can be equipped with flame-retardant additives and/or non-combustible fibers, such as for example glass fibers or aramid fibers. As a result, the absorber material can achieve flame resistance in accordance with UL 94 HB. In a further embodiment, the absorber material is present as an absorber pad. An absorber pad is understood to mean an absorber material which has been cut up and welded at the edges. Another subject matter of the present invention comprises an absorber pad containing an absorber material according to one or more of the described embodiments. The absorber pad can have a wide variety of symmetrical and/or asymmetrical geometric shapes. Typically, the absorber pad has two different types of seams, namely the peripheral seams and the internal seams. An internal seam should be understood to mean a seam which delimits at least one pocket on each side. Preferably at least two, more preferably at least 80%, of the internal seams intersect. In a further preferred embodiment, the external seams are continuous and the internal seams are discontinuous. This makes it possible to combine the advantageous properties of both types of seam. A further subject matter of the invention is an actively and/or passively cooled current-carrying system, in particular a power storage system, comprising an absorber material, comprising a casing and superabsorbent particles arranged therein for absorbing and distributing liquids in a current-carrying system, wherein the casing is formed of at least two plies arranged in a planar fashion on one another, wherein regions of the plies are connected to one another such that the casing is segmented in the form of pockets separated from one another by seams, and wherein at least some of the pockets have the superabsorbent particles. Preferred current-carrying systems are current-carrying systems selected from a power storage system, a current-carrying energy converter, a transformer, a power electronics system, a control electronics system, in particular a processor-controlled system, a charging station, an inverter, a rectifier, an electrolyzer and/or combinations thereof. In a preferred embodiment, the current-carrying system is a battery system that comprises a battery housing. The battery housing preferably contains battery cells. The battery cells are preferably thermally conductively connected to a cooling system. A pressure equalizing element is preferably provided in the wall of the battery housing for equalizing the pressure between the interior and the exterior of the battery housing. The absorber pad is preferably arranged underneath the cooling system. As a result, the escaping cooling liquid or the deposited condensate can be particularly efficiently absorbed. The absorber pad is therefore preferably arranged in the bottom region of the current-carrying system, i.e. between the cooling system and the bottom of the battery housing. Additionally or alternatively, the absorber pad can be arranged in the side region of the current-carrying system, i.e. between the cooling system and the side walls of the battery housing. FIG.1shows a cross section of an absorber material1according to the invention, comprising a casing2and superabsorbent particles3arranged therein. The casing2comprises two plies arranged in a planar fashion on one another in the form of textile fabrics, wherein regions of the plies are connected to one another such that the casing is segmented in the form of pockets4separated from one another by welded seams5. At least some of the pockets have the superabsorbent particles3. FIG.2shows a plan view of an absorber material1according to the invention, divided up into twelve pockets4and welded seams5. FIG.3shows a power storage system11according to the invention, in the form of a battery comprising a battery housing6. The battery housing6contains battery cells7. The battery cells7are thermally conductively connected to a cooling system8. A pressure equalizing element9is provided in the wall of the housing for equalizing the pressure between the interior and the exterior of the battery housing6. The absorber material1is arranged underneath the cooling system8, since this makes it possible to absorb escaping cooling liquid10or deposited condensate10. The absorber material1is arranged in the bottom region12of the power storage system11, i.e. between the cooling system8and the bottom of the battery housing6. The absorber material1comprises a casing2and superabsorbent particles3arranged therein. The casing2further comprises a textile fabric and is divided up into pockets4. The absorber material1is shown here in the unswollen state. FIG.4shows a power storage system11not according to the invention, comprising a battery housing6. The battery housing6contains battery cells7. The battery cells7are thermally conductively connected to a cooling system8. A pressure equalizing element9is provided in the wall of the housing for equalizing the pressure between the interior and the exterior of the battery housing6. The absorber material1is arranged underneath the cooling system8, since this makes it possible to absorb the escaping cooling liquid10or the deposited condensate10. The absorber material1is arranged in the bottom region12of the power-storing system11, i.e. between the cooling system8and the bottom of the battery housing6. The absorber material1comprises a casing2and superabsorbent particles3arranged therein. The casing2further comprises a textile fabric and is not divided up into pockets. Furthermore, the manner in which escaping cooling liquid10or deposited condensate10penetrates laterally into the absorber material and is prevented from further penetration by the swelling of the absorber material is shown. FIG.5shows a power storage system11according to the invention, comprising a battery housing6. The battery housing6contains battery cells7. The battery cells7are thermally conductively connected to a cooling system8. A pressure equalizing element9is provided in the wall of the housing for equalizing the pressure between the interior and the exterior of the battery housing6. The absorber material1is arranged underneath the cooling system8, since this makes it possible to absorb escaping cooling liquid10or deposited condensate10. The absorber material1is arranged in the bottom region12of the power-storing system11, i.e. between the cooling system8and the bottom of the battery housing6. The absorber material1comprises a casing2and superabsorbent particles3arranged therein. The casing2further comprises a textile fabric and is divided up into pockets4. Furthermore, the manner in which escaping cooling liquid10or deposited condensate10penetrates unhindered into the absorber material laterally and from the front via the seams5between the pockets4is shown. The absorber material is shown here in the swollen state. FIG.6shows the measuring apparatus15for determining the absorption kinetics. A glass bottle16is filled with the cooling liquid17and provided with a rubber hose18(10×2 mm, 50 cm long) in an airtight manner. Here, the rubber hose18is sealable by means of a clamp. The glass bottle16is secured upside down to a stand19, with the stand19placed on scales20in order to log the reduction in weight during the kinetics measurement. The opening of the rubber hose18, on the bottom at the edge, is in an instrument tray21(MF resin) having an inner surface of 315×210×50 mm (l×w×h) in such a way that the opening of the hose is parallel to the ground. The hose is fixed without deformation with a hose clamp22at the edge of the instrument tray21. The distance to the bottom of the tray can be varied. FIG.7shows various embodiments of the seam5. In this case, the black region represents the direct seam area. Seam a represents a continuous seam which consists entirely of direct seam area. The seams b to g are discontinuous in various embodiments. In the seam b, the black rectangles schematically represent the direct seam areas and the region between the black rectangles represents the indirect seam area. In the seam c and d, the borders of the rectangles schematically represent the direct seam areas and the region between and inside the rectangles represents the indirect seam area. In the seam e, f, g and h, the black regions schematically represent the direct seam areas and the regions therebetween represent the indirect seam area. The seam h is formed as a centrally perforated welded seam. FIG.8shows the cross section of a seam5between two pockets4. The seam5is in the form of a welded seam. The pockets4are to the left and right of the welded seam. The thickness of the welded seam increases in the direction of the pockets. Correspondingly, the density of the welded seam decreases in the direction of the pockets. This transition is continuous. The region of highest compression is located in the center of the welded seam5. FIG.9shows various pocket geometries (rectangular, triangular, hexagonal, scalloped, curved). FIG.10shows the absorption kinetics of various absorption pads with a different number of chambers. It is clear that the absorption pads according to the invention with four or eight chambers have a higher rate of absorption than a system with just one chamber. This is advantageous because the escaping cooling liquid can be absorbed more quickly. The invention is explained in more detail below with reference to several examples: Example 1: Production of Different Absorber Materials In a continuous production process, 2 casing substances are connected to one another by means of ultrasonic welding methods, with ultrasound in both the longitudinal and transverse directions. The sonotrode is operated at 30 kHz and the casing substances are welded at a speed of 10 m/min. The geometry of the welded seam is continuous and corresponds to structure a inFIG.7, the width being 3 mm. The pockets formed in this way are filled with the corresponding amount of superabsorbent particles (see table) before the final closure. The filling is effected via an automated metering device which is integrated into the continuous production plant. The seams for the optimized distribution of the liquid to be absorbed are produced directly in terms of shape and size in the production process with the welding tools used. The final size of the absorber pads is produced by cutting directly in the plant or as a concatenated process step directly thereafter. The following absorber pads were produced: TABLE 1Absorber pad I notAbsorber pad IIAbsorber pad IIIaccording to theaccording to theaccording to theinventioninventioninventionTextile fabric (two plies)40 g/m2PET/co-PES40 g/m2PET/co-PES40 g/m2PET/co-PESnonwoven, calenderednonwoven, calenderednonwoven, calenderedAbsorber pad size (mm)200 × 290200 × 290200 × 290Number of pockets148Type of welded seamaAa(FIG. 7)Total superabsother (g)12.512.512.5Width of welded seam (mm)333Superabsorber (g/pocket)12.53.1251.56Partially neutralizedPartially neutralizedPartially neutralizedType of superabsorberpolyaclylic acidpolyaclylic acidpolyaciylic acidAbsorption capacity (g)2513263201 min5 min31945944615 min40259858530 min52467063560 min639721670 It is clear that the absorption pads according to the invention with four or eight pockets have a higher rate of absorption than a system with one pocket, for the same amount of superabsorber. Moreover, it was found that the absorption pads according to the invention exhibit good retention for the cooling liquid and swell in a controlled manner. Absorption Kinetics Measurement: The measuring apparatus is constructed as shown inFIG.6and 200 g of the cooling liquid17are initially charged in the instrument tray. The distance of the hose end from the bottom of the instrument tray is set to 3 mm in such a way that cooling liquid flows out of the bottle as the liquid level drops. If the system is in equilibrium, i.e. no further cooling liquid flows out of the bottle, the manufactured absorber pad is placed in the instrument tray in such a way that the superabsorber particles are located in a corner region of the pad. The time is stopped and the reduction in weight is logged using the scales. The values of the kinetics are shown in table 1 andFIG.10. While the invention has been illustrated and described in detail in the drawings and foregoing description, such illustration and description are to be considered illustrative or exemplary and not restrictive. It will be understood that changes and modifications may be made by those of ordinary skill within the scope of the following claims. In particular, the present invention covers further embodiments with any combination of features from different embodiments described above and below. Additionally, statements made herein characterizing the invention refer to an embodiment of the invention and not necessarily all embodiments. The terms used in the claims should be construed to have the broadest reasonable interpretation consistent with the foregoing description. For example, the use of the article “a” or “the” in introducing an element should not be interpreted as being exclusive of a plurality of elements. Likewise, the recitation of “or” should be interpreted as being inclusive, such that the recitation of “A or B” is not exclusive of “A and B,” unless it is clear from the context or the foregoing description that only one of A and B is intended. Further, the recitation of “at least one of A, B and C” should be interpreted as one or more of a group of elements consisting of A, B and C, and should not be interpreted as requiring at least one of each of the listed elements A, B and C, regardless of whether A, B and C are related as categories or otherwise. Moreover, the recitation of “A, B and/or C” or “at least one of A, B or C” should be interpreted as including any singular entity from the listed elements, e.g., A, any subset from the listed elements, e.g., A and B, or the entire list of elements A, B and C.
32,828
11857948
DETAILED DESCRIPTION A packing material for the chromatography of polymers, especially olefin-based polymers have been discovered, which provides improved resolution, lower system back pressure, and at lower cost, than current commercially available stationary phases, such as commercially available porous graphite stationary phases. This new material can be reproducibly fabricated without coupling agents, yields improved peak shapes, and provides a simplified separation mechanism that will enable better modelling and SCBD/or CCD deconvolution, leading to a better understanding the microstructure of olefin-based polymers. It has been unexpectedly discovered that good stable mechanical adherence of graphene coating to a non-porous spherical particles can be achieved. No coupling agent and no intermediate layer between particle surface and the graphene is needed. The coating comprising graphene forms the outer surface on the nonporous (preferably spherical) particles, and the graphene comes into contact with the polymer (olefin-based polymer) solution, during the chromatography process. A packing material for chromatography, said packing material comprising non-porous particles, and wherein a portion of the surface area of the particles is coated with a coating composition comprising graphene and/or graphene oxide-, to form coated particles. The packaging material may comprise a combination of two or more embodiments described herein. A “portion of the surface area of the particles” is from “greater than 0” to 100% of the total surface area of the particles, which is coated by the coating composition. The coating is visibly observed. In one embodiment, from “greater than 0” to 10%, or from “greater than 0” to 20%, or from “greater than 0” to 30%, or from “greater than 0” to 40%, or from “greater than 0” to 50%, of the total surface area of the particles, is coated by the coating composition. In one embodiment, from “greater than 0” to 60%, or from “greater than 0” to 70%, or from “greater than 0” to 80%, or from “greater than 0” to 90%, of the total surface area of the particles, is coated by the coating composition. In one embodiment, from 1% to 10%, or from 2% to 20%, or from 3% to 30%, or from 4% to 40%, or from 5% to 50%, of the total surface area of the particles, is coated by the coating composition. Typically the coated particles show a uniform appearance, are of a free flowing nature, and show no sign of particle phase separation. The color of the coated particles darkens with increased graphene loading. In one embodiment, the particles are spherical particles. In one embodiment, the coating composition comprises graphene. In one embodiment, the chromatography is of at least one polymer. In a further embodiment, the polymer is an olefin-based polymer. In a further embodiment, the olefin-based polymer is selected from an ethylene-based polymer or a propylene-based polymer. In one embodiment, the olefin-based polymer is an ethylene-based polymer, further an ethylene-based copolymer. In one embodiment, the olefin-based polymer is a propylene-based polymer, further a propylene-based copolymer. In one embodiment, the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Suitable alpha-olefins include the C3-C10 alpha-olefins, and preferable propylene, 1-butene, 1-hexene and 1-octene. In one embodiment, the propylene-based polymer is a propylene/alpha-olefin interpolymer, and further a propylene/alpha-olefin copolymer, or a propylene/ethylene interpolymer and further a propylene/ethylene copolymer. Suitable alpha-olefins include the C4-C10 alpha-olefins, and preferable 1-butene, 1-hexene and 1-octene. In one embodiment, the coating composition comprises ≥(greater than or equal to) 80 wt %, or ≥85 wt %, or ≥90 wt %, or ≥95 wt %, or ≥98 wt %, or ≥99 wt % graphene, based on the weight of the coating composition. In a further embodiment, the particles are spherical particles. In one embodiment, the coating composition is present in an amount from 1 to 20 wt %, or from 1 to 15 wt %, or from 1 to 10 wt % based on the weight of the coated particles, as determined by TGA. In one embodiment, the coating composition is present in an amount from 2 to 20 wt %, or from 2 to 15 wt %, or from 2 to 10 wt % based on the weight of the coated particles, as determined by TGA. In one embodiment, the coating composition is present in an amount from 3 to 20 wt %, or from 3 to 15 wt %, or from 3 to 10 wt % based on the weight of the coated particles, as determined by TGA. In one embodiment, the coating composition is present in an amount from 3 to 20 wt %, or from 3 to 15 wt %, or from 3 to 10 wt % based on the weight of the coated particles, as determined by TGA. In a further embodiment, the particles are spherical particles. In one embodiment, the non-porous particles have a porosity less than or equal to (≤) 6.0%, or ≤5.0%, or ≤4.0%, or ≤3.0%, or ≤2.0%, or ≤1.0%, or ≤0.5%, or ≤0.2%, or ≤0.1%, or ≤0.05%, or ≤0.02%, or ≤0.01% for pore sizes from 0.003 to 1 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the particles have a porosity≥zero for pore sizes from 0.003 to 1 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the particles have a porosity of zero for pore sizes from 0.003 to 1 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the non-porous particles have a porosity≤0.008%, or ≤0.006%, or ≤0.004%, or ≤0.002%, or ≤0.001% for pore sizes from 0.003 to 1 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the particles have a porosity≥zero for pore sizes from 0.003 to 1 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the non-porous particles have D50≥2 microns, or ≥5 microns, or ≥10 microns, or ≥20 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the particles have a D50≤200 μm, or ≤180 μm, or ≤160 μm, or ≤140 μm. In a further embodiment, the particles are spherical particles. In one embodiment, the particles have an average diameter (or D50 value)≤200 microns, or ≤190 microns, or ≤180 microns, or ≤170 microns, or ≤150 microns, or ≤140 microns, or ≤130 microns. In a further embodiment, the non-porous particles are spherical particles. In one embodiment, the non-porous particles have an average diameter (or D50 value)≥40 microns, or ≥50 microns, or ≥60 microns, or ≥70 microns, or ≥80 microns, or ≥90 microns, or ≥100 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the particles have an average diameter from 1 to 200 microns, or from 10 to 180, or from 20 to 160 microns. In a further embodiment, the particles are spherical particles. In one embodiment, the non-porous particles have a D90<4*D50, or a D90<3*D50, or a D90<2*D50. In a further embodiment, the particles are spherical particles. In a further embodiment, the particles are spherical particles. In one embodiment, the particles have a D10>D50/10, or a D10>−D50/8, a D10>D50/6, or a D10>D50/4. In a further embodiment, the particles are spherical particles. In one embodiment, the non-porous particles have a particle size distribution, such that D10≥2 microns, D90≤3.1×D50, and the ratio of (D90−D10)/D50<3.5, further <3.0, further <2.0, further <(less than) 1.5, and further <1.3. In a further embodiment, the particles are spherical particles. In one embodiment, the coated particles have a D90<4*D50, or a D90<3*D50, or a D90<2*D50. In a further embodiment, the coated particles are spherical particles. In a further embodiment, the coated particles are spherical particles. In one embodiment, the coated particles have a D10>D50/10, or a D10>−D50/8, a D10>D50/6, or a D10>D50/4. In a further embodiment, the coated particles are spherical particles. In one embodiment, the coating composition comprises ≤1.00 wt %, or ≤0.50 wt %, or ≤0.20 wt %, or ≤0.10 wt %, or ≤0.05 wt %, or ≤0.02 wt %, or ≤0.01 wt %, or ≤0.001 wt % of graphene oxide, based on the weight of the coating composition. In a further embodiment, the particles are spherical particles. In one embodiment, the non-porous particles are selected from the following: metal, silicates (for example, lime glass), diamond, silicon carbide, metal particles, clays, talc, or a combination thereof. In one embodiment, the particles are glass beads or silicon carbide beads. In one embodiment, the particles are silica or glassy carbon particles. In a further embodiment, the particles are spherical particles. In one embodiment, the non-porous particles do not comprise a surface treatment, such as a coupling agent. Coupling agents are chemicals, which comprises a chemical group capable of reacting with the base particle, to form a chemical bond, and another chemical group capable of reacting with graphene and/or graphene oxide to form a chemical bond. Thus, the graphene and/or graphene oxide is bonded to the base particle via the reacted coupling agent. In one embodiment, the coated particles do not comprise a coupling agent. In one embodiment, the coating composition does not comprise a crosslinking agent. In one embodiment, wherein for each coated particle, there is no material located between the outer surface of the particle and the coating composition. In one embodiment, wherein for each coated particle, the coating composition is in contact with the outer surface of the particle. In one embodiment, the non-porous particles have a total surface area greater than or equal to (≤) 100 m2/g, or ≤90 m2/g, or ≤80 m2/g, or ≤70 m2/g, or ≤60 m2/g (square meter per grams of particles). In a further embodiment, the particles are spherical particles. In one embodiment, the particles have a total surface area≥1 m2/g, or ≥2 m2/g, or ≥3 m2/g, or ≥4 m2/g, or ≥5 m2/g (square per grams of particles). In a further embodiment, the non-porous particles are spherical particles. In one embodiment, the non-porous particles have a total surface area≤50 m2/g, or ≤40 m2/g, or ≤30 m2/g, or ≤20 m2/g, or ≤10 m2/g (square meter per grams of particles). In a further embodiment, the particles are spherical particles. In one embodiment, the particles have a total surface area≥1 m2/g, or ≥2 m2/g, or ≥3 m2/g, or ≥4 m2/g, or ≥5 m2/g (square per grams of particles). In a further embodiment, the particles are spherical particles. In one further embodiment, the coated particles comprise ≥90 wt % of the particles, based on the weight of the coated particles. In a further embodiment, the particles comprises ≥95 wt %, further ≥98 wt %, further ≥99 wt % of the particles, based on the weight of the coated particles. In a further embodiment, the particles are spherical particles. In one embodiment, the “packing material” is thermally stable at a temperature range from −15° C. to 230° C. In one embodiment, the “packing material” is chemically stable at a temperature range from −15° C. to 230° C. In one embodiment, the “packing material” is thermally and chemically stable at a temperature range from −15° C. to 230° C. Chemically stable means that the packing material does not undergo chemical reaction with mobile phase or with polymer solution; and does not undergo thermal decomposition. Thermally stable describes a packing material, which at the temperature(s) of operation, does not undergo substantial thermal expansion or contraction, which expansion or contraction causes the column bed to move or to generate voids, or which causes deteriora-tion of the column performance in a relatively short period of time. In one embodiment, the coated particles are subject to a further thermal treatment in the presence of a gas or a gas mixture, selected from the following: ethane, methane, argon, hydrogen, air, and nitrogen. In one embodiment, the coated particle is subject to a further thermal treatment in the presence of a gas or a mixture of gases in the presence of inorganic salts, for example, NaCl, BaCl2, or inorganic compounds, such as Al2O3. In one embodiment, the packing material comprises at least one filler (for example, an inert filler). Fillers include, but are not limited to, inorganic materials, such as, but not limited to, glass, and stainless steel shot. Also is provided is an apparatus for polymer chromatography, comprising at least one column that comprises the packaging material of any one of the embodiments described herein. In one embodiment, the apparatus further comprises a detector selected from an Infrared (IR) detector, a Differential Reflective Index Detector (DRI), an Evaporative Light Scattering Detector (ELSD), UV-vis detector or a Differential Viscometer (DP). In one embodiment, the apparatus further comprises a means to subject the packing material to a temperature gradient. In a further embodiment, the temperature gradient (cooling or heating) is ≥0.5° C. per minute, or ≥1.0° C. per minute, or ≥2.0° C. per minute. A temperature gradient device (for example, a GC oven (Agilent Technologies), used in a CEF from PolymerChar) is an instrument that is used to thermally treat, or cool, a column (for example, a chromatography column) in a controlled manner. Other examples are Hewlett Packard GC ovens, and Analytical TREF ovens (for example, see Gillespie et al., U.S. 2008/0166817A1). In one embodiment, the apparatus further comprises a means to subject the packing material to a solvent gradient. A solvent gradient device (for example, a dual pump system with a mixer (Agilent Technologies) as available from PolymerChar) is an instrument that is used to mix two or more solvents in a controlled manner, and wherein the solvent mixture is used as an eluent in a column (for example, a chromatography column). Examples include binary Shimadzu LC-20 AD pumps (see Roy et al, Development of Comprehensive Two-Dimensional High Temperature Liquid Chromatography×Gel Permeation Chromatography for Characterization of Polyolefins, Macromolecules 2010, 43, 3710-3720) and binary Agilent pumps from HT-LC instruments (PolymerChar). In one embodiment, the apparatus further comprises a means to subject the packing material to a temperature gradient, and a means to subject the packing material to a solvent gradient, for example, by using a combination of at least one oven and at least one pump as described above. In a further embodiment, the temperature gradient during cooling is ≥0.1° C. per minute, or ≥0.5° C. per minute, or ≥1.0° C. per minute, or ≥5.0° C. per minute, or ≥10.0° C. per minute, or ≥20.0° C. per minute or ≥30.0° C. per minute. In a further embodiment, the temperature gradient during heating is ≥0.1° C. per minute, or ≥0.5° C. per minute, or ≥1.0° C. per minute, or ≥5.0° C. per minute, or ≥10.0° C. per minute, or ≥20.0° C. per minute. In one embodiment, apparatus further comprises a means to subject the packing material to a solvent gradient, while retaining the polymer fractions on the column at the end of solvent gradient, followed by a mean to subject the packing material to a temperature gradient, for example, by using a combination of at least one oven and at least one pump as described above. In a further embodiment, simultaneous solvent gradient and temperature gradient is used, which leads to a further improved resolution, and/or further improved detector quantification ability, and/or a further reduction of analysis time. In a further embodiment, the solvent gradient uses, but is not limited to, decane and ODCB as a solvent pair. In a further embodiment, the temperature gradient is ≥0.1° C. per minute during cooling, or ≥1.0° C. per minute during heating. In one embodiment, the apparatus further comprises a second packing material that is different from the first packing material. For example, the second packing material may differ from the first packing material in one or more features, such as, chemical composition, mean particle size, particle size distribution, pore size and/or pore size distribution. In one embodiment, the apparatus further comprises a means to subject the second packing material to a temperature gradient, for example by a combination of the ovens and pumps in the PolymerChar apparatus described above. In a further embodiment, the temperature gradient is ≥0.1° C. per minute, or ≥0.5° C. per minute, or ≥1.0° C. per minute, or ≥2.0° C. per minute. Suitable temperature gradient devices are discussed above. In one embodiment, the apparatus further comprises a means to subject the second packing material to a solvent gradient. Suitable solvent gradient devices are discussed above. In one embodiment, the apparatus further comprises a means to subject the second packing material to both a temperature gradient and a solvent gradient, for example, by using a combination of at least one oven and at least one pump as described above. In a further embodiment, the temperature gradient is ≥0.1° C. per minute, or ≥0.5° C. per minute, or ≥1.0° C. per minute, or ≥2.0° C. per minute. In one embodiment, the apparatus is connected, in-line, at-line or on-line, to either a polymerization process or an isolation process of the polymer. In one embodiment, the eluent is selected from the following: TCB, ODCB, TCE, naphthalene, C10 or higher aliphatic alcohol, decane, dibutoxymethane, or xylene with DRI, ELSD. One or more embodiments provide chromatography methods to analyze a polymer, the method comprising: a) dissolving a composition comprising the polymer in at least one solvent, to form a polymer solution; b) injecting at least a portion of the polymer solution onto a column, comprising the packaging material of one or more embodiments described herein; c) generating a chromatogram. In one embodiment, after step b), the packaging material is cooled at a rate≥0.2° C./min, or ≥0.5° C./min, or ≥1.0° C./min, or ≥1.5° C./min, or ≥2.0° C./min, or ≥3.0° C./min, or ≥4.0° C./min, or ≥5.0° C./min, or ≥6.0° C./min, or ≥7.0° C./min, or ≥8.0° C./min, or ≥9.0° C./min, or ≥10.0° C./min, or ≥11.0° C./min, or ≥12.0° C./min, or ≥13.0° C./min, or ≥14.0° C./min, or ≥20.0° C./min, 25 or ≥30.0° C./min. In one embodiment, before step c), the packaging material is heated at a rate≥0.2° C./min, or ≥0.5° C./min, or ≥1.0° C./min, or ≥1.5° C./min, or ≥2.0° C./min, or ≥3.0° C./min, or ≥4.0° C./min, or ≥5.0° C./min, or ≥6.0° C./min, or ≥7.0° C./min, or ≥8.0° C./min, or ≥9.0° C./min, or ≥10.0° C./min, or ≥11.0° C./min, or ≥12.0° C./min, or ≥13.0° C./min, or ≥14.0° C./min, or ≥20.0° C./min, 25 or ≥30.0° C./min. In one embodiment, a flow of eluent is maintained through the packing material. In one embodiment, the eluent flows through the packing material at a rate≤0.5 ml/min during cooling. In one embodiment, the flow rate of the eluent, through the packing material is from 0.5 to 3.0 mL/min, or from 0.5 to 2.0 mL/min or from 2.0 mL/min to 10 mL/min, or from 0.5 to 1.0 mL/min during heating. In one embodiment, the eluent comprises less than 1000 ppm water, based on the weight of the eluent. In one embodiment, a flow of eluent is maintained through the packing material. In one embodiment, the eluent flows through the packing material at a rate≤0.01 ml/min during cooling. In one embodiment, the flow rate of the eluent, through the packing material is from 0.01 to 0.5 mL/min, or from 0.01 to 0.4 mL/min or from 0.01 mL/min to 0.3 mL/min. In one embodiment, the eluent is selected from the following: TCB, ODCB, TCE, naphthalene, C10 or higher aliphatic alcohol, decane, xylene. In one embodiment, the polymer is an olefin-based polymer. In one embodiment, the olefin-based polymer is an ethylene-based polymer. In one embodiment, the olefin-based polymer is a propylene-based polymer. In one embodiment, the olefin-based polymer has a density from 0.850 to 0.960 g/cc, or from 0.860 to 0.960, or from 0.870 to 0.960 g/cc (1 cc=1 cm3). In one embodiment, the olefin-based polymer is an ethylene-based polymer. In one embodiment, the olefin-based polymer is a propylene-based polymer. In one embodiment, the polymer has a concentration in the solution of greater than 0.1 milligrams polymer per milliliter of solution. In a further embodiment, the polymer is an olefin-based polymer. In one embodiment, the olefin-based polymer is an ethylene-based polymer. In one embodiment, the olefin-based polymer is a propylene-based polymer. In one embodiment, a simultaneous solvent gradient and temperature gradient is used, which leads to a further improved resolution, and/or further improved detector quantification ability, and/or a further reduction of analysis time. In a further embodiment, the solvent gradient uses, but is not limited to, decane and ODCB as a solvent pair. In a further embodiment, the temperature gradient is ≥0.1° C. per minute during cooling, or ≥1.0° C. per minute during heating. In one embodiment, the chromatography method is used to determine the short chain branching distribution of the olefin-based polymer. In one embodiment, the chromatography method is used to determine the comonomer content of the olefin-based polymer. In one embodiment, chromatography method further comprises one of the following: i) a flow of solvent during at least one cooling stage, or ii) a flow of solvent during at least one cooling stage, in combination with a temperature rising elution fractionation (TREF) chromatography, or iii) a solvent gradient HTLC. The inventive chromatography method can be coupled, on or off line, with other analytical methods; for example, a multidimensional chromatography. For example, the effluent from an SEC column, containing a copolymer of a selected molecular size, can be analyzed by the chromatography method to determine the comonomer ratio of the selected molecular sizes. See also Roy et al., Development of Comprehensive Two-Dimensional High Temperature Liquid Chromatography×Gel Permeation Chromatography for Characterization of Polyolefins, Macromolecules (2010), 43, 3710-3720; Gillespie et al., “APPARATUS AND METHOD FOR POLYMER CHARACTERIZATION”, US2008/0166817A1; each incorporated herein by references. The term “multidimensional chromatography,” as used herein, refers to the coupling together of multiple separation mechanisms (for example, see J. C. Giddings (1990), Use of Multiple Dimensions in Analytical Separations, in Hernan Cortes Editor,Multidimensional Chromatography: Techniques and Applications(1st ed. pp. 1), New York, NY: Marcel Dekker, Inc.). The inventive chromatography method can be used in a preparative scale, where large quantity of polymer (in the term of grams, kilograms) is fractionated according to its CCD. The inventive chromatography method can be used in at-line process control and/or quality control to provide a fast feedback of CCD and/or SCBD and deconvolution for olefin-based polymer. The inventive chromatography method may comprise a combination of two or more embodiments as described herein. The inventive apparatus may comprise a combination of two or more embodiments as described herein. The packaging material may comprise a combination of two or more embodiments as described herein. Polymers The packing materials, and apparatus and methods using the same, can be used to analyze polymers, such as, for example, the measurement of CCD and/or short chain branching distribution (SCBD) of olefin-based polymers, such as ethylene-based polymers, and propylene-based polymers. Other suitable polymers are formed from aliphatic and aromatic hydrocarbons, optionally containing heteroatoms. In one embodiment, the olefin-based polymer is an ethylene-based polymer. In one embodiment, the olefin-based polymer is an ethylene/alpha-olefin interpolymer. In a further embodiment, the alpha-olefin is a C3-C10 alpha-olefin, and preferably selected from propylene, 1-butene, 1-hexene, and 1-octene. In one embodiment, the olefin-based polymer is an ethylene/alpha-olefin copolymer. In a further embodiment, the alpha-olefin is a C3-C10 alpha-olefin, and preferably selected from propylene, 1-butene, 1-hexene, and 1-octene. In one embodiment, the olefin-based polymer is a copolymer of ethylene and an alpha-olefin. In a further embodiment, the alpha-olefin is 1-butene or 1-octene. In one embodiment, the olefin-based polymer is a polyethylene homopolymer. In one embodiment, the olefin-based polymer is a propylene-based polymer. In one embodiment, the olefin-based polymer is a propylene/alpha-olefin interpolymer. In a further embodiment, the alpha-olefin is ethylene, or C4-C10 alpha-olefin, and preferably selected from ethylene, 1-butene, 1-hexene, and 1-octene. In one embodiment, the olefin-based polymer is a propylene/alpha-olefin copolymer. In a further embodiment, the alpha-olefin is a C2, or C4-C10 alpha-olefin, and preferably selected from ethylene, 1-butene, 1-hexene, and 1-octene. In one embodiment, the olefin-based polymer is a polypropylene homopolymer. In one embodiment, the olefin-based polymer has a density≤0.970 g/cc; or ≤0.960 g/cc; or ≤0.950 g/cc (1 cc=1 cm3). In one embodiment, the olefin-based polymer has a density≤0.940 g/cc; or ≤0.930 g/cc; or ≤0.920 g/cc. In one embodiment, the olefin-based polymer has a density≤0.910 g/cc; or ≤0.900 g/cc; or ≤0.890 g/cc. In one embodiment, the olefin-based polymer has a density≥0.850 g/cc; or ≥0.860 g/cc; or ≥0.870 g/cc. In one embodiment, the olefin-based polymer has a density from 0.830 g/cc to 0.960 g/cc, or from 0.840 g/cc to 0.950 g/cc, or from 0.850 g/cc to 0.940 g/cc. In one embodiment, the olefin-based polymer comprises from 2 mole percent to 29 mole percent of an alpha-olefin, as determined by13C NMR. Preferred alpha-olefins are discussed above. In one embodiment, the olefin-based polymer comprises from 5 mole percent to 9 mole percent of an alpha-olefin, as determined by13C NMR. Preferred alpha-olefins are discussed above. Olefin-based polymers include, but are not limited to, low density polyethylene (LDPE), high density polyethylene (HDPE), heterogeneously branched linear polymers (include Ziegler-Natta polymerized polymers, such as LLDPE, and include products such as DOWLEX Linear Low Density Polyethylene (LLDPE) available from The Dow Chemical Company), homogeneously branched substantially linear polymer (such as AFFINITY Polyolefin Plastomers and ENGAGE Polyolefin Elastomers, both available from The Dow Chemical Company) homogeneously branched linear polymers (such as EXACT Polymers available from ExxonMobil), olefin multiblock copolymers (such as INFUSE and INTUNE Olefin Block Copolymers available from The Dow Chemical Company). Olefin-based polymers also include polypropylene homopolymers, impact propylene based copolymers, and random propylene based copolymers. An olefin-based polymer may comprise a combination of two or more embodiments as described herein. Ethylene copolymers include, but are not limited to, ethylene vinyl acetate (such as Elvax® available from E.I. DuPont deNemours and Company), ethylene/alkyl (meth)acrylate copolymers (such as Elvaloy® available from E.I. DuPont deNemours and Company), ethylene/alkyl (meth)acrylic acid copolymers (such as Nucrel® available from E.I. DuPont deNemours and Company or PRIMACOR available from S.K. Global Chemical), ionomers derived from ethylene/(meth)acrylic acid copolymers (such as Surlyn® available from E.I. DuPont deNemours and Company), and/or anhydride-modified copolymers (such as Fusabond® available from E.I. DuPont deNemours and Company). The ethylene acid copolymers include, but are not limited to, those containing a softening comonomer selected from the group consisting of vinyl esters, alkyl vinyl esters, and alkyl (meth)acrylates. Suitable examples of alkyl acrylates include, but are not limited to, ethyl acrylate, methyl acrylate, n-butyl acrylate, iso-butyl acrylate, or combinations thereof. In various embodiments, the alkyl acrylate has an alkyl group with from 1 to 8 carbons. In various embodiments, the anhydride-modified copolymer is a maleic anhydride-grafted ethylene-based polymer in which an ethylene-based polymer has a maleic anhydride grafting monomer grafted thereto. Suitable ethylene-based polymers for the maleic anhydride-grafted ethylene-based polymer include, without limitation, polyethylene homopolymers and copolymers with α-olefins, copolymers of ethylene and vinyl acetate, and copolymers of ethylene and one or more alkyl (meth)acrylates. Definitions Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight, and all test methods are current as of the filing date of this disclosure. The term “packing material,” as used herein, refers to the stationary phase or the substrate of a column, for example, a stainless steel column used for HT-TGIC (thermal gradient) and HTLC (in solvent gradient). The term “graphene,” as used herein, refers to the carbon layers in graphite. It is in a form of platelets in solid form. Graphene is a two-dimensional carbon allotrope with the carbon atoms arranged in a two-dimensional honeycomb lattice. Graphene has a low density of 0.03 to 0.60 g/mL. It is impossible to use graphene alone as packing material for HT-TGIC (for example) due to high back pressure and poor short-term and long-term column bed stability. The graphene does not contain a bonded coupling agent (for example, carboxylic acid containing compounds). The term “graphene oxide,” as used herein, refers to the oxidized graphene. It is impossible to use graphene oxide alone as packing material for HT-TGIC (for example) due to high back pressure and poor short-term and long-term column bed stability. The graphene oxide does not contain a bonded coupling agent (for example, carboxylic acid containing compounds). The term “non-porous particles,” as used herein, refers to particles that have a porosity≤6.0%, for base particle in the pore size range 0.003 to 1.0 microns. See Mercury Porosimetry for Pore Size Distribution and Porosity. The term “spherical particles,” as used herein, refers to totally round, or almost round particles. The number average ratio of “largest diameter” to “smallest diameter” of the sample (∑i=1n⁢⁢100⁢⁢(largest⁢⁢diameterSmallest⁢⁢diameter)i∑n=1n⁢⁢100⁢⁢ni, where niis the particle number i) is from 3.0 to 1.0. The ratio of 1.0 indicates the perfect spherical particle. A sample containing at least 100 particles that are randomly selected, is determined by scanning electron microscopy (SEM). The term “average diameter,” as used in reference to the spherical particles, refers to the D50 value. The term “solvent,” as used herein, refers to a substance, or a mixture of substances (for example, liquids), capable of dissolving another substance (solute). The term “eluent,” as used herein, refers to a solvent used in a chromatography process to move, or elute, one or more substances from a stationary support material. The term “polymer,” as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term interpolymer as defined hereinafter. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and/or within a polymer. The term “interpolymer,” as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes copolymers (employed to refer to polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers. The term “olefin-based polymer,” as used herein, refers to a polymer that comprises a 50 wt % or a majority amount of polymerized olefin monomer, for example ethylene or propylene, (based on weight of the polymer) and, optionally, at least one comonomer. The term “ethylene-based polymer,” as used herein, refers to a polymer that comprises 50 wt % or a majority amount of polymerized ethylene monomer (based on weight of the polymer) and, optionally, at least one comonomer. The term “ethylene-based interpolymer,” as used herein, refers to an interpolymer that comprises 50 wt % or a majority amount of polymerized ethylene monomer (based on weight of the interpolymer) and at least one comonomer. The term “ethylene/α-olefin interpolymer,” as used herein, refers to an interpolymer that comprises 50 wt % or a majority amount of polymerized ethylene monomer (based on the weight of the interpolymer) and at least one α-olefin. The term, “ethylene/α-olefin copolymer,” as used herein, refers to a copolymer that comprises 50 wt % or a majority amount of polymerized ethylene monomer (based on the weight of the copolymer), and an α-olefin, as the only two monomer types. The term, “polyethylene homopolymer,” as used herein, refers to a polymer that comprises only polymerized ethylene monomer. The term “propylene-based polymer,” as used herein, refers to a polymer that comprises a majority amount of polymerized propylene monomer (based on weight of the polymer) and, optionally, at least one comonomer. The term “propylene-based interpolymer,” as used herein, refers to an interpolymer that comprises a majority amount of polymerized propylene monomer (based on weight of the interpolymer) and at least one comonomer. The term “propylene-based copolymer,” as used herein, refers to a copolymer that comprises a majority amount of polymerized propylene monomer (based on weight of the copolymer) and one comonomer, as the only two monomer types. The term “propylene/α-olefin interpolymer,” as used herein, refers to an interpolymer that comprises a majority amount of polymerized propylene monomer (based on the weight of the interpolymer) and at least one α-olefin. The term, “propylene/α-olefin copolymer,” as used herein, refers to a copolymer that comprises a majority amount of polymerized propylene monomer (based on the weight of the copolymer), and an α-olefin, as the only two monomer types. The term, “ethylene polar copolymer,” as used herein, refers to a copolymer of ethylene and at least one comonomer, wherein the ethylene polar copolymer comprises a majority amount of polymerized ethylene monomer (based on the weight of the copolymer) on the polymer chain, and also comprises at least one polar component chemically bonded to the polymer chain after polymerization, for example, LLDPE grafted with MAH. The term, “polar comonomers,” as used herein, refers to a monomer consisting of at least one unsaturated double C═C bond and one atom not hydrogen or carbon in its chemical structure, such as maleic anhydride, n-butyl acrylate, glycidyl methacrylate copolymer, methyl acrylate as the only two monomer types. The term “acid copolymer” as used herein refers to a polymer comprising copolymerized units of an α-olefin, an α, β-ethylenically unsaturated carboxylic acid, and optionally other suitable commoner(s) such as, an α, β-ethylenically unsaturated carboxylic acid ester. The term “(meth)acrylic”, as used herin, alone or in combined form, such as “(meth)acrylate”, refers to acrylic or methacrylic, for example, “acrylic acid or methacrylic acid”, or “alkyl acrylate or alkyl methacrylate”. The term “ionomer” as used herin refers to a polymer that comprises ionic groups that are carboxylate salts, for example ammonium carboxylates, alkali metal carboxylates, alkaline earth carboxylates, transition metal carboxylates, and/or combinations of such carboxylates. Such polymers are generally produced by partially or fully neutralizing the carboxylic acid groups of precursor or parent polymers that are acid copolymers, as defined herein, for example by reaction with a base. An example of an alkali metal ionomer as used herein is a zinc/sodium mixed ionomer (or zinc/sodium neutralized mixed ionomer), for example a copolymer of ethylene and methacrylic acid wherein all or a portion of the carboxylic acid groups of the copolymerized methacrylic acid units are in the form of zinc carboxylates and sodium carboxylates. The term “composition,” as used herein, includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. The term “temperature gradient chromatography,” as used herein, refers to a separation technique, typically a polymer separation, based on a temperature gradient. Preferred examples include TREF and CEF. The term “TREF,” as used herein, refers to Temperature Rising Elution Fractionation chromatography that uses a separation technique based on the different crystallizations of the polymer molecules within a polymer sample, and which uses a static or zero eluent flow during the crystallization (cooling) of the polymer sample onto a stationary support. The term “CEF,” as used herein, refers to Crystallization Elution Fractionation chromatography that uses a separation technique based on the different crystallizations of the polymer molecules within a polymer sample, and which uses a dynamic eluent flow during the crystallization (cooling) of the polymer sample onto a stationary support. The term “HT-TGIC,” as used herein, refers to High Temperature Thermal Gradient Interaction Chromatography (HT-TGIC), a separation technique to analyze CCD and/or SCBD distributions in olefin based polymers (Cong et al., Macromolecules, 2011, 44, 3062-3072). This chromatography is based on the interaction of the graphite with a polymer sample, and uses either dynamic eluent or static flow during the cooling of the polymer sample onto a stationary support, and subsequent elution during heating of the polymer samples from a stationary support. The term “CCD”, as used herein, refers to the chemical composition distribution of polymer. For olefin-based polymers, CCD is defined as the Comonomer Composition Distribution of the polymers, which are obtained through the techniques, such as TREF, or CEF or HT-TGIC. The term “SCBD”, as used herein, refers to the chemical composition distribution of polymer. For olefin-based polymers, SCBD is defined as the Short Chain Branching Distribution of the polymers, which are obtained through the techniques, such as TREF, or CEF or HT-TGIC. The terms “comprising,” “including,” “having,” and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically listed. Test Methods Density Samples are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing, using ASTM D792, Method B. Melt Index Melt index, MI or I2, is measured in accordance with ASTM D 1238, Condition 190° C./2.16 kg, and is reported in grams eluted per 10 minutes. The “I10” melt index is measured in accordance with ASTM D 1238, Condition 190° C./10 kg, and is reported in grams eluted per 10 minutes. For propylene-based polymers, the melt flow rate (MFR) is measured in accordance with ASTM D-1238, condition 230° C./2.16 kg. High Temperature Size Exclusion Chromatography The chromatographic system consists of either a Polymer Laboratories Model PL-210 (Agilent) or a Polymer Laboratories Model PL-220 (Agilent) or PolymerChar HT GPC (Spain). The column and carousel compartments are operated at 140° C. Three Polymer Laboratories, 10-μm Mixed-B columns are used with a solvent of 1,2,4-trichlorobenzene. The samples are prepared at a concentration of “0.1 g of polymer” in “50 mL of solvent” or “16 mg of polymer in 8 mL of solvent.” The solvent used to prepare the samples contain 200 ppm of BHT. Samples are prepared by agitating lightly for four hours, at 160° C. The injection volume used is “100 microliters,” and the flow rate is “1.0 mL/min.” Calibration of the GPC column set is performed with twenty one narrow molecular weight distribution polystyrene standards purchased from Polymer Laboratories. The molecular weight (MW) of the standards ranges from 580 to 8,400,000 g/mol, and the standards are contained in six “cocktail” mixtures. Each standard mixture has at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at “0.001 g in 20 mL of solvent” for molecular weights equal to, or greater than, 1,000,000 g/mol, and at “0.005 g in 20 mL of solvent” for molecular weights less than 1,000,000 g/mol. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 1: Mpolyethylene=A(Mpolystyrene)B(Eq. 1), where M is the molecular weight, A has a value of 0.4316 and B is equal to 1.0 (T. Williams and I. M. Ward,Polym. Letters,6, 621-624 (1968)). A third order polynomial is determined to build the logarithmic molecular weight calibration as a function of elution volume. Polyethylene equivalent molecular weight calculations are performed using GPCOne software for PolymerChar GPC instrument. Polydispersity (PDI) is defined as the ratio of weight average molecular weight (Mw) divided by number average molecular weight (Mn) High Temperature Size Exclusion Chromatography (HT-SEC) for Size Exclusion Effect The purpose of the HT-SEC experiments was to quantify the difference in the size exclusion chromatographic property between this invention and those of a commercial graphite column. The SEC effect of the substrate is highly undesired when using HTLC and HT-TGIC to quantify SCBD of olefin-based polymers. This SEC effect introduces errors into the adsorption based separation mechanism of HTLC of polyolefins. The standard column configuration consisted of a stainless steel tube, 100 mm length×4.6 mm internal diameter (L×D), with stainless steel frits of 2 μm porosity from Valco. The commercial HYPERCARB graphite column (100×4.6 mm, 5 micron graphite particles) was purchased from Thermo Fisher. The inventive substrates, and the base particles before coating were packed into a stainless steel tube, 100×4.6 mm (L×D), with stainless steel frits of 2 μm porosity from Valco. All SEC data was obtained using a commercial SEC instrument manufactured by Polymer Char, of Spain. This instrument was equipped with an IR5 infrared detector. Distilled o-dichlorobenzene (ODCB) was used as the mobile phase. The flow rate for all of the columns was set at 0.3 mL/min. A 140 μL and was used. Narrow distribution polystyrene (PS) standards (Polymer Laboratories, UK), with reported molecular weights of 8,400,000 Dalton, 2,950,000 Dalton, 492,500 Dalton, 151,700 Dalton, 49,170 Dalton, 21,000 Dalton and 3,250 Dalton, were used. Each narrow distribution polystyrene standard was dissolved in ODCB at 150° C. for 15 minutes. The concentration of PS was 0.3 mg/mL. The retention volume is defined as the retention volume at the peak of polystyrene standards. High Temperature Thermal Gradient Interaction Chromatography HT-TGIC measurement uses a commercial Crystallization Elution Fractionation instrument (CEF) (Polymer Char, Spain), to perform high temperature thermal gradient interaction chromatography (HT-TGIC) measurement (Cong, et al., Macromolecules, 2011, 44 (8), 3062-3072). The CEF instrument is equipped with an IR-5 detector (such as that sold commercially from PolymerChar, Spain). Ortho-dichlorobenzene (ODCB, 99% anhydrous grade) and Silica gel 40 (particle size 0.2-0.5 mm) (such as commercially available from EMD Chemicals) are used. The silica gel is dried in a vacuum oven at 160° C. for at least two hours before use. The ODCB is sparged with dried nitrogen (N2) for one hour before use. The ODCB is further dried by pumping the ODCB through a column or columns packed with dried silica, at 0.1 mL/min to 2.0 ml/min. Dried ODCB was hereinafter referred to as “ODCB.” The stock solution of Blend 4 (a mixture of EO1, EO2, EO3 and EO4 as 1:1:1:1 (wt:wt:wt:wt) was used for HT-TGIC analysis, by dissolving at 150° C., for 60 minutes, with shaking by autosampler. The experimental parameters were: stabilization temperature of 150.0° C.; thermal cooling rate of 3.0/min from 150.0 to 30.0° C.; isothermal time at 30.0° C., at 2.0 minutes flow rate during cooling at zero; Soluble Fraction time (SF) of 2 minutes; elution flow rate of 0.5 mL/min; elution thermal rate at 3° C./min from 30.0° C. to 160.0° C.; injection loop of 140 uL. The raw chromatogram was exported with GPCOne software. For the SF time, the elution temperature was extrapolated by using elution thermal rate as shown inFIG.1. The elution temperature of rest of the elution time was recorded by the instrument as RTD elution temperature. Particle Size Distribution Analysis (Uncoated Base Particles) The laser diffraction particle size analyzer utilizes the Fraunhofer theory of light scattering. Laser diffraction based particle size analysis is based on particles passing through a laser beam scatter light, at an angle where the scattered light intensity is directly related to the size of particle. A Beckman Coulter LS13 320 laser diffraction instrument, equipped with a Universal Liquid Module, was used to determine the particle size distribution of the base particles prior to coating). A sample (0.25 gram) was dispersed in 40 ml of clean and bubble free deionized water (DI). The instrument does a routine background check before the actual run, and subtracts any particles that may be present, before loading the particles to be analyzed. The mixture was stirred with a magnetic stirrer to uniformly disperse the particles at room temperature. One drop of Micro 90 surfactant (Thermo Fisher Scientific) was added to the mixture of the base particles (Glass-Particle-PL2015SL-S2). Drops of the dilute dispersion were spiked into the liquid module port of the analyzer, until 8% obscuration was achieved. The instrument was then set to run mode. Each run was 60 seconds. Three consecutive runs are done, one minute apart, to assure the obscuration remained constant, and the particles were not dissolving or agglomerating. An equivalent spherical diameter was used to characterize the size distribution of the particles. Particle size measurements were performed over the size range of 0.4 to 2000 microns. Particles outside the measurement range were not included in the reported statistics by the software. Data acquisition and computation of average particle size were done with the software provided by Beckman Coulter LS 13 320 instrument. The D10, D50 and D90 values are defined as the diameter of cumulative distribution curve at 10% point, 50% point and 90% point, respectively. The instrument was checked with NIST Traceable Particle Size Standards (latex standards) for normal operation. Mercury Porosimetry for Pore Size Distribution and Porosity Pore size distribution was obtained by mercury porosimetry. The mercury porosimetry analysis was performed on a Micromeritics Autopore IV 9520, available from Micromeritics. The samples were mechanically out-gassed, while under vacuum, prior to analysis, to remove any physically adsorbed species (i.e., moisture) from the surface of the sample. Test conditions included a Hg fill pressure of 0.50 psia, a Hg contact angle of 130°, a Hg surface tension of 485 dyn/cm, a Hg density 13.53 g/mL, a “30 minute evacuation time,” a large bore penetrometer (powder type: 1.131 stem volume) with 5-cc bulb, a “30 seconds equilibration time,” a 92-point pressure table (75 intrusion plus 17 extrusion pressure points), and mechanical evacuation<50-μm Hg. The low to high pressure cross over point was collected at approximately 46 psia (3.3 um). The pressure table used was generated to allow an even incremental distribution of pressures, on a log scale, from 0.5 to 60,000 psia, and was used for detecting pore size from 0.003-400-μm diameter. Mercury was forced into smaller and smaller pores as the pressure was increased incrementally, from a vacuum, to a maximum of nearly 60,000 psia. To verify that the instrument was working properly, a Silica-Alumina reference material (Micromeritics lot A-501-46) was analyzed. The reported median pore diameter (volume) of the reference sample was 0.0072±0.0005 μm. The Autopore reported the median pore diameter (volume) of the reference material as 0.0071 μm. Porosity was calculated by excluding the inter particle intrusion, using the data processing software equipped with Micromeritics Autopore IV 9520. The percentage of porosity (% porosity) was calculated as the total volume of the pore (in the range of 0.003 microns to 1.0 microns) divided by the total volume then multiplying by 100. Skeletal density was computed after the volume of all pores, larger than about 0.003 jam, had been excluded from the volume presumed occupied by the material. Thermogravimetric Analysis (TGA) TGA was performed using a TA TGA Q5000 V3.17 Build 265. The experimental conditions were: a 10.00° C./min rate, from room temperature to 800.00° C., and a sample weight of 10-30 mg into a 100 microliter platinum pan. The sample was run in air at 25 mL/min air. Graphene does not have appreciable weight loss at a temperature of approximately 2000° C. in an inert atmosphere. In an oxygen containing environment, graphene can be oxidized. About 10% of the graphene weight lost occurs before 650° C., and 90% of the graphene weight lost occurs by 700° C. (Gao et al.,Nanoscale Res Lett,2013, 8:32)). TGA is used to measure the amount of graphene and/or graphene oxide coated on the substrate, by using the weight loss % at temperature of 700° C. Nitrogen Adsorption/Desorption (B.E.T.) Nitrogen adsorption/desorption analysis was performed on a Micromeritics Accelerated Surface Area & Porosimetry instrument (ASAP 2405). The samples were out-gassed at 200° C., for approximately 24 hours, while under vacuum, prior to analysis. Approximately 0.5 gram of the “as-received” sample was used for the analysis. Typically, B.E.T. surface areas are measured with a precision of <3% RSD (relative standard deviation. The instrument employs a static (volumetric) method of dosing samples, and measures the quantity of gas (nitrogen) that can be physically adsorbed on a solid at liquid nitrogen temperature. For the multi-point B.E.T. measurement, the volume of nitrogen uptake was measured at pre-selected relative pressure points, at constant temperature. The relative pressure was the ratio of the applied nitrogen pressure to the vapor pressure of nitrogen at the analysis temperature of 77 K. Pore sizes from about 17 to 3,000 Angstroms diameter are detected by this method. Test conditions for the nitrogen adsorption/desorption isotherms include a 15 second equilibration interval, a 97-point pressure table (40 adsorption points, 40 desorption points, a multi-point B.E.T. surface area, 20 micropore points, and 1-point total pore volume), a 5%/5 mmHg P/Po tolerance, and a 120 min Po interval. The total surface area is defined as B.E.T surface area. The B.E.T. surface area (m2/g) was performed using the data processing software equipped from Micromeritics Accelerated Surface Area & Porosimetry instrument (ASAP 2405). SEM Dry powder was sprinkled on aluminum sample stub to which had been adhered a double-sided carbon tape. The prepared specimen was coated with iridium using a EMS 150T plasma coater from “Quorum Technologies” in order to render the particulates conductive under the electron beam. Secondary electron micrographs were acquired using a FEI Nova 600 Schottky field emission secondary electron microscope (SEM). The SEM was operated at 3 kV spot 5, and under a working distance of ˜4 mm-6 mm. EXPERIMENTAL The base particles used for coating with graphene, and the graphene were purchased, and used without a further purification unless specified See Table 1. Amorphous SilicaSC70-2 TABLE 1Information about base materials and graphene nanoplatelets using in coatingDescriptionAbbreviationManufacturerChemical composition*Solid glassGlass-Particle-Cospheric, Santa Barbara,CAS#308076-03-1 Glass oxidemicrospheresP2015SL-52CA, USA(99%), Alkyl trialkylsilane <1%P2015SL-S2Solid glassGlass-Particle-Cospheric, Santa Barbara,CAS#308076-03-1 Glass oxide,microspheresP2015SLCA, USA(100%)P2015SLGlass Beads 20-27Glass Particle-MO-SCI Specialtymicrons (GL0191B)20-27 umProducts, Rolla, MoSPI-Chem GlassyGlassy-Structure Probe, Inc.CAS #7440-44-0 (100%)Carbon sphericalCarbon-West Chester, PApower 10-20 umParticleSilicon Carbide 600Silicon-Beta Diamond Products,Silicon Carbide CAS#409-21-2,GritCarbideInc.97-100% GraphiteCAS#7782-42-5, 0-3%Glass ParticlesGlass-Particle-MO-SCI SpecialtyGL0191B6125 micronsProducts, Rolla, MoAmorphous non-SC70-2Nippon Steel & SumukinSiO2 (≥99.9%)porous silicaMaterials Co., Ltd. MicronCoc., Himeji City, Hyogo671-1124, Japan10581 NickelNickel particleAlfa AesarCAS#7440-02-0powder, spherical, -300 mesh, 99.8%purityGraphene nanoGrapheneGraphene Supermarket Inc.platelets A12*Values reported by vendor. A homopolymer polyethylene (EO-1) with a density of 0.956 g/cm3, melt index (I2) of 1.0, a melt index ratio (I10/I2) of 6.7, a weight average molecular weight (Mw, ethylene equivalent) of 115,000 Daltons, and a polydispersity (Mw/Mn) of 2.6; and ethylene-octene copolymers, EO-2, EO-3 and EO-4, with their specified microstructures, are listed in Table 2. A stock solution of EO-1:EO-2:EO-3:EO-4=1:1:1:1 (wt) was prepared in ODCB at a concentration of 4 mg/mL (1 mg/mL, each) at 150.0° C., for 2 hours under stirring. The stock solution was transferred into 10 mL autosampler vials for HT-TGIC analysis. See Table 2. TABLE 2Characterization Data for EO-1 to EO-7MwMeltmeasured byOcteneSampleindexconventionalcontent***,ID*DensityI2I10/I2GPC**mol %EO-10.9571.06.71150000.00EO-20.9241.06.41045001.33EO-30.9041.06.41029003.99EO-40.8651.06.912340013.88h-PE0.9571.0118,0000.00*Homogeneously branched, substantially linear polymer.*See a) Metallocene-based polyolefins Volumes One and Two, edited by John Scheirs and Walter Kaminsky, Wiley series in Polymer Science, John Wiley & Sons, Ltd., (2000); and b) Innovations in Industrial and Engineering Chemistry - A Century of Achievements and Prospects for the New Millennium, ACS Symposium Series 1000, edited by William H. Flank, Martin A. Abraham, and Michael A. Matthews, American Chemical Society Copyright 2009; and c) History of Polyolefins, Edited by Raymond B. Seymour and Tai Cheng, D. Reidel Publishing Company, 1986.**See Hermel, et al., U.S. Pat. No. 8,372,931 and cited references. Weight average molecular weight (Mw) by Conventional GPC referred to the backbone molecular weight of ethylene based polyolefin.***Octene content measurement was based on Cong et al., Macromolecules 2011, 44, 3062-3072. Representative Procedure A to Make Inventive Packaging Material by Coating Graphene onto Base Particles The steps in making the inventive substrates by coating graphene onto particles consisted of the following: 1. Weigh 15.0 g of the base particle, such as spherical glass beads, spherical glassy carbon beads or silicon carbide, into a 40 mL glass vial. 2. Weigh the amount of graphene (G) into the vial necessary to give the desired loading, in weight percentage. A nominal 6.25 wt % loading is defined as the amount of graphene divided by total weight of graphene plus base particle, and multiplying by 100%. 3. Mix the two ingredients by shaking and rotating the vial until the mixture has a uniform color. The material is ready for making the columns for HT-TGIC without the rest of steps. The rest of steps can be used to yield more consistent and more easily handled substrates. 4. Add n-hexane, Fisher HPLC grade, to the vial until a small headspace remains, and cap the vial. 5. Place the vial into a sonication bath (Branson model 1510) containing deionized water at room temperature. The level of the water was set according the manufacturer's instruction, but not above the vial cap. It may be necessary to support the vial to prevent it from overturning. The vial sonication time was set to 20 minutes. 6. Pour the sonicated mixture into a glass evaporation dish and allow the hexane to evaporate in an area with proper ventilation. A small amount of hexane was used to rinse the vial, and this rinse was added to the dish. 7. After two hours, there was no visible hexane and the mixture was stirred with a glass rod to break up any remaining clumps, giving a free-flowing, powdery solid of uniform color. 8. The flow powdery solid can be heated in a vacuum oven at 150 C under N2 for 3 hours, then cooled down to room temperature in a dessicator before use. 9. Store the mixture in a clean glass vial with cap. This material is ready to be packed into a column for HT-TGIC analysis. Representative Procedure B to Make Inventive Packing Material by Coating Graphene onto Metal Particles (1) Metal particles (for example, “10581 Nickel powder”) were screened to produce a narrow particle size distribution by particle fractionation techniques, such as sieving. Here, a sieve of a 325 US mesh size was used. (2) Metal particles in general may have oxides on the surface. Acid cleaning, such as with dilute HCl, was used to clean the oxidized surface. Alternatively, the acid washing and the following coating with graphene can be combined in one step. Here the “sieved nickel” was suspended in about 0.1M aqueous HCl solution for about 2 minutes, the nickel was filtered, and washed with deionized water. (3) Metal particles were mixed with graphene in methanol. The mixture was stirred for 20 minutes at room temperature. The slurry was filtered and dried under vacuum. (4) The substrate was packed into a column according the procedure below. (5) The wt % of graphene coated was calculated as the percentage of the amount of graphene divided by the total weight of metal particles and graphene. Hardware for Packing Columns Unless otherwise stated, the standard column configuration consisted of a 0.25 inch outside diameter stainless steel tube, 100 mm in length, and an internal diameter of 4.6 mm, with stainless steel frits of 2 m porosity from Valco. The columns were cleaned with acetone, and dried in air, before being packed with the inventive materials and comparative particles specified in Table 3. An Agilent 1200 Liquid Chromatography Pump was used for the slurry packing method. A packing reservoir was constructed of 4.6 mm internal diameter stainless steel tubing with Valco end fittings. The reservoir was 100 mm in length. A Valco ¼ inch union allowing butt to butt connections between the analytical and the packing reservoir was used to connect the two lengths of tubing. Methodologies for Packing Columns The columns for use in high temperature solvent gradient, thermal gradient interaction chromatography (HT-TGIC, or simply TGIC), and HT-GPC had the following properties: 1. Packed columns exhibit good mass transfer properties including low back pressure, 100 bar or less, at standard operating conditions of flow and temperature, low sensitivity to shock from abruptly changing conditions, and lack of channels and void spaces. 2. Packed columns which were long enough to permit studies of the effect of dynamic cooling on component resolution. The dynamic cooling is a process of using a slow flow during the cooling process to further enhance HT-TGIC separation (Cong et al., Macromolecules, 2011, 44(8), 3062-3072). The empty column was suspended vertically. Substrate was added in small increments through a funnel, while the column was tapped or vibrated to settle the substrate. When the substrate is level with the end of the column, the packing reservoir was connected. The substrate was added to the reservoir in the same manner, until the reservoir was also filled. The reservoir and column with end fitting was then assembled, and connected to the Agilent pump. The 1,2,4-trichlorobenzene (TCB) was pumped at a flow of 2-5 mL/min, through the reservoir until air was displaced from the column. TCB was pumped at 2-5 mL/min through the column for at least twenty minutes, or until the system pressure reaches 2500 PSIG. The column was disconnected from the packing reservoir, and any excess packing at the end of the column was removed with a flat blade scraper to provide an even surface level with the end of the tubing. The end fitting with frit was tightened into place, and the column was ready for conditioning. TABLE 3Properties of the Packing Materials% Porosityof basewt % ofparticle inGraphenethe porewt % ofmeasuredSize of the base particlesize rangeBaseGrapheneby(microns) uncoated0.003 toparticleused.**TGA.**D10D50D903D504D501.0 micronsComp. Ex. #1PorousN/AN/A7*7*7*212838.1GraphiteInv. Ex. #l:Glass7.0%6.7%1.26.511.719.5262.9Glass-Particle-Particle_PL2015P2015SLCoated-(spherical)7 wt %-GrapheneInv. Ex. #2:Glass5%1.03.59.110.514.01.0Glass-Particle-Particle-PL20I5-S2P2015SL-Coated-S25.0 wt %-(spherical)Graphene)Inv. Ex. #3Glassy6.25%99.1%0.1(Glassy CarbonCarboncoated with(spherical)6.25%Graphene)Inv. Ex. #4:Silicon5.1%3.4%2.34.36.612.917.20.7Silican-CarbideCarbide-600 GritCoated-(rod-5.1 wt %-shaped)Graphene)Inv. Ex. #5:Glass-3.0%0.0129.0135.6387.0516.0Glass-Particle-Particle-125 microns-125Coated-microns3 wt %(spherical)GrapheneInv. Ex. #6:Nickel3.0%Nickel-particleParticle-(spherical)Coated-3 wt %Graphene*According to Manufacturer.**based on weight of particle and graphene.N/A = not applicable. Inventive Example #1—Glass-Particle-PL2015-Coated-7.0 wt %-Graphene The Inventive Example #1 (Glass-Particle-PL2015-Coated-7 wt %-Graphene) was made by mixing 15.0 g of Glass-Particle-PL2015 with 1.13 g of Graphene in a 40 mL glass vial. The amount of graphene was to sufficient to cover all of the surface area of the base particles. The Glass-Particle-PL2015 had an average particle size of D10, D50 and D90 at 1.2 microns, 6.5 microns, 11.7 microns, respectively, and a very low porosity at 2.5% (Table 3). The vial was shaken by hand, until the mixture had a uniform color. Next, 30 mL n-hexane (Fisher HPLC grade) was added to the vial to displace air and to cover the surface of the mixture. The vial was capped. The vial was then placed into a sonication bath (Branson model 1510) containing deionized water, at room temperature. The level of the water was set according to the manufacturer's instruction, but not above the vial cap. It may be necessary to support the vial to prevent it from overturning. The vial sonication time was set to 20 minutes. The sonicated mixture was poured into a glass evaporation dish, to allow the hexane to evaporate in an area with proper ventilation. A small amount of hexane was used to rinse the vial, and the rinse was added to the dish. The dried power was obtained as the inventive example #1. The properties of the Inventive Example #1 are listed in Table 3. A reduced SEC effect of the Inventive Example #1 was characterized by its ability to separate PS standards in ODCB at a constant temperature. The commercial HYPERCARB column, packed with porous graphite, is well known for its superior SEC effect (Cong, et al., Size exclusion chromatography of polymers WO 2012166861 A1). As shown inFIG.2, the graphitic HYPERCARB column was well capable of separating PS in the molecular weight range of 2,950,000 Daltons to 3250 Daltons. PS at 2,950,000 Daltons eluted first, followed by PS with 492,500 Daltons, followed by 151,700 Daltons, followed by 49,171 Daltons, and lastly by PS at 21,000 Daltons. The large peak, at retention volume of 1.5 mL, was from decane, which was used as flow marker. In contrast, much less separation in these polystyrene standards were achieved by the Inventive Example #1 (FIG.3). Decane was not added into PS standard, because of the poor SEC effect; the PS peak overlapped with decane peak for the Inventive Examples. Retention volume is plotted against “log10MW” of PS standards. The steeper the slope, the less the SEC effect achieved. As shown inFIG.4, the comparative #1 HYPERCARB graphite column had a slope of −4.91, while the Inventive Example #1 had a much steeper slope of −13.13. The Inventive Example #1 had a much less “SEC effect” than the Comparative Example #1, and this led to a better HT-TGIC separation and simplified separation mechanism in HT-TGIC with the Inventive Example #1. The HT-TGIC (see above test method) separates ethylene-α-olefin copolymers based on the comonomer content, from zero comonomer content up to approx. 50 mol % comonomer (Cong et al., Macromolecules, 2011, 44, 3062-3072; Monabal., Adv Polym Sci, 2013, 257: 203).FIG.5shows the HT-TGIC chromatogram overlay of the Inventive Example #1, the Comparative Example #1(HYPERCARB graphite column at 5 micron particle size), and the Comparative Example #2 (Glass-Particle-PL2015 with zero graphene). Comparative Example #1 is the state-of-art column for interaction chromatography of polyolefins. As shown inFIG.5, the HYPERCARB column was capable of separating all of the four components in the Blend 4 mixture, and the amorphous material EO-4, containing 13 mol % octene, eluted around 95° C. This is a well-known advantage of interaction chromatography in SCBD analysis for polyolefin, where a crystallization based technique is unable to separate polyethylene containing more than 8 mol % of comonomer. Bare glass particles of PL2015 are a common substrate for crystallization based technology (Monrabal,Macromol. Symp.356, 147; Hermel-Davidock et al., U.S. Pat. No. 8,372,931)), and behave in the TREF mode; the eluting peak temperature of EO-1 was below 97.4° C. On the contrary, coating 7 wt % of graphene onto glass particle PL 2015, significantly changes the elution profile. The elution temperature of Blend 4, using the Inventive Example #1, was much higher than the Comparative Example #2 (crystallization based technique). It was very similar to HYPERCARB, because interaction chromatography is the primary mode of separation. In addition, the peak shape of the Blend 4, obtained with the Inventive Example #1, was much sharper and symmetrical than those obtained by Comparative Example #1, which elution was confounded by the more pronounced SEC effect in the Comparative Example #1. This is due to the substantially low porosity of the base particle, or basically nonporous base particle, and the homogeneous interaction sites of graphene coated on very low porosity glass particles for the adsorption of polyolefin chains. The Inventive Example #1 has a much improved resolution (R) as the substrate for High Temperature Thermal Gradient Interaction Chromatography (HT-TGIC) than that of porous graphite HYPERCARB (Comparative #1). The resolution R is defined as the difference in the peak temperature between EO1 and EO1 divided by the sum of the half width of EO1 and EO2. The higher R is, the better the resolution. Resolution of the inventive example=(148.73 C−142.78 C)/{(149.655 C− 147.45 C)+(145.85 C−140.13 C)}=0.75, while R of the Comparative #1 was calculated as (144.99 C−139.79 C)/{(146.49 C−143.04 C)+(142.70 C−137.53 C)}=0.60. In other word, there was 25% increase in the resolution by using the Inventive Example #1 in HT-TGIC. The plot of elution peak temperature of EO-1, EO-2 and EO-3 versus octene mole % is shown inFIG.6. The inventive Example #1 yielded a slope of (−6.21) while the Comparative Example #1 (HYPERCARB for HT-TGIC) was (−3.85), which was less steep, indicating that the Inventive Example #1 gave much higher resolution than the comparative HYPERCARB column. The improved Separation (IS) is defined as the percentage of the change in the slope in elution temperature versus octene content. The correlation of peak temperature versus octene mol % is obtained using same HT-TGIC method specified in the experimental section with a column of “100×4.6 mm.” The “IS” is [(−6.21)−(−3.85)/(−3.85)]*100%=236%. The Comparative #2 (Base glass particles) worked as crystallization mode, thus had a much lower elution temperature than the Inventive #1 (HT-TGIC mode) and the Comparative #1 (HT-TGIC mode), and was thus unable to fractionate ethylene based polyolefins with a high comonomer content. In summary, it has been discovered that the inventive packing material significantly reduced the SEC effect (see above test methods), due to the decreased porosity of the base particles, when compared with current state-of-art HYPERCARB column; provided an equivalent separation to that of crystallization based techniques for EO polymer with octene content less than 7 mol %; and also covered a much wider range of comonomer content than crystallization based techniques. Inventive Example #2—GlassParticle-PL2015SL-S2-Coated-7 Wt % Graphene The Inventive Example #2 (Glass-Particle-PL2015SL-S2-Coated-7 wt %-Graphene) is made the same procedure as the Inventive Example #1, except base particle was Glass-Particle-PL2015-S2. The properties of the Inventive Example #2 are listed in Table 3. Similar as with Glass-Particle-PL2015, used in the Inventive Example #1, Glass-Particle-PL2015-S2 is basically non-porous. See above HT-TGIC test method. FIG.7shows the HT-TGIC chromatogram overlay of Blend 4 obtained by the Inventive Example #2, Comparative Example #1 and Comparative Example #2. The elution temperature of Blend 4 with the Inventive Example #2 was much higher than the Comparative Example #2 (crystallization based technique), but very similar to the Comparative Example #1(interaction chromatography). In addition, the peak shape of the Blend 4, obtained with the Inventive Example #2, is much sharper than that obtained by Comparative column #1. This is due to the substantially low porosity of the base particle, and the homogeneous interaction site of graphene, which was coated on the basically non-porous base glass particle for adsorption of the ethylene-based polymer chains. Inventive Example #3—Glassy-Carbon-Coated 6.3% Graphene (Blend 4 was at 3 Mg/mL) The Inventive Example #3 (Glassy-Carbon-Particle-Coated-6.3 wt %-Graphene) is made in the same manner as the Inventive Example #1, except that the base particle used glassy carbon particles, instead of glass particles, and the amount of graphene was different. Glassy carbon made by SPI is a “non-graphitizing or non-graphitizable carbon, which combines glassy and ceramic properties with those of graphite. Unlike graphite, glassy carbon has a fullerene-related microstructure and has no porosity”. (http://www.2spi.com/category/labware-crucibles-glassy-carbon/). See above HT-TGIC test method. The properties of the Inventive Example #3 is listed in Table 3. Similar to Glass-Particle-PL2015, used in the Inventive Example #1, glassy carbon is basically non-porous. A reduced SEC effect of the Inventive Example #3 was seen inFIG.8. In contrast to the Comparative Example #1 (HYPERCARB column,FIG.2), much less separation in these polystyrene standards were achieved by the Inventive Example #3 (FIG.9). Decane was not added to the PS standards, because of the poor SEC effect. Retention volume was plotted against log10MW. As shown inFIG.9, the Comparative #1 HYPERCARB graphite column has a slope of −4.91, while the Inventive Example #3 had a much steeper slope of −13.97. In conclusion, the Inventive Example #3 had a much reduced SEC than the Comparative Example #1. FIG.10shows the chromatogram overlay of Blend 4, obtained with the Inventive Example #3, and the Comparative Example #1(HYPERCARB graphite column at 5 micron particle size), and Comparative Example #3 (Glassy carbon particle with zero graphene). Glassy Carbon Particle, with zero graphene, behaved as a TREF separation; the eluting peak temperature of EO-1 was below 97.5° C.; there were some extra shoulders showing up between 30° C. to 97.5° C. On the contrary, coating 6.3 wt % of graphene onto glassy-carbon-particles significantly changed the elution profile. The elution temperature of Blend 4 with the Inventive Example #3 was much higher than the Comparative Example #3 (crystallization based technique). Inventive Example #3 separated the ethylene based polymers using interaction chromatography. In addition, the peaks of the Blend 4, obtained with the Inventive Example #2, were much sharper than that obtained by Comparative Example #1. This is due to the substantially low porosity of the base particle, and the homogeneous interaction site of graphene, which was coated on the basically non-porous base glass particle for adsorption of the ethylene-based polymer chains. Inventive Example #4—Silicon-Carbide-Coated 5.0 wt % Graphene The Inventive Example #4 (Silicon-Carbide-Coated-5.0 wt %-Graphene) was made in the same manner as the Inventive Example #1, except that base particle used silicon carbide particles instead of glass particles, and the level of graphene dosage was lower, due to the higher density of silicon carbide compared to glass. The properties of the inventive example #4 are listed in Table 3. Similar to other base particles, the silicon carbide particle is basically non-porous. See above HT-TGIC test method. FIG.11shows the HT-TGIC chromatogram overlay of the Inventive Example #4, the Comparative Example #1 (HYPERCARB graphite column at 5 micron particle size), and Comparative Example #4 (silicon carbide with zero graphene). Bare silicon carbide was reported to have a weak HT-TGIC effect (Cong et al., EP 2 714 226 B1), eluting at 101.5° C. which was approx. 5° C. higher than that of glass particles of crystallization based techniques. Coating of 5.0 wt % of graphene onto glassy-carbon-particle, significantly changed the elution profile of the Blend 4. The elution temperatures of Blend 4 components in the Inventive Example #4 were much higher than the Comparative Example #4 (crystallization based technique), but very similar to those obtained by HYPERCARB, which is interaction chromatography. In addition, the peak shape of the Blend 4 obtained with the Inventive Example #4 was much sharper with much better resolution, than that obtained by Comparative Example #1. This is due to the substantially low porosity of the base particle, and the homogeneous interaction site of graphene, which was coated on the basically non-porous base glass particle for adsorption of the ethylene-based polymer chains. It was discovered that the adhesion between graphene and the base particle was strong enough that shredding of the particles was not observed, which would be detected by online light scattering detector. The chromatographic stability was very uniform over the time. Inventive Example #5—Glass-Particle-125 Microns-Coated 3.0 wt % Graphene (Column Size 4.6 (ID)×150 (Length) (Mm) The Inventive Example #5 used substantially nonporous glass particles of 125 microns as the base particle, which were coated with 3.0 wt % graphene, using coating steps 1-3 (see above coating procedure A). The inventive packing material was packed into 150×4.6 (L×D) column.FIG.12shows the HT-TGIC chromatogram of Blend 4. EO-4, at 13.88 mol % octene, eluted at 87° C., which proved that the Inventive Example #5 separated ethylene based polymers using interaction based mechanism. The order of elution was inversely correlated to the octene content, or proportional to the density of the EO polymer. See above HT-TGIC test method. Inventive Example #6—Nickel-Particle-Coated 2.0 wt % Graphene (Column Size 4.6 (ID)×150 (Length) (Mm) The Inventive Example #6 used nonporous nickel particles of 44 microns, as the base particle, and these particles were coated with 2.0 wt % Graphene, using the coating procedure for metal particles (see above coating procedure B). The inventive packing material was packed into “150×4.6 mm (L×D) column.”FIG.13shows the HT-TGIC chromatogram of EO-1 eluting at 146° C., which proved that the Inventive Example #6 separated ethylene-based polymers by HT-TGIC separation mode. See above HT-TGIC test method. An example of an inventive apparatus is shown inFIG.14. As seen in this figure, the inventive packing material is used in an HTLC column. The packing material can be subject to a temperature gradient and a solvent gradient. Simultaneously applying a solvent gradient and a temperature gradient can lead to a further improved resolution, and/or reduced analysis time, and/or better separation.FIG.15depicts a temperature profile and a solvent profile for the simultaneous application of a temperature gradient and a solvent gradient to the inventive packing material. The solid line represents the thermal gradient. The dotted line represents the solvent gradient. Inventive Example #7—“Fractionated SC70-2 Silica”-Coated 5.0 wt % Graphene (Column Size 4.6 (ID)×250 (Length) (Mm) for Ethylene Polar Copolymer Resin Other than Ethylene Alph-Olefin Copolymers Amorphous silica SC70-2 was purified by multiple cycles of sedimentation in distilled water to remove the particles with a diameter larger than 30 micron and less than 5 microns. The particle size was measured by SEM. The purified SC70-2 is herein defined as “Fractionated SC70-2 silica”. The purified SC70-2 was coated with 5.0% graphene A12 according to method A of coating procedure. FIG.16shows the HT-TGIC chromatograms of an ethylene/n-butyl acrylate/glycidyl methacrylate copolymer, (Trade mark of E.I. DuPont deNemours and Company). LOTRYL® 30BA02 (the trade mark of Arkerna) and homopolymer polyethylene (h-PE) with inventive ‘Fractionated SC70-2 silica”-coated 5% graphene as substrate. LOTRYL® 30BA02 is a random copoymer of ethylene and butyl acrylate produced in high pressure radical polymerization process. It contains 28-32 wt % of butyl acrylate. Comparing with h-PE, the presence of 28-32 wt % of n-butyl acrylate (n-BA) comononmer led to a lower elution temperature than h-PE. This indicates that IT-TGIC using the inventive substrate can fractionate ethylene polar copolymer using comonomers other than alpha-olefin comonomers (C3 to C10). GMA has three oxygen atoms, while n-BA has only two oxygen per monomer. GMA is more polar comonomer than n-BA, thus GMA has a stronger interaction with graphene than ethylene units. The ethylene/n-butyl acrylate/glycidyl methacrylate copolymer chromatogram showed a bimodal distribution. This indicates that HT-TGIC using inventive substrate can be used to characterize the comonomer distributions in ethylene polar copolymers with more than one comonomer. This technique can be used to differentiate two monomer systems from three monomer systems for the ethylene polar copolymers using comonomers other than alpha olefin comonomers. Inventive Example #7—“Fractionated SC70-2 Silica”-Coated 5.0 wt % Graphene (Column Size 4.6 (ID)×250 (Length) (Mm) for Maleic Anhydride (MAH) Modified LLDPE FIG.17shows the HT-TGIC chromatograms of LLDPE before and with maleic anhydride (MAH) (Mw of 70, 800 and PDI of 2.5) with inventive graphene coated particles as substrate. LLDPE itself appeared at a lower elution temperature than h-PE (at 150° C.). Due to the incorporation of alph-olefin comonomers into LLDPE polymer chains, therefore, LLDPE elute at a temperature below 150° C. Surprisingly, HT-TGIC chromatogram of LLDPE grafted with 1 wt % MAH showed a much longer tailing at high elution temperature (high elution time), and continuously eluted after 40 minutes. The fraction with a much higher elution time is due to presence of grafted MAH. As MAH is a polar group, once LLDPE chains grafting with maleric anhydride, a much stronger interaction between the chains with grafted maleric anhydride and graphene led to an increase in elution temperature (elution time). This inventive materials quantify the properties of the chains grafted with MAH. With the addition of MAH sensitive detector such as C═O sensitive infrared detector and/or molecular weight sensitive detector such as light scattering detector, this inventive material is capable of providing MAH content and Mw at each elution temperature.
80,748
11857949
DESCRIPTION OF EMBODIMENT Hereinafter, an embodiment of the present invention will be described in detail, but a material, a dimension, and the like given as examples in the following description are just examples, the present invention is not limited thereto, and the embodiment can be appropriately modified as long as the gist thereof is not changed, to be practiced. The packing material encompasses one that can be used alone as a packing material, and one that can be used by modifying the surface depending on the purpose. In addition, as used herein, “(meth)acryl” means acryl and methacryl, and the same also applies to “(meth)acryloyl.” [Packing Material] The packing material of the present embodiment has a structure in which a specific skeleton is bonded to a porous organic polymer carrier as shown below. (Porous Organic Polymer Carrier) The porous organic polymer carrier (hereinafter, abbreviated as the carrier α) contains 60 to 95 mol % of a repeating unit derived from glycidyl methacrylate and 5 to 40 mol % of a repeating unit derived from a polyfunctional monomer. The porous organic polymer carrier contains preferably a repeating unit derived from glycidyl methacrylate at a ratio of 65 to 95 mol % and a repeating unit derived from a polyfunctional monomer at a ratio of 5 to 35 mol %, and further preferably a repeating unit derived from glycidyl methacrylate at a ratio of 75 to 92 mol % and a repeating unit derived from a polyfunctional monomer at a ratio of 8 to 25 mol %. When the ratio of the repeat unit derived from a polyfunctional monomer is low, the final packing material may provide a high back pressure and be unsuitable for use, and when the ratio of the repeat unit derived from a polyfunctional monomer is high, non-specific adsorption may occur to make the intended fractionation impossible. The carrier α of the present embodiment can also be obtained by using glycidyl acrylate. The polyfunctional monomer is a compound having two or more ethylenic double bonds in the molecule thereof. The polyfunctional monomer is preferably one having two or more (meth)acryloyl groups in the molecule thereof. Specific examples thereof include alkanediol di(meth)acrylate wherein the alkane has 1 to 12 carbon atoms, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and also include polyfunctional urethane (meth)acrylate. These compounds may be used singly or in combinations of two or more. Preferably, at least one selected from ethylene glycol dimethacrylate and glycerin-1,3-dimethacrylate is included. Ethylene glycol dimethacrylate and/or glycerin-1,3-dimethacrylate may account for 50 mol % or more, based on the total amount of the polyfunctional monomer, accounts for preferably 80 mol % or more, and from the viewpoint of pore formation or the like, ethylene glycol dimethacrylate and/or glycerin-1,3-dimethacrylate further preferably accounts for the total amount. The copolymer may include a further monomer unit in a range that does not greatly change a property of the porous particle as long as the copolymer includes 95 mol % or more in total of the glycidyl methacrylate and the polyfunctional monomer as monomer units. Examples of a monomer having a glycidyl group that can be used as a further monomer include 3,4-epoxycyclohexylmethyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, as well as methyl (meth)acrylate and ethyl (meth)acrylate. The degree of crosslinking of the copolymer is 5 mol % to 40 mol %, preferably 5 mol % to 35 mol %, and more preferably 8 to 25 mol %. The degree of crosslinking is represented by (Total number of moles of polyfunctional monomer/total number of moles of all monomers)×100=degree of crosslinking(mol %). When the degree of crosslinking is low, the final packing material may be unsuitable for use because of the high back pressure of a column for size exclusion chromatography, and when the degree of crosslinking is high, non-specific adsorption may occur to make the intended fractionation impossible. (Surface Structure) In the present embodiment, one end of at least one alkylene group selected from a linear alkylene group, a cycloalkylene group, a linear alkylcycloalkylene group, and a cycloalkyldialkylene group, having 4 to 9 carbon atoms, is bonded to the carrier α. The one end of the alkylene group is bonded to the carrier α via an ether bond formed by a ring-opening reaction of a glycidyl group derived from glycidyl methacrylate included in the carrier α. In addition, the other end of the alkylene group is bonded to a polyol directly or indirectly via an ether bond. The ether bond encompasses both one derived from a polyol and one derived from an epoxy compound used when introducing a polyol such as epichlorohydrin. That is, the structure thereof is a structure having a hydrophobic skeleton forming a hydrophobic layer derived from an alkylene group on the surface of the carrier and further, a hydrophilic skeleton forming a hydrophilic layer derived from a polyol on the surface of the hydrophobic layer. Such a structure is preferably introduced at a density of 500 μmol/g to 2000 μmol/g, and preferably 700 μmol/g to 1800 μmol/g, based on the dry mass of the carrier. The introduction density can be measured from the amount of the glycidyl group, the amount of the polyol, further, the amount of a glycidyl group introduced midway in the production method described later, or the like, and the introduction density can also be adjusted by adjusting these. The alkylene group is a divalent group formed by removing one hydrogen at each of the hydrocarbons at both ends of the longest molecular chain or, in the case of cycloalkyl, the hydrocarbons at the farthest position in the cyclic structure from alkyl such as linear alkyl or cycloalkyl, or linear alkylcycloalkyl (alkylcycloalkyl, cyclodialkyl), having 4 to 9 carbon atoms. In addition, the straight chain or the aliphatic ring may have an alkyl group as a side chain. Specific examples of the alkylene group include butylene, hexylene, heptylene, 1,4-cyclohexylene, 1-methylene-4-cyclohexyl, and cyclohexane-1,4-dimethylene. When the number of carbon atoms is small, the alkali resistance may be insufficient, and when the number of carbon atoms is too large, non-specific adsorption may occur and the intended fractionation may be impossible. The alkylene group preferably includes at least one selected from a butylene group and a cyclohexane-1,4-dimethylene group because the alkali resistance suppression of non-specific adsorption, etc., are excellent in a well-balanced manner, and the intended fractionation efficiency is good. The polyol is preferably one that contains two or more hydroxyl groups, is stable to an alkali, and has sufficient hydrophilicity, and examples thereof include polyether polyol and polylactone polyol. The polyol is bonded to the alkylene group constituting the hydrophobic skeleton directly or indirectly via an ether bond. At least one hydroxyl group remains in the polyol bonded to the alkylene group. When a diol compound is used as a raw material for introducing an alkylene group constituting a hydrophobic skeleton, two hydroxyl groups of the diol compound are both changed into ether-bonded oxygen by reaction, providing distinguishment from a constitutional portion derived from the polyol in which at least one hydroxyl group remains. Specific examples of the polyol include various known saturated and unsaturated low molecular weight glycols such as ethylene glycol, diethylene glycol, or triethylene glycol, polyethylene polyol, and a polyalkylene glycol such as polyethylene glycol. Further examples thereof that can be used also include a sugar alcohol such as a tritol such as glycerin; a tetritol such as erythritol or threitol; a pentitol such as arabinitol or xylitol; a hexitol such as sorbitol or mannitol; or a heptitol such as volemitol or perseitol. The structure bonded via an ether bond from the polyol is distinguished from the above alkylene group having 4 to 9 carbon atoms in terms of the chain length, the structure having a hydroxyl group, or the like The average molecular weight of the polyol is not particularly limited as long as the average molecular weight is 5000 or less. When the average molecular weight of the polyol is 5000 or more, the inside of a pore of the carrier α may be clogged to make the intended fractionation impossible. The polyol used in the present invention is desirably a polyol having an octanol-water partition coefficient (log P) of −1.2 or less. The octanol-water partition coefficient (log P) is, for example, ethylene glycol (−1.36), triethylene glycol (−1.98), polyethylene glycol (lower than −1.98), sorbitol (−2.20), glycerin (−1.76), isopropylene glycol (−1.07), and 1,4-butanediol (−0.88). In addition, a polyol that does not have a structure inducing hydrolysis by an alkali, such as an ester, a thioester, a carbonate, a thiocarbonate, a carbamate, a thiocarbamate, or a siloxane is desirable in that it is stable to an alkali. The weight average molecular weight of the polyol is not particularly limited, and may be 50 or more from the viewpoint of hydrophilicity, and may be 200 or less from the viewpoint of ease of introduction or the like. Among the polyols described above, ethylene glycol, polyethylene glycol, erythritol, sorbitol, and volemitol, which are easy to introduce, are preferable, and ethylene glycol, polyethylene glycol, and sorbitol, which are available at low cost, are more preferable. The polyol may be bonded to the alkylene group via an ether bond, and can be directly bonded, and may be bonded to the alkylene group indirectly via a structure by epichlorohydrin used when introducing a glycidyl group as described later. When polyethylene glycol is used as an example of the polyol, the packing material of the present invention is schematically represented by the following chemical formula, but the present invention is not particularly limited to this example. Method for Producing Packing Material The packing material of the present embodiment can be produced by the following steps (A) to (D). The method for producing the packing material includes:a step (A) of polymerizing a raw material monomer including glycidyl methacrylate and a polyfunctional monomer in the presence of a diluent and a polymerization initiator to obtain a carrier α, which is a porous organic polymer carrier,a step (B) of reacting a glycidyl group derived from glycidyl methacrylate of the carrier α with one hydroxyl group of a diol compound including a linear or aliphatic ring-containing alkylene group having 4 to 9 carbon atoms in a structure thereof to obtain a carrier β to which an end of the diol compound including the alkylene group in the structure thereof is bonded;a step (C) of reacting an other hydroxyl group of the diol compound including the alkylene group in the structure thereof bonded to the carrier β with epichlorohydrin to obtain a carrier γ in which a glycidyl group is introduced into the carrier β; anda step (D) of reacting the glycidyl group of the carrier γ with a hydroxyl group of a polyol in the presence of water to obtain a carrier δ to which one end of the polyol is bonded as an ether bond. [Step (A)] A carrier α is prepared from a copolymer having glycidyl methacrylate and polyfunctional monomer as monomer units. The carrier α is obtained by copolymerizing these monomers in the presence of a diluent and a polymerization initiator. These can be produced with reference to the method described in JP2007-170907, WO2006/132333, or the like. Desirably, the glycidyl methacrylate concentration of the raw material monomer is 60 to 95 mol %, and preferably 70 to 95 mol %. Desirably, the polyfunctional monomer concentration of the raw material monomer is 5 mol % to 40 mol %, and preferably 5 mol % to 30 mol %. In addition, as described above, a further monomer component may be included. In order to introduce a pore into the carrier α, a diluent is added to the monomer mixture, which is then polymerized. The diluent is an organic solvent having the property of being soluble in the monomer mixture, being inert to polymerization, and further, not dissolving the copolymer produced. By removing the diluent by cleaning or the like after completion of polymerization, a portion occupied by the diluent is made hollow to form a porous pore in a particle of the carrier α. Examples of the diluent that can be used include an aromatic hydrocarbon such as toluene, xylene, diethylbenzene, dodecylbenzene, or chlorobenzene; a saturated hydrocarbon such as hexane, heptane, pentane, octane, nonane, or decane; an alcohol such as isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, or nonyl alcohol; an aliphatic halogenated hydrocarbon such as dichloromethane, dichloroethane, or trichloroethane; and an aliphatic or aromatic ester such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, diethyl succinate, methyl benzoate, ethyl benzoate, or propyl benzoate. These diluents can be used singly or as a mixture of two or more. The amount of the diluent added affects the exclusion limit molecular weight and the percentage by volume of the pore volume (representing the proportion of the pore volume to the total volume of the packing material particles) of the packing material. Because of this, the diluent is added by appropriately regulating the amount thereof. The amount of these diluents added is used at a volume of 0.8 to 4.0 times, preferably 1.0 to 3.0 times, the total volume of the raw material monomers at the temperature at the time of supply. The polymerization initiator used during polymerization is not particularly limited as long as it is a known radical polymerization initiator that generates a radical. Examples thereof include an azo-based initiator such as 2,2′-azobisisobutyronitrile, 2,2′-azobis(methyl isobutyrate), and 2,2′-azobis(2,4-dimethylvaleronitrile). Among these, 2,2′-azobis(2,4-dimethylvaleronitrile) is desirably used from the viewpoint of the affinity of the chemical structure. The concentration of the polymerization initiator is not particularly limited, and is preferably 0.1 to 5 parts by mass per 100 parts by mass in total of the monomers. An oil phase containing the monomers is prepared using the monomer mixture, the diluent, and the polymerization initiator. The oil phase is formed into oil droplets by stirring and suspending the oil phase in an aqueous medium containing an appropriate dispersion stabilizer. Polymerization in this state (suspension polymerization) generates a copolymer in the form of porous particles having appropriate particle diameters. Besides the method by stirring as described above, a method in which a monomer solvent containing the diluent is added dropwise to the aqueous medium through a porous membrane or a microchannel formed on a quartz substrate can be applied to the production method of oil droplets. Known stabilizers can be used as the dispersion stabilizer contained in the aqueous medium. A water-soluble polymer compound such as gelatin, sodium polyacrylate, or polyvinyl alcohol is usually used. Polyvinyl alcohol is generally used. The concentration of the dispersion stabilizer is preferably 0.1 to 5 mass % based on the aqueous medium. The aqueous medium may include a water-soluble component such as a salt in addition to water. Examples of the salt include a generally used salt such as sodium chloride or calcium chloride. The solubility differs among salts used and thus the concentration of a salt used cannot be unconditionally specified, and for example, it is also possible to use sodium chloride by dissolving the same at 0.1 to 15 mass % and calcium chloride by dissolving the same at 1 to 40 mass %. The salt is added for salting out. Usually, the suspension polymerization reaction is carried out by purging with nitrogen gas, then heating to 40 to 100° C. under stirring, and under atmospheric pressure for 5 to 16 hours. At this time, the monomers included in each oil droplet are polymerized with the diluent included therein, and a polymer grows in the form of a network, and thus the diluent can subsequently be removed to obtain a porous particle. After the reaction, the porous particle can be easily separated from the aqueous medium by filtration or the like. Further, the porous particle is cleaned with a solvent such as acetone or methanol to remove the diluent. The porous particle is dried, then the resulting porous particle having a glycidyl group is classified using a sieve or an air classifier. The carrier α thus obtained in the step (A) is a porous particle having a glycidyl group derived from glycidyl methacrylate, and has the above average particle diameter and pore. [Step (B)] Next, the glycidyl group derived from glycidyl methacrylate of the carrier α is reacted with a diol compound including a linear or aliphatic ring-containing alkylene group having 4 to 9 carbon atoms in the structure thereof to obtain a carrier β made of a porous organic polymer. The glycidyl group present on the surface of the porous particle is ring-opened and reacts with a terminal hydroxyl group of the diol compound to bond the diol compound to the porous particle via an ether bond derived from the terminal hydroxyl group. An alkylene moiety of this diol compound ultimately constitutes a hydrophobic portion of the packing material. Specifically, the diol compound and the carrier α are reacted with each other in the presence of a solution including a catalyst. Examples of the diol compound include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,4-cyclohexanediol, 4-(hydroxymethyl)cyclohexanol, and 1,4-cyclohexanedimethanol. When the number of carbon atoms is in the above range, the alkali resistance is high and the hydrophobicity is not too strong, and thus the induction of non-specific adsorption can be suppressed. The amount of the diol compound used is preferably 100 parts by mass to 2000 parts by mass per 100 parts by mass of the carrier α. In addition, the amount of the diol compound used is preferably 100 mol % to 2000 mol % based on glycidyl methacrylate included in the carrier α. If the amount of the diol compound used is in the above range, the packing material can be obtained because the alkali resistance and suppression of non-specific adsorption are excellent in a well-balanced manner and the intended fractionation efficiency is good. It is preferable to adjust the amount of the diol compound used and the reaction conditions such that 80 mol % or more, preferably 90 mol % or more, of glycidyl methacrylate included in the carrier α reacts with the diol compound. Examples of the catalyst that can be used include a boron trifluoride diethyl ether complex, zinc borofluoride, trimethylsilyltrifluoromethanesulfonic acid, sulfuric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and dichloroacetic acid. The amount of the catalyst is preferably 0.1 parts by mass to 100 parts by mass, and more preferably 0.5 parts by mass to 20 parts by mass, per 100 parts by mass of the carrier α. Within this range, the diol compound can be introduced, and the reaction of an ester group or the like of the porous particle can be prevented. By cleaning the obtained carrier β with dimethylsulfoxide or the like, the excess diol compound, catalyst, and the like are removed. [Step (C)] Next, a glycidyl group is introduced into the carrier s using epichlorohydrin to obtain a carrier γ. That is, the hydrogen atom of one unreacted hydroxyl group of the diol compound introduced into the carrier β causes an elimination reaction with the chlorine atom of epichlorohydrin, and a glycidyl group is introduced into the carrier β via —OCH2CH(OH)CH2— derived from the structure of epichlorohydrin. In addition to epichlorohydrin, any glycidyl group-containing compound can be used, and specific examples thereof include 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and glycerin diglycidyl ether. Among these, epichlorohydrin is preferably used because it is easy to introduce. Introduction of a glycidyl group-containing compound such as epichlorohydrin is carried out by a reaction resulting from adding 100 to 300 parts by mass of the glycidyl group-containing compound based on the mass of the carrier β together with the carrier β in the presence of a catalyst in the absence of a solvent or in a solvent such as dimethylsulfoxide and stirring these uniformly. This introduces a glycidyl group into the end of the diol compound bonded to the carrier β that is not bonded to the carrier β. The amount of a glycidyl group-containing compound such as epichlorohydrin may be excessive based on the amount of one unreacted hydroxyl group of the diol compound introduced into the carrier β, and assuming that 100% of the alkylene group has been introduced into the glycidyl group derived from glycidyl methacrylate, the amount of the glycidyl group-containing compound is preferably in the range of 100 mol % to 1000 mol % based on the terminal hydroxyl group (mol) of the alkylene group. An alkali metal hydroxide is used as the catalyst, and examples thereof include an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The amount thereof is preferably 1 part by mass to 100 parts by mass, and further, more preferably 5 parts by mass to 50 parts by mass, per 100 parts by mass of the carrier β. [Step (D)] A carrier γ in which a glycidyl group has been introduced is reacted with a polyol in the presence of water to immobilize any one end of the polyol to obtain a carrier δ. At this time, if necessary, a catalyst may be used, and the above alkali metal hydroxide can be used. Any one terminal hydroxyl group of a polyol compound reacts with a glycidyl group, and the terminal of the polyol compound is introduced onto the surface of the carrier γ via an ether structure. The polyol compound has a plurality of hydroxyl groups, and thus at least one hydroxyl group remains. Also in the step (D), the reaction can be carried out by adding an alkali metal hydroxide to the carrier γ and the polyol compound that are caused to be coexistent with each other in the solvent and heating and stirring these. The amount of water may be 1 to 3 times the dry mass of the carrier γ. The amount of the polyol compound used is preferably 10 parts by mass to 1500 parts by mass per 100 parts by mass of the carrier γ. When the amount of the polyol compound is small, the amount introduced tends to be small, resulting in insufficient hydrophilicity, and when the amount thereof is too large, an increased amount of the solvent may be required for dissolution. The amount of the polyol compound used is preferably in the range of 100 mol % to 20,000 mol % based on the glycidyl group (mol) introduced into the carrier γ. When the amount of the polyol compound is small, the amount introduced tends to be small, resulting in insufficient hydrophilicity, and when the amount thereof is too large, an increased amount of the solvent may be required for dissolution. By washing the obtained carrier δ, that is, the packing material of the present embodiment, with water, the excess polyol alcohol and alkali metal hydroxide are removed. In addition, an unreacted glycidyl group may remain in the obtained packing material. When a glycidyl group remains, the hydrophobicity of the packing material increases, and there is concern that a highly hydrophobic water-soluble compound such as a protein is hydrophobically adsorbed. Because of this, in order to enhance the hydrophilicity, the remaining glycidyl group is desirably ring-opened using a mineral acid. Examples of the mineral acid include sulfuric acid, nitric acid, and hydrochloric acid. Among these, sulfuric acid is particularly preferable. The concentration of the mineral acid used may be about 0.01 M to 1.0 M, and is particularly preferably about 0.1 to 0.5 M. If the concentration of the mineral acid is 0.01 M or more, the ring-opening is sufficiently carried out, and if the concentration of the mineral acid is 1.0 M or less, an ester group or the like in the carrier is not hydrolyzed to form an ionic functional group. By washing the resulting particle with water, the excess mineral acid is easily removed. Properties of Packing Material The average particle diameter of the packing material is not particularly limited as long as it is 10 μm or more, and is preferably in the range of 15 to 100 μm from the viewpoint of the column packing property or the like. Here, the average particle diameter is represented by the volume-average particle diameter. The volume-average particle diameter is a value obtained using an image analysis-based particle size distribution measuring apparatus. When an image analysis-based particle size distribution measuring apparatus is used to measure the volume-average particle diameter of a particle, the volume-average particle diameter is a particle diameter obtained by imaging 2000 or more crosslinked polymer particles using the image analysis-based particle size distribution measuring apparatus to obtain two-dimensional particle images (preferably still images), obtaining the equivalent circle diameter (diameter of a circle having an area equal to the projected area of a particle) of each particle from the two-dimensional particle images, calculating the volume of the particle from the equivalent circle diameter, and averaging the diameters based on the volume. At this time, each particle is regarded as a sphere having the same diameter as the above equivalent circle diameter. Examples of the image analysis-based particle size distribution measuring apparatus that can be used include a flow particle image analyzer (trade name: FPIA-3000, manufactured by Sysmex Corporation). The average particle diameter of the packing material can be adjusted by adjusting the polymerization conditions during the production of the carrier. The packing material has a pore. The size of the pore is appropriately selected depending on the purpose. The packing material of the present embodiment has suitable hydrophilicity and exclusion limit molecular weight. The hydrophilicity and the exclusion limit molecular weight can be adjusted by the type and amount of the diluent or the ratios of glycidyl methacrylate and the polyfunctional monomer. The average particle diameter and the pore diameter of the packing material is not changed by the surface structure. The exclusion limit molecular weight suitable for protein purification is 1,000,000 to 100,000,000, and more preferably 50,000,000 to 20,000,000. Within this range, a protein can be efficiently separated. The exclusion limit molecular weight can be determined by a generally known method by connecting a column packed with the packing material to a high-performance liquid chromatograph, allowing ion exchanged water as the mobile phase to flow at a flow rate of 1.0 mL per minute, injecting a reference material having various molecular weights into the column, and using the elution volume thereof. In the present embodiment, a differential refractive index detector (trade name: RI-201H, manufactured by Showa Denko K.K.) is used, and a pullulan standard (trade name: Shodex (registered trademark) STANDARD P-82, manufactured by Showa Denko K.K.) is used as the reference material. In order to separate a large protein by size exclusion chromatography, the exclusion limit molecular weight is appropriately selected according to the molecular weight of the protein. For example, when a large protein such as IgM having a molecular weight of about 900,000 or IgG having a molecular weight of about 150,000 is separated, if the exclusion limit is less than 1,000,000, the molecular weight of IgM falls outside the exclusion limit and IgM cannot be separated. Because of this, by packing the packing material into a housing for liquid chromatography, a high-performance column for size exclusion chromatography can be obtained, and further, a chromatography apparatus including the column for size exclusion chromatography can be obtained. In addition, by using this column for size exclusion chromatography, a method for separating and a method for fractionating a biopolymer that can precisely separate and further fractionate the biopolymer, respectively, using an aqueous eluent can be provided. In addition, the packing material has high alkali resistance, and thus can be cleaned and reused, and can be used continuously for a long period of time. EXAMPLES Hereinafter, the advantageous effects of the present invention will be made clearer with reference to Examples. The present invention is not limited to the following Examples and can be appropriately modified as long as the gist thereof is not changed, to be practiced. Example 1 <Step (A): Synthesis of porous particle having glycidyl group> 27.8 g of glycidyl methacrylate (trade name: Blemmer G (registered trademark) manufactured by NOF Corporation), 11.3 g of glycerin-1,3-dimethacrylate (trade name: NK Ester 701, SHIN-NAKAMURA CHEMICAL Co., Ltd.), and 1.9 g of 2,2′-azobis(2,4-dimethylvaleronitrile) were dissolved in 58.7 g of diethyl succinate as a diluent, and nitrogen gas was bubbled for 30 minutes to provide an oil phase. Next, separately from the oil phase, 10.0 g of PVA-224 (manufactured by Kuraray Co., Ltd., polyvinyl alcohol having a degree of saponification of 87.0% to 89.0%) as a dispersion stabilizer and 10.0 g of sodium chloride as a salting-out agent were dissolved in 480 g of ion exchanged water to provide an aqueous phase. The aqueous phase and the oil phase were placed in a separable flask and dispersed at a rotation speed of 430 rpm for 20 minutes using a stirring rod equipped with a half-moon stirring blade, then the inside of the reactor was purged with nitrogen, and the reaction was carried out at 60° C. for 16 hours. After that, the resulting polymer was transferred onto a glass filter and thoroughly washed with hot water at about 50 to 80° C., denatured alcohol, and water in the order presented to obtain 100.4 g of a porous particle (carrier al). The amount of glycidyl methacrylate used was 79.8 mol % based on the total amount of the monomers, and the amount of glycerin-1,3-dimethacrylate used was 20.2 mol % based on the total amount of the monomers. <Step (B): Introduction reaction of alkylene group> 98 g of the carrier α1 was weighed onto a glass filter and thoroughly cleaned with diethylene glycol dimethyl ether. After cleaning, the carrier α1 was placed in a 1 L separable flask, 150 g of diethylene glycol dimethyl ether and 150 g (920 mol % based on glycidyl methacrylate) of 1,4-butanediol were placed in the separable flask, and stirring and dispersion were carried out. After that, 1.5 ml of a boron trifluoride diethyl ether complex was added, the temperature was raised to 80° C. while stirring at 200 rpm, and the resulting mixture was subjected to the reaction for 4 hours. The mixture was cooled, then the porous particle (carrier β1) bonded to a diol compound including an alkylene group in the structure thereof was collected by filtration and then washed with 1 L of ion exchanged water to obtain 152 g of a carrier β1. The progress of the reaction was confirmed by the following procedure. A part of the dry porous particle into which an alkylene group had been introduced was mixed with potassium bromide, and the resulting mixture was pelletized by applying a pressure and then measured using FT-IR (trade name: Nicolet (registered trademark) iS10, manufactured by Thermo Fisher Scientific Inc.) to check the height of an absorbance peak at 908 cm−1due to the glycidyl group in the infrared absorption spectrum. As a result, no absorbance peak at 908 cm−1was observed by FT-IR. <Step (C): Introduction Reaction of Glycidyl Group> 150 g of the carrier β1 was weighed onto a glass filter and thoroughly cleaned with dimethylsulfoxide. After cleaning, the carrier β1 was placed in a separable flask, 262.5 g of dimethyl sulfoxide and 150 g of epichlorohydrin were added, the resulting mixture was stirred at room temperature, 37.5 ml of a 30% sodium hydroxide aqueous solution (manufactured by KANTO CHEMICAL CO., INC.) was further added, and the resulting mixture was heated to 30° C. and stirred for 6 hours. After completion of the reaction, the obtained product was transferred onto a glass filter and thoroughly washed with water, acetone, and water in the order presented to obtain 172 g of a porous particle into which a glycidyl group had been introduced (carrier γ1). The introduction density of the glycidyl group in the obtained carrier γ1 was measured by the following procedure. 5.0 g of the carrier γ1 was sampled, and the dry mass thereof was measured and as a result, found to be 1.47 g. Next, the same amount of the carrier γ1 was weighed into a separable flask and dispersed in 40 g of water, 16 mL of diethylamine was added while stirring at room temperature, and the resulting mixture was heated to 50° C. and stirred for 4 hours. After completion of the reaction, the reaction product was transferred onto a glass filter and thoroughly washed with water to obtain a porous particle A into which diethylamine had been introduced. The obtained porous particle A was transferred into a beaker and dispersed in 150 mL of a 0.5 mol/L potassium chloride aqueous solution, and titration was carried out using 0.1 mol/L hydrochloric acid with the point at which the pH reached 4.0 as the neutralization point. From this, the amount of diethylamine introduced into the porous particle A into which diethylamine had been introduced was calculated, and the density of the glycidyl group of the carrier γ1 was calculated from the following expression. As a result, the density of the glycidyl group was 880 μmol/g. Density(μmol/g) of glycidyl group={0.1×volume(μL) of hydrochloric acid at neutralization point/dry mass(g) of porous particle into which glycidyl group has been introduced} <Step (D): Introduction Reaction of Polyol> 150 g of the carrier γ1, 600 mL of water, and 1000 g (13000 mol % based on glycidyl group) of D-sorbitol (log P=−2.20, manufactured by KANTO CHEMICAL CO., INC.) were placed in a 3 L separable flask and stirred to form a dispersion. After that, 10 g of potassium hydroxide was added, the temperature was raised to 60° C. while stirring at 200 rpm, and the resulting mixture was subjected to the reaction for 15 hours. The mixture was cooled, and then the reaction product was collected by filtration and washed thoroughly with water to obtain 152 g of a porous particle into which polyol had been introduced (carrier 61). The obtained carrier 61 was classified into 16 to 37 μm using a sieve to obtain 140.5 g of a packing material 1. <Evaluation of Alkali Resistance> The alkali resistance was evaluated by calculating the amount of a carboxy group produced by hydrolysis of sodium hydroxide according to the following procedure. First, 4 g of the packing material was dispersed in 150 mL of a 0.5 mol/L potassium chloride aqueous solution, and titration was carried out using 0.1 mol/L sodium hydroxide aqueous solution with the point at which the pH reached 7.0 as the neutralization point. From this, the amount of a carboxy group before hydrolysis included in the packing material was calculated from the following expression. Amount(μmol/mL) of carboxy group=0.1×volume(μL) of sodium hydroxide aqueous solution at the time of neutralization/apparent volume (mL) of packing material Here, the apparent volume of the packing material is the volume of the packing material phase measured after preparing a slurry liquid by dispersing 4 g of the packing material in water, transferring the slurry liquid to a graduated cylinder, and then allowing the same to stand for a sufficient time. Subsequently, 4 g of the packing material was weighed into a separable flask, 20 mL of a 5 mol/L sodium hydroxide aqueous solution was added, and the resulting mixture was treated at 50° C. for 20 hours while stirring at 200 rpm. The mixture was cooled, then the packing material was collected by filtration, then washed with a 0.1 mol/L HCl aqueous solution and water in the order presented, and the amount of a carboxy group contained in the obtained packing material was calculated by the same method as above. From the difference between the amount of a carboxy group before and that after the reaction with the 5 mol/L sodium hydroxide aqueous solution, the amount of a carboxy group produced by the reaction with the 5 mol/L sodium hydroxide aqueous solution was calculated. As a result, the amount of a carboxy group produced was 21 μmol/mL. If the amount of a carboxy group produced is 40 μmol/mL or less, the alkali resistance is considered to be high. <Evaluation of Non-Specific Adsorption> The obtained packing material was packed into a stainless steel column (manufactured by Sugiyama Shoji Co., Ltd.) having an inner diameter of 8 mm and a length of 300 mm by a balanced slurry method. Using the obtained column, a non-specific adsorption test was carried out by the method shown below. The column packed with the packing material was connected to a Shimadzu Corporation HPLC system (liquid feed pump (trade name: LC-10AT, manufactured by Shimadzu Corporation), autosampler (trade name: SIL-10AF, manufactured by Shimadzu Corporation), and photodiode array detector (trade name: SPD-M10A, manufactured by Shimadzu Corporation)), and a 50 mmol/L sodium phosphate buffer aqueous solution as a mobile phase was passed at a flow rate of 0.6 mL/min. Using the same sodium phosphate aqueous solution as the mobile phase as a solvent, their respective sample solutions of 0.7 mg/mL thyroglobulin (Mw of 6.7×105), 0.6 mg/mL γ-globulin (Mw of 1.6×105), 0.96 mg/mL BSA (Mw of 6.65×104), 0.7 mg/mL ribonuclease (Mw of 1.3×104), 0.4 mg/mL aprotinin (Mw of 6.5×103), and 0.02 mg/mL uridine (Mw of 244) (all manufactured by Merck Sigma-Aldrich) are prepared, and 10 μL of each is injected from the autosampler. The elution time of each observed using the photodiode array detector at a wavelength of 280 nm was compared to confirm that there was no contradiction between the order of elution volume and the order of molecular weight size. As a result, the elution volumes of the samples from the column packed with the packing material 1 were 8.713 mL, 9.691 mL, 9.743 mL, 10.396 mL, 11.053 mL, and 11.645 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. When there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof, there was no non-specific adsorption, which is indicated as 0 in Table 1, and when there was a contradiction therebetween, non-specific adsorption was induced, which is thus indicated as X. Example 2 A porous particle (carrier al) was obtained in the same manner as in Example 1, and then a packing material 2 was obtained as follows. 98 g of the carrier α1 was weighed onto a glass filter and thoroughly cleaned with diethylene glycol dimethyl ether. After cleaning, the porous particle was placed in a 1 L separable flask, 150 g of diethylene glycol dimethyl ether and 150 g (580 mol % based on the glycidyl group) of 1,4-cyclohexanedimethanol were placed in the separable flask, and stirring and dispersion were carried out. After that, 1.5 ml of a boron trifluoride diethyl ether complex was added, the temperature was raised to 80° C. while stirring at 200 rpm, and the resulting mixture was subjected to the reaction for 4 hours. The mixture was cooled, then the resulting porous particle (carrier $2) bonded to a diol compound including an alkylene group in the structure thereof was collected by filtration and then washed with 1 L of ion exchanged water to obtain 165 g of a carrier 32. The progress of the reaction was confirmed by the following procedure. A part of the dry porous particle into which an alkylene group had been introduced was mixed with potassium bromide, and the resulting mixture was pelletized by applying a pressure and then measured using FT-IR (trade name: Nicolet (registered trademark) iS10, manufactured by Thermo Fisher Scientific Inc.) to check the height of a absorbance peak at 908 cm−1due to the glycidyl group in the infrared absorption spectrum. As a result, no absorbance peak at 908 cm−1was observed by FT-IR. <Step (C): Introduction Reaction of Glycidyl Group> 150 g of the carrier $2 was weighed onto a glass filter and thoroughly cleaned with dimethylsulfoxide. After cleaning, the carrier $2 was placed in a separable flask, 262.5 g of dimethyl sulfoxide and 150 g of epichlorohydrin were added, the resulting mixture was stirred at room temperature, 37.5 ml of a 30% sodium hydroxide aqueous solution (manufactured by KANTO CHEMICAL CO., INC.) was further added, and the resulting mixture was heated to 30° C. and stirred for 6 hours. After completion of the reaction, the porous particle was transferred onto a glass filter and thoroughly washed with water, acetone, and water in the order presented to obtain 180 g of a porous particle into which a glycidyl group had been introduced (carrier γ2). The introduction density of the glycidyl group in the obtained carrier γ2 was measured in the same manner as in Example 1. As a result, the density of the glycidyl group was 900 μmol/g. <Step (D): Introduction Reaction of Polyol> 150 g of the carrier γ2 was weighed onto a glass filter and thoroughly cleaned with diethylene glycol dimethyl ether. After cleaning, the carrier γ2 was placed in a 1 L separable flask, 150 g of diethylene glycol dimethyl ether and 150 g (5760 mol % based on the glycidyl group) of ethylene glycol (log P=−1.36) were placed in the separable flask, and stirring and dispersion were carried out. After that, 1.5 mL of a boron trifluoride diethyl ether complex was added, the temperature was raised to 80° C. while stirring at 200 rpm, and the resulting mixture was subjected to the reaction for 4 hours. The mixture was cooled, and then the reaction product was collected by filtration and washed thoroughly with water to obtain 152 g of a polyol-introduced porous particle (carrier δ2). The carrier δ2 was classified into 16 to 37 μm using a sieve to obtain 140.5 g of a packing material 2. The alkali resistance of the obtained packing material 2 was evaluated in the same manner as in Example 1. As a result, the amount of a carboxy group produced was 15.2 μmol/mL, and it was confirmed that the packing material 2 had excellent alkali resistance. Further, the non-specific adsorption of the obtained packing material 2 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 8.814 mL, 9.635 mL, 9.778 mL, 10.37 mL, 10.898 mL, and 12.347 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. Example 3 A carrier γ2 was obtained in the same manner as in Example 2. 150 g of the obtained carrier γ2 was weighed onto a glass filter and thoroughly cleaned with diethylene glycol dimethyl ether. After cleaning, the porous particle was placed in a 1 L separable flask, 150 g of diethylene glycol dimethyl ether and 150 g of polyethylene glycol #200 (manufactured by KANTO CHEMICAL CO., INC., average molecular weight of 190 to 210, log P is unclear, but the close compound tetraethylene glycol (Mw of 194) has a log P of −2.02) (1790 mol % based on glycidyl group) were placed in the separable flask, and stirring and dispersion were carried out. After that, 1.5 mL of a boron trifluoride diethyl ether complex was added, the temperature was raised to 80° C. while stirring at 200 rpm, and the resulting mixture was subjected to the reaction for 4 hours. The mixture was cooled, and then the reaction product was collected by filtration and washed thoroughly with water to obtain 152 g of a porous particle into which a polyol had been introduced (carrier 63). The carrier δ3 was classified into 16 to 37 μm using a sieve to obtain 140.5 g of a packing material 3. The alkali resistance of the obtained packing material 3 was evaluated in the same manner as in Example 1. As a result, the amount of a carboxy group produced was 16.1 μmol/mL, and it was confirmed that the packing material 3 had excellent alkali resistance. Further, the non-specific adsorption of the obtained packing material 3 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 8.517 mL, 9.241 mL, 9.47 mL, 10.034 mL, 10.484 mL, and 11.927 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. Example 4 A packing material 4 was obtained in the same manner as in Example 3 except that 33.2 g of glycidyl methacrylate (trade name: Blemmer G (registered trademark) manufactured by NOF Corporation), 5.9 g of glycerin-1,3-dimethacrylate (trade name: NK Ester 701, SHIN-NAKAMURA CHEMICAL Co., Ltd.), 58.7 g of diethyl succinate, and 1.9 g of 2,2′-azobis(2,4-dimethylvaleronitrile) were used to provide an oil phase. The amount of glycidyl methacrylate used was 90.0 mol % based on the total amount of the monomers, and the amount of glycerin-1,3-dimethacrylate used was 10.0 mol % based on the total amount of the monomers. The alkali resistance of the obtained packing material 4 was evaluated in the same manner as in Example 1. As a result, the amount of a carboxy group produced was 11.5 μmol/mL, and it was confirmed that the packing material 4 had excellent alkali resistance. Further, the non-specific adsorption of the obtained packing material 4 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 7.52 mL, 8.214 mL, 8.451 mL, 9.062 mL, 9.511 mL, and 11.915 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. Example 5 A packing material 5 was obtained in the same manner as in Example 3 except that 21.5 g of glycidyl methacrylate (trade name: Blemmer G (registered trademark) manufactured by NOF Corporation), 17.6 g of glycerin-1,3-dimethacrylate (trade name: NK Ester 701, SHIN-NAKAMURA CHEMICAL Co., Ltd.), 58.7 g of diethyl succinate, and 1.9 g of 2,2′-azobis(2,4-dimethylvaleronitrile) were used to provide an oil phase. The amount of glycidyl methacrylate used was 66.2 mol % based on the total amount of the monomers, and the amount of glycerin-1,3-dimethacrylate used was 33.8 mol % based on the total amount of the monomers. The alkali resistance of the obtained packing material 5 was evaluated in the same manner as in Example 1. As a result, the amount of a carboxy group produced was 18.3 μmol/mL, and it was confirmed that the packing material 5 had excellent alkali resistance. Further, the non-specific adsorption of the obtained packing material 5 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 8.692 mL, 9.434 mL, 9.625 mL, 10.236 mL, 10.759 mL, and 12.457 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. Example 6 A packing material 6 was obtained in the same manner as in Example 3 except that 33.2 g of glycidyl methacrylate (trade name: Blemmer G (registered trademark) manufactured by NOF Corporation), 5.9 g of ethylene glycol dimethacrylate (trade name: NK Ester 1G, SHIN-NAKAMURA CHEMICAL Co., Ltd.), 29.3 g of butyl acetate, 29.3 g of chlorobenzene, and 1.9 g of 2,2′-azobis(2,4-dimethylvaleronitrile) were used to provide an oil phase. The amount of glycidyl methacrylate used was 88.7 mol % based on the total amount of the monomers, and the amount of ethylene glycol dimethacrylate used was 11.3 mol % based on the total amount of the monomers. The alkali resistance of the obtained packing material 6 was evaluated in the same manner as in Example 1. As a result, the amount of a carboxy group produced was 12.5 μmol/mL, and it was confirmed that the packing material 6 had excellent alkali resistance. Further, the non-specific adsorption of the obtained packing material 6 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 9.613 mL, 10.427 mL, 10.444 mL, 11.066 mL, 11.582 mL, and 12.575 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. Comparative Example 1 The porous particle (carrier al) obtained in the same manner as in Example 1 was subjected to the step D of Example 1. <Step (D): Introduction Reaction of Polyol> 98 g of carrier al, 600 mL of water, and 1000 g (3050 mol % based on glycidyl group) of D-sorbitol (manufactured by KANTO CHEMICAL CO., INC.) were placed in a 3 L separable flask and stirred to form a dispersion. After that, 10 g of potassium hydroxide was added, the temperature was raised to 60° C. while stirring at 200 rpm, and the resulting mixture was subjected to the reaction for 15 hours. The mixture was cooled, and then the reaction product was collected by filtration and washed thoroughly with water to obtain 130 g of a porous particle into which a polyol had been introduced (carrier δ7). The carrier δ7 was classified into 16 to 37 μm using a sieve to obtain 115 g of a packing material 7. The alkali resistance of the obtained packing material 7 was evaluated in the same manner as in Example 1. As a result, the amount of a carboxy group produced in the packing material 7 was 120.3 μmol/mL, resulting in poor alkali resistance. Further, the non-specific adsorption of the obtained packing material 7 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 8.606 mL, 9.769 mL, 9.9567 mL, 10.703 mL, 11.470 mL, and 12.112 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. Comparative Example 2 A packing material 8 was obtained in the same manner as in Example 1 except that 150 g of ethylene glycol was used instead of 1,4-butanediol as an alkylene group-introducing agent. The alkali resistance of the obtained packing material 8 was evaluated in the same manner as in Example 1. As a result, the amount of a carboxy group produced in the packing material 8 was 108.4 μmol/mL, resulting in poor alkali resistance. Further, the non-specific adsorption of the obtained packing material 8 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 9.708 mL, 9.8946 mL, 10.6452 mL, 11.5374 mL, and 12.1656 mL, and it was confirmed that there was no contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that no non-specific adsorption was induced. Comparative Example 3 A packing material 9 was obtained in the same manner as in Example 2 except that no glycidyl group was introduced and no polyol was introduced. That is, the carrier $2 obtained in the step (B) of Example 2 was used as the packing material 9. The non-specific adsorption of the obtained packing material 9 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 8.590 mL, 10.316 mL, 9.603 mL, 10.484 mL, 13.863 mL, and 12.861 mL, and it was confirmed that there was a contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that non-specific adsorption was induced. Because of this, the alkali resistance was not evaluated. Comparative Example 4 A packing material 10 was obtained in the same manner as in Example 1 except that 150 g (480 mol % based on glycidyl methacrylate) of 1,10-decanediol was used instead of 1,4-butanediol as an alkylene group-introducing agent. The non-specific adsorption of the obtained packing material 10 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 9.991 mL, 10.15 mL, 10.063 mL, 10.691 mL, 12.172 mL, and 11.531 mL, and it was confirmed that there was a contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that non-specific adsorption was induced. Because of this, the alkali resistance was not evaluated. Comparative Example 5 A packing material 11 was obtained in the same manner as in Example 3 except that 13.7 g of glycidyl methacrylate (trade name: Blemmer G (registered trademark) manufactured by NOF Corporation), 25.4 g of glycerin-1,3-dimethacrylate (trade name: NK Ester 701, SHIN-NAKAMURA CHEMICAL Co., Ltd.), 58.7 g of diethyl succinate, and 1.9 g of 2,2′-azobis(2,4-dimethylvaleronitrile) were used to provide an oil phase. The amount of glycidyl methacrylate used was 46.4 mol % based on the total amount of the monomers, and the amount of glycerin-1,3-dimethacrylate used was 53.6 mol % based on the total amount of the monomers. The non-specific adsorption of the obtained packing material 11 was evaluated in the same manner as in Example 1. As a result, the elution volumes of the samples were 8.872 mL, 10.131 mL, 9.82 mL, 10.422 mL, 12.782 mL, and 12.553 mL, and it was confirmed that there was a contradiction between the order of the molecular weights of the samples and the order of the elution volumes thereof and that non-specific adsorption was induced. Because of this, the alkali resistance was not evaluated. It was confirmed that the exclusion limit molecular weights of the packing materials obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were all 1,000,000 or more. Comparative Example 6 A packing material 12 was obtained in the same manner as in Example 3 except that 37.1 g of glycidyl methacrylate (trade name: Blemmer G (registered trademark) manufactured by NOF Corporation), 2.0 g of glycerin-1,3-dimethacrylate (trade name: NK Ester 701, SHIN-NAKAMURA CHEMICAL Co., Ltd.), 58.7 g of diethyl succinate, and 1.9 g of 2,2′-azobis(2,4-dimethylvaleronitrile) were used to provide an oil phase. The amount of glycidyl methacrylate used was 96.7 mol % based on the total amount of the monomers, and the amount of glycerin-1,3-dimethacrylate used was 3.3 mol % based on the total amount of the monomers. Packing into a stainless steel column using the obtained packing material 12 was attempted. However, the back pressure was high, making liquid feeding difficult, and this made it impossible to carry out the packing. Because of this, neither of the evaluations was able to be carried out. Results of the above Examples and Comparative Examples are shown in Table 1. From the above results, by adopting the configuration of the present invention, a packing material having suppressed non-specific adsorption and high alkali resistance can be obtained. When no hydrophobic portion is provided or when the alkylene chain is short, the alkali resistance is low as shown in Comparative Examples 1 and 2. In addition, it was found that when the alkylene chain is too long or when no hydrophilic portion is provided, the hydrophobicity is strong, and non-specific adsorption is induced as shown in Comparative Examples 3 and 4. In addition, in Comparative Example 5 having many repeating units derived from a polyfunctional monomer, it was found that non-specific adsorption was induced, and in Comparative Example 6 having fewer repeating units derived from a polyfunctional monomer, it was found that the back pressure applied to the apparatus was high, making column packing difficult. TABLE 1Amount ofcarboxyDegree ofgroupPolyfunctionalcrosslinkingNon-specificproducedMonomer[mol %]Alkylene groupPolyoladsorption5)[μmol/mL]Ex. 1GDMA1)20.2Butylene groupSorbitol◯21Ex. 2GDMA20.2Cyclohexane-1,4-dimethyleneEG3)◯15.2groupEx. 3GDMA20.2Cyclohexane-1,4-dimethylenePEG2004)◯16.1groupEx. 4GDMA10Cyclohexane-1,4-dimethylenePEG200◯11.5groupEx. 5GDMA33.8Cyclohexane-1,4-dimethylenePEG200◯18.3groupEx. 6EDMA2)11.3Cyclohexane-1,4-dimethylenePEG200◯12.5groupComp.GDMA20.2—Sorbitol◯120.3Ex. 1Comp.GDMA20.2Ethylene groupEG◯108.4Ex. 2Comp.GDMA20.2Cyclohexane-1,4-dimethylene—X—Ex. 3groupComp.GDMA20.2Decanylene groupSorbitolX—Ex. 4Comp.GDMA53.6Cyclohexane-1,4-dimethylenePEG200X—Ex. 5groupComp.GDMA3.3Cyclohexane-1,4-dimethylenePEG200UnmeasurableEx. 6group1)GDMA: Glycerin-1,3-dimethacrylate2)EDMA: Ethylene glycol dimethacrylate3)EG: Ethylene glycol4)PEG200: Polyethylene glycol #2005)◯: No non-specific adsorption, X: Non-specific adsorption
57,632
11857950
DETAILED DESCRIPTION OF THE DISCLOSURE The following description includingFIGS.1-9show preferred embodiments of the present disclosure. It will be clear from this description of the disclosure that the disclosure is not limited to these illustrated embodiments but that the disclosure also includes a variety of modifications and embodiments thereto. Therefore, the present description should be seen as illustrative and not limiting. While the disclosure is susceptible of various modifications and alternative constructions, it should be understood, that there is no intention to limit the disclosure to the specific form disclosed, but, on the contrary, the disclosure is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the disclosure as defined in the claims. Transition-Aluminas (Al2O3) are used as catalysts and supports for metals, metal oxides, nanoparticles, single atoms, especially in automotive applications. Vehicle conditions expose catalysts to extremely harsh conditions. Temperatures may reach above 1,000° C. in the presence of exhaust gases, oxygen and water steam. Gamma-alumina is most often used as a catalyst/catalyst support/mechanical binder. But with gamma-alumina, phase transformations (to theta/delta and alpha alumina phases) occur above 800° C. During the phase transformation, the surfaces become unstable, leading to deactivation of catalysts. This catalytic activity drop can be caused by alumina encapsulating the active phase (for example, in the case of palladium or its oxide) or by dissolution of the active metal in the alumina bulk (for rhodium, for example). Heating typically leads to a phase transformation of gamma-alumina to a mixture of delta/theta phases before they finally transform to alpha-alumina. Phase transformation itself is a problem. Therefore, gamma-alumina catalysts significantly deactivate when exposed to water/steam conditions (hydrothermal aging) at 900° C. and above. The present invention overcomes this problem by utilizing pure theta-alumina with high surface area that has a high proportion of highly stable (100) facet and that accommodates a rod-like or lath-like morphology. It can be prepared by heating gamma-alumina or boehmite-precursor with rod-like or lath-like morphology at high temperature (1000° C. and above). These resulting theta-alumina supports are hydrothermally stable up to 1150° C. and based on x-ray diffraction they do not contain other transition-alumina phases. Examples of such materials are shown inFIGS.1,2and3.FIG.1shows a DFT-optimized (100) facet of theta-alumina. The surface features alternating rows of tetra- and penta-coordinate A1 atoms wherein oxygen; and aluminum atoms are intermixed. The surface energy of the facet is calculated to be 597 mJ/m2.FIG.2shows an XRD pattern of pure theta-alumina with rod-like morphology and surface area ˜75 m2/g. This sample was prepared via thermal treatment of boehmite with rod-like morphology at 1,050° C. for 4 hours.FIG.3shows representative HAADF-STEM images of the theta-alumina sample whose x-ray diffraction patters is shown inFIG.2. These crystals have rod-like morphology (the relative proportion of (100) facet is >20%). In one example, a theta-alumina catalyst support was prepared from boehmite by heating in air at 1050° C. for 4 hours. Preferably the boehmite precursor has a relative ratio of (001) facet of 20% and more (and preferably between 30 to 50%). During heat treatment transformation of boehmite, the (001) facet of boehmite becomes (100) facet of theta-alumina. We calculated the surface energy of (100) facet of theta-alumina to be below 600 mJ/m2: this extremely low value provides high stability (FIG.1). Samples with a well-defined rod-like and lath-like morphology (transform into pure-theta alumina after heating at 1,000-1,150 C for duration between 0.1 to 1,0000 hours. Transformation of boehmite to transition aluminas and transformation between transition aluminas (such as gamma, delta and theta-phases) are topotactic. Transformation of boehmite (or gamma-alumina) to theta-alumina is promoted by the presence of (100) facets of the resulting phase. Transformation of boehmite with initial morphology different than rod-like and lath-like (i.e., having lower proportion of (100) facets of the resulting phase than 20%) results in a mixture of multiple phases that evolves continuously with time at temperatures between 1,000 and 1,150 C. Because phase-transition of gamma-alumina into theta-phase is a topotactic transformation, no surface area loss occurs. The as synthesized theta-alumina has surface area between 10-150 m2/g, preferably between 30 and 100 m2/g. In one example, the sample area was 75 m2/g. After hydrothermal aging (exposure to flow of air in 10% steam) theta-alumina maintains essentially the same surface area. In my particular embodiment, the theta-alumina sample hydrothermally aged at 1,000° C. for 16 hours has a surface area of 75 m2/g. This theta-alumina support can then be used to prepare hydrothermally and thermally stable catalysts for challenging catalytic applications. In one example, we loaded 3 wt % PdO nanoparticles (by total palladium weight) on high surface area theta-alumina and studied them for catalytic methane oxidation (we chose methane because among all hydrocarbons it represents the most challenging hydrocarbon to oxidize) and compared catalytic activities in methane oxidation of fresh (calcined at 600° C.), and this sample after hydrothermal aging at 800° C., 900° C., 1,000° C. ° C. in the flow of air and 10% steam. The catalytic testing results are summarized inFIG.4A-C. The initial rod-like morphology of theta-alumina is well-preserved after 1,000° C. hydrothermal aging. Examples and results are shown inFIGS.4and5. Rhodium supported on alumina is critical for reduction of nitric oxide. Nitric oxide is an environmental pollutant emitted by vehicles. Rhodium was loaded (0.07 wt %) on theta-alumina using conventional incipient wetness impregnation and the performance of the fresh (fresh means the sample was calcined at 600° C.) and hydrothermally aged (aged in the flow of air and 10% steam at 1,000° C. for 16 hours) samples was compared. Catalytic performance of the sample is shown inFIG.6As seen inFIG.6, NO conversion remains robust after aging at 1,000° C. in the flow of air and 10% steam. This alleviates the well-known problem of alumina-rhodium catalysts deactivation due to dissolution of metal in the alumina bulk at elevated temperatures.FIG.7shows microscopy images of well-preserved theta-alumina morphology.FIG.7also shows that Rh atoms remain well-dispersed on the surface after severe hydrothermal aging. These results are not limited to putting just rhodium or palladium on theta-alumina. They can be extended to combinations of any metal and non-metals with theta-alumina: such as palladium, platinum, rhodium, ruthenium, iron, silver, cerium, chromium, lithium, potassium, sodium, rubidium, cesium, magnesium, barium, calcium, strontium, lanthanum, praseodymium, boron, manganese, vanadium, cobalt, nickel, copper, gold, thallium, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, indium, tin, antimony, tellurium, scandium, tantalum, hafnium, tungsten, rhenium, osmium, iridium, lead, bismuth, fluorine, chlorine, bromine, praseodymium, neodymium, samarium, titanium, copper, silicon, phosphorus and multiple combinations thereof. Because of the stable nature of the theta-alumina support (that does not lose surface area and undergo phase transformations under extremely severe thermal and hydrothermal conditions), the material can be used for any process requiring high thermal and hydrothermal stability. Our invention provides hydrothermally stable high surface area theta-alumina that does not require the use of rare earth metals and/or barium to assure its stability under hydrothermal conditions. Thus, we succeeded in preparing Rh and Pd-containing catalysts supported on theta-alumina active in NO reduction and hydrocarbon oxidation that can survive hydrothermal aging up to 1,150° C. with little-to-no deactivation. Results of this testing is shown inFIGS.4and6. Typical high surface area commercial gamma-aluminas (such as SBA-200, surface area ˜180 m2/g) transform into a mixture of delta/theta above 900° C. and start forming low-surface-area alpha-alumina already at 1,000-1,150° C. When we supported similar loading of Rh (˜0.07 wt %) and PdO (3 wt % Pd) on SBA-200 gamma-alumina, after hydrothermal aging at temperatures even below 1,000° C. these catalysts had lower activity in nitric oxide reduction and methane oxidation compared with Rh and Pd supported on high surface area theta-alumina after hydrothermal aging (FIGS.8and9) The use of transition Alumina in the form of theta-phase, (which is the most stable polymorph of transition Aluminas), and optimizing the morphology for high temperature stability provided significant advantages over the prior art. FIG.4A-Cshows activity of PdO on theta-alumina for methane combustion in the fresh state both under dry and wet conditions going up and down in temperature. The sample shows completely stable methane combustion activity. We then performed extremely harsh hydrothermal aging on this sample continuously in the presence of 10% H2O/Air flow at each temperature for 16 hours (800, 900 and 1,000° C. aged). In this set of experiments, we noted that remarkably, the sample survives with little deterioration whereas typical Pd sample on SBA-200 gamma-alumina is considerably deactivated after 950° C. aging (FIG.8). HAADF-STEM images of the sample inFIG.5after many hydrothermal aging cycles show that theta-alumina rods in 3 wt % Pd/theta-rods sample do not change and relatively large well-faceted PdO nanoparticles (that are needed for high activity due to (110) facets on PdO surface) are present. FIGS.6and7show the activity and stability of single-atom Rhodium supported on theta-alumina sample with low (0.07 wt %) loading of Rh in NO reduction. The sample is active and stable, consistent with previous finding of catalytic activity of isolated Rh(I) ions for NO reduction by CO. Hydrothermal aging at 1,000° C. does not lead to any significant changes in activity unlike typical Rh/alumina samples (for which Rh is known to dissolve inside alumina during alumina phase-change; shown inFIG.9), thus alleviating the previous problems for Rh-alumina supported samples that suffer high deactivation after hydrothermal aging. Mostly single Rh atoms are present on the sample after HTA treatment, with very few sub-nanometer sized Rh nanoparticles that could be found, consistent with preserved activity of this sample as shown inFIG.7. The method we describe based on pre-heating gamma-alumina or boehmite of varying morphologies to high temperature (1,000-1,150° C.) and ensuring complete structural evolution to the most stable transition alumina polymorphs, is a general method to produce high surface area alumina-containing materials with enhanced hydrothermal stability. Pure theta-alumina can be used not only as a catalyst but as thermally/hydrothermally stable binder material. Due to its well-preserved morphology after aging and initial textural meso- and microporosity, it maintains its high permeance. EXAMPLES Rod-like boehmite was synthesized using the following method: Al(NO3)3·9H2O (7.15 g) was dissolved in distilled water (80 ml). Then, glacial acetic acid was added to the solution. The resulting solution was transferred to a 125 ml Teflon-lined autoclave, sealed and kept at 200° C. for 12 hours. pH was adjusted with glacial acetic acid to ensure the pH was ˜4 after 12 hours in the autoclave. After cooling to room temperature, the powder was collected by filtration, washed with distilled water, and dried at 200° C. The as-synthesized boehmite powder was then calcined at 800° C. for 2 h to convert it to rhombus-platelet γ-alumina with surface area of approximately 75 m2/g. Commercial SBA-200 γ-alumina from SASOL with surface area ˜180 m2/g was used without additional pretreatment. Rod-like γ-alumina was transformed into pure theta-alumina rods by heat-treating at 1,050° C. for 4 hours. Note that further heating this sample at 1,050° C. for longer time or at 1,150° C. does not lead to any change of the sample. γ-Al2O3(SBA-200) and theta-alumina (rod-like) were loaded with 3 wt % of Pd by wet impregnation (incipient wetness) using [Pd(NH3)4](NO3)2in water (10% by weigh solution). The sample was calcined in dry air flow at 600° C. for 5 hours to decompose nitrate. γ-Al2O3(SBA-200) and theta-alumina (rods) were loaded with 0.07 wt % Rh using rhodium nitrate hydrate (36 wt % Rh) via incipient wetness impregnation. The sample was then dried and calcined 600° C. for 5 hours to decompose nitrate. The results of testing on these materials are described in the attached figures. While various preferred embodiments of the disclosure are shown and described, it is to be distinctly understood that this disclosure is not limited thereto but may be variously embodied to practice within the scope of the following claims. From the foregoing description, it will be apparent that various changes may be made without departing from the spirit and scope of the disclosure as defined by the following claims.
13,407
11857951
DETAILED DESCRIPTION As used above, and throughout the description herein, the following terms, unless otherwise indicated, shall be understood to have the following meanings. If not defined otherwise herein, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this technology belongs. In the event that there is a plurality of definitions for a term herein, those in this section prevail unless stated otherwise. The term “block copolymer” or “block polymer” refers to a macromolecule consisting of long sequences of different repeat units. Exemplary block polymers include, but are not limited to AnBm, AnBmAm, AnBmCk, or AnBmCkAn. The term “copolymer” refers to a polymer derived from more than one species of monomer. The term “graft copolymer” refers to a type of copolymer which one or more blocks of homopolymer are grafted as branches onto a main chain i.e. it is a branched copolymer with one or more side chains of a homopolymer attached to the backbone of the main chain. The term “metal nanoparticle” refers to a submicron scale entities made of pure metals (e.g., nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, and tungsten), combination of metals (e.g. PtSn), or their compounds. The term “number average molecular weight (Mn)” refers to the total weight of the polymer divided by the number of molecules in the polymer. The term “polymeric blend” refers to a mixture in which at least two polymers are blended together to create a new material with different physical properties. The term “polyolefinic polymer” refers to a polymer produced from an olefin with the general formula CnH2nas a monomer. Catalyst One aspect of the present application relates to a catalyst which comprises a silica core having an outer surface and a mesoporous silica shell having an outer surface and an inner surface with the inner surface being inside the outer surface of said mesoporous silica shell proximate to and surrounding the outer surface of said silica core. The outer surface of the mesoporous silica shell has openings leading to pores within the mesoporous silica shell which extend toward the outer surface of said silica core. The catalyst also includes catalytically active metal nanoparticles positioned within the pores proximate to said core, wherein the catalytic metal nanoparticles comprise about 0.0001 wt % to about 1.0 wt % of the catalyst. In another embodiment of the catalyst, the catalytic metal nanoparticle comprises about 0.085 wt % of the catalyst. In another embodiment of the catalyst, the catalytic metal nanoparticle comprises about 0.28 wt % of the catalyst. In another embodiment of the catalyst, the catalytic metal nanoparticle comprises about 0.35 wt % of the catalyst. In another embodiment of the catalyst, the catalytic metal nanoparticle comprises about 0.40 wt % of the catalyst. In another embodiment of the catalyst, the silica core further comprises a functional group selected from the group consisting of: amines, carboxylic acids, alcohols, thiols, phosphorus, and combinations thereof. In another embodiment of the catalyst, the catalytic metal nanoparticles are positioned on the outer surface of the silica core. In another embodiment of the catalyst, the catalyst has a mean particle diameter of about 100 nm to about 1000 nm. In another embodiment of the catalyst, the catalyst has a mean particle diameter of about 240 nm. In another embodiment of the catalyst, the silica core has a mean particle diameter of about 50 nm to about 500 nm. In another embodiment of the catalyst, the silica core has a mean particle diameter of about 127 nm. In another embodiment of the catalyst, the metal for the catalytic metal nanoparticle is selected from the group consisting of nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, and combinations thereof. In another embodiment of the catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 1 nm to about 10 nm. In another embodiment of the catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 1.7 nm. In another embodiment of the catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 2.9 nm. In another embodiment of the catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 3.2 nm. In another embodiment of the catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 5.0 nm. In another embodiment of the catalyst, the mesoporous silica shell has a thickness of about 50 nm to about 500 nm. In another embodiment of the catalyst, the mesoporous silica shell has a thickness of about 65 nm. In another embodiment of the catalyst, the mesoporous silica shell has a thickness of about 110 nm. In another embodiment of the catalyst, the mesoporous silica shell has a thickness of about 120 nm. In another embodiment of the catalyst, the mesoporous silica shell has a thickness of about 220 nm. In another embodiment of the catalyst, the mesoporous silica shell has a thickness of about 300 nm. In another embodiment of the catalyst, the mesoporous silica shell has a pore diameter of about 1 nm to about 10 nm. In another embodiment of the catalyst, the mesoporous silica shell has a pore diameter of about 2.4 nm. In another embodiment of the catalyst, the pores have a length of about the thickness of the mesoporous silica shell measured between its inner and outer surfaces. Methods of Use Another aspect of the present application relates to a process for catalytically hydrogenolysizing a polyolefinic polymer, which comprises providing a polyolefinic polymer and subjecting said polyolefinic polymer to a hydrogenolysis reaction in the presence of a catalyst to cleave the polymer into hydrocarbon segments. The catalyst comprises a silica core having an outer surface and a mesoporous silica shell having an outer surface and an inner surface with the inner surface being inside the outer surface of said mesoporous silica shell proximate to and surrounding the outer surface of said silica core, wherein the outer surface of the mesoporous silica shell has openings leading to pores within the mesoporous silica shell which extend toward the outer surface of said silica core. The catalyst also includes catalytic metal nanoparticles positioned within the pores proximate to said core to cleave said polyolefinic polymer entering said mesoporous silica shell through the openings into hydrocarbon segments. In carrying out the process, the catalyst used has the characteristics described herein. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle comprises about 0.0001 wt % to about 1.0 wt % of the catalyst. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle comprises about 0.085 wt % of the catalyst. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle comprises about 0.28 wt % of the catalyst. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle comprises about 0.35 wt % of the catalyst. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle comprises about 0.40 wt % of the catalyst. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle has a mean particle diameter of about 1 nm to about 10 nm. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle has a mean particle diameter of about 1.7 nm. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle has a mean particle diameter of about 2.9 nm. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle has a mean particle diameter of about 3.2 nm. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the catalytic metal nanoparticle has a mean particle diameter of about 5.0 nm. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said polyolefinic polymer is selected from the group consisting of physical mixtures of polymers, polymeric blends, copolymers, block copolymers, graft copolymers, and combinations thereof. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said polyolefinic polymer is selected from the group consisting of high density polyethylene, isostatic polypropylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, and combinations thereof. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said polyolefinic polymer is high density polyethylene having a number average molecular weight (Mn) of 5000-100000 Da. In some embodiments of the number average molecular weight (Mn) is 5000-75000 Da, 10000-100000 Da, 10000-75000 Da, 10000-50000 Da, or 5000-50000 Da. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said polyolefinic polymer has a longitudinal extent between opposed ends. The step of subjecting said polyolefinic polymer to a hydrogenolysis reaction comprises extending an end of said polyolefinic polymer through the openings and into the pores of said mesoporous silica shell and cleaving said polyolefinic polymer into hydrocarbon segments in the pores using the catalytic metal nanoparticle. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the pores have dimensions selected to produce a size distribution of the hydrocarbon segments as a result of hydrogenolysis. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, the pores have a diameter selected to permit a length of said polyolefinic polymer to enter the pores which yield a particular segment length as a result of hydrogenolysis. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said subjecting is carried out at a pressure of about 1 psi to about 1000 psi. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said subjecting is carried out at a pressure of about 10 psi to about 1000 psi, about 50 psi to about 1000 psi, about 100 psi to about 1000 psi, about 150 psi to about 1000 psi, about 200 psi to about 1000 psi, about 250 psi to about 1000 psi, about 300 psi to about 1000 psi, about 400 psi to about 1000 psi, about 500 psi to about 1000 psi, about 600 psi to about 1000 psi, about 700 psi to about 1000 psi, about 800 psi to about 1000 psi, about 900 psi to about 1000 psi, about 1 psi to about 900 psi, about 1 psi to about 800 psi, about 1 psi to about 700 psi, about 1 psi to about 600 psi, about 1 psi to about 500 psi, about 1 psi to about 400 psi, about 1 psi to about 300 psi, about 1 psi to about 250 psi, about 1 psi to about 200 psi, about 1 psi to about 150 psi, about 1 psi to about 100 psi, about 1 psi to about 50 psi, or about 1 psi to about 10 psi. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said subjecting is carried out at a pressure of about 200 psi. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said subjecting is carried out at a temperature of about 150° C. to about 400° C. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said subjecting is carried out at a temperature of about 200° C. to about 400° C., about 250° C. to about 400° C., about 300° C. to about 400° C., about 350° C. to about 400° C., about 150° C. to about 350° C., about 150° C. to about 300° C., about 150° C. to about 250° C., or about 150° C. to about 200° C. In another embodiment of the process for catalytically hydrogenolysizing a polyolefinic polymer, said subjecting is carried out at a temperature of about 250° C. Methods of Preparing the Catalyst The catalyst of the present application can be prepared by dispersing SiO2spheres in an alcoholic solvent and functionalizing them with a group such as an amine. The functionalized SiO2spheres are then dried before being resuspended in an alcoholic solvent and then treated with Pt nanoparticles suspended in an alcoholic solvent. The Pt/SiO2spheres were dried before being resuspended in an alcoholic solvent and then a shell of mesoporous silica (mSiO2) was grown on top of the Pt/SiO2spheres, the shell having pores organized radially from the silica sphere and the pore length being equal to the thickness of the mSiO2shell. This three-layered spherical shell-type construction (mSiO2/Pt/SiO2) places the Pt nanoparticles at the terminal end of linear channels (i.e., at the bottom of wells). A further aspect of the present application relates to a method of preparing a catalyst which comprises adding a functional group to a silica core having an outer surface to produce a functionalized silica core. The functionalized silica core is contacted with a plurality of catalytic metal nanoparticles wherein the catalytic metal nanoparticles adhere to the surface of the functionalized silica core to produce a functionalized silica core supported catalytic metal nanoparticles. The functionalized silica core supported catalytic metal nanoparticles is then contacted with a silicon compound to produce a mesoporous silica shell having an outer surface and an inner surface with the inner surface being inside the outer surface of said mesoporous silica shell proximate to and surrounding the outer surface of said functionalized silica core supported catalytic metal nanoparticles. The outer surface of the mesoporous silica shell has openings leading to pores within the mesoporous silica shell which extend toward the outer surface of said functionalized silica core supported catalytic metal nanoparticles. In another embodiment of the method of preparing a catalyst, the functional group is selected from the group consisting of: amines, carboxylic acids, alcohols, thiols, phosphorus, and combinations thereof. In carrying out the method of preparing a catalyst, the catalyst has the characteristics described above. In another embodiment of the method of preparing a catalyst, the metal for the plurality of catalytic metal nanoparticles is selected from the group consisting of nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, rhenium, chromium, molybdenum, tungsten, and combinations thereof. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles comprises about 0.0001 wt % to about 1.0 wt % of the catalyst. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles comprises about 0.00025 wt % to about 1.0 wt % of the catalyst, about 0.0005 wt % to about 1.0 wt % of the catalyst, about 0.00075 wt % to about 1.0 wt % of the catalyst, about 0.001 wt % to about 1.0 wt % of the catalyst, about 0.0025 wt % to about 1.0 wt % of the catalyst, about 0.005 wt % to about 1.0 wt % of the catalyst, about 0.0075 wt % to about 1.0 wt % of the catalyst, about 0.01 wt % to about 1.0 wt % of the catalyst, about 0.025 wt % to about 1.0 wt % of the catalyst, about 0.05 wt % to about 1.0 wt % of the catalyst, about 0.075 wt % to about 1.0 wt % of the catalyst, about 0.1 wt % to about 1.0 wt % of the catalyst, about 0.2 wt % to about 1.0 wt % of the catalyst, about 0.3 wt % to about 1.0 wt % of the catalyst, about 0.4 wt % to about 1.0 wt % of the catalyst, about 0.5 wt % to about 1.0 wt % of the catalyst, about 0.6 wt % to about 1.0 wt % of the catalyst, about 0.7 wt % to about 1.0 wt % of the catalyst, about 0.8 wt % to about 1.0 wt % of the catalyst, or about 0.9 wt % to about 1.0 wt % of the catalyst. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles comprises about 0.085 wt % of the catalyst. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles comprises about 0.28 wt % of the catalyst. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles comprises about 0.35 wt % of the catalyst. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles comprises about 0.40 wt % of the catalyst. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles has a mean particle diameter of about 1 nm to about 10 nm. In another embodiment of the method of preparing a catalyst, the plurality of catalytic metal nanoparticles has a mean particle diameter of about 2 nm to about 10 nm, about 3 nm to about 10 nm, about 4 nm to about 10 nm, about 5 nm to about 10 nm, about 6 nm to about 10 nm, about 7 nm to about 10 nm, about 8 nm to about 10 nm, about 9 nm to about 10 nm, about 1 nm to about 9 nm, about 1 nm to about 8 nm, about 1 nm to about 7 nm, about 1 nm to about 6 nm, about 1 nm to about 5 nm, about 1 nm to about 4 nm, about 1 nm to about 3 nm, or about 1 nm to about 2 nm. In another embodiment of the method of preparing a catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 1.7 nm. In another embodiment of the method of preparing a catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 2.9 nm. In another embodiment of the method of preparing a catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 3.2 nm. In another embodiment of the method of preparing a catalyst, the catalytic metal nanoparticle has a mean particle diameter of about 5.0 nm. In another embodiment of the method of preparing a catalyst, the silicon compound is selected from the group consisting of: orthosilicates, metasilicates, pyrosilicates, and combinations thereof. According to any embodiment of the present application, the catalytic metal nanoparticle comprises about 0.00025 wt % to about 1.0 wt % of the catalyst, about 0.0005 wt % to about 1.0 wt % of the catalyst, about 0.00075 wt % to about 1.0 wt % of the catalyst, about 0.001 wt % to about 1.0 wt % of the catalyst, about 0.0025 wt % to about 1.0 wt % of the catalyst, about 0.005 wt % to about 1.0 wt % of the catalyst, about 0.0075 wt % to about 1.0 wt % of the catalyst, about 0.01 wt % to about 1.0 wt % of the catalyst, about 0.025 wt % to about 1.0 wt % of the catalyst, about 0.05 wt % to about 1.0 wt % of the catalyst, about 0.075 wt % to about 1.0 wt % of the catalyst, about 0.1 wt % to about 1.0 wt % of the catalyst, about 0.2 wt % to about 1.0 wt % of the catalyst, about 0.3 wt % to about 1.0 wt % of the catalyst, about 0.4 wt % to about 1.0 wt % of the catalyst, about 0.5 wt % to about 1.0 wt % of the catalyst, about 0.6 wt % to about 1.0 wt % of the catalyst, about 0.7 wt % to about 1.0 wt % of the catalyst, about 0.8 wt % to about 1.0 wt % of the catalyst, or about 0.9 wt % to about 1.0 wt % of the catalyst. According to any embodiment of the present application, the catalyst has a mean particle diameter of about 110 nm to about 1000 nm, about 120 nm to about 1000 nm, about 130 nm to about 1000 nm, about 140 nm to about 1000 nm, about 150 nm to about 1000 nm, about 160 nm to about 1000 nm, about 170 nm to about 1000 nm, about 180 nm to about 1000 nm, about 190 nm to about 1000 nm, about 200 nm to about 1000 nm, about 210 nm to about 1000 nm, about 220 nm to about 1000 nm, about 230 nm to about 1000 nm, about 240 nm to about 1000 nm, about 250 nm to about 1000 nm, about 260 nm to about 1000 nm, about 270 nm to about 1000 nm, about 280 nm to about 1000 nm, about 290 nm to about 1000 nm, about 300 nm to about 1000 nm, about 310 nm to about 1000 nm, about 320 nm to about 1000 nm, about 330 nm to about 1000 nm, about 340 nm to about 1000 nm, about 350 nm to about 1000 nm, about 360 nm to about 1000 nm, about 370 nm to about 1000 nm, about 380 nm to about 1000 nm, about 390 nm to about 1000 nm, about 400 nm to about 1000 nm, about 410 nm to about 1000 nm, about 420 nm to about 1000 nm, about 430 nm to about 1000 nm, about 440 nm to about 1000 nm, about 450 nm to about 1000 nm, about 460 nm to about 1000 nm, about 470 nm to about 1000 nm, about 480 nm to about 1000 nm, about 490 nm to about 1000 nm, about 500 nm to about 1000 nm, about 510 nm to about 1000 nm, about 520 nm to about 1000 nm, about 530 nm to about 1000 nm, about 540 nm to about 1000 nm, about 550 nm to about 1000 nm, about 560 nm to about 1000 nm, about 570 nm to about 1000 nm, about 580 nm to about 1000 nm, about 590 nm to about 1000 nm, about 600 nm to about 1000 nm, about 610 nm to about 1000 nm, about 620 nm to about 1000 nm, about 630 nm to about 1000 nm, about 640 nm to about 1000 nm, about 650 nm to about 1000 nm, about 660 nm to about 1000 nm, about 670 nm to about 1000 nm, about 680 nm to about 1000 nm, about 690 nm to about 1000 nm, about 700 nm to about 1000 nm, about 710 nm to about 1000 nm, about 720 nm to about 1000 nm, about 730 nm to about 1000 nm, about 740 nm to about 1000 nm, about 750 nm to about 1000 nm, about 760 nm to about 1000 nm, about 770 nm to about 1000 nm, about 780 nm to about 1000 nm, about 790 nm to about 1000 nm, about 800 nm to about 1000 nm, about 810 nm to about 1000 nm, about 820 nm to about 1000 nm, about 830 nm to about 1000 nm, about 840 nm to about 1000 nm, about 850 nm to about 1000 nm, about 860 nm to about 1000 nm, about 870 nm to about 1000 nm, about 880 nm to about 1000 nm, about 890 nm to about 1000 nm, about 900 nm to about 1000 nm, about 910 nm to about 1000 nm, about 920 nm to about 1000 nm, about 930 nm to about 1000 nm, about 940 nm to about 1000 nm, about 950 nm to about 1000 nm, about 960 nm to about 1000 nm, about 970 nm to about 1000 nm, about 980 nm to about 1000 nm, about 990 nm to about 1000 nm, about 100 nm to about 990 nm, about 100 nm to about 980 nm, about 100 nm to about 970 nm, about 100 nm to about 960 nm, about 100 nm to about 950 nm, about 100 nm to about 940 nm, about 100 nm to about 930 nm, about 100 nm to about 920 nm, about 100 nm to about 910 nm, about 100 nm to about 900 nm, about 100 nm to about 890 nm, about 100 nm to about 880 nm, about 100 nm to about 870 nm, about 100 nm to about 860 nm, about 100 nm to about 850 nm, about 100 nm to about 840 nm, about 100 nm to about 830 nm, about 100 nm to about 820 nm, about 100 nm to about 810 nm, about 100 nm to about 800 nm, about 100 nm to about 790 nm, about 100 nm to about 780 nm, about 100 nm to about 770 nm, about 100 nm to about 760 nm, about 100 nm to about 750 nm, about 100 nm to about 740 nm, about 100 nm to about 730 nm, about 100 nm to about 720 nm, about 100 nm to about 710 nm, about 100 nm to about 700 nm, about 100 nm to about 690 nm, about 100 nm to about 680 nm, about 100 nm to about 670 nm, about 100 nm to about 660 nm, about 100 nm to about 650 nm, about 100 nm to about 640 nm, about 100 nm to about 630 nm, about 100 nm to about 620 nm, about 100 nm to about 610 nm, about 100 nm to about 600 nm, about 100 nm to about 590 nm, about 100 nm to about 580 nm, about 100 nm to about 570 nm, about 100 nm to about 560 nm, about 100 nm to about 550 nm, about 100 nm to about 540 nm, about 100 nm to about 530 nm, about 100 nm to about 520 nm, about 100 nm to about 510 nm, about 100 nm to about 500 nm, about 100 nm to about 490 nm, about 100 nm to about 480 nm, about 100 nm to about 470 nm, about 100 nm to about 460 nm, about 100 nm to about 450 nm, about 100 nm to about 440 nm, about 100 nm to about 430 nm, about 100 nm to about 420 nm, about 100 nm to about 410 nm, about 100 nm to about 400 nm, about 100 nm to about 390 nm, about 100 nm to about 380 nm, about 100 nm to about 370 nm, about 100 nm to about 360 nm, about 100 nm to about 350 nm, about 100 nm to about 340 nm, about 100 nm to about 330 nm, about 100 nm to about 320 nm, about 100 nm to about 310 nm, about 100 nm to about 300 nm, about 100 nm to about 290 nm, about 100 nm to about 280 nm, about 100 nm to about 270 nm, about 100 nm to about 260 nm, about 100 nm to about 250 nm, about 100 nm to about 240 nm, about 100 nm to about 230 nm, about 100 nm to about 220 nm, about 100 nm to about 210 nm, about 100 nm to about 200 nm, about 100 nm to about 190 nm, about 100 nm to about 180 nm, about 100 nm to about 170 nm, about 100 nm to about 160 nm, about 100 nm to about 150 nm, about 100 nm to about 140 nm, about 100 nm to about 130 nm, about 100 nm to about 120 nm, or about 100 nm to about 110 nm. According to any embodiment of the present application, the silica core has a mean particle diameter of about 55 nm to about 500 nm, about 60 nm to about 500 nm, about 65 nm to about 500 nm, about 70 nm to about 500 nm, about 75 nm to about 500 nm, about 80 nm to about 500 nm, about 85 nm to about 500 nm, about 90 nm to about 500 nm, about 95 nm to about 500 nm, about 100 nm to about 500 nm, about 110 nm to about 500 nm, about 120 nm to about 500 nm, about 130 nm to about 500 nm, about 140 nm to about 500 nm, about 150 nm to about 500 nm, about 160 nm to about 500 nm, about 170 nm to about 500 nm, about 180 nm to about 500 nm, about 190 nm to about 500 nm, about 200 nm to about 500 nm, about 210 nm to about 500 nm, about 220 nm to about 500 nm, about 230 nm to about 500 nm, about 240 nm to about 500 nm, about 250 nm to about 500 nm, about 260 nm to about 500 nm, about 270 nm to about 500 nm, about 280 nm to about 500 nm, about 290 nm to about 500 nm, about 300 nm to about 500 nm, about 310 nm to about 500 nm, about 320 nm to about 500 nm, about 330 nm to about 500 nm, about 340 nm to about 500 nm, about 350 nm to about 500 nm, about 360 nm to about 500 nm, about 370 nm to about 500 nm, about 380 nm to about 500 nm, about 390 nm to about 500 nm, about 400 nm to about 500 nm, about 410 nm to about 500 nm, about 420 nm to about 500 nm, about 430 nm to about 500 nm, about 440 nm to about 500 nm, about 450 nm to about 500 nm, about 460 nm to about 500 nm, about 470 nm to about 500 nm, about 480 nm to about 500 nm, about 490 nm to about 500 nm, about 50 nm to about 490 nm, about 50 nm to about 480 nm, about 50 nm to about 470 nm, about 50 nm to about 460 nm, about 50 nm to about 450 nm, about 50 nm to about 440 nm, about 50 nm to about 430 nm, about 50 nm to about 420 nm, about 50 nm to about 410 nm, about 50 nm to about 400 nm, about 50 nm to about 390 nm, about 50 nm to about 380 nm, about 50 nm to about 370 nm, about 50 nm to about 360 nm, about 50 nm to about 350 nm, about 50 nm to about 340 nm, about 50 nm to about 330 nm, about 50 nm to about 320 nm, about 50 nm to about 310 nm, about 50 nm to about 300 nm, about 50 nm to about 290 nm, about 50 nm to about 280 nm, about 50 nm to about 270 nm, about 50 nm to about 260 nm, about 50 nm to about 250 nm, about 50 nm to about 240 nm, about 50 nm to about 230 nm, about 50 nm to about 220 nm, about 50 nm to about 210 nm, about 50 nm to about 200 nm, about 50 nm to about 190 nm, about 50 nm to about 180 nm, about 50 nm to about 170 nm, about 50 nm to about 160 nm, about 50 nm to about 150 nm, about 50 nm to about 140 nm, about 50 nm to about 130 nm, about 50 nm to about 120 nm, about 50 nm to about 110 nm, about 50 nm to about 100 nm, about 50 nm to about 95 nm, about 50 nm to about 90 nm, about 50 nm to about 85 nm, about 50 nm to about 80 nm, about 50 nm to about 75 nm, about 50 nm to about 70 nm, about 50 nm to about 65 nm, about 50 nm to about 60 nm, or about 50 nm to about 55 nm. According to any embodiment of the present application, the catalytic metal nanoparticle has a mean particle diameter of about 2 nm to about 10 nm, about 3 nm to about 10 nm, about 4 nm to about 10 nm, about 5 nm to about 10 nm, about 6 nm to about 10 nm, about 7 nm to about 10 nm, about 8 nm to about 10 nm, about 9 nm to about 10 nm, about 1 nm to about 9 nm, about 1 nm to about 8 nm, about 1 nm to about 7 nm, about 1 nm to about 6 nm, about 1 nm to about 5 nm, about 1 nm to about 4 nm, about 1 nm to about 3 nm, or about 1 nm to about 2 nm. According to any embodiment of the present application, the mesoporous silica shell has a thickness of about 55 nm to about 500 nm, about 60 nm to about 500 nm, about 65 nm to about 500 nm, about 70 nm to about 500 nm, about 75 nm to about 500 nm, about 80 nm to about 500 nm, about 85 nm to about 500 nm, about 90 nm to about 500 nm, about 95 nm to about 500 nm, about 100 nm to about 500 nm, about 110 nm to about 500 nm, about 120 nm to about 500 nm, about 130 nm to about 500 nm, about 140 nm to about 500 nm, about 150 nm to about 500 nm, about 160 nm to about 500 nm, about 170 nm to about 500 nm, about 180 nm to about 500 nm, about 190 nm to about 500 nm, about 200 nm to about 500 nm, about 210 nm to about 500 nm, about 220 nm to about 500 nm, about 230 nm to about 500 nm, about 240 nm to about 500 nm, about 250 nm to about 500 nm, about 260 nm to about 500 nm, about 270 nm to about 500 nm, about 280 nm to about 500 nm, about 290 nm to about 500 nm, about 300 nm to about 500 nm, about 310 nm to about 500 nm, about 320 nm to about 500 nm, about 330 nm to about 500 nm, about 340 nm to about 500 nm, about 350 nm to about 500 nm, about 360 nm to about 500 nm, about 370 nm to about 500 nm, about 380 nm to about 500 nm, about 390 nm to about 500 nm, about 400 nm to about 500 nm, about 410 nm to about 500 nm, about 420 nm to about 500 nm, about 430 nm to about 500 nm, about 440 nm to about 500 nm, about 450 nm to about 500 nm, about 460 nm to about 500 nm, about 470 nm to about 500 nm, about 480 nm to about 500 nm, about 490 nm to about 500 nm, about 50 nm to about 490 nm, about 50 nm to about 480 nm, about 50 nm to about 470 nm, about 50 nm to about 460 nm, about 50 nm to about 450 nm, about 50 nm to about 440 nm, about 50 nm to about 430 nm, about 50 nm to about 420 nm, about 50 nm to about 410 nm, about 50 nm to about 400 nm, about 50 nm to about 390 nm, about 50 nm to about 380 nm, about 50 nm to about 370 nm, about 50 nm to about 360 nm, about 50 nm to about 350 nm, about 50 nm to about 340 nm, about 50 nm to about 330 nm, about 50 nm to about 320 nm, about 50 nm to about 310 nm, about 50 nm to about 300 nm, about 50 nm to about 290 nm, about 50 nm to about 280 nm, about 50 nm to about 270 nm, about 50 nm to about 260 nm, about 50 nm to about 250 nm, about 50 nm to about 240 nm, about 50 nm to about 230 nm, about 50 nm to about 220 nm, about 50 nm to about 210 nm, about 50 nm to about 200 nm, about 50 nm to about 190 nm, about 50 nm to about 180 nm, about 50 nm to about 170 nm, about 50 nm to about 160 nm, about 50 nm to about 150 nm, about 50 nm to about 140 nm, about 50 nm to about 130 nm, about 50 nm to about 120 nm, about 50 nm to about 110 nm, about 50 nm to about 100 nm, about 50 nm to about 95 nm, about 50 nm to about 90 nm, about 50 nm to about 85 nm, about 50 nm to about 80 nm, about 50 nm to about 75 nm, about 50 nm to about 70 nm, about 50 nm to about 65 nm, about 50 nm to about 60 nm, or about 50 nm to about 55 nm. According to any embodiment of the present application, the mesoporous silica shell has a pore diameter of about 2 nm to about 10 nm, about 3 nm to about 10 nm, about 4 nm to about 10 nm, about 5 nm to about 10 nm, about 6 nm to about 10 nm, about 7 nm to about 10 nm, about 8 nm to about 10 nm, about 9 nm to about 10 nm, about 1 nm to about 9 nm, about 1 nm to about 8 nm, about 1 nm to about 7 nm, about 1 nm to about 6 nm, about 1 nm to about 5 nm, about 1 nm to about 4 nm, about 1 nm to about 3 nm, or about 1 nm to about 2 nm. The above disclosure is general. A more specific description is provided below in the following examples. The examples are described solely for the purpose of illustration and are not intended to limit the scope of the present application. Changes in form and substitution of equivalents are contemplated as circumstances suggest or render expedient. Although specific terms have been employed herein, such terms are intended in a descriptive sense and not for purposes of limitation. EXAMPLES General Methods and Techniques Solid State NMR 13C cross-polarization (CP) and directly-excited (Bloch decay) magic-angle-spinning (MAS) NMR spectra were acquired using a 600 MHz Varian NMR system equipped with a 3.2-mm double-resonance probe. The samples were tightly-packed into 3.2-mm pencil-type rotors and spun to 16 kHz. The Bloch decay spectra were acquired using a 5 μs13C excitation pulse and a 10 s recycle delay while the CPMAS experiments used a 3.2 μs1H excitation pulse, a 1 ms contact time, and a 5 s recycle delay. High powered (80 kHz) SPINAL-64 decoupling was applied in all experiments and the resolution was found to be limited by the13C-13C homonuclear dipolar coupling interactions, with faster spinning yielding an improved resolution. The number of scans totaled 128(92) for the mSiO2, 47126(47126) for the silica gel, 128(288) for the 200 nm Stöber silica, and 4096(1306) for the 50 nm Stöber silica, with the first number being that for the CPMAS experiment and second being associated with the Bloch decay. 8320 scans were accumulated for the Bloch decay spectrum of the non-enriched 7 kg/mol PE on the mSiO2. 8192 scans were accumulated in the case of the mSiO2that was dried at 300° C. under vacuum. Chemical shifts were referenced to DSS (4,4-dimethyl-4-silapentane-1-sulfonic acid) using the universal shielding scale. The two-dimensional13C exchanged spectroscopy (EXSY) spectra were acquired using a 400 MHz Agilent DD2 solid-state NMR spectrometer equipped with a 3.2-mm MAS probe. Samples were spun to a MAS rate of 15 kHz. 2.5 s13C π/2 pulses were used. A presaturation loop consisting of 50 pairs of alternating 0° and 900 phased pulses was applied prior to a recovery period, which was set to 3 s.1H SPINAL-64 decoupling (100 kHz) was applied during the t1evolution period and the acquisition. Mixing times varied between 0 and 4 s. Experiments were conducted at 72, 93, and 114° C. The exact temperatures were determined via ex situ measurement of the change in the chemical shift of Pb(NO3)2with respect to the static spectrum collected at 25° C. The observed temperatures take into account sample heating due to MAS. The number of scans and t1increments varied between 64 to 192 and 64 to 88, respectively. Greater numbers of scans and t1increments were used for the higher temperature experiments. Electron Microscopy Transmission electron microscopy (TEM) images were obtained on a Tecnai G2 F20 electron microscope operated at 200 kV. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image was acquired using a FEI Titan Themis 300 probe-corrected scanning transmission electron microscope under 200 kV accelerating voltage. Dynamic Light Scattering Dynamic light scattering for particle size determination was recorded using a Malvern Zetasizer Nano ZS100 with MPT-2 autotitrator with ethanol as the solvent. X-Ray Diffraction Powder X-ray diffraction (PXRD) patterns were measured by a Bruker D8 Advance Twin diffractometer with Cu Kαradiation (40 kV, 40 mA, λ=0.1541 nm). Nitrogen Adsorption N2physisorption experiments, Brunauer-Emmett-Teller (BET) surface area analysis, and Barrett-Joyner-Halenda (BJH) mesopore size analysis were conducted using a Micromeritics 3Flex surface characterization analyzer at 77 K. Elemental Analysis The Pt NP loadings for the catalysts were determined by inductively coupled plasma mass spectrometry (ICP-MS; Thermo Scientific X Series II). The samples are first treated with hydrofluoric acid (50 μL, 48-51%, Acros Organics) to etch away silica and then digested with aqua regia (4 mL). The final solution is diluted with 2 v/v % nitric acid to target concentrations. Gel Permeation Chromatography High temperature gel permeation chromatography (HT-GPC) was performed on an Agilent PL-GPC 220 equipped with a refractive index (RI) detector and three PL-Gel Mixed B columns. GPC columns were eluted at 1.0 mL/min with 1,2,4-trichlorobenzene (TCB) containing 0.01 wt. % di-tert-butylhydroxytoluene (BHT) at 150° C. The samples were prepared in TCB (with BHUT) at a concentration of 1.0 mg/ML unless otherwise stated and heated at 150° C. for at least 1 h prior to injection. HT-GPC data calibration was done with monomodal polyethylene standards from Varian and Polymer Standards Service. Gas Chromatography Flame Ionization Detection (GC-FID). Gas chromatography (GC) analyses were performed on an Agilent 6890 gas chromatograph equipped with a split/splitless injector and a flame ionization detector (FID). The column was a 30 m×0.32 mm HP-5 (Agilent) with a film thickness of 0.25 μm. These experiments were performed to establish the reproducibility of the GC methods on separate instruments and to compare with GC data detected using MS. Separations were performed under temperature-programmed conditions from 60 to 325° C. at 4.0° C./min with initial and final hold times of 2 and 10 minutes, respectively. Helium carrier gas was employed with a constant flow of 4.5 mL/min. Injector and detector temperatures were maintained at 320 and 345° C., respectively. In initial studies, oil samples extracted with dichloromethane after 24 h of hydrogenolysis were taken up in dichloromethane and 1 μL of solution was injected (splitless mode). The solvent vent time was 2 minutes. In subsequent analyses, the residue was taken up in a mixture consisting of 2 parts dichloromethane and 1 part toluene, and 4 μL was injected (split mode) with a split ratio of 10:1. Blank injections (dichloromethane only) were included between each experiment to ensure residual hydrocarbons are were not present on the column. Retention times of known species, including pure C28H58(octacosane, Sigma-Aldrich, 0504) and an American Society for Testing and Material's 20 component (Restek ASTM D2287-12 STANDARD) test mixture of saturated alkanes dissolved in dichloromethane, were used to identify the species in catalytic reaction mixtures. Example 1—Synthesis of Polymer and Inorganic Catalytic Materials mSiO2 Decyltrimethylammonium bromide (C10TAB, 0.74 mmol) was dissolved in ultrapure water (480 mL). 2 M NaOH (3.5 mL) was added, and the solution was stirred at 80° C. for 1 h. Tetraethyl orthosilicate (TEOS, 5.0 mL) was added in dropwise fashion over 5 min. The mixture was stirred at 80° C. for 2 h to provide a white suspension. The solution was filtered using a filter frit, and the solid was washed with water (1×200 mL) and then methanol (3×200 mL). The solid was allowed to dry on the filter at room temperature, and then the solid was dried under vacuum. The dried sample (1.0 g) was suspended in acidic methanol (100 mL) with 12 N HCl (0.8 mL), and the suspension was then heated at reflux (80° C.) for 6 h. The solid was isolated by filtration, washed with water (3×200 mL) and methanol (3×200 mL), and then dried under vacuum. The data characterizing the mSiO2material is given below. 50 nm Stöber Silica Ethanol (200 proof, 190 mL) was mixed with water (10 mL) and NH3·H2O (˜28 wt %, 5 mL). This solution was equilibrated at 40° C. for 1 h. TEOS (2.75 mL) was then added to the solution at 40° C., and the reaction mixture was maintained at 40° C. for 2 h. The silica spheres were separated by centrifugation and washed with ethanol (3×100 mL). The data characterizing the 50 nm particles of Stöber silica is given below. 127 nm Stöber Silica 127 nm SiO2spheres were prepared using the Stöber method. The above solution of 45 nm seed particles (1 mL) was mixed with deionized water (2.6 mL), ethanol (18 mL), and NH3·H2O (˜28 wt %, 1.7 mL). The mixture was stirred at 500 rpm for 1 h at room temperature. Three portions of TEOS (1.5 mL total volume) were added in a dropwise fashion to the solution, with 30 min intervals between the addition of each portion. The reaction was stirred at room temperature for 6 h. The SiO2spheres were then washed with an ethanol/water solution (50/50 v/v; 5×20 mL) and then dried under vacuum at room temperature. The data characterizing the 127 nm particles of Stöber silica is given below. 200 nm Stöber Silica 200 nm SiO2spheres were synthesized by a four-step seeded growth approach. First, 24 nm SiO2seeds were prepared. For this, L-arginine (18.2 mg) and ultrapure water (13.9 mL) were thoroughly mixed. Then, cyclohexane (0.9 mL) was added gently to the water-arginine mixture to layer the cyclohexane on top of the aqueous solution. The solution was heated to 60.0±0.2° C. for 30 min with stirring at 300 rpm. TEOS (1.10 mL) was added to the mixture. The reaction was allowed to proceed for 20 h at 60° C. After this time, the aqueous layer (bottom) was separated from the organic layer and stored in a refrigerator. These 24 nm SiO2seed particles were then used for the synthesis of 45 nm SiO2seed particles. The 24 nm seed suspension (4 mL) was diluted with ultrapure water (14.4 mL). Cyclohexane (2 mL) was then added to this solution. The mixture was heated at 60° C. for 30 min with stirring at 300 rpm. TEOS (1.408 mL) was then immediately added to the top layer, and the mixture was allowed to stand at 60° C. for 30 h. After this time, the bottom layer was separated and stored in a refrigerator. 82 nm SiO2seed particles were then grown using the Stöber method, initiated from the 45 nm seed particles (1 mL). The above solution was diluted with deionized water (2.6 mL) and ethanol (18 mL). Subsequently, NH3·H2O (˜28 wt %, 1.7 mL) was added to the solution. The solution was stirred at 500 rpm for 1 h at room temperature. Three portions of TEOS (0.8 mL total) were added in a dropwise fashion to the solution, with 30 min intervals between the addition of each portion. The solution was then stirred for 6 h and stored in the refrigerator. Finally, 200 nm SiO2spheres were prepared as follows: the solution of 82 nm seed particles (1 mL) was diluted with deionized water (2.6 mL) and ethanol (18 mL). NH3·H2O (˜28 wt %, 1.7 mL) was then added to the solution, which was mixed at 500 rpm for 1 h. Two portions of TEOS (0.44 mL total) were added dropwise to the solution, with 30 min intervals between the addition of each portion. The reaction mixture was stirred for 6 h. After 6 h, 200 nm SiO2spheres were obtained and stored in the refrigerator for further use. The SiO2spheres were then washed with an ethanol/water solution (50/50 v/v; 5×20 mL) and then dried under vacuum at room temperature. The data characterizing the 200 nm particles of Stöber silica is given below. Pt Nanoparticles K2PtCl4(41.5 mg), tetradecyltrimethylammonium bromide (C14TAB, 505 mg), and polyvinylpyrrolidone (PVP-K30, Mw=40,000, 222 mg) were added to ethylene glycol (20 mL). The atmosphere of the vessel was inertized with Ar, and the solution was heated at 140° C. for 2 h. Acetone (180 mL) was added to precipitate “as prepared” Pt NPs. The precipitate was further washed with an ethanol/hexane mixture (1/4 v/v; 5×20 mL), and ethanol (20 mL) was added to the material for storage. Pt SiO2 In a typical synthesis, SiO2(1 g) spheres were dispersed in isopropanol (175 mL). A solution of 3-aminopropyl triethoxysilane (APTS, 200 μL) in isopropanol (25 mL) was added to this dispersion to functionalize the silica spheres with NH2groups. The reaction mixture was allowed to age at 80° C., and then the SiO2spheres were washed with ethanol (3×20 mL) by centrifugation at 8000 rpm. The NH2-functionalized SiO2spheres were then dried under vacuum at room temperature and annealed at 100° C. in air for 5 h. NH2-functionalized SiO2spheres (400 mg) were dispersed in ethanol (120 mL). 3.2±0.5 nm Pt nanoparticles suspended in ethanol (220 mL) were added in a dropwise fashion to a vigorously stirred dispersion of NH2-functionalized SiO2spheres. The resulting mixture of SiO2-supported Pt nanoparticles (Pt/SiO2) was sonicated for 30 min. The Pt/SiO2spheres were separated from the solution by centrifugation at 8000 rpm and washed with ethanol (5×30 mL). mSiO2/Pt/SiO2with 1.7 nm Pores Pt/SiO2spheres (25 mg) were dispersed in ethanol (10 mL) by sonication for 0.5 h at room temperature. A premixed solution of dodecyltrimethylammonium bromide (C12TAB, 132 mg) in H2O (50 mL) and ethanol (16.3 mL) was added to the above Pt/SiO2dispersion, and the mixture was sonicated for another 0.5 h. NH3·H2O (˜28 wt %, 550 μL) was then added to the solution. After 0.5 h of gentle stirring, a solution of TEOS (600 μL) in ethanol (5 mL) was added to the above solution in a dropwise manner in 4 portions (150 μL each) every 0.5 h. The solution was stirred for 6 h at room temperature. The mSiO2/Pt/SiO2particles were separated by centrifugation, washed with ethanol (3×20 mL), and finally dispersed into a mixture of methanol (15 mL) and concentrated hydrochloric acid (1 mL). This mixture was heated at reflux (80° C.) for 24 h to remove the C12TAB surfactant. After refluxing, mSiO2/Pt/SiO2catalysts were washed thoroughly with ethanol (6×15 mL) by centrifugation at 8000 rpm. mSiO2/Pt/SiO2with 2.4 nm Pores Pt/SiO2spheres (25 mg) were dispersed in ethanol (10 mL) by sonication for 30 min at room temperature. A premixed solution of hexadecyltrimethylammonium bromide (C16TAB, 165 mg) in H2O (50 mL) and ethanol (16.3 mL) was added to the above Pt/SiO2dispersion, and the mixture was sonicated for another 30 min. Then 550 μL of concentrated NH3·H2O (˜28 wt %) was added to the solution. After 30 min of gentle stirring, a solution of TEOS (720 μL) in ethanol (5 mL) was added to the above solution in a dropwise manner (4×180 μL) every 30 min. The solution was stirred for 6 h at room temperature. The mSiO2/Pt/SiO2particles were separated on a centrifuge, washed with ethanol (3×20 mL), and finally dispersed into a mixture of methanol (15 mL) and concentrated hydrochloric acid (1 mL). This mixture was heated at reflux (80° C.) for 24 h to remove the C16TAB surfactant. After refluxing, mSiO2/Pt/SiO2catalysts were washed thoroughly with ethanol (6×15 mL) by centrifugation at 8000 rpm. mSiO2/Pt/SiO2with 3.5 nm Pores This catalyst was prepared in the same way as the 2.4 nm-pore mSiO2/Pt/SiO2catalyst given in the main text, except n-hexane (20 mL) was added to the mixture priory to the TEOS addition, and the shell growth time was increased from 6 h to 12 h. Pt/MCM-41 200 mg MCM-41 was dispersed in Milli-Q water (10 mL) by sonicating for 0.5 h, then H2PtCl6(4.1 mg) was added to the solution. The reaction mixture was heated at 60° C. in an oil bath and stirred at 300 rpm for 12 h until the water completely evaporated. The resulting powder was reduced at 220° C. for 2 h under 10% H2/Ar (5/45 mL/min) in a tube furnace. Pt/SBA-15 K2PtCl4(4.1 mg) was dissolved into Milli-Q water (420 μL). Half of the solution (210 L) was added dropwise onto the SBA-15 powder (200 mg) with stirring. The mixture was allowed to stand for 12 h and then was dried under reduced pressure. After drying, this procedure was repeated with the other portion of the K2PtCl4solution (210 μL). The dried powder was reduced at 220° C. for 2 h under 10% H2/Ar (5/45 mL/min) in a tube furnace. NiMo γ-Al2O3 Ni(NO3)2(139.4 mg) and (NH4)6Mo7O24·4H2O (59.8 mg) were dissolved in Milli-Q water (380 μL). Half of the solution (190 μL) was added dropwise onto the γ-Al2O3powder (200 mg, Alfa Aesar) with stirring. The mixture was allowed to stand for 12 h and then was dried under reduced pressure. After drying, this procedure was repeated with the second portion of solution (190 μL). The dried powder was calcined at 973 K for 6 h in a muffle furnace. Catalyst Data FIG.7shows the TEM images of the three samples, (a) mSiO2, (b) 50 nm Stöber silica, and (c) 200 nm Stöber silica prior to polyethylene adsorption. All samples show uniform spherical shapes and are relatively monodisperse. The respective diameters for the mSiO2and the 50 and 200 nm Stöber silica particles were measured to be 488±24 (5.0%), 50.1±5.7 (11.3%), and 221.1±5.7 (2.6%) nm. An enlarged view of the mSiO2is shown inFIG.8. FIG.9shows the TEM images of the 127 nm Stöber SiO2spheres and the corresponding Pt/SiO2and mSiO2/Pt/SiO2. All samples are relatively monodispersed and uniform. The diameter of the 127 nm Stöber silica particles is 127±7 (5.5%) nm and the thickness of the mesoporous shell for core-shell material structure is 110±8 (7.2%) nm. The average pore diameter for the mesoporous shell is 2.4 nm.FIG.10shows TEM images of the mSiO2/Pt/SiO2with average 1.7 and 3.5 nm-diameter pores in the mesoporous shell. The mesoporous shells are 97±8 and 115±5 nm thick for the 1.7 and 3.5 nm-diameter pore mSiO2/Pt/SiO2, respectively.FIG.11shows the TEM images of Pt/SBA-15, Pt/MCM-41, and NiMo/γ-Al2O3. The DLS sizes of the mSiO2, the 50 Stöber silica, and 200 nm Stöber silica were 190, 96, and 241 nm, respectively. These sizes are in agreement with those determined by TEM with the minor difference being attributed to the ethanol solvation environment. The DLS size of C10TAB-produced mSiO2is nevertheless significantly smaller than their geometric sizes determined by TEM, likely due to their mesoporous surface. FIG.12shows the typical low angle diffraction peak of MCM-type mSiO2. Nitrogen physisorption results are listed in Tables 1 and 2 below, and the isotherms are shown inFIGS.13,15,17, and19with the pore size distributions shown inFIGS.14,16,18, and20. The mSiO2(used in13C SSNMR experiments) have a large surface area and a high mesoporosity with a uniform pore size of 1.5 nm. The Stöber silicas have a low surface area with almost no pores (the broad peak at 50 nm is likely due to the interparticle assembly), in agreement with their solid morphology. The Davisil silica gel has a moderate surface area that is in between those measured for the Stöber silicas and the mSiO2. The mSiO2/Pt/SiO2(1.7, 2.4, and 3.5 nm pore) catalysts have large surface area as well. For mSiO2/Pt/SiO2with 2.4 nm pores, loading the Pt onto the core-shell structure only slightly changes the surface area in comparison to mSiO2/SiO2(2.4 nm pore). Pt/SBA-15, Pt/MCM-41, and NiMo/γ-Al2O3have BET surface areas of 980, 1030, and 190 m2/g, respectively. The averaged pore diameters for Pt/SBA-15, Pt/MCM-41, and NiMo/γ-Al2O3are 7.7, 2.0, and 8.2 nm, respectively. TABLE 1N2physisorption data silica materialsused in PE adsorption13C NMR studies.BETBJHsurfaceporeporeTEMDLSareavolumesizesizessizessample(m2/g)(cm3/g)(nm)(nm)(nm)mSiC214200.831.5448(24)190silica gel-Davisil4800.7512.02500-5000aND50 nm Stöber SiO255NANA50.1(5.7)96200 nm Stöber SiO214NANA221.1(5.7)241aSize as reported by vendor (Aldrich). TABLE 2N2Physisorption data for hydrogenolysis catalysts.BETBJHsurfaceporeporeTEMareavolumesizesizessample(m2/g)(cm3/g)(nm)(nm)127 nm SiO2300.03NA127(7)mSiO2/SiO2(2.4 nm pore)11100.862.4337(10)mSiO2/Pt/SiO2(2.4 nm pore)10700.842.4342(11)mSiO2/Pt/SiO2(1.7 nm pore)13000.661.7313(12)mSiO2/Pt/SiO2(3.5 nm pore)10601.223.5350(10) 13C-Enriched Polyethylene C2H4(99% enriched 1,2-13C2) was obtained from Cambridge Isotope Lab in a 250 mL glass vessel and used without purification. Methylaluminoxane (MAO) was obtained from Sigma-Aldrich as a 10 wt % solution in toluene; the volatile materials were evaporated, and the white solid MAO residue was washed with pentane (5×10 mL) to give a shiny white solid after exhaustive drying. The {κ2-N(C6F5)=CHC6H2tBu2O}2TiCl2polymerization catalyst was synthesized following the literature procedure. 13C-labeled polyethylene was prepared by the following procedure: A Schlenk round bottom flask was charged with a toluene solution (50 mL) of MAO (0.044 g, 0.74 mmol). 1,2-13C2H4(250 mL at 1 atm) was condensed into the reaction vessel cooled in a liquid nitrogen bath. The vessel was sealed and allowed to warm to room temperature, and then the mixture was cooled to 0° C. The Ti-phenoxyimine catalyst (0.002 g, 0.002 mmol), dissolved in a minimal amount of toluene, was added to the reaction mixture through a septum. The resulting solution was stirred at 0° C. for 10 min and then allowed to warm to room temperature. Stirring was continued for 30 min at room temperature. The solution was then poured into a 5% HCl in MeOH solution to precipitate the polymer. The precipitate was isolated by filtration and dried under reduced pressure to yield13C-labeled polyethylene as a white solid (0.43 g). The polymer was characterized by HT-GPC (Mn=132,000 kg/mol; Mw=429,800; Ð=3.2). Example 2—General Description of Hydrogenolysis Examples PE hydrogenolysis experiments were performed in Parr autoclaves with an overhead mechanical stirrer adapted with an impeller for mixing viscous suspensions. HDPE (3 g, Mn=5,900) and catalyst (0.0013 Pt wt % with respect to PE) were loaded into a glass-lined autoclave, which was sealed and refilled using alternating vacuum and argon cycles (3×). The reactor was then pressurized with H2(120 psi), mixed, and heated at 250° C. The pressure at 250° C. is 200 psi. After a designated time, the reactor was allowed to cool, and the pressure was released. The gaseous portion was analyzed by GC-MS. The mass of the products was measured to determine conversion to gaseous products, and the solid residue was extracted with methylene chloride (3×20 mL) at 100° C. with mixing. Methylene chloride extracts were combined and concentrated to provide a waxy oil product, which was analyzed by GC-MS and GC-FID, and the remaining insoluble residue was analyzed by HT-GPC. HDPE and the catalytic materials (either mSiO2/Pt/SiO2, Pt/SiO2, or mSiO2/SiO2) were physically mixed and then placed in a glass-lined Parr autoclave reactor equipped with a mechanical impeller-style stirrer. The reactor atmosphere was cycled between Ar and vacuum three times, and then the reactor was filled with H2(120 psi) and sealed. The reactor was placed in a heating mantle and heated to 250° C. for the predetermined time (6, 24 or 48 h); under these conditions the pressure reading is 200 psi. After a designated time, the reactor was vented, the gaseous portion was analyzed by GC-MS, and the reactor was allowed to cool. (In complementary experiments, the reactor was allowed to cool, then the reactor was vented, and the gaseous products were analyzed by GC-MS; this was done to ensure that the overall yields and distributions of low molecular weight products were not affected by workup and analysis protocols). The mass of the gaseous products was determined by taking the difference of the combined masses of the solid residue, impeller and glass reaction liner before and after the reaction. A sample of the solid residue was removed for analysis by HT-GPC. The solid residue was extracted with methylene chloride (3×20 mL) at 80° C. with mixing. Methylene chloride extracts were combined and concentrated to provide a waxy oil product, which was analyzed by GC-MS. Molecular Weight Data The polymeric residues produced from the catalytic hydrogenolysis reactions were analyzed by HT-GPC. A sample of the crude reaction mixture was dissolved in TCB and analyzed by HT-GPC directly. The remaining material was extracted with methylene chloride (as described above) to remove the small, soluble products, and the residual solid was then dissolved in TCB and analyzed by HT-GPC. These samples were compared to virgin polyethylene (HDPE) used for the catalytic experiments, and to ‘virgin HDPE’ that had been extracted with methylene chloride (to match the post-catalysis workup). Catalytic hydrogenolysis and thermal, catalyst-free reactions of the HDPE result in lower Mn, which is statistically weighted to emphasize contributions of lower molecular weight species to the distribution. Once the soluble, small molecule species are extracted into methylene chloride, a comparison of Mn, Ð (Mw/Mn), and Mpwould indicate the presence of new, shorter polymeric chains. Equivalent Mn, Ð, and M values for treated and untreated polymer, after methylene chloride extraction of soluble species, would indicate that the remaining insoluble chains have not undergone significant hydrogenolysis steps. The HT-GPC data are summarized in Table 3. TABLE 3HT-GPC analysis of polymeric solids obtained after hydrogenolysis(pre-extraction) and residual polymeric materials after extraction(post-extraction) with methylene chloride at 80° C.Conver-TimesionMnMwCatalyst(h)(%)(kDa)(kDa)ÐHDPE starting——Pre-extraction5.926.34.45materialPost-extraction6.630.04.6mSiO2/Pt/SiO2a66.7Pre-extraction3.032.210.7Post-extraction6.137.36.1Pt@SiO2b68.0Pre-extraction5.625.44.5Post-extraction6.730.54.5mSiO2/Pt/SiO2c2410.3Pre-extraction4.529.96.7Post-extraction6.831.94.7Pt@SiO2d2420.3Pre-extraction4.056.314.0Post-extraction3.742.911.7mSiO2/Pt/SiO2c4824.1Pre-extraction4.435.27.9Post-extraction6.331.04.9Pt@SiO2d4827.5Pre-extraction3.615.54.3Post-extraction3.917.44.5mSiO2/SiO263.0Pre-extraction4.122.55.5(Pt-free)Post-extraction4.821.44.5amSiO2/Pt/SiO2catalyst (0.042 Pt wt/silica wt %; 0.00087 Pt wt/HDPE wt %).bPt/SiO2catalyst (0.478 Pt wt/silica wt %; 0.00099 Pt wt/HDPE wt %).cmSiO2/Pt/SiO2catalyst (0.06 Pt wt/silica wt %; 0.0013 Pt wt/HDPE wt %).dPt/SiO2catalyst (1.7 Pt wt/silica wt %; 0.0013 Pt wt/HDPE wt %). Gas Chromatography-Mass Spectrometry (GC-MS) Headspace analysis. Gas samples taken from the headspace of the Parr reactor were analyzed by the gas chromatography using an Agilent Technologies 7890A GC system equipped with an Agilent Technologies 5975C inert MSD mass spectrometer. A capillary column, Agilent J&W DB-5ht [(5%-phenyl)-methylpolysiloxane, 0.25 mm, 30 m, 0.1 μm] was used for compound separation. Samples were injected manually using a gas-tight syringe. Oil analysis. The full description of GC-MS analysis methods is described above. The GC-MS of this calibration mixture is shown inFIG.21. The carbon numbers in samples are estimated as follows: A GC-MS of ASTM standard was integrated. A plot of integrated area vs carbon number (shown inFIG.22) allows the determination of the response of all Cn(since ASTM standard does not include C13, C19, C21, etc.) by interpolation. The regions of C6-C20and C20-C40are linear, but with inequivalent slopes. Therefore, these two regions were fit separately. The relative mass ratio as a function of carbon number F(Cn) was calculated by dividing the area of each peak (or calculated peaks for the appropriate range using the linear fits fromFIG.22) by that of the C12(which was arbitrarily chosen—note that this protocol was also tested with C24and, expectedly, gives an equivalent scaling factors for each peak). relative⁢mass⁢ratio=F⁡(Cn)=integrated⁢peak⁢area⁢of⁢Cnintegrated⁢peak⁢area⁢of⁢C12(1) The relative mass ratio for each Cnallows estimation of the GC-MS response for hydrocarbon species as a function of Cn. In GC-MS of catalytic mixtures below, the observed integrated intensities for each carbon number are appropriately scaled based on the relative mass ratio (Cn). relative⁢intensity⁢for⁢a⁢carbon⁢number=G⁡(Cn)=observed⁢integrated⁢intensity⁢of⁢catalytic⁢sampleF⁡(Cn)(2) The percentage of each carbon number is determined by dividing that carbon number's relative intensity by the sum of the relative intensities for all carbon species observed. %⁢Cn=G⁡(Cn)∑36n=6G⁡(Cn)×100⁢%(3) Simulated Distillation Gas Chromatography Flame Ionization Detection (SimDist GC-FID) Simulated distillation gas chromatography (GC) was used to analyze the higher molecular weight components of oily products, as this method can separate carbon numbers up to at least C40and provides complementary data to GC using a capillary column. SimDist GC-FID analyses were performed on an Agilent 7890A gas chromatograph equipped with a split/splitless injector and a flame ionization detector (FID). The column was a 5 m×0.53 mm MXT-1HT SimDist (Restek) with a film thickness of 0.10 μm. Separations were performed under temperature-programmed conditions with the column oven programmed from 35 to 70° C. at 10.0° C./min, 70 to 280° C. at 3° C./min, and then 280 to 430° C. at 15° C./min with initial and final hold times of 0.5 and 10 minutes, respectively. Helium carrier gas was employed with a constant flow of 3 mL/min. Injector and detector temperatures were maintained at 350 and 430° C., respectively. 1.5 μL of solution was injected in the splitless mode. The solvent vent time was 2 minutes. A mixture of saturated alkanes (Restek ASTM D2287-12 STANDARD described above) dissolved in dichloromethane was used to identify the species formed in catalytic reactions. A SimDist GC-FID of Restek ASTM D2287-12 STANDARD is shown below inFIG.23. Example 3—Polymer Upcycling Catalysis On the basis of the aforementioned NMR characterization of HDPE chain adsorption and translocation in mSiO2pores and motivated by the potential advantages of processive polymer deconstruction, a catalyst was designed with Pt nanoparticles located solely at the pore end (detailed below). In this inorganic architecture, PE chains must enter and diffuse to fill the pore length to access the Pt active sites. Platinum nanoparticles were chosen as catalytic entities because of their established performance in catalytic hydrogenolysis of carbon-carbon bonds in small hydrocarbons and recently in HDPE. The porous catalyst was synthesized by loading 3.2±0.5 nm-diameter Pt nanoparticles onto amine-functionalized silica spheres (diameter ˜127±7 nm) and then growing a 110±8 nm thick shell of mesoporous silica (mSiO2) with 2.4±0.2 nm-diameter pores organized radially from the silica sphere. The pore length is equal to the thickness of the mSiO2shell, as displayed by the transmission electron microscopy (TEM) image (seeFIG.4a). This three-layered spherical shell-type construction (mSiO2/Pt/SiO2) places the Pt nanoparticles at the terminal end of linear channels (i.e., at the bottom of wells); this architecture and Pt nanoparticle localization is supported by the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image (FIG.4b). Pt nanoparticles supported on silica spheres (Pt/SiO2,FIG.9b) without a mSiO2shell serve as a control catalyst, on which HDPE chains could be randomly adsorbed and cleaved. Hydrogenolysis reactions using these two catalysts at ca. 0.001 Pt wt % loading (corresponding to a very small amount of reactive species, 1 mg Pt in 100 g HDPE) were then performed solvent-free with ca. 3 g HDPE and 200 psi H2at 250° C. as standard conditions. The products and their distribution were analyzed by gas chromatography (GC) and HT-GPC, which, taken together, give an accurate representation of the hydrocarbon distribution from low molecular mass to high molecular mass. HT-GPC analysis of the residual polymeric materials, before and after extraction of species with carbon numbers Cn<40, distinguishes the performance of the porous and nonporous catalytic architectures (FIG.5a,b). Next, the yield and composition of species in the headspace of the pressurized reactor and of the isolated oils were analyzed individually, and then the data from the two phases were combined to give the representative mass-weighted distribution, normalized to account for yields of the two phases, of low molecular mass carbon numbers (to C35,FIG.5c). Comparing the populations of hydrocarbon species obtained from hydrogenolysis of HDPE using the mSiO2/Pt/SiO2catalyst to those obtained from nonporous Pt/SiO2catalyst reveals several characteristic features of processive behavior in the former catalyst. Specifically, products afforded by the processive, porous catalyst show (1) identical molecular mass properties of bulk HDPE before and after catalytic hydrogenolysis, (2) a narrower distribution of small molecule carbon numbers that is independent of Pt-catalyzed conversion, and (3) few detectable species with intermediate molecular masses in between those of the produced fragments and the residual polymer. FIG.5shows (a) Combined table of HT-GPC and GC data showing narrow conversion-independent product distributions from mSiO2/Pt/SiO2and broader, conversion-dependent product distributions obtained with Pt/SiO2. The data is presented as pairs of analyses for each experiment, before and after extraction with methylene chloride. The HT-GPC data of all condensed-phase organic materials, prior to extraction with methylene chloride, reveals a substantial decrease in Maand increase in D for both catalytic architectures. (b) HT-GPC analysis of molecular mass and distributions of HDPE (black), HDPE after hydrogenolysis using mSiO2/Pt/SiO2, and HDPE after hydrogenolysis using Pt/SiO2for 24 h, showing equivalent bulk polymer properties after catalysis using the porous catalyst and change in the bulk HDPE after hydrogenolysis by the nonporous catalyst. (c) Combined distributions of the gas and liquid products (weighted by % yield of the products in the two phases) obtained from the hydrogenolysis of HDPE using mSiO2/Pt/SiO2(top) and Pt/SiO2(bottom) after 6 h at 250° C. under 200 psi of H2. First, hydrogenolysis of HDPE using Pt/SiO2results in a significant transformation of Mnand dispersity D (Mw/Mn) of the polyethylene fraction, whereas the comparable mSiO2/Pt/SiO2-catalyzed hydrogenolysis provides equivalent molecular mass properties to those of the starting HDPE (seeFIGS.5aandb) as expected for a processive process. Using the 24 h experiment under standard conditions as a representative example, hydrogenolysis of HDPE employing mSiO2/Pt/SiO2as the catalyst (0.0013 Pt wt %) provides condensed-phase organic materials; analysis of this crude mixture by HT-GPC reveals a substantial decrease in Mnand increase in D compared to untreated HDPE. Extraction of all soluble low molecular mass species (7.2%) from the crude reaction mixture with refluxing dichloromethane gives residual insoluble HDPE (Mn=6.8 kDa and Ð=4.7) with equivalent properties to those of the unreacted, dichloromethane-washed HDPE starting material (Mn=6.6 kDa and Ð=4.6). Likewise, hydrogenolysis using the mSiO2/Pt/SiO2catalyst for 6 h (6.7% conversion) and 48 h (25% conversion) afford residual HDPE with similar Mnand D values. That is, the bulk properties of the HDPE are largely unchanged during hydrogenolysis with mSiO2/Pt/SiO2, even as the HDPE is consumed and small molecular mass species are produced. Reactions of HDPE and H2with the nonporous Pt/SiO2catalyst under equivalent standard conditions (0.0013 Pt wt %) also result in hydrogenolysis (20.3% conversion after 24 h). The HT-GPC data reveals that residual HPDE is significantly transformed even after extraction with CH2Cl2, highlighting the contrasting behavior of Pt/SiO2and mSiO2/Pt/SiO2. In particular, the molecular mass of the insoluble polymeric material is reduced (Mn=3.7 kDa) and the dispersity (Ð=11.7) is considerably broadened from the values of both the virgin and unreacted/dichloromethane-washed polyethylene starting materials. Moreover, characteristics of the polymer are altered as a function of the extent of conversion. For example, the dispersity decreases with higher conversion as a result of a larger fraction of highest molecular mass species undergoing cleavage, whereas at lower conversion, the HDPE properties are not distinguished outside of error from starting materials. Catalyst-free thermal treatment of HDPE under H2also results in polymer with lower Mn, before and after washing with methylene chloride. Second, the carbon number distribution of molecular species produced by mSiO2/Pt/SiO2gives the appearance of a bell-like distribution, centered at C12-C16numbered chains that comprise ca. 40% of the hydrocarbons present after 10% conversion (seeFIG.5c). The higher molecular mass species from C26-C36(above which each Cnspecies is less than 0.01%) are only 2% of the observed products. This C14-centered bell-like distribution, measured at low conversion, represents the intrinsic selectivity of the catalyst. Remarkably, this Pt-hydrogenolysis produced distribution is also largely independent of the conversion level from ˜5% up to 25%, although the relative quantity of the lowest and highest molecular mass species varies somewhat. These species are attributed, which appear outside of the normal distribution in the samples, to background reactions because they are the predominant products in control reactions using Pt-free mSiO2/SiO2material (i.e., acid catalyzed) or in the absence of any inorganic additive. A 17 kDa (Ð=1.1) polyethylene was also tested in this mSiO2/Pt/SiO2-catalyzed hydrogenolysis, which also produced a bell-like distribution of chain lengths. Finally, quantitative conversion of the HDPE to gaseous and dichloromethane-soluble species was observed after 5.5 d at 250° C., and for that experiment ca. 4-fold higher catalyst loading (albeit still low at 0.0039 Pt wt %) gave 57% isolated oils. The carbon number distribution again centers around low molecular mass species (C9-C15is ca. 55%). At this long reaction time, it is likely that smaller molecular mass hydrocarbons also undergo hydrogenolysis steps. In contrast, the hydrocarbon chains obtained from Pt/SiO2appeared as a flattened distribution of species with carbon numbers from Cis to C26(5.8±0.2% for each species after ca. 20% conversion). In addition, the higher range, C26-C36is significant at ca. ˜17% of the distribution. Note that HT-GPC results indicate that the higher molecular mass species produced by Pt/SiO2are more abundant than indicated by GC data inFIG.5cdue to their lower solubility. As such, the GC analysis only describes the lower end of a much broader distribution. Nonetheless, it is clear that the Cndistribution is sensitive to the extent of reaction with the nonporous Pt/SiO2as hydrogenolysis catalyst. After 48 h (27% conversion), for example, each individual Cnspecies is less than 4.5% of the sample, and the majority species range all the way from C13to C30. Additional control experiments employing porous supports for Pt, namely Pt/mSiO2(mSiO2=MCM-41 or SBA-15) which lack the shell/site/core architecture, are active for HDPE hydrogenolysis at 250° C., but Pt/MCM-41 gives a broad distribution of hydrocarbon products rather than processive-like selectivity, while Pt/SBA-15 affords a wide, distribution flattened from C18-C23. A conventional hydrocracking catalyst NiMo/γ-Al2O3also gives a broad distribution of hydrogenolysis products. Finally, the entire distribution of hydrocarbon products from mSiO2/Pt/SiO2-catalyzed hydrogenolysis contains only low molecular mass hydrocarbons (mainly from C12to ca. C18) and the original HDPE chains, while hydrocarbon fragments resulting from partial deconstruction of HDPE chains are not present in significant quantities. This result is inferred from a composite analysis of the GC-MS and HT-GPC data, comparing results for the two catalyst architectures before and after extraction with methylene chloride. In particular, the polymeric materials produced by hydrogenolysis with the random Pt/SiO2catalyst contain significant quantities of insoluble, lower molecular mass species not present in the starting polymer, as revealed by the change in Mnvalues which are sensitive to low molecular mass species in the population. In contrast, new species in this intermediate molecular mass range are not present in reactions using the mSiO2/Pt/SiO2catalyst because they are not found in the low molecular mass fraction (from GC analysis) or in the insoluble residual polymer fraction, since molecular mass properties of CH2Cl2-washed polymer are equivalent before and after reaction. This point is further supported by the distinct distributions of lower molecular mass species obtained by GC-MS (and simulated distillation column GC-FID), which show that the porous catalyst favors lower molecular mass products. The contrasting results for the two catalytic architectures indicate that, when using mSiO2/Pt/SiO2as the catalyst, (1) a fraction of the HDPE chains are not affected during catalysis, (2) all conversion into smaller hydrocarbons occurs from a subset of polyethylene chains, and (3) any transformed chain is entirely deconstructed into small, dichloromethane-soluble molecules. These results are consistent with a processive catalytic process, in which the polymer chains are not released from the catalytic pores, while small molecular mass products are allowed to escape. Remarkably, catalytic hydrogenolysis of HDPE at 300° C. for 24 h gives quantitative conversion to a narrow C16-centered distribution of hydrocarbon chains, with the same median as produced at 250° C. with partial conversion. This narrow distribution indicates that the catalyst also operates through a processive mechanism at high conversion and higher temperature, in reactions in which rates of polymer adsorption and desorption, polymer transport within the pores, carbon-carbon bond hydrogenolysis, and product desorption have increased. Pore diameter may also affect rates of adsorption/desorption and diffusion processes without affecting hydrogenolysis rates. Impressively, mSiO2/Pt/SiO2catalysts with smaller (1.7 nm) diameter pores give a distribution centered at shorter chains, and larger (3.5 nm) diameter pores afford longer chain products (FIG.6). Thus, the physical dimensions of the pores may be used to tune the median of the product distribution. Example 4—Hydrogenolysis at 6 h Reactions at 250° C. Conversion of HDPE (Mn=5.9 kDa, Ð=4.5) into soluble small molecules with mSiO2/Pt/SiO2(0.042 Pt wt/silica wt %; 0.00087 Pt wt/HDPE wt %) was 6.7% after 6 h, determined by the sum of mass of extracted, isolated oils and the mass of gaseous species produced (the latter was assessed by difference in mass of reaction mixture before and after catalytic reactions). Conversion is defined as: Conversion⁢of⁢HDPE={1-mass⁢of⁢residual⁢HDPEinitial⁢mass⁢of⁢HDPE}×1⁢0⁢0⁢%(4) Conversion was slightly higher (8.0%) with the nonporous Pt/SiO2catalyst (0.478 Pt wt/silica wt %; 0.00099 Pt wt/HDPE wt %). These low conversion conditions are used to evaluate the intrinsic behavior of the catalytic materials. The products were analyzed in two parts, namely volatile species contained in the headspace and non-volatile, extractable oils. In these experiments, the volatile species were obtained by venting the reactor at reaction temperature (250° C.). Oils were obtained by repeated extraction of the residual solids with methylene chloride at 80° C. Yields of gas phase, oil phase, and residual solid, tabulated in Table 4, are defined as: yield={mass⁢of⁢productsinitial⁢mass⁢of⁢HDPE}×1⁢0⁢0⁢%(5) The residual solids were analyzed by HT-GPC, and the results of that analysis are described above. As a control, thermal treatment of the same HDPE under H2in the presence of a silica-only material (composed of mesoporous silica-coated solid silica spheres, mSiO2/SiO2) results in only ca. 3 wt % conversion to small molecule products. In contrast to the catalytic experiments in the presence of platinum, most observed low molecular weight species from this ‘thermal’ treatment were unsaturated (olefinic) in nature, which suggests homolytic cleavage of PE chains rather than catalyst-mediated hydrogenolysis. These results indicate that catalysts located at the internal terminus of a pore are active for hydrogenolysis of PE, even though a background thermal degradation of HDPE contributes to the molecular species present in the experiments. TABLE 4Catalytic data and mass balance ofreactions performed at 250° C. for 6 hPtConversionConversionloadingHDPEto volatilesto liquidsSolid residueCatalyst(wt %)a(g)bin g (%)in g (%)in g (%)mSiO2/0.000873.1300.1050.1072.918Pt/SiO2c(3.35%)(3.42%)(93.2%)Pt/SiO2d0.000993.0320.1210.1212.790(3.99%)(3.99%)(92.0%)mSiO2/0.000873.0080.0730.1532.782Pt/SiO2e(2.4%)(5.09%)(92.5%)Pt/SiO2f0.00183.0090.0560.3492.604(1.9%)(11.6%)(86.5%)mSiO2/—3.0030.0580.0312.914SiO2(1.93%)(1.03%)(97.0%)Thermalg—2.9470.0180.0202.909(0.61%)(0.68%)(98.7%)awt % Pt with respect to HDPE.bHDPE properties: Mn= 5.9 kDa, Ð = 4.5.cPt loading on mSiO2/Pt/SiO2catalyst (0.042 Pt wt/silica wt %); the pressurized reaction vessel was vented and headspace was sampled at 250° C. to examine volatile species under reaction conditions.dPt loading on Pt/SiO2catalyst (0.478 Pt wt/silica wt %); the pressurized reaction vessel was vented and headspace was sampled at 250° C. to examine volatile species under reaction conditions.ePt loading on mSiO2/Pt/SiO2catalyst (0.040 Pt wt/silica wt %); the pressurized reaction vessel was vented and sampled at room temperature to examine volatile species.fPt loading on Pt/SiO2catalyst (0.59 Pt wt/silica wt %); reaction vessel was vented and sampled at room temperature to examine volatile species.gThe pressurized reaction vessel was vented and the headspace was sampled at 250° C. to examine volatile species. Gas chromatograms of the products and corresponding carbon number distribution from mSiO2/Pt/SiO2catalyzed hydrogenolysis reactions are shown inFIGS.24to26and31to34, while those of the Pt/SiO2-catalyzed reactions are shown inFIGS.27to29and35to37; comparisons of carbon number distribution are given inFIGS.30and38. GC and carbon number distributions for control experiments without Pt and without inorganic oxide are given inFIGS.39to44. Example 5—Hydrogenolysis at 24 h Reactions at 250° C. Conversion of HDPE (Mn=5.9 kDa, Ð=4.5) into soluble small molecules by hydrogenolysis with mSiO2/Pt/SiO2(0.06 Pt wt/silica wt %; 0.0013 Pt wt/HDPE wt %; 2.4 nm diameter mesopores) was 10.3% after 24 h, determined by the sum of masses of extracted, isolated oils and the mass of gaseous species produced (assessed by difference in mass of reaction mixture before and after catalytic reactions). Conversion is defined as above in 6 h reactions. Conversion was higher (20.3%) after 24 h in hydrogenolysis reactions using the nonporous Pt/SiO2catalyst (1.7 Pt wt/silica wt %; 0.0013 Pt wt/HDPE wt %) under identical conditions. Similar conversions are obtained with Pt/MCM-41 compared to mSiO2/Pt/SiO2, while the larger pore-sized Pt/SBA-15 catalytic material gave lower conversions. A hydrocracking catalyst NiMo/γ-Al2O3also shows similar conversion of HDPE. Yields of gas phase, oil phase, and residual solid are tabulated in Table 5. Of the low molecular weight products obtained from hydrogenolysis catalyzed by mSiO2/Pt/SiO2, 30.1% were released from the headspace while 69.3% were oils. A smaller percentage of the products from Pt/SiO2-catalyzed hydrogenolysis were released from the headspace (21.5%) than from the mesoporous silica-based catalyst, and a larger percentage of oils (78.5%) were produced by Pt/SiO2. Despite the similar pores sizes of mSiO2/Pt/SiO2and Pt/MCM-41, the latter gives a broad unselective distribution. NiMo/γ-Al2O3also gives a broad distribution of hydrocarbon products. That is, the mSiO2/Pt/SiO2catalyst favors a distribution with lower molecular weight hydrocarbon chains. The residual polymeric materials that were not extracted into methylene chloride were analyzed by HT-GPC (described above). TABLE 5Catalytic data and mass balance of reactions performed for 24 h at 250° C.Pt loadingHDPEYield ofYield ofSolidCatalyst(wt %)a(g)bvolatiles (g)liquids (g)residue (g)mSiO2/Pt/SiO2c0.00133.0240.096 (3.17%)0.217 (7.18%)2.711 (89.7%)Pt/SiO2d0.00133.0010.131 (4.37%)0.478 (15.9%)2.392 (79.7%)mSiO2/Pt/SiO2e0.00210.503f0.012 (2.4%)0.081 (16.1%)0.410 (81.5%)mSiO2/Pt/SiO2g0.000872.9990.157 (5.2%)0.385 (12.8%)2.457 (81.9%)Pt/SiO2h0.000873.0080.271 (9.0%)0.487 (16.2%)2.250 (74.8%)Pt/MCM-41i0.00083.0230.081 (2.7%)0.420 (13.9%)2.522 (83.4%)Pt/SBA-15j0.00083.0370.038 (1.2%)0.195 (6.4%)2.804 (92.4%)NiMo/Al2O398.8 mg3.0590.057 (1.9%)0.360 (11.8%)2.642 (86.3%)mSiO2/SiO2kn.a.2.9640.098 (3.3%)0.072 (2.5%)2.794 (94.3%)aPt wt/HDPE %. The reaction vessels were vented and sampled at room temperature to examine volatile species.bHDPE properties: Mn= 5.9 kDa, Ð = 4.5 unless otherwise specified.cmSiO2/Pt/SiO2catalyst (0.06 Pt wt/silica wt %), 2.4 nm diameter mesopores.dPt/SiO2catalyst (1.7 Pt wt/silica wt %).emSiO2/Pt/SiO2catalyst (0.04 Pt wt/silica wt %; 2.4 nm pores).fLow polydispersity polyethylene sample from Scientific Polymer Products (Mn= 15.4 kDa, Ð = 1.1).gmSiO2/Pt/SiO2catalyst (0.040 Pt wt/silica wt %).hPt/SiO2catalyst (0.59 Pt wt/silica wt %).i0.9 Pt wt/silica wt %.j0.8 Pt wt/silica wt %.k0.065 g of mSiO2/SiO2. Gas chromatograms of the products and corresponding carbon number distribution from mSiO2/Pt/SiO2catalyzed hydrogenolysis reactions are shown inFIGS.45to48and61to63.1H NMR and DEPT-13513C NMR spectra are shown inFIGS.49,50,56, and57from samples produced by the mSiO2/Pt/SiO2catalyst. Gas chromatograms of the products and corresponding carbon number distribution from Pt/SiO2catalyzed hydrogenolysis reactions are shown inFIGS.51to53. SimDist GC-FID, as a second method for analytical separation of hydrogenolysis oil products that highlights the broad distribution of hydrogenolysis oil products (15.9% yield) from reaction of HDPE using Pt/SiO2is shown inFIG.54. The1H NMR spectrum of oils obtained by hydrogenolysis using Pt/SiO2(1.7 Pt wt/silica wt %) as catalyst are shown inFIG.56and the DEPT-135 NMR are shown inFIG.57. SimDist GC-FID, as a second method for analytical separation of hydrogenolysis oil products that highlights the broad distribution of hydrogenolysis oil products (15.9% yield) from reaction of HDPE using Pt/SiO2(Comparisons of carbon number distributions from mSiO2/Pt/SiO2and Pt/SiO2are given inFIGS.55and67for the two sets of experiments. Gas chromatograms of the products and corresponding carbon number distribution from monodisperse polyethylene (Mn=15.4 kDa,=1.1) from mSiO2/Pt/SiO2-catalyzed hydrogenolysis are shown inFIGS.58to60. Gas chromatograms of the products and corresponding carbon number distribution for the hydrogenolysis reaction of HDPE (Mn=5.9 kDa,=4.5) using Pt/SiO2(0.59 Pt wt/silica wt %) as catalyst are shown inFIGS.64-66. Gas chromatograms of the products and corresponding carbon number distribution from Pt/MCM-41 and Pt/SBA-15 catalyzed hydrogenolysis reactions are shown inFIGS.68to70and71to73, respectively. Gas chromatograms of the products and corresponding carbon number distribution from NiMo/Al2O3catalyzed hydrogenolysis reactions are shown inFIGS.74to76. Gas chromatograms for a control experiment, without Pt, is given inFIG.77. Example 6—Hydrogenolysis at 48 h Reactions at 250° C. Conversion of HDPE into soluble small molecules by hydrogenolysis with mSiO2/Pt/SiO2(0.06 Pt wt/silica wt %; 0.0013 Pt wt/HDPE wt %) after 48 h at 250° C. under H2(200 psi) was 24.1% (as described above in the experimental for 6 h reactions), determined by the sum of mass of extracted, isolated oils and the mass of gaseous species produced (assessed by difference in mass of reaction mixture before and after catalytic reactions). Conversion was only slightly higher (27.5%) after 48 h in hydrogenolysis reactions using the nonporous Pt/SiO2catalyst (1.7 Pt wt/silica wt %; 0.0013 Pt wt/HDPE wt %) under identical conditions. Yields of gas phase, oil phase, and residual solid are tabulated in Table 6. Of the low molecular weight products obtained from hydrogenolysis catalyzed by mSiO2/Pt/SiO2, 23.4% were released from the headspace as volatile species while 76.7% were present in the oily condensed phase. An even smaller percentage of the products from Pt/SiO2-catalyzed hydrogenolysis were released from the headspace (10.0%) than from the mesoporous silica-based catalyst, and a corresponding larger percentage of oils (90.0%) were formed. Thus, over the sequence of times measured (6 h, 24 h, 48 h), the mSiO2/Pt/SiO2catalyst favors a distribution with lower molecular weight hydrocarbon chains compared to Pt/SiO2. The residual polymeric materials that were not extracted into methylene chloride were analyzed by HT-GPC (described above). TABLE 6Catalytic data and mass balance ofreactions performed at 250° C. for 48 hPtConversionConversionloadingHDPEtotoSolidCatalysta(wt %)b(g)cvolatiles (g)liquids (g)residue (g)mSiO2/0.00133.0160.1700.5562.290Pt/SiO2d(5.64%)(18.4%)(75.9%)Pt/SiO2e0.00133.0010.0820.7422.177(2.73%)(24.7%)(73.5%)mSiO2/0.000873.0390.1190.5472.373Pt/SiO2f(3.9%)(18.0%)(78.1%)Pt/SiO2g0.00183.0140.3240.9981.692(10.7%)(33.1%)(56.1%)aThe reaction vessel was vented and sampled at room temperature to examine volatile species.bPt wt/HDPE wt %.cHDPE properties: Mn= 5.9 kDa, Ð = 4.5.dmSiO2/Pt/SiO2catalyst (0.06 Pt wt/silica wt %).ePt/SiO2catalyst (1.7 Pt wt/silica wt %).fmSiO2/Pt/SiO2catalyst (0.040 Pt wt/silica wt %).gPt/SiO2catalyst (0.59 Pt wt/silica wt %). Gas chromatograms of the products and corresponding carbon number distribution from mSiO2/Pt/SiO2catalyzed hydrogenolysis reactions are shown inFIGS.78to80, while those of the Pt/SiO2-catalyzed reactions are shown inFIGS.81to83; a comparison of carbon number distribution is given inFIGS.78-84. GC-MS of hydrogenolysis oil products (56.6% yield) from reaction of HDPE (Mn=5.9 kDa, Ð=4.5) using mSiO2/Pt/SiO2(0.59 Pt wt/silica wt %) as catalyst are shown inFIG.85. Example 7—Hydrogenolysis with Quantitative Conversion at 250° C. HDPE was converted into soluble small molecules by hydrogenolysis with mSiO2/Pt/SiO2(0.06 Pt wt/silica wt %; 0.0013 Pt wt/HDPE wt %) after 136 h at 250° C. under H2(200 psi) yielding 94% gases and oils (as described above in the experimental for 6 h reactions), determined by the sum of mass of extracted, isolated oils and the mass of gaseous species produced (assessed by difference in mass of reaction mixture before and after catalytic reactions). Yields of gas phase, oil phase, and residual solid are tabulated in Table 7. TABLE 7Catalytic data and mass balance of thereaction performed for 136 h and 250° C.PtConversionConversionSolidloadingHDPEtotoresidueCatalyst(wt %)a(g)bvolatiles (g)liquids (g)(g)mSiO2/Pt/SiO2c0.00392.0150.7541.140.12(37.4%)(56.6%)(6%)aPt wt/HDPE wt %.bHDPE properties: Mn= 5.9 kDa, Ð = 4.5.cmSiO2/Pt/SiO2catalyst (0.06 Pt wt/silica wt %). The reaction vessel was vented and sampled at room temperature to examine volatile species. Example 8—Hydrogenolysis at 300° C. for 24 h Conversion of HDPE (Mn=5.9 kDa,=4.5) into soluble small molecules by hydrogenolysis with 2.4 nm pore mSiO2/Pt/SiO2(0.27 Pt wt/silica wt %; 0.004 Pt wt/HDPE wt %) was 97.9% after 24 h at 300° C. under H2(200 psi at room temperature, 250 psi at 300° C.) as described in above, determined by the sum of mass of extracted, isolated oils and the mass of gaseous species produced (assessed by difference in mass of reaction mixture before and after catalytic reactions). Yields of gas phase, oil phase, and residual solid are tabulated in Table 8. TABLE 8Catalytic data and mass balance of thereactions performed at 300° C.PtConversionConversionloadingHDPEtotoSolidCatalyst(wt %)a(g)bvolatiles (g)cliquids (g)residue (g)1.7 nm0.0043.0341.0431.5320.459mSiO2/(34.4%)(50.5%)(15.1%)Pt/SiO2d2.4 nm0.0043.0730.7442.2640.065mSiO2/(24.2%)(73.7%)(2.1%)Pt/SiO2e3.5 nm0.0043.0270.6512.3200.056mSiO2/(21.5%)(76.6%)(1.0%)Pt/SiO2fPt/SiO2g0.0043.0400.4490.72251.868(14.8%)(23.8%)(61.4%)mSiO2/n.a.2.9920.0190.2312.752SiO2(0.64%)(7.72%)(91.6%)aPt wt/HDPE wt %.bHDPE properties: Mn= 5.9 kDa, Ð = 4.5.cThe reaction vessel was vented and sampled at room temperature to examine volatile species.d035 Pt wt/silica wt %.e0.27 Pt wt/silica wt %.f0.033 Pt wt/silica wt %.g2.8 Pt wt/silica %. Gas chromatograms of the products and corresponding carbon number distribution from 1.7 nm diameter pore mSiO2/Pt/SiO2catalyzed hydrogenolysis reactions at 300° C. for 24 h are shown inFIGS.86to88, data from 2.4 nm diameter pores are shown inFIGS.89to91, and data from 3.5 nm diameter pores are shown inFIGS.92to94. A stack-plot comparing GC traces of the three catalysts is giving inFIG.95. Gas chromatograms of the products and corresponding carbon number distribution from Pt/SiO2-catalyzed hydrogenolysis reactions at 300° C. for 24 h are shown inFIGS.95to98. Pt-free control reaction data is given inFIGS.99to101. Example 9—Conversion of 50 g of HDPE at 300° C. Over conversion of 50 g of HDPE (Mn=5.9 kDa,=4.5) into soluble small molecules by hydrogenolysis occurred with 2.4 nm pore mSiO2/Pt/SiO2(0.27 Pt wt/silica wt %; 0.018 Pt wt/HDPE wt %) over 4 d and 16 h at 300° C. under H2(200 psi at room temperature, 250 psi at 300° C.). Yields of gas and liquid products are given in Table 9. TABLE 9Catalytic data and mass balance of thereaction performed for 112 h and 300° C.PtSolidloadingHDPEConversion toConversion toresidueCatalyst(wt %)a(g)bvolatiles (g)liquids (g)(g)mSiO2/0.01850.01233.944 (67.9%)16.068 (32.1%)—Pt/SiO2caPt wt/HDPE wt %.bHDPE properties: Mn= 5.9 kDa, Ð = 4.5.cmSiO2/Pt/SiO2catalyst (0.27 Pt wt/silica wt %). The reaction vessel was vented and sampled at room temperature to examine volatile species. The GC-MS trace of the sampled headspace for the thermal reaction and the GC-MS of oil products of 50 g of HDPE (Mn=5.9 kDa, Ð=4.5) in the presence of 2.4 nm diameter pore mSiO2/Pt/SiO2(0.27 Pt wt/silica wt %) material (reaction time 112 hours) is show inFIGS.102and103respectively. Example 10—Post-Consumer HDPE from Grocery-Type Shopping Bags HDPE from used grocery shopping bags (Mn=10.6 kDa, Mw=150.1 kDa,=14.1). After use, the bags were cut into small pieces and loaded into the glass liner of the reactor autoclave. The reactor vessel, containing the waste HDPE was heated under vacuum at 40° C. for 12 h. The reactor was cooled and the mSiO2/Pt/SiO2catalyst was added. The reactor was pressurized with N2and evacuated 3×, and then it was pressurized with H2, heated to the reaction temperature, and mixed using an overhead mechanical stirrer. Yields of gas, liquid and solid products are given in Table 10. TABLE 10Catalytic data and mass balance of the reactions performed.PtConversionConversionloadingHDPEtotoSolidCatalysta(wt %)b(g)volatiles (g)liquids (g)residue (g)mSiO2/0.00211.2390.2220.2510.766Pt/SiO2c(17.9%)(20.3%)(61.8%)mSiO2/0.00721.5040.1600.5020.842Pt/SiO2d(10.6%)(33.4%)(56.0%)a2.4 nm diameter pore mSiO2/Pt/SiO2catalyst (0.04 Pt wt/silica wt %).bPt wt/HDPE wt %. The reaction vessel was vented and sampled at room temperature to examine volatile species.c48 h reaction at 250° C.d24 h reaction at 300° C. Gas chromatograms of the products from the catalytic reaction at 250° C. for 48 h are shown inFIGS.104and105. Gas chromatograms of the products from the catalytic reaction at 300° C. for 24 h are shown inFIGS.106and107. Example 11—Catalytic Hydrogenolysis of Isotactic Polypropylene Conversion of iPP into soluble small molecules by hydrogenolysis with 2.4 nm diameter pore mSiO2/Pt/SiO2(0.0008 Pt wt/silica wt %; 0.04 Pt wt/iPP wt %) after 24 h at 300° C. under H2(200 psi at room temperature, 250 psi at 300° C.) was 78.9% (as described above in the example for 6 h reactions), determined by the sum of mass of extracted, isolated oils and the mass of gaseous species produced (assessed by difference in mass of reaction mixture before and after catalytic reactions). Yields of gas phase, oil phase, and residual solid are tabulated in Table 11. TABLE 11Catalytic data and mass balance of theiPP hydrogenolysis reaction at 300° C.PtConversionConversionSolidloadingHDPEtotoresidueCatalyst(wt %)a(g)volatiles (g)liquids (g)(g)mSiO2/Pt/SiO2b0.00083.0940.6512.4430.002(21.0%)(78.9%)Pt/SiO20.00083.0541.4431.611—(47.2%)(52.8%)aPt wt/HDPE wt %. The reaction vessel was vented and sampled at room temperature to examine volatile species.bmSiO2/Pt/SiO2catalyst (0.04 Pt wt/silica wt %, 2.4 nm diameter pore).c2.3 Pt wt/silica wt %. The GC-MS trace of the sampled headspace and the GC-MS of oil products for the hydrogenolysis reaction of iPP using 2.4 nm diameter pore mSiO2/Pt/SiO2(0.04 Pt wt/silica wt %) as catalyst (reaction time 112 hours) is show inFIGS.108and109respectively. The GC-MS trace of the sampled headspace and the GC-MS of oil products for the hydrogenolysis reaction of iPP using 2.4 nm diameter pore mSiO2/Pt/SiO2(0.04 Pt wt/silica wt %) as catalyst (reaction time 24 hours) is show inFIGS.110and111respectively. Example 12—Dynamics of Polyethylene in Silica Materials The interactions between silica and HDPE are characterized by13C solid-state nuclear magnetic resonance (SSNMR) spectroscopy, which inform upon both the conformation and dynamics of polyethylene adsorbed on a support. Briefly, the γ-gauche effect enables the identification of anti (linear, zig-zag, 32 ppm), gauche (bending, 27 ppm), and mobile (˜29 ppm) conformers by their13C NMR chemical shift. This approach has, for example, been used to detect the ordering of alkyl chains on surfaces, as well as to observe chain diffusion in bulk polyethylene. Also, note that polydimethoxysilane and polyethylene oxide were shown to thread into zeolite or metal-organic frameworks (MOF) pores, respectively. A priori, one might conjecture that these oxygen-containing polymers form stronger interactions with solid materials than polyethylene, especially because the oxygen-free polyvinylidene fluoride did not readily enter the pores of the MOF. Monolayers of13C-enriched polyethylene (*PE,) with a number-average molecular mass (Mn) of 130 kDa (extended chain length of ˜1 μm) were introduced onto Davisil silica gel or mesoporous silica nanoparticles (mSiO2) with an average particle diameter of 450 nm featuring 1.5 nm-wide, ca. 200 nm long pores organized radially from the center of the particle. The13C magic-angle-spinning (MAS) SSNMR spectrum obtained for the *PE/Davisil revealed anti, mobile, and gauche conformers similar to that obtained by Inoue, D., et. al., “Structural and Dynamical Studies of13C-Labeled Polyethylene Adsorbed on the Surface of Silica Gel by High-Resolution Solid-State13C NMR Spectroscopy,”Acta. Polymer.46, 420-423 (1995), which is hereby incorporated by reference). Remarkably, the13C MAS SSNMR spectrum of *PE/mSiO2features signals of only anti and mobile conformers (FIG.2). The prominence of the anti-conformer, compared to the gauche, in *PE/mSiO2would suggest that the mesoporous material is able to induce the formation of long, zig-zag PE domains, consistent with the polymer being threaded into the linear channels of the mSiO2. Prior work suggests that the mobile peak originates from PE chains situated away from the material surface (i.e., located outside of the pore). Several additional experiments further supported these assignments. First, the integrated intensity of the anti and mobile resonances (1:4), obtained by deconvolution of the spectrum inFIG.2b, matched the estimated percentage (20%) of ca. 1 m-long polymer chains that could enter roughly 200 nm long pores. Second, cross-polarization (CP) and J-mediated Incredible Natural Abundance DoublE QUAntum Transfer Experiment (INADEQUATE) experiments revealed separate domains composed of anti and mobile methylene units, and the former domain was rigid and extended. Finally, shorter chain HDPE (Mn=7 kDa,13C at natural abundance) loaded onto the mSiO2provided a spectrum that exclusively featured a single sharp resonance with the chemical shift of the anti-conformer (FIG.2c). Importantly, this result confirmed the suspected spectral distinction of intra- and extra-pore polymer. Additional experiments employing spherical silica particles and a series of surface modifications, confirm that the topology of the material is directing the conformation of the polymer. Taken together, the data lead to the conclusion that HDPE chains thread the mouths of 1.5 nm diameter pores in mSiO2, insert a portion of the chain length that matches the length of the pore, and adopt an extended conformation templated by the linear pore. These intra- and extra-pore polymer assignments in combination with 2D exchange spectroscopy (EXSY), as demonstrated by Schmidt-Rohr, et. al., “Chain Diffusion between Crystallized and Amorphous Regions in Polyethylene Detected by 2D Exchange13C NMR,”Macromol.24, 5288-5293. (1991), which is hereby incorporated by reference in its entirety), allow detailed interrogation of the dynamic behavior of the species in this system. In EXSY experiments, two time evolution periods are separated by a mixing time (tmix) during which the molecules are free to diffuse. Chain diffusion creates off-diagonal cross-peaks in the spectrum wherein a given carbon is found inside the pore for the first evolution period, and outside for the second, for instance. Diffusion cross-peaks were easily identified (top-left and bottom-right corners of the black square) in a representative13C EXSY spectrum (FIG.3a). Interestingly, the cross-peak corresponded to exchange between the inner-pore region and a small, higher chemical shift shoulder of the mobile resonance, rather than exchange directly between rigid and mobile domains. This higher chemical shift signal was assigned to methylene groups located near the mouth of the pore because the higher shift indicates the species has slightly higher probability of adopting the anti-conformation than in the mobile domain. This environment is analogous to the interfacial region present in between the amorphous and crystalline regions of bulk polyethylene. The13C EXSY experiment was repeated for tmixvalues of up to 4 s at temperatures from 72 to 114° C. to estimate the kinetics and thermodynamics of the chain diffusion through the channel. Interestingly, it was observed that the cross-peak intensities did not converge to those expected from pure statistical exchange but that instead a very significant fraction, ca. 70%, of the intra-pore polymer never exits the pore, even at 114° C. (the intensities plotted inFIG.3bcan be read as fractions of intra-pore polymer that can freely leave the pore). As expected, the fraction of the polyethylene that can freely escape the silica channel increases with temperature. Importantly, however, this result demonstrates that the material itself never fully releases the polymer chain. An estimation of equilibrium behavior based on these data suggests that a significant fraction of *PE remains adsorbed in pores at catalytically-relevant temperatures. In addition, experiments performed on eicosane (C20H42) show that lower molecular mass fragments do not adsorb strongly onto silica or into 1.5 nm pores. That is, the numerous cumulative dispersion interactions between pore and long hydrocarbon polymer result in strong binding, whereas fewer interactions with small molecules should allow relatively efficient release. Together, this behavior provides the properties required to mimic the processive enzymatic polymer deconstruction process for polymer upcycling depicted inFIG.1b. The polymer must also be able to thread through the pore at a reasonable rate for efficient processive catalysis. To probe this translocation rate, a relationship between the cross-peak intensities (1) and the diffusion length (L=rI=√{square root over (Defftmix)}) was exploited to extract effective intra-pore diffusion coefficients (Deff); where r is the pore length (200 nm). The diffusion coefficient depends on the mixing time (FIG.3c), due to the binding of the polymer, but the initial diffusion coefficient, corresponding to the rate when the polymer is closest to its equilibrium position, is within experimental error with the diffusion coefficient of PE in the melt. Similarly the activation energy for the translation through the pore (80±24 kJ/mol,FIG.3d) agrees with that measured in bulk PE, These results, therefore, show that while the silica pore is able to bind to PE, this binding is not so strong as to prevent short-range diffusion of the polymer. EXSY experiments performed using the catalytic architecture discussed in the next section show the same behavior. Example 13—Polyethylene-Surface Interactions Solid-State NMR To confirm that the resonance at 32 ppm indeed corresponds to a rigid and more extended polyethylene conformer we have performed1H-13C cross-polarization (CP)MAS as well as a J-mediated Incredible Natural Abundance DoublE QUAntum Transfer Experiment (INADEQUATE). In consideration of the fact that a threaded polymer should exhibit much lower molecular mobility, and since the CP transfers are mediated by1H-13C dipolar couplings, which in turn are weakened by molecular motions, the mobile part of polymer will be underrepresented in the resulting CPMAS spectrum when compared to the quantitative13C MAS spectrum shown inFIG.2in the main text. Indeed, the relative peak intensities in the spectrum shown inFIG.112(top) clearly confirm the high mobility of polyethylene fragments resonating at 29 ppm. The INADEQUATE experiment returns a non-zero intensity for all13C sites having non-magnetically-equivalent13C neighbors. As such, while a correlation within the all-anti domain is expected (since homonuclear13C-13C dipolar coupling prevents magnetic equivalence), a mobile-mobile correlation is not, since this site is homogeneously-broadened and liquid-like, as evidenced by its narrowing at elevated temperatures and inefficient cross-polarization. A correlation between both resonances would result in a non-zero intensity at 29 ppm. In this experiment, only the signal from the anti conformer survived the double quantum filter, demonstrating that indeed the two resonances belong to separate domains and that there are indeed long, all anti, polyethylene segments when the polymer is loaded onto this material (FIG.112). To substantiate the inventor's theory that the textural properties of the material are what is controlling the polymer's folding two additional control experiments were performed. The first of these was gauged at determining whether the surface chemistry (functional group/OH, densities) could also influence the folding of the polymer. To this aim, the mesoporous silica material was partly dehydroxylated, which was found to linearly-orient the polymer molecules, and repeated the13C MAS NMR experiment, following the polymer loading and washing procedure outlined above. The obtained spectrum was essentially identical to that obtained with the relatively wet surface (seeFIG.113) with the exception that the signal amplitudes were decreased by a factor of 38. This indicates that the polymer-surface interactions must be weaker in the dehydroxylated material, vide infra, and hence more of it was washed away by the solvent, but otherwise the conformation of the polymer at the material surface is unaffected by this change. Secondly, the results obtained from the polymer on the mSiO2were compared with that obtained on a comparable material, albeit without the pores. As such, non-porous silica spheres of a comparable diameter as the mSiO2(200 nm) as well as spheres of a smaller diameter (50 nm) were prepared. The spectra acquired with the use of CP as well as Bloch decay are shown inFIG.114. The CP spectra emphasize the more rigid parts of the polymer. As can be seen, the13C MAS NMR spectra for the mSiO2and 200 nm spheres are strikingly different, evidencing that the polymer is entering the pores of the mSiO2. Aside from that, less polymer was loaded onto the silica spheres, as expected, due to their reduced surface areas, and since this polymer was now able to access the longer external surfaces, it was considerably more rigid. In the case of the smaller spheres (50 nm), the diameter was too small to support long cumulative polymer-surface contacts and the polymer loading was drastically reduced. The remaining polymer was then also far more mobile than in the case of the 200 nm spheres. Thirdly, to determine whether the mSiO2material would release show chain alkanes following a hydrolysis reaction the conformation of eicosane in the mesoporous silica material was studied. Here eicosane was simply melted into the mSiO2material in situ in the NMR rotor which contained an excess of the mSiO2. Performing this experiment with polyethylene yields a resonance at 32 ppm, as shown in the main text. With eicosane, however, even at 45° C. (it's melting point is around 37° C.) no rigid signals were observed (seeFIG.115), indicating that the short oligomer is free and does not adsorb strongly to the silica surface. Finally, to confirm the generality of the observations made on the mSiO2material as well as the principles' transferability to the mSiO2/Pt/SiO2material,13C-PE was loaded onto a Pt-free core-shell material which was then investigated using13C EXSY at a temperature of 72° C. The exchange spectra are shown inFIG.116below for mixing times of 0 and 1 s where no cross-peaks are expected as well as where the cross-peak amplitudes were expected to saturate. Vertical slices taken along the 32 ppm axis are also shown. The cross-peak saturates to a level of 0.3 corresponding to translocations of up to 30 nm, in good agreement with that measured for the mSiO2material which possessed longer pores. This result demonstrates that the processive behavior observed for mSiO2is a general feature that is also present in the material used for catalysis. Analysis of the EXSY Data EXSY data were processed using TopSpin 4.0.4. For all spectra, the region of the F2 axis spanning 31 ppm to 34 ppm was summed, and the resulting projection was fit using one or two pseudo-Voigt functions. For spectra collected at a given temperature, the region corresponding to the pore interior was initially fit using the zero mixing time spectrum (which should have no exchange peak). The peak position and breadth were then constrained and used in the fit of spectra with longer mixing times. In addition to the function fitting the pore interior, a second function was used to fit the interfacial region assigned to polymer at the pore mouth. The parameters of this function were allowed to vary freely and were checked for consistency between spectra with different mixing times. The peak position and breadth were found to be consistent within the resolution limit of the F1 axis (approx. 0.2 ppm). For the 72° C. spectra, artifacts arising from the truncation of the mobile peak lead to spurious intensity in the interfacial region. This intensity was accounted for via fitting the 0 s mixing time spectra and subtracting the intensity from spectra with non-zero mixing times. Representative spectra are presented inFIG.117. Uncertainties in the parameters of the functions making up the fit, and hence the uncertainties in the ratio of the peaks, were estimated via Monte Carlo modeling. Spectra were fit using DMfit version 20150521. These data were used to calculate Arrhenius activation energies for intra-pore diffusion (FIG.118). Example 14—Pt Nanoparticle Size General Procedure 24 nm Stöber Silica. L-arginine (18.2 mg) and ultrapure water (13.9 mL) were thoroughly mixed. Cyclohexane (0.9 mL) was added gently to form a two-layer system. The solution was heated to 60° C. for 30 min with stirring at ˜300 rpm. TEOS (1.10 mL) was added to the mixture, which was then heated at 60° C. for 20 h. After this time, the aqueous layer (bottom) was separated from the organic layer and stored in a refrigerator. 45 nm Stöber Silica. The suspension of 24 nm Stöber silica seed particles (4 mL) was diluted with ultrapure water (14.4 mL). Cyclohexane (2 mL) was then added gently to form a two-layer system. The mixture was heated to 60° C. for 30 min with stirring at ˜300 rpm. TEOS (1.408 mL) was then quickly added, in a single portion, to the top layer, and the reaction mixture was heated at 60° C. for 30 h. After this time, the bottom layer was separated from the organic layer and stored in a refrigerator. 120 nm Stöber Silica. 120 nm SiO2spheres were prepared using the Stöber method. The above aqueous solution of 45 nm Stöber silica seed particles (1 mL) was mixed with ultrapure water (2.6 mL), ethanol (18 mL), and ammonium hydroxide (1.7 mL). The mixture was stirred at 500 rpm for 1 h at room temperature. Three portions of TEOS (1.5 mL total volume) were added in a dropwise fashion to the solution every 30 min (0.5 mL per addition). The reaction was stirred at room temperature for 6 h. The SiO2spheres were separated, washed with an ethanol/water solution (50/50 v/v; 5×20 mL), and then dried under vacuum at room temperature. 1.7 nm Pt NPs. NaOH (12.5 mL, 0.5 M) in ethylene glycol was added to a solution of H2PtCl6·6H2O (0.25 g, 0.48 mmol) in 12.5 mL of ethylene glycol. The mixture was heated at 160° C. for 3 h accompanied by N2bubbling. A 6-mL aliquot of the resulting solution was transferred to a vial. The particles were precipitated by adding HCl (1 mL, 2 M), and dispersed in ethanol containing polyvinylpyrrolidone (PVP-K30, Mw=40,000, 12.2 mg). The solvent was evaporated, and the residue was redispersed in water. 2.9 nm Pt NPs. PVP-K30 (Mw=40,000; 133 mg) was dissolved in an aqueous solution of H2PtCl6·6H2O (20 mL, 6 mM) and methanol (180 mL). The mixture was heated at reflux (80° C.) for 3 h. The solvent was evaporated, and the residue was redispersed in water. 5 nm Pt NPs. K2PtCl4(41.5 mg), C14TAB (505 mg), and PVP-K30 (Mw=40,000; 222 mg) were added to ethylene glycol (20 mL). The vessel was purged with argon to create an inert atmosphere, and the solution was heated at 140° C. for 2 h. Acetone (180 mL) was added to precipitate “as prepared” Pt NPs. The precipitate was further washed with an ethanol/hexanes mixture (1/4 v/v; 5×20 mL), and ethanol (20 mL) was added to the material for storage. NH2—SiO2. In a typical synthesis, 120 nm SiO2spheres (1 g) were dispersed in isopropanol (175 mL). A solution of APTS (200 μL) in isopropanol (25 mL) was added to this dispersion to functionalize the silica spheres with NH2groups. The reaction mixture was allowed to age at 80° C., and then the SiO2spheres were washed with ethanol (3×20 mL) and separated by centrifugation at 8000 rpm. The NH2—SiO2spheres were dried under vacuum at room temperature and annealed at 100° C. in air for 5 h. Pt—X/SiO2. Typically, 600 mg NH2—SiO2spheres were dispersed in ethanol (180 mL). Pt NPs solution was taken out according to the desired loading and diluted to a final volume of 220 mL with ethanol. The 220 mL diluted Pt NPs solution was added to 180 mL NH2—SiO2suspension dropwise with vigorous magnetic stirring (500 rpm). After addition, the resulting Pt—X/SiO2suspension was further sonicated for 30 min. After separation, the Pt—X/SiO2precipitate was washed with ethanol 5 times and stored in ethanol. MSiO2/Pt—X/SiO2. Pt/SiO2spheres (25 mg) were dispersed in ethanol (10 mL) by sonication for 30 min at room temperature. A pre-mixed solution of C16TAB (165 mg) in H2O (50 mL) and ethanol (16.3 mL) was added to the above Pt/SiO2dispersion, and the mixture was sonicated for another 30 min. We then added ammonium hydroxide (550 uL) to the suspension. After 30 min of gentle stirring, a solution of TEOS (720 μL) in ethanol (5 mL) was added in a dropwise manner in portions (4×180 μL) every 30 min to the above suspension. The suspension was stirred for 6 h at room temperature. The mSiO2/Pt—X/SiO2particles were separated on a centrifuge, washed with ethanol (3×20 mL), and finally dispersed into a mixture of methanol (15 mL) and concentrated hydrochloric acid (1 mL). This mixture was heated at reflux (80° C.) for 24 h to remove the C16TAB surfactant. After refluxing, mSiO2/Pt—X/SiO2catalysts were washed thoroughly with ethanol (6×15 mL) by centrifugation at 8000 rpm. N2physisorption data for mSiO2/Pt—X/SiO2catalysts is shown in table 12. TABLE 12BET surfacepore volumeBJH poreTEM sizessamplearea (m2/g)(cm3/g)size-ad(nm)(nm)mSiO2/Pt-1.7/SiO29810.812.4348 (15)mSiO2/Pt-2.9/SiO29690.812.4350 (15)mSiO2/Pt-5.0/SiO29430.832.4350 (15) The HT-GPC analysis of molecular mass and distributions of PE (Alfa Aesar 041321) is shown inFIG.190. Methods and Conditions for Catalytic Reactions Ethylene hydrogenation. Ethylene hydrogenation experiments were conducted in a gas flow reactor. Typically, catalysts were mixed with quartz sand (200 mg). The reaction gases were composed of He (flowing at 156 mL/min; 99.999%), C2H4(2.4 mL/min; 99.9%), and H2(24 mL/min; 99.995%) at 1 atm. Catalysts were preactivated in the reactor by heating at 200° C. while flowing 10% 02/He for 1 h, He for 0.5 h, and then 10% H2/He for 1 h. A cooling bath was used to maintain catalyst bedding at 20° C. The gas composition was monitored online using an HP 5890 gas chromatography equipped with a capillary column (HP PLOT Q, 30 m×0.32 mm×0.25 μm) with a flame ionization detector (FID). The ethylene hydrogenation activity was assessed using the rate at the initial portion of the reaction. The Pt NPs catalysts undergo deactivations during the hydrogenation reaction at rates that are related to particle size. Polyethylene hydrogenolysis. Polyethylene hydrogenolysis experiments were performed in Parr autoclaves equipped with an overhead mechanical stirrer. Polyethylene (3.0 g) and the catalyst were loaded into a glass-lined autoclave, which was sealed and purged using alternating vacuum and argon cycles (3×). The reactor was pressurized with H2, mixing was initiated, and the vessel heated at 300° C. for a preset time (6, 8, 12, 15 or 20 h). Then, the reactor was allowed to cool, and the headspace was sampled and analyzed using a GC-FID. Methylene chloride was added to the reactor, which was sealed and heated to 80° C. The resulting suspension was filtered, and ethylene chloride was evaporated from the filtrate to provide the extracted wax product. The remaining solid on the filter was dried, its mass was determined. The yield of gases was calculated by subtracting the initial mass of the polymer by the mass of extracted waxes and solid residue. The extracted wax was analyzed using GC-MS. Comparisons between catalytic materials. The mass of Pt used in catalytic PE hydrogenolysis experiments is normalized to give equivalent conversion to that of mSiO2/Pt-5.0/SiO2-catalyzed hydrogenation of ethylene under equivalent conditions. mass⁢(reference)×activity⁢(reference)×wt.%⁢Pt⁢(reference)=mass⁢(catalyst)×activity⁢(catalyst)×wt.%⁢Pt⁢(catalyst)⁢mass⁢(catalyst)=mass⁢(reference)×activity⁢(reference)×wt.%⁢Pt⁢(reference)activity⁢(catalyst)×wt.%⁢Pt⁢(catalyst)⁢reference=m⁢SiO2/Pt-5./SiO2⁢mass⁢(reference)=0.36⁢g⁢m⁢SiO2/Pt-5./SiO2⁢used⁢in⁢HDPE⁢hydrogenolysis⁢activity⁢(reference)=initial⁢experimental⁢rate⁢of⁢C2⁢H6⁢formation⁢using⁢m⁢SiO2/Pt-5./SiO2=20.5mmol⁢C2⁢H6·gPt-1⁢s-1⁢wt.%⁢Pt⁢(reference)=mass⁢Ptmass⁢m⁢SiO2/Pt-5./SiO2=0.28wt.%⁢(determined⁢by⁢ICP-MS)⁢activity⁢(catalyst)=initial⁢experimental⁢rate⁢of⁢C2⁢H6⁢formation⁢using⁢m⁢SiO2/Pt-X/SiO2⁢wt.%⁢Pt⁢(catalyst)=mass⁢Ptmass⁢m⁢SiO2/Pt-X/SiO2⁢(determined⁢by⁢ICP-MS) Gas Chromatography Analysis Headspace analysis method. Gas Chromatography-Flame Ionization Detector (GC-FID). Gas samples taken from the headspace of the Parr reactor were analyzed by GC-FID using an Agilent Technologies 7890A GC system equipped with a flame ionization detector. A capillary column, Agilent J&W GS-GasPro [0.32 mm×15 m], was used for compound separation. Samples were injected manually using a gas-tight syringe. Method for analyzing extracted waxes. Gas chromatography-mass spectrometry (GC-MS). An Agilent Technologies 7890 A GC system equipped with an Agilent Technologies 5975 C inert MSD mass spectrometer was used to analyze the nature of the extracted liquid products. A capillary column, Agilent J&W DB-5ht ((5%-phenyl)-methylpolysiloxane, 0.25 mm×30 m×0.1 m) was used for compound separation. Samples were prepared by dissolving 20 mg of the extracted liquid products in 2 mL of dichloromethane. Quantification of GC-MS extractable waxes. The composition of the extracted wax fraction, in terms of amounts of each chain length in the samples, is estimated using our previous reported approach, given here for convenience: A GC-MS of the ASTM standard was integrated. A plot of integrated area vs. carbon number (shown inFIG.21) allows the determination of response of all Cn(since ASTM standard does not include C13, C19, C21, etc.) by interpolation. The regions of C6-C20and C20-C40are linear, but with inequivalent slopes. Therefore, these two regions were fit separately. The relative mass ratio as a function of carbon number F(Cn) was calculated by dividing the area of each peak (or calculated peaks for the appropriate range using the linear fits fromFIG.22) by that of the C12(which was arbitrarily chosen—note that this protocol was also tested with C24and, expectedly, gives an equivalent scaling factor for each peak). relative⁢mass⁢ratio=F⁡(Cn)=integrated⁢peak⁢area⁢of⁢Cnintegrated⁢peak⁢area⁢of⁢C12 The relative mass ratio for each Cnallows the estimation of the GC-MS response for hydrocarbon species as a function of the Cn. In GC-MS of catalytic mixtures below, the observed integrated intensities for each carbon number are appropriately scaled based on the relative mass ratio F(Cn). relative⁢intensity⁢for⁢a⁢carbon⁢number=G⁡(Cn)=observed⁢integrated⁢intensity⁢of⁢catalytic⁢sampleF⁡(Cn) The percentage of each carbon number is determined by dividing that carbon number's relative intensity by the sum of the relative intensities for all carbon species observed. %⁢Cn=G⁡(Cn)∑366G⁡(Cn)×100⁢% High Temperature—Gel Permeation Chromatography Number-averaged and weight-averaged molecular weights (Mnand Mw) and molecular weight distributions (Mw/Mn) of the polymers were determined by high-temperature gel permeation chromatography (HT-GPC; Agilent-Polymer Laboratories 220) equipped with RI and viscometer detectors. Monodisperse polyethylene standards (PSS Polymer Standards Service, Inc.) were used for calibration ranging from ˜330 Da to ˜120 kDa. The column set included 3 Agilent PL-Gel Mixed B columns and 1 PL-Gel Mixed B guard column. 1,2,4-trichlorobenzene (TCB) containing 0.01 wt % 3,5-di-tert-butyl-4-hydroxytoluene (BHT) was chosen as the eluent at a flow rate of 1.0 mL/min at 160° C. The samples were prepared in TCB at a concentration of ˜5.0 mg/mL and heated at 150° C. for 24 h prior to injection. Catalyst Design and Preparation Mesoporous shell/catalyst/core (mSiO2/Pt—X/SiO2) materials containing Pt NPs with average diameters of 1.7 nm (mSiO2/Pt-1.7/SiO2), 2.9 nm (mSiO2/Pt-2.9/SiO2), and 5 nm (mSiO2/Pt-5.0/SiO2) were synthesized to investigate the effects of Pt particle size on catalytic polyolefin hydrogenolysis in a confined environment specifically and uniformly located at the closed ends of mesopores. All other meso- and nanostructural properties of the mSiO2/Pt—X/SiO2materials are equivalent across the three catalysts, including the 120 nm size of the SiO2core, as well as the 2.4 nm diameter and the 120 nm length of the mesopores in the silica shell. The uniform meso- and nanoscale architecture of these catalysts was created through the synthetic approach. Common 120 nm monodisperse solid silica spheres, prepared via a seeded growth process, react with aminopropyl trimethoxysilane to give surface-functionalized NH2—SiO2spheres. Polyvinylpyrrolidone (PVP)-capped Pt NPs, either 1.7 (±0.3), 2.9 (±0.5), or 5.0 (±1.0) nm in diameter (FIG.125) were immobilized onto the NH2—SiO2spheres (Pt—X/SiO2, X=1.7, 2.9, or 5.0 nm), then the 120 nm thick, radially-aligned mesoporous silica shell was grown on the Pt—X/SiO2. Transmission electron microscopy (TEM) reveals that, as desired, the silica core sizes and mesoporous shell thickness are equivalent across the three samples, and the Pt NPs are localized at the core-shell interface (FIG.120). Pt NPs are more clearly observed in the sample prepared with 5.0 nm Pt NPs compared to the smaller Pt NPs, which are nonetheless also clearly localized at the core-shell interface in the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images. The N2isotherms from Brunauer-Emmett-Teller (BET) analysis, 943-981 m2/g range of surface areas, 0.81-0.83 cm3/g pore volumes, and 2.4 nm pore diameters calculated from the BJH model were all nearly identical for three catalysts (FIGS.126,127). That is, the characterization data indicates that the only significant physical difference between mSiO2/Pt-1.7/SiO2, mSiO2/Pt-2.9/SiO2, and mSiO2/Pt-5.0/SiO2is the size of the platinum NPs. We also note that 1.7 nm Pt NPs are smaller, on average, than the 2.4 nm mesopore diameter, while the average sizes of the Pt NPs in the other two catalytic materials are larger than that of the mesopores. The active surface area of platinum, which varies between the three mSiO2/Pt—X/SiO2catalytic materials on a per mass basis, should be kept constant to compare the catalysts' behavior in polyolefin hydrogenolysis reactions. Active Pt in the mSiO2/Pt—X/SiO2materials was estimated using the structure-insensitive ethylene hydrogenation reaction (Table 13). The mSiO2/Pt-1.7/SiO2material, as expected, catalyzes ethylene hydrogenation with the highest initial activity (95.2 mmol C2H6·gPt−1s−1), while the activity of mSiO2/Pt-5.0/SiO2(20.5 mmol C2H6·gPt−1s−1) is the lowest. The higher activity per mass of smaller NP Pt catalyst is attributed to their higher dispersion. The amount of catalyst used for hydrogenolysis reactions was normalized to have the same number of Pt active sites based on the performance of mSiO2/Pt-5.0/SiO2in ethylene hydrogenation. TABLE 13Reaction rate data for ethylenehydrogenation on mSiO2/Pt-X/SiO2catalysts.Mass of catalystLoadingused for(Pt wt/ActivityhydrogenolysisCatalystsilica wt %)a(mmol · gPt−1s−1)b(g)cmSiO2/Pt-1.7/SiO20.08595.20.0256mSiO2/Pt-2.9/SiO20.4037.00.0140mSiO2/Pt-5.0/SiO20.2820.50.0360aPt loading for each mSiO2/Pt-X/SiO2catalyst was measured by inductively coupled plasma (ICP)-MS.bReaction conditions: C2H4(10 Torr), H2(100 Torr), He (650 Torr), total flow 182.4 mL/min, at 293K, activity calculated based on ethane production.cTypical mass of each mSiO2/Pt-X/SiO2catalysts used for polyethylene hydrogenolysis reaction. Polyethylene hydrogenolysis experiments examining the effects of Pt NP sizes employ these three mSiO2/Pt—X/SiO2catalysts. Typical reaction conditions use linear polyethylene (ca. 3 g PE, Mn=20 kDa, Mw=90 kDa, ρ=0.92 g/mL) and 0.89 MPa of H2pressure, heated at 300° C. for 6-20 h, in a mechanical impeller-mixed autoclave containing from 0.02-0.1 mg Pt, under solvent-free conditions. At the end of each experiment, the reactors contained a condensed-phase fraction as well as volatile species in the headspace. The volatile species were quantified by comparison of the mass of condensed phase materials before and after the conversion, and the C1-C9hydrocarbons composition of the volatiles was quantified by gas chromatography-flame ionized detector (GC-FID). Soluble species were extracted from the condensed phase using methylene chloride to give a yield of ‘extracted waxes’. The yield is defined as the weight of waxes divided by the total weight of initially added polymer. The quantified composition of the extracted waxes was analyzed by calibrated GC-mass spectrometry (MS), which showed mostly linear C8˜C50hydrocarbons. Analysis of the quantities of each fraction and their composition, in terms of molecular weight and distribution, provides key insight for comparing performance of the three mSiO2/Pt—X/SiO2catalytic materials. The relative activity of the catalysts for carbon-carbon bond cleavage is estimated by comparing conversion of PE into small molecules, per surface active site of Pt under equivalent reaction conditions. The most active catalyst converts the largest amount of insoluble solid polymer. The activity of catalytic materials may also be compared by analyzing the amounts of volatile and extracted species formed per unit time, with volatile species corresponding to more carbon-carbon bond cleavages. For example, formation of 1 g of CH4corresponds to a ca. 19-fold greater number of C—C bond hydrogenolysis steps than 1 g of C20H42; in contrast, conversion of a solid polymeric material with Mn−20 kDa into a polymer with Mn˜10 kDa corresponds to only one C—C bond hydrogenolysis step, on average. Thus, such assays of catalytic activity are best considered qualitatively. These two estimates indicate that catalyst activity follows the trend mSiO2/Pt-1.7/SiO2>mSiO2/Pt-2.9/SiO2>mSiO2/Pt-5.0/SiO2over the course of the PE deconstructions (Table 14). For example, based on the amount of unextracted CH2Cl2-insoluble materials after reaction, mSiO2/Pt-1.7/SiO2affords 25% conversion of PE after 6 h at 300° C. under 0.89 MPa, whereas only 15% and 6% consumption of PE are observed using mSiO2/Pt-2.9/SiO2or mSiO2/Pt-5.0/SiO2, respectively (FIG.128). In addition, mSiO2/Pt-1.7/SiO2gives the most soluble species (16%) and the most gas-phase species (9%), while mSiO2/Pt-5.0/SiO2produces the least amount of soluble and volatile species (4 and 2%, respectively). These data indicate that the smallest Pt NP catalyst is most active at short reaction times (at the lowest experimentally accessible conversion under these conditions). This trend continues over the course of the experiments. After 12 h, mSiO2/Pt-1.7/SiO2catalyzes the hydrogenolysis of 62% of PE, while mSiO2/Pt-5.0/SiO2gives only 26% conversion. TABLE 14Gas, extractable waxes, and insoluble products formedat different reaction time from mSiO2/Pt-X/SiO2-catalyzed hydrogenolysis (X =1.7, 2.9, and 5.0 nm).aReaction Time (h)CatalystaProduct681220mSiO2/Pt-PE (g)3.0293.0303.0153.0071.7/SiO2gas0.274 (9.1%)0.349 (11.6%)0.345 (11.4%)1.993 (66.3%)liquid0.476 (15.7%)0.880 (29.0%)1.523 (50.5%)1.014 (33.7%)solid2.279 (75.2%)1.801 (59.4%)1.147 (38.0%)n.a.mSiO2/Pt-PE (g)3.0043.0013.0023.0182.9/SiO2gas0.255 (8.4%)0.250 (8.3%)0.360 (12.0%)0.451 (14.9%)liquid0.195 (6.4%)0.611 (20.4%)1.315 (43.8%)2.138 (70.8%)solid2.554 (85.2%)2.139 (71.3%)1.327 (44.2%)0.428 (14.2%)mSiO2/Pt-PE (g)3.0663.0003.0013.0665.0/SiO2gas0.119 (3.9%)0.140 (4.7%)0.259 (9.8%)0.303 (9.8%)liquid0.058 (1.9%)0.255 (8.5%)0.525 (17.5%)1.892 (61.7%)solid2.889 (94.2%)2.604 (86.8%)2.216 (73.8%)0.807 (26.2%)aReaction conditions: 3 g of PE (Mn= 20 kDa, Mw= 90 kDa, ρ = 0.92 g/mL), with 0.0007-0.003 wt. % Pt with respect to PE, 0.89 MPa H2, 300° C. The yields of extracted waxes also follow the trend mSiO2/Pt-1.7/SiO2>mSiO2/Pt-2.9/SiO2>mSiO2/Pt-5.0/SiO2. After 6 h, for example, the most active catalyst mSiO2/Pt-1.7/SiO2provides 15.7% extractable waxes, whereas mSiO2/Pt-2.9/SiO2or mSiO2/Pt-5.0/SiO2form only 6.4% and 1.9%, respectively. In general, the yields of extractable fractions increase during the batch conversion following this trend, until all the unextractable solids are consumed. At that point, the yield of wax decreases. The yield of extracted material obtained using the catalyst mSiO2/Pt-1.7/SiO2decreases from 74% after 15 h to 34% after 20 h (FIG.121). Although more volatile species are formed both initially (6 h) and at high conversion (20 h) with the mSiO2/Pt-1.7/SiO2catalyst than using the larger Pt NP catalysts, following a similar trend as described above for extractable waxes, intermediate conversions reveal a powerful, particle-size independent effect on selectivity. Specifically, similar quantities of volatile species are obtained after 12 h with each of the catalytic materials (ca. 10-12%), even with dramatically different conversions of polymer. The mass fraction of volatile species formed using mSiO2/Pt-1.7/SiO2is roughly constant from the first 6 h (at 25% conversion of PE) to 15 h (at 86% conversion of PE), indicating that the solid polymeric materials undergo selective hydrogenolysis to the extractable waxes over that portion of the reaction (FIG.121). In addition, the percentage of mass corresponding to volatile species increases from ca. 4% after 6 h (at 5% conversion of PE) to 10% after 12 h (26% conversion of PE) using the mSiO2/Pt-5.0/SiO2catalyst. That is, the quantity of volatile species obtained from mSiO2/Pt-1.7/SiO2after 6 h is comparable to that of mSiO2/Pt-5.0/SiO2after 12 h, corresponding to equivalent conversions of PE (FIGS.129and131). After 20 h, quantitative conversion of polyethylene is achieved with mSiO2/Pt-1.7/SiO2. Concurrently, the quantity of volatile species dramatically increases, and the fraction of extractable waxes dramatically decreases. This behavior is attributed to over-hydrogenolysis, which involves further conversion of oligomeric primary products into lower value light hydrocarbons. The over-hydrogenolysis process only becomes dominant once most or all the long-chain PE is consumed. A test of this idea involves the hydrogenolysis reaction using mSiO2/Pt-1.7/SiO2for 15 h, which a priori was postulated to give high yield of extractable waxes and similar (˜10-12%) yields of volatile species at high PE conversion, based on over-hydrolysis at 20 h and the behavior of the other two catalytic materials in Table 14. The result from this experiment matches our expectation, giving 73.6% yield of extractable waxes with only 12.4% of gases. Remarkably, all three Pt-sized catalysts give similar mass fractions of volatile products at conversions of PE ranging from 25-70% (e.g., 10-12% volatiles), suggesting that the over-hydrogenolysis process occurs only at high PE conversion, regardless of the Pt NP size. mSiO2/Pt—X/SiO2materials also catalyze the hydrogenolysis of a second, smaller polyethylene sample (Mn=5.9 kDa, Mw=30 kDa) under identical conditions (ca. 3 g of PE, 300° C., 0.89 MPa H2) (Table 15). A related trend in activity, in which mSiO2/Pt-1.7/SiO2produces the most liquids and gases (87.3% by mass) after 6 h, while mSiO2/Pt-2.9/SiO2and mSiO2/Pt-5.0/SiO2catalyze the hydrogenolysis of ca. 64% of the polyethylene to extractable waxes and gases. The distribution of chain lengths in the extracted waxes is similar for the three mSiO2/Pt-X/SiO2catalysts. In addition, similar over-hydrogenolysis is observed after 24 h using mSiO2/Pt-1.7/SiO2as the catalyst, giving 55% of volatile species by mass at that time. This 5.9 kDa Mnpolyethylene is more reactive than the longer 20 kDa Mapolyethylene studied above, producing a higher mass percentage of gases and extractable waxes for each catalyst under equivalent conditions. Note that the overall catalytic process involves diffusion and adsorption of chains into the pores, polymer chain adsorption onto Pt, single (or multiple) C—C bond cleavage steps of the chain, and diffusion of the smaller polymer fragments. The relative rates of these steps will affect the overall rate of polymer conversion. Thus, the combined rates of these steps are faster for the shorter polymer (Mn=5.9 kDa) than the longer one (Mn=20 kDa). TABLE 15Data from mSiO2/Pt-X/SiO2-catalyzedhydrogenolysis of the Mn= 5.9 kDa PE.aReactant/Reaction Time (h)CatalystProducts61220mSiO2/PE (g)3.0103.0093.013Pt-1.7/SiO2gas0.886 (29.4%)1.320 (43.8%)1.664 (55.3%)extracted1.756 (58.3%)1.551 (51.5%)1.349 (44.7%)waxsolid0.363 (12.3%)0.137 (4.5%)n.a.mSiO2/PE (g)3.0043.0023.018Pt-2.9/SiO2gas3.0443.0363.010extracted0.451 (14.8%)0.446 (14.7%)0.403 (13.3%)waxsolid1.486 (48.8%)1.788 (58.8%)1.925 (63.9%)mSiO2/PE (g)3.0333.0193.009Pt-5.0/SiO2gas0.638 (21.3%)0.514 (17.0%)0.496 (17.1%)extracted1.272 (41.9%)1.647 (54.7%)1.676 (55.8%)waxsolid1.112 (36.6 %)0.859 (28.4%)0.834 (27.1%)aReaction conditions: 3 g of PE (Mn= 5.9 kDa, Mw= 36 kDa, ρ = 0.94 g/mL), with 0.0007-0.003 wt. % Pt with respect to PE, H2(0.89 MPa), 300° C. The rates of the individual steps, also, could affect the mean chain length and shape of the distribution of hydrocarbon products in the extractable liquids and waxes. Alternatively, or in addition to a kinetic effect, the average length of the platinum NP that is accessible to the polymer chains could influence the hydrocarbon product distribution via a templating mechanism, as noted in the Introduction. In such a scenario in which the NP templates the product chain length, 1.7 nm and 5.0 nm platinum NPs would give the shortest and longest average chain lengths, respectively. Our previous observation that the diameter of the pores in the mesoporous shell influences the distribution could also come from such kinetic or templating effects. Given that each of the mSiO2/Pt—X/SiO2catalysts could provide hydrocarbon species characteristic of the sizes of their NPs, it was surprising that instead, the mean and distribution of product chain length in the extracted wax products are very similar for the three catalysts and over a wide range of conversions. Comparisons show similar compositions of the extractable fractions, determined by calibrated GC-MS, obtained after equivalent reaction times, or at similar conversions of solid polymer or having similar percent yields (by mass) of extracted species. Most of the experiments afford soluble hydrocarbon wax products with a mean chain length of ca. C23and similarly shaped distributions, as seen by visual inspection (FIG.122) and statistical analysis of the histograms. For example, the mean chain length and distributions of the extracted waxes, obtained using the three Pt NP-sized catalysts, are virtually identical from reactions performed to ca. 75% conversion of PE (60-70% yield of wax). Moreover, the distributions of Cnchains in the extracted waxes are statistically indistinguishable, in terms of the mean product sizes [C23] and between the variances in product size [±7 carbons] as determined by one-way analysis of variance (ANOVA). The distribution of chain lengths in the extracted oil fraction is also independent of conversion throughout the catalytic regime that produces the most extractable oils. For example, mSiO2/Pt-1.7/SiO2provides C23-centered bell-like distributions of chain lengths as the extracted wax yields range from 30% after shorter reactions (8 h) to 73% after longer times (15 h). At lower conversions obtained with shorter reaction times, the C23-centered distribution is distorted by a lower molecular weight fraction, giving a ‘shoulder’ to the bell-shaped distribution at ˜C14(FIG.123, 8 h data andFIG.124). These non-Gaussian lower molecular weight species are likely formed as part of the process that initially produces shorter gas-phase species, and the relative abundance of these species decreases as conversion to a C23-centered distribution of wax products increases during the catalytic reactions. Similarly, over-hydrogenolysis, at high conversions that afford large amounts of gaseous products, also produces a large molar fraction of the extracted products with shorter chain lengths (C9-C15) than observed in the C23-centered distributions from shorter reaction times. The above observations result from the combined effects of the mesoporous shell/active site/core architecture and the high activity of the Pt NP sites. Control reactions, in which platinum-free mesoporous silica shell/solid silica core materials (mSiO2/SiO2) are heated with PE under H2at 300° C. for 12 h, result in minimal conversion of the solid polymer (3.6%) and even less extractable oil product (1.2%; Table 16). TABLE 16Gas, extractable waxes, and insoluble products formedfrom mSiO2/SiO2-catalyzcd hydrogenolysis reaction.aPEReactionVolatile productsExtracted productsSolid residueCatalyst(g)time (h)(%)(%)(%)mSiO2/SiO23.043120.074 g (2.4%)0.0.037 g (1.2%)2.932 g (96.4%)aReaction conditions: 3 g of PE (Mn= 20 kDa, Mw= 90 kDa, ρ = 0.92 g/mL), 0.89 MPa H2, 300° C. The small amount of extracted liquids contains the signature features of mSiO2/Pt/SiO2experiments at low conversion, namely a ca. C23-centered broad distribution of chain lengths with a shoulder around C14(FIG.140,143). The similarity of these distributions suggests that a background reaction, involving interactions of PE and mSiO2but not Pt sites, occurs at an early stage of all the conversions. A second control experiment shows that the Pt particles supported on the silica core (Pt—X/SiO2) but lacking the mesoporous silica shell are much less effective than the mSiO2/Pt—X/SiO2catalysts. For example, conversion of PE is only 4.6% after 12 h using Pt-1.7/SiO2, in comparison to 62% obtained under equivalent conditions with mSiO2/Pt-1.7/SiO2. The low conversion was also obtained using Pt-2.9/SiO2(4.3%); and Pt-5.0/SiO2(13.5%; Table 17). The higher activity of Pt-5.0/SiO2compared to Pt-1.7/SiO2is likely due to less structural changes of the former under catalytic conditions. The extracted wax products from the Pt—X/SiO2catalytic materials appear as a flat distribution of chain lengths (FIGS.179,182, and185). TABLE 17Gas, extracted waxes, and insoluble products formedfrom Pt-X/SiO2-catalyzed hydrogenolysis reaction.aReactionVolatilesExtractedSolidCatalystPE (g)Time (h)products (%)products (%)residue (%)Pt-1.7/3.075120.056 g0.084 g2.935 gSiO2(1.8%)(2.7%)(95.4%)Pt-2.9/3.029120.036 g0.094 g2.899 gSiO2(1.2%)(3.1%)(95.7%)Pt-5.0/3.008120.194 g0.212 g3.007 gSiO2(6.4%)(7.1%)(86.4%)aReaction conditions: 3 g of PE (Mn= 20 kDa, Mw= 90 kDa, ρ = 0.92 g/mL), with 0.0007-0.003 wt. % Pt with respect to PE 0.89 MPa H2, 300° C. The quantity of volatile species, time-dependence of the mass-based fractions of products (gases, methylene chloride-extracted waxes, and the residual solid), GC-FID trace of the sampled headspace, the GC-MS of extracted waxes, and the carbon number distribution of extracted waxes for the hydrogenolysis reaction from mSiO2/Pt-1.7/SiO2-catalyzed, mSiO2/Pt-2.9/SiO2-catalyzed, mSiO2/Pt-5.0/SiO2-catalyzed, and mSiO2/SiO2-catalyzed hydrogenolysis at various catalyst loadings and reaction times is shown inFIGS.130,132-139,141,142,144-181,183, and184. FIG.186shows the bubble wrap plastic waste obtained from backyard as litter, no pre-cleaning was performed prior to reactions. The GC-FID trace of the sampled headspace, the GC-MS of extracted waxes, and the carbon number distribution of extracted waxes for the hydrogenolysis reaction using mSiO2/Pt-1.7/SiO2(0.085 Pt wt/silica wt %) as catalyst is shown inFIGS.187-189. The inequivalent behavior of mSiO2/Pt—X/SiO2and Pt—X/SiO2catalytic architectures are at least partly related to changes in Pt NPs during hydrogenolysis reactions. The TEM image of catalytic Pt-1.7/SiO2materials, collected post-catalysis at high conversion (62%) after methylene chloride extraction to remove the hydrocarbon products, revealed a significant amount of detached, sintered, and aggregated Pt NPs. In contrast, TEM of mSiO2/Pt-1.7/SiO2collected on as-synthesized and post-reaction materials indicates that Pt NPs are located at the shell/core interface even after mixing in melted PE, hydrogenolysis treatment, and extraction and separation from organic products with no apparent aggregation (FIG.128). This contrast further highlights the importance of the architecture of mSiO2/Pt—X/SiO2in which confinement of Pt NPs prevents aggregation, and the mSiO2overcoat prevents the detaching of particles from the support. Influence of the mSiO2/Pt—X/SiO2catalytic architecture on PE hydrogenolysis. The mSiO2/Pt—X/SiO2architecture is responsible for the very efficiently catalyzed PE conversions, which require very low platinum loading. The three mSiO2/Pt—X/SiO2catalysts operate effectively at 0.7-3.4×10−5g Pt/g PE, converting Ma=20 kDa into long oligomeric hydrocarbon waxes in over 70% yield after 15-20 h at 300° C. With these catalysts and low Pt loading, PE with Mnof 5.9 kDa is also converted into waxy hydrocarbons in 40-60% yield within 6 h. For comparison, the Pt-1.7/SiO2catalyst, composed of identical colloidal Pt NPs similarly immobilized on identical Stöber SiO2core as the mSiO2/Pt/SiO2, gives only 4.6% conversion with 0.7-1.4×10−5g Pt/g PE under comparable conditions. Although the poor performance of Pt/SiO2is at least partly associated with catalyst degradation, an active site-immobilized and highly selective catalyst with Pt NPs on its external surface, 5c-Pt/SrTiO3, also requires 2.4×10−3g Pt/g PE to reduce Mnfrom 8.15 kDa to 2.15 kDa (in 97% yield) after 24 h at 300° C. under 1.17 MPa of H2, and produces a desirable Mnof 600 Da after 96 h. A Ru/C catalyst needs 1.3×10−2g Ru/g PE at the low temperature of 200° C. and 2 MPa of H2to convert PE with Mnof 1.7 kDa into 45% yield of liquid alkane distributions centered at C16. Alternatively, 1.5×10−3g Ru/CeO2/g low density polyethylene (LDPE) converts Mnof 1.7 kDa into 90% yield of C5-C45liquids and waxes at 240° C. after 8 h under 6 MPa of H2. The ability of mSiO2/Pt—X/SiO2materials to be effective at low Pt loading is a consequence of high reactivity for carbon-carbon bond cleavage in polyolefins and long lifetime. The latter feature is further supported by this catalyst remaining equivalently effective and selective after multiple recovery and re-use cycles. We attribute the long lifetime of the catalyst, under these reaction conditions, to effects of both architecture and the synthetic approach. The isolation of individual Pt NPs in the bottom of a mesoporous silica channel limits their dissociation from the silica support during catalytic hydrogenolysis. Because rates of hydrocarbon hydrogenolysis are structure-sensitive, sintering into larger Pt NPs will have an outsized negative effect on deactivation. We also noted above that 1.7 nm Pt NPs are smaller than the 2.4 nm diameter mesoporous channels; however, release of Pt NPs from mSiO2/Pt-1.7/SiO2was not detected, in contrast to their observed release from the silica surface of Pt—X/SiO2during catalysis. Likely, the Pt NPs are embedded into the walls of the mesoporous silica shell. Thus, the persistent confinement of these particles at the shell/core interface needed for long catalyst lifetime originates from not only geometric factors. Likely, the growth of the mSiO2shell also chemically immobilizes Pt NPs in the catalytic material. The mSiO2/Pt—X/SiO2architecture also appears to impart high activity for these catalytic conversions. Although precise rate constants of carbon-carbon bond cleavage are not readily measured, due to the thousands of possible individual steps associated with many inequivalent bonds in the distribution of species in the reactor, the relative activities of these catalysts may be assessed qualitatively. One indicator of high activity is the small amount of Pt in the reactor that is capable of converting PE into small molecules in a relatively short amount of time. The long catalyst lifetime noted above contributes to the apparent high activity of this qualitative assessment because the analysis is not performed at low conversion (where catalyst deactivation would be avoided); thus, comparisons of activity with Pt—X/SiO2have little value. Nonetheless, comparisons of metal loading in catalysts that transform a large fraction of the polyolefins, identified above for hydrogenolysis catalysts, suggest that the Pt centers in mSiO2/Pt—X/SiO2are especially active. Moreover, the active sites in this material are at the closed end of 120 nm-long mesopores, which require polymers to enter and translocate through the pores to reach the Pt NPs. These steps are not rate-controlling, as evidenced by the shorter reaction times to reach equivalent liquid yields using catalysts with smaller Pt NPs, probably because the pores are constantly filled with polymer chains under these conditions. Interestingly, the shorter reaction times needed for full conversion of smaller (Mn=5.9 kDa) PE suggests that chain length influences the overall reaction rate, perhaps as a result of more favorable matching of polymer and pore lengths. The rate of carbon-carbon bond cleavage at a particular catalytic site should be very similar for all H2C—CH2linkages in hydrocarbon chains, whereas adsorption or translocation in the pores could be affected by the molecular mass of a chain. The architecture of the mSiO2/Pt—X/SiO2catalysts is also responsible for high selectivity and high yields of an approximately bell-shaped distribution of the extracted wax products. As the PE deconstruction proceeds over time, the yield of each species in the distribution of the extracted wax products increases. At high conversion (ca. 85%), selectivity for the waxy distribution with mSiO2/Pt-1.7-SiO2is 85%, calculated as the mass of waxy liquids/total mass of deconstructed products (waxy liquids and gas). The selectivities of both mSiO2/Pt-2.9/SiO2at 85% conversion or mSiO2/Pt-5.0/SiO2at 72% conversion are also ca. 85% for the statically indistinguishable waxy product distribution. That is, the three sized Pt NP catalysts provide equivalent chain-length distribution of the products and equivalent selectivity for those distributions. This characteristic selective production of a certain range of hydrocarbon oligomers is noticeably absent from the control catalyst (Pt—X/SiO2) at any stage of conversion. As noted in the Introduction, the average chain length of the products is affected by the characteristics of the mesoporous silica shell in the mSiO2/Pt/SiO2catalysts. On the basis of this behavior and extensive solid-state13C NMR studies of conformational and dynamic behavior of absorbed polyethylene, we proposed that the polymer chains could only thread in a specific manner to reach the active Pt site. Thus, the C—C bond cleavage in a polymeric chain is confined to a certain average length, resulting in selective distributions of alkanes. That is, the mesoporous architecture confers selectivity, templating a narrow range of products from hydrogenolysis, rather than the NP sites where the carbon-carbon bond cleavage occurs. Influence of the Pt NPs on hydrogenolysis. Time-dependence of PE consumption, time-dependence of wax yields indicate faster reactions for smaller Pt NPs in mSiO2/Pt—X/SiO2compared to larger ones, a signature of a structure-sensitive catalytic reaction. For example, 29% yield of extracted wax is obtained after 8 h using mSiO2/Pt-1.7/SiO2, whereas only 8.5% yield is produced by mSiO2/Pt-5.0/SiO2after the same amount of time. Similarly, at high conversion, ˜75% yield of extracted wax is obtained with mSiO2/Pt-1.7/SiO2after 15 h, whereas mSiO2/Pt-2.9/SiO2requires 20 h. The shorter reaction times for conversions of equivalent amounts of PE to comparable distributions of smaller hydrocarbon chains is a qualitative indicator of higher catalytic rates for the smaller NPs, from experiments using equivalent platinum active sites in the reactor. The rate of PE hydrogenolysis catalyzed by the active sites in smaller Pt NPs is higher than that of sites in larger Pt NPs. In contrast, the similar rates for the small and large Pt NPs as well as Pt surfaces is a hallmark of structure insensitive reactions. Thus, this qualitative assessment reveals that PE hydrogenolysis rates are increased with greater proportions of edge and corner sites compared to facets in the Pt NPs, and we infer that hydrogenolysis catalysis using mSiO2/Pt—X/SiO2is a structure-sensitive catalytic reaction. Hydrogenolysis of light linear, branched, and cyclic alkanes have been demonstrated to be structure sensitive on metal surfaces, whose activity (and selectivity) varies with the exposed single crystal facet. This structure sensitivity naturally transfers to NP catalysts, because the distribution of surface atoms at the facets changes with the size of the NP. For example, the rate of ethane hydrogenolysis, in terms of turnover frequency (TOF), for 1.7 nm Pt/SBA-15 (1.2×10−2s−1) is double compared to that of 2.9 nm Pt/SBA-15 (0.6×10−2s−1). This trend, involving smaller metal NPs characterized by faster reactions, is observed for these silica-supported Pt NPs operating under gas-solid conditions, while larger NPs on other supports (such as Pt/Al2O3) have been shown to have higher activity than smaller NPs. Small Pt NPs, prepared by one ALD cycle in the 1c-Pt/SrTiO3catalyst, have higher activity for PE hydrogenolysis than medium and large Pt NPs, revealing that Pt NP size effect and associated structure sensitivity is also important in condensed phase C—C bond hydrogenolysis. Structure sensitivity is often also manifested in terms of selectivity. For example, larger Pt NPs catalyze hydrogenolysis of small hydrocarbons in solid-gas reactions to give more branched products than linear ones, favoring cleavage of carbon-carbon bonds of secondary carbons over those involving tertiary carbons. In 1c-Pt/SrTiO3-catalyzed hydrogenolysis of HDPE in the condensed phase, the higher rate of C—C bond cleavage also provides more light hydrocarbon products and gives poor selectivity to high quality liquids than in reactions using the larger Pt NPs in 5c-Pt/SrTiO3. As noted above, remarkably, the selectivity of PE hydrogenolysis catalyzed by small, medium, and larger Pt NPs in mSiO2/Pt—X/SiO2is independent of the particle size. As an additional comparison, similar amounts of volatiles species (˜9%) and extracted waxes (˜18%) are obtained at similar conversions for the three catalysts. This result reveals that smaller Pt NPs in mSiO2/Pt-1.7/SiO2form similar amounts of light hydrocarbon products as in mSiO2/Pt-5.0/SiO2, in contrast to the behavior of Pt/SrTiO3catalysts. The synthesis of smaller (1.7 nm), intermediate (2.9 nm), and larger (5.0 nm) Pt NPs in the identical mSiO2/Pt—X/SiO2architecture provides a family of efficient, highly active, and highly selective catalysts with characteristic features and excellent behavior, across the three Pt NP sizes, in polyethylene hydrogenolysis. The smallest Pt NP is smaller than the 2.4 nm diameter of the mesopore in mSiO2/Pt—X/SiO2, while the largest Pt NP is larger than the pore diameter. The conversions catalyzed by these catalysts proceed in three stages. The first approximately 25% of PE conversion is poorly selective for the mSiO2/Pt—X/SiO2catalysts, giving approximately 65% (by mass) of products as waxy hydrocarbons. The second stage, involving another 60-75% conversion of the PE, is highly selective for a narrow C23-centered distribution of the desired wax-like products. This distribution is templated by the mSiO2/Pt-X/SiO2architecture, rather than by the size of the Pt NPs. Adsorption of PE chains into mesopores limits conformations to affect the average product chain length. This prominent pore template effect is further demonstrated by the independence of the C23-based bell-shaped distribution of the extracted wax products to Pt NP size as well as reaction time or conversion (prior to over-hydrogenolysis). This pore-templated cleavage phenomenon was also observed in mSiO2/Pt-5.0/SiO2-catalyzed hydrogenolysis of PE at 250° C., which showed features consistent with a processive mechanism. We note that the present conditions (300° C.) result in decreased Mnof the residual PE over the reaction, which is not consistent with highly processive behavior. Thus, the pore-templated carbon-carbon bond cleavage, which is a component of the processive mechanism, also functions in related processes with a low degree of processivity. The present study also indicates that the size of the exposed Pt surface, dictated either by Pt NP size or pore diameter of the mesoporous shell, is unlikely to be responsible for selecting the average chain-length of the product. Once nearly all of the PE is consumed, undesired over-hydrogenolysis of the wax into volatile species is observed in the third stage. At this stage, the average carbon number decreases from the C23-centered distribution as the reaction proceeds. Thus, mSiO2/Pt—X/SiO2is not only selective for hydrogenolysis of PE to waxes but also remarkably selective for hydrogenolysis of PE in the presence of a large amount of C23-centered waxes. The three stages of PE hydrogenolysis occur faster with smaller Pt NPs than with larger ones, corresponding to an increase in catalytic rate without significantly diminishing selectivity. Upcycling Post-Consumed Bubble Wrap by Pt-catalyzed Hydrogenolysis The products formed (gas, extracted waxes, and insoluble products) from mSiO2/Pt-1.7/SiO2-catalyzed hydrogenolysis reaction of post-consumer bubble wrap is shown in Table 18. TABLE 18VolatileExtractedSolidTimeproductswaxresidueCatalystPE (g)(h)(%)products (%)(%)mSiO2/Pt-1.7/SiO23.002120.310 g0.865 g1.827 g(10.3%)(28.8%)(60.9%)Conditions: 0.0007 wt/PE wt % heated in the reactor for 12 h at 300° C. under H2(at 0.89 MPa). Although preferred embodiments have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions, and the like can be made without departing from the spirit of the invention and these are therefore considered to be within the scope of the invention as defined in the claims which follow.
153,293
11857952
DETAILED DESCRIPTION OF THE EMBODIMENTS The present disclosure provides a graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis, including a titanium substrate and a titanium dioxide nanomesh deposited on the titanium substrate, where the titanium dioxide nanomesh is woven from titanium dioxide nanowires; the titanium dioxide nanowires include anatase-type titanium dioxide nanowires and rutile-type titanium dioxide nanowires, and are loaded with graphitic carbon particles. The graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis includes the titanium substrate. The titanium substrate includes preferably a titanium mesh with a mesh number of preferably 200 mesh to 300 mesh. The graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis further includes a titanium dioxide nanomesh deposited on the titanium substrate, where the titanium dioxide nanomesh is woven from titanium dioxide nanowires; the titanium dioxide nanowires include anatase-type titanium dioxide nanowires and rutile-type titanium dioxide nanowires are loaded with graphitic carbon particles. A mass of the graphitic carbon particles is preferably 5% to 20%, more preferably 10% to 15% of a mass of the titanium dioxide nanowires. The present disclosure further provides a preparation method of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis, including the following steps:using the titanium substrate as an anode and a platinum sheet as a cathode in an electrolyte for anodic oxidation to obtain a titanium dioxide nanotube array/titanium substrate composite;annealing the titanium dioxide nanotube array/titanium substrate composite to obtain a mixed crystal-type titanium dioxide nanotube/titanium substrate composite; andimpregnating the mixed crystal-type titanium dioxide nanotube/titanium substrate composite in an organic carbon source solution for a hydrothermal reaction to obtain the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis. In the present disclosure, the raw materials provided herein are all preferably commercially-available products unless otherwise specified. The titanium substrate as the anode and the platinum sheet as the cathode are placed in the electrolyte for anodic oxidation to obtain the titanium dioxide nanotube array/titanium substrate composite. In the present disclosure, the titanium substrate includes preferably a titanium mesh with a mesh number of preferably 200 mesh. The titanium substrate before use is preferably subjected to pretreatment, including preferably ultrasonic treatment and mixed acid treatment in sequence. The ultrasonic treatment includes preferably conducting propanol ultrasonic, methanol ultrasonic and isopropanol ultrasonic treatments in sequence, each being conducted for preferably 10 min. After the ultrasonic treatment, an obtained titanium substrate is preferably subjected to ultrasonic water washing and drying; where the ultrasonic water washing is conducted for preferably 5 min; and the drying is conducted by preferably blow-drying. A reagent for the mixed acid treatment is preferably a mixed acid including hydrofluoric acid and glacial acetic acid at a volume ratio of preferably 1:8. The mixed acid treatment is conducted preferably under ultrasonic conditions for preferably 1 min to 3 min, more preferably 2 min. The mixed acid treatment can remove an oxide film on the titanium substrate. After the mixed acid treatment, an obtained titanium substrate is preferably subjected to water washing, ethanol washing and drying in sequence; where the water washing and the ethanol washing each are conducted for preferably 2 min to 5 min; and the drying is conducted by preferably blow-drying. In the present disclosure, the titanium substrate and the platinum sheet each have a purity of preferably greater than or equal to 98%. In the present disclosure, the electrolyte is preferably an ethylene glycol aqueous solution containing ammonium fluoride. The electrolyte has preferably 0.5 wt % to 0.6 wt %, more preferably 0.52 wt % to 0.58 wt %, and most preferably 0.54 wt % to 0.56 wt % of the ammonium fluoride. The electrolyte has preferably 5 vol % to 5.5 vol %, more preferably 5.1 vol % to 5.4 vol %, and most preferably 5.2 vol % to 5.3 vol % of water. The fluoride ions in electrolyte affect a chemical etching rate of anodic oxidation, thereby affecting a microscopic morphology (such as tube diameter, tube length, and arrangement order) of the titanium dioxide nanotube. The ammonium fluoride-containing electrolyte with a solute content of 0.5 wt % to 0.6 wt % can obtain a better anodic oxidation effect, thereby improving a catalytic activity of an obtained photocatalytic composite. In the present disclosure, the anodic oxidation is conducted at 40 V to 80 V, more preferably 50 V to 70 V, and most preferably 60 V and 20° C. to 40° C., more preferably 25° C. to 35° C., and most preferably 25° C. to 30° C. for 100 min to 140 min, more preferably 110 min to 130 min, and most preferably 120 min with an electrode spacing of 5 cm to 10 cm, more preferably 6 cm to 9 cm, and most preferably 7 cm to 8 cm. In the present disclosure, the anodic oxidation is conducted preferably by stirring. In the present disclosure, after the anodic oxidation, an obtained anode is preferably subjected to ethanol washing and drying in sequence to obtain the titanium dioxide nanotube array/titanium substrate composite. In the present disclosure, amorphous titanium dioxide nanowires are deposited on the titanium substrate during the anodic oxidation, and then woven to form an amorphous titanium dioxide nanomesh; as the amorphous titanium dioxide nanomesh is obtained by deposition through anodic oxidation, the titanium dioxide phase is not easy to fall off, improving a catalytic performance of the composite for electrocatalysis. In the present disclosure, the titanium dioxide nanotube array/titanium substrate composite is annealed to obtain the mixed crystal-type titanium dioxide nanotube/titanium substrate composite. The annealing is conducted at an annealing temperature of preferably 450° C. to 650° C., more preferably 530° C. to 650° C. for preferably 2 h with a heating rate of 5° C./min to 15° C./min, more preferably 8° C./min to 12° C./min from a room temperature to the annealing temperature. The annealing is preferably conducted in an air atmosphere. The annealing is preferably conducted in a muffle furnace. In the present disclosure, after the annealing, the composite is preferably cooled down to room temperature with the furnace. In the present disclosure, the amorphous titanium dioxide nanowires are recrystallized during the annealing to form a mixture of the rutile-type titanium dioxide nanowires and the anatase-type titanium dioxide nanowires. The mixed crystal-type titanium dioxide phase enhances a catalytic performance of the composite for electrocatalysis. In the present disclosure, the mixed crystal-type titanium dioxide nanotube/titanium substrate composite is impregnated in the organic carbon source solution for the hydrothermal reaction to obtain the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis. In the present disclosure, a solute in the organic carbon source solution includes preferably one or more of glucose, soybean oil, tryptophan, and sucrose, more preferably the glucose. The organic carbon source solution has a mass concentration of preferably 0.25 g/mL to 0.35 g/mL, more preferably 0.30 g/mL. A solvent in the organic carbon source solution is preferably deionized water and/or ethanol. In the present disclosure, the hydrothermal reaction is conducted at preferably 160° C. to 180° C., more preferably 165° C. to 175° C., and most preferably 170° C. for preferably 10 h to 13 h, more preferably 11 h to 12 h. In the present disclosure, an obtained hydrothermal reaction product is preferably subjected to washing and drying. There is no special limitation on parameters of the washing and drying, as long as the hydrothermal reaction product can be fully washed and dried. In the present disclosure, after the mixed crystal-type titanium dioxide nanotube/titanium substrate composite is subjected to the impregnation and hydrothermal reaction in the organic carbon solution, organic carbon in the organic carbon solution forms the graphitic carbon and is loaded on the titanium dioxide nanowires. This increases a conductivity of the composite for electrocatalysis, thereby further increasing an electrocatalytic activity of the composite for electrocatalysis. The present disclosure further provides use of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis or a graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis prepared by the preparation method in degradation of an organic pollutant by electrocatalysis. In the present disclosure, the organic pollutants include preferably one or more of methyl blue, methyl blue, and methyl orange. In the present disclosure, the use preferably includes the following steps:placing the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis as an anode and a platinum electrode as a cathode in an aqueous solution of the organic pollutant, and conducting electrification for the degradation by electrocatalysis. In the present disclosure, the anode and the cathode have a distance of preferably 5 cm to 10 cm. The degradation by electrocatalysis is conducted at preferably 40 V to 80V. In the present disclosure, the aqueous solution of the organic pollutant has a salinity of preferably 1,000 mg/L. The following describes in detail the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis, and the preparation method and the use thereof provided by the present disclosure with reference to the examples which, however, are not to be construed as limiting the scope of protection of the present disclosure. Example 1 A preparation method of a graphitic carbon-doped and mixed crystal-type titanium dioxide nanomesh composite for electrocatalysis included the following steps:(1) Pretreatment of titanium mesh (with a purity of 98%, 200 mesh): a pure titanium mesh was placed in beakers containing propanol, methanol, and isopropanol in sequence, and ultrasonically cleaned in an ultrasonic cleaner for 10 min, after taking out, the titanium mesh was further ultrasonically cleaned with deionized water for 5 min, and blow-dried for later use; the titanium mesh was ultrasonically cleaned for 2 min using a mixed acid (HF: glacial acetic acid=1:8), to remove an external oxide film; and the titanium mesh was washed with the deionized water and ethanol each for 3 min in sequence, dried and sealed.(2) A Pt sheet (purity 98%) was used as a cathode, and the titanium mesh with a smooth surface pretreated in step (1) was used as an anode, where a distance between the two electrodes was 7 cm, and anodic oxidation was conducted in an electrolyte containing an ethylene glycol solution including 0.5 wt % NH4F and 3 vol % H2O; the whole anodic oxidation was conducted by constant-temperature magnetic stirring, at 25° C. and 60 V for 120 min; the anode was transferred in an ethanol solution, and dried to obtain a titanium dioxide nanotube array/titanium substrate composite.(3) The titanium dioxide nanotube array/titanium substrate composite was placed in a muffle furnace, heated to 550° C. at 10° C./min in an air atmosphere, kept for 2 h, and cooled with the furnace to obtain a mixed crystal-type titanium dioxide nanotube/titanium substrate composite.(4) A glucose powder was weighed and completely dissolved in deionized water to obtain a glucose solution with a glucose concentration of 0.3 g/mL, and the glucose solution was transferred into a hydrothermal reaction kettle; the mixed crystal-type titanium dioxide nanotube/titanium substrate composite obtained in step (3) was immersed into the glucose solution, and the hydrothermal reaction kettle was heated in a blast drying oven at 170° C. for 12 h; the composite was taken out, cleaned, and dried to obtain a composite for electrocatalysis, namely the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis (C—TiO2); where a mass of graphitic carbon particles was 5% of a mass of the titanium dioxide nanowires. FIG.1shows an XRD spectrum of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis. It can be seen fromFIG.1that by comparing with a spectrum standard card of a rutile phase and an anatase phase, it can be known that the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis is composed of the rutile phase and the anatase phase; and graphitic carbon XRD diffraction peaks can also be clearly seen. FIG.2shows an XPS scanning image of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis. It can be seen fromFIG.2that a surface of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis mainly includes three elements Ti, O and C, and a C is peak exists with a peak height significantly higher than a carbon peak of a test pollutant. This confirms the existence of C in the sample, namely the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis. FIG.3andFIG.4show SEM images of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis at different magnifications. It can be seen fromFIG.3andFIG.4that the titanium dioxide nanowires are woven into a nanomesh structure, and the titanium dioxide nanowires are loaded with graphitic carbon nanoparticles. FIG.5shows an EDS layered image of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis;FIG.6shows a mapping diagram of C element distribution; andFIG.7shows a TEM image of the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis. It can be seen fromFIG.5toFIG.7that the surface of the sample mainly includes three elements Ti, O and C, with an extremely uniform distribution, indicating that the sample has C, namely the graphitic carbon-doped and mixed crystal-type titanium dioxide nanotube composite for electrocatalysis. Comparative Example 1 Only steps (1) to (3) of Example 1 were repeated to prepare a pure TiO2nanotube mesh array (referred to as TiO2). Use of an obtained catalytic material in degradation of an organic dye methyl blue by electrocatalysis specifically included the following steps: 50 mL of a methyl blue solution with a concentration of 12 mg/L was used as an electrolyte, the catalytic materials in Example 1 and Comparative Example 1 were used as an anode separately, and a platinum electrode was used as a cathode; electrocatalysis was conducted with an electrode spacing of 1.1 cm, at a current of 0.3 A and a solution salinity of 6,000 mg/L; at room temperature, a supernatant was collected every 30 min to measure an absorbance using a UV-Vis spectrophotometer, a concentration was calculated according to an F factor, and a degradation rate curve was drawn. The results are shown inFIG.8, corresponding to the TiO2. Example 2 Repeated Experiment The C—TiO2in Example 1 was taken out after 150 min of electrocatalytic test, placed in deionized water for 5 min, and dried to obtain C—TiO2—B for a secondary electrocatalytic test: 50 mL of a methyl blue solution with a concentration of 12 mg/L was used as an electrolyte, the C—TiO2—B was used as an anode, and a platinum electrode was used as a cathode; electrocatalysis was conducted with an electrode spacing of 1.1 cm, at a solution salinity of 6,000 mg/L; at room temperature, a supernatant was collected every 30 min to measure an absorbance using a UV-Vis spectrophotometer, a concentration was calculated according to an F factor, and a degradation rate curve was drawn. The results are shown inFIG.8, corresponding to the C—TiO2—B. It can be seen fromFIG.8that a degradation rate of methyl blue by electrocatalysis is 98.02%, showing that the C—TiO2has a significantly higher electrocatalytic effect than the pure TiO2nanotube network array; compared with the primary electrocatalytic test, the degradation rate of methyl blue solution does not decrease at 150 min, indicating that the carbon-doped titanium dioxide nanotube composite for electrocatalysis has a relatively desirable reusable effect. The above descriptions are merely preferred implementations of the present disclosure. It should be noted that a person of ordinary skill in the art may further make several improvements and modifications without departing from the principle of the present disclosure, but such improvements and modifications should be deemed as falling within the protection scope of the present disclosure.
17,399
11857953
When describing the simplified schematic illustrations ofFIGS.1-2, the numerous valves, temperature sensors, electronic controllers, and the like, which may be used and are well known to a person of ordinary skill in the art, may not be included. Further, accompanying components that are often included in systems such as those depicted inFIGS.1-2, such as air supplies, heat exchangers, surge tanks, and the like also may not be included. However, a person of ordinary skill in the art understands that these components are within the scope of the present disclosure. Additionally, the arrows in the simplified schematic illustrations ofFIGS.1-2refer to process streams. However, the arrows may equivalently refer to transfer lines, which may transfer process streams between two or more system components. Arrows that connect to one or more system components signify inlets or outlets in the given system components and arrows that connect to only one system component signify a system outlet stream that exits the depicted system or a system inlet stream that enters the depicted system. The arrow direction generally corresponds with the major direction of movement of the process stream or the process stream contained within the physical transfer line signified by the arrow. The arrows in the simplified schematic illustration ofFIGS.1-2may also refer to process steps of transporting a process stream from one system component to another system component. For example, an arrow from a first system component pointing to a second system component may signify “passing” a process stream from the first system component to the second system component, which may comprise the process stream “exiting” or being “removed” from the first system component and “introducing” the process stream to the second system component. Reference will now be made in greater detail to various aspects, some of which are illustrated in the accompanying drawing. DETAILED DESCRIPTION The present disclosure is directed to methods for making boronated zeolite catalysts and processes for cracking butene-containing streams to produce light olefins, such as ethylene and propylene. The methods of making the boronated zeolite catalysts can include preparing an initial slurry comprising water, a shape selective zeolite, boric acid, and a weak acid selected from the group consisting of oxalic acid, citric acid, or oxalic acid and citric acid; hydrothermally treating the initial slurry at a temperature of from 70° C. to 90° C. to produce a hydrothermally treated slurry comprising dealuminated zeolite particles; adjusting the pH of the hydrothermally treated slurry to an intermediate pH of from 8 to 9 to produce a basic slurry; hydrothermally treating the basic slurry at a temperature of from 70° C. to 90° C. to produce a boronated zeolite slurry; removing liquids from the boronated zeolite slurry to produce a boronated zeolite filtrate; washing the boronated zeolite filtrate, and drying and calcining the boronated zeolite filtrate to produce the boronated zeolite catalyst. The processes of the present disclosure for converting mixed butenes to light olefins can include contacting a butene-containing stream with the boronated zeolite catalyst in a reactor, wherein contacting causes at least a portion of the mixed butenes to undergo cracking reactions to form a product stream comprising ethylene and propylene. The methods of making the boronated zeolite catalyst of the present disclosure can enable a one-pot dealuminati on and boronation of zeolite particles, reducing the number of drying and calcination steps required to form the boronated zeolite catalyst. The boronated zeolite catalysts of the present disclosure can enable efficient cracking of butene-containing streams, among other features. As used in the present disclosure, the term “cracking” refers to a chemical reaction where a molecule having carbon-carbon bonds is broken into more than one molecule by the breaking of one or more of the carbon-carbon bonds. As used in the present disclosure, the term “catalytic cracking” refers to cracking conducted in the presence of a catalyst. Some catalysts may have multiple forms of catalytic activity, and calling a catalyst by one particular function does not render that catalyst incapable of being catalytically active for other functionality. As used in the present disclosure, the term “catalyst” refers to any substance that increases the rate of a specific chemical reaction, such as cracking reactions. As used throughout the present disclosure, the terms “butenes” or “mixed butenes” may be used interchangeably and may refer to combinations of one or a plurality of isobutene, 1-butene, trans-2-butene, or cis-2-butene. As used throughout the present disclosure, the term “normal butenes” may refer to a combination of one or a plurality of 1-butene, trans-2-butene, or cis-2-butene. As used throughout the present disclosure, the term “2-butenes” may refer to trans-2-butene, cis-2-butene, or a combinations of these. As used throughout the present disclosure, the term “C4” may be used to refer to compositions or streams comprising compounds having 4 carbon atoms, the term “C4+” may be used to refer to compositions or streams comprising compounds having 4 or more than 4 carbon atoms, and the term “C5+” may be used to refer to compositions or streams comprising compounds having 5 or more than 5 carbon atoms. The term “time on-stream” refers to the amount of time that the reaction system is operated with a flow of reactants at reaction conditions. In particular, the “time on-stream” refers to the amount of time that the catalyst, such as the boronated zeolite catalyst, is maintained in contact with the flow of the reactants, such as the butenes in the butene-containing stream, at the reaction conditions, such as at the reaction temperature. As used in the present disclosure, the term “reactor” refers to any vessel, container, conduit, or the like, in which a chemical reaction, such as catalytic cracking, occurs between one or more reactants optionally in the presence of one or more catalysts. A reactor can include one or a plurality of “reaction zones” disposed within the reactor. The term “reaction zone” refers to a region in a reactor where a particular reaction takes place. It should be understood that components of a stream are disclosed as passing from one system component to another when a stream comprising that component is disclosed as passing from that system component to another. For example, a disclosed “butene-containing stream” passing to a first system component or from a first system component to a second system component should be understood to equivalently disclose “butenes” passing to the first system component or passing from a first system component to a second system component. The composition of cracking catalysts used in catalytic cracking play a significant role on reaction yields from catalytic cracking. Boronated zeolite catalysts can be used as cracking catalysts for catalytically cracking hydrocarbons. Conventional methods for producing cracking catalysts comprising boronated zeolites require costly preparation, such as requiring multiple drying and calcination steps. These additional processing steps are energy intensive and increase the economic cost of preparing the cracking catalysts, which increase the cost of producing light olefins, such as ethylene, propylene, or both, from a hydrocarbon feed. Accordingly, aspects of the present disclosure are directed to methods of making a cracking catalyst comprising a boronated zeolite and processes for cracking butene-containing streams to form product streams comprising ethylene and propylene with the cracking catalyst. The method for preparing the boronated zeolite can include preparing an initial slurry comprising water, a shape selective zeolite, boric acid, and a weak acid; hydrothermally treating the initial slurry to produce a hydrothermally treated slurry comprising dealuminated zeolite particles; adjusting the pH of the hydrothermally treated slurry to an intermediate pH of from 8 to 9 to produce a basic slurry; hydrothermally treating the basic slurry at a temperature of from 70° C. to 90° C. to produce a boronated zeolite slurry; recovering the boronated zeolite; and calcining the boronated zeolite catalysts. In embodiments, the methods of the present disclosure can include preparing an initial slurry comprising water, a shape selective zeolite, boric acid, and a weak acid selected from the group consisting of oxalic acid, citric acid, and oxalic acid and citric acid. The initial slurry can be prepared by combining the water, boric acid, and the weak acid to form a solution. The shape selective zeolite can then be added to the solution to form the initial slurry. In embodiments, the initial slurry can have a pH of from 1 to 5. Shape selective zeolites can be active to catalytically crack hydrocarbon compounds, such as mixed butenes or other olefins, to produce one or more lighter olefins, such as ethylene, propylene, or both. Without being bound by any particular theory, it is believed that the shape selective zeolite may have a greater propensity to crack the relatively lighter hydrocarbons, such as mixed butenes and other olefins, compared to other types of zeolites, such as large pore zeolite s. The shape selective zeolite can be an MFI structured zeolite. In embodiments, the shape selective zeolite is ZSM-5 zeolite. As used in the present disclosure, “ZSM-5” refers to zeolites having an MFI framework type according to the IUPAC zeolite nomenclature and consisting of silica and alumina. ZSM-5 refers to “Zeolite Socony Mobil-5” and is a pentasil family zeolite that can be represented by the chemical formula NanAlnSi96-nO192·16H2O, where 0<n<27. In embodiments, the molar ratio of silica to alumina in the shape selective zeolite of the initial slurry can be greater than or equal to 15, greater than or equal to 50, greater than or equal to 100, greater than or equal to 200 or even greater than or equal to 250. In embodiments, the molar ratio of silica to alumina in the shape selective zeolite of the initial slurry can be from 15 to 800, from 15 to 400, from 15 to 300, from 15 to 200, from 15 to 100, from 15 to 50, from 50 to 800, from 50 to 400, from 50 to 300, from 100 to 800, from 100 to 400, from 100 to 300, from 200 to 800, from 200 to 400, from 200 to 300, from 250 to 800, from 250 to 400, or from 250 to 300. Conventional methods of boronating zeolites have been limited to lower silica to alumina ratios, because increasing the silica to alumina molar ratio decreases the proportion of alumina, which makes it difficult to dealuminate the zeolite. The methods of the present disclosure may enable a shape selective zeolite with a greater silica to alumina molar ratio to be used as the starting zeolite compared to conventional methods of boronating zeolites. In particular, the methods of the present disclosure may increase an amount of dealumination of the zeolite and increase an amount of boron deposition, while improving catalytic cracking activity compared to conventional methods of preparing boronated zeolites. In embodiments, the initial slurry can include less than or equal to 20 wt. % shape selective zeolite based on the total weight of the initial slurry. In embodiments, the initial slurry can include less than or equal to 15 wt. %, or less than or equal to 10 wt. % shape selective zeolite based on the total weight of the initial slurry. In embodiments, the initial slurry can include the shape selective zeolite in an amount of from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, or from 12 wt. % to 14 wt. %, based on the total weight of the initial slurry. In embodiments, the initial slurry can include less than or equal to 1 wt. %, less than or equal to 0.5 wt. %, or less than or equal to 0.1 wt. % boric acid based on the total weight of the initial slurry. In embodiments, the initial slurry can include boric acid in an amount of from 0.01 wt. % to 1 wt. %, from 0.01 wt. % to 0.5 wt. %, from 0.01 wt. % to 0.3 wt. %, from 0.01 wt. % to 0.2 wt. %, or from 0.01 wt. % to 0.1 wt. %, based on the total weight of the initial slurry. In embodiments, the initial slurry can include a weak acid selected from the group consisting of oxalic acid, citric acid, and oxalic acid and citric acid. In embodiments, the weak acid is oxalic acid. In embodiments, the weak acid is citric acid. In embodiments, the initial slurry can include less than or equal to 1 wt. % of the weak acid based on the total weight of the initial slurry. In embodiments, the initial slurry can include the weak acid in an amount of from 0.01 wt. % to 1 wt. %, from 0.01 wt. % to 0.5 wt. %, from 0.01 wt. % to 0.3 wt. %, or from 0.01 wt. % to 0.2 wt. % based on the total weight of the initial slurry. Without intending to be bound by any particular theory, it is believed that an initial slurry having greater than 1 wt. % of the weak acid may result in greater extent of dealumination of the zeolite, increasing the silica to alumina ratio of the dealuminated zeolite particles to a value greater than desired. In embodiments, hydrothermally treating the initial slurry can include heating the initial slurry to a temperature of from 70° C. to 90° C. for a duration of time to produce a hydrothermally treated slurry. In embodiments, the initial slurry can be hydrothermally treated for a duration of time from 12 hours to 36 hours. In embodiments, the initial slurry can be hydrothermally treated for about 24 hours. Hydrothermally treating the initial slurry can remove at least a portion of aluminum from the shape selective zeolite. In embodiments, the method can further comprise allowing the hydrothermally treated slurry to return to room temperature after hydrothermally treating the initial slurry. Without intending to be bound by any particular theory, it is believed that the removal of aluminum from the framework can lead to a decrease in the number of sites where framework hydrolysis can occur under hydrothermal and thermal conditions. This removal of aluminum results in an increased thermal and hydrothermal stability in dealuminated zeolites. The unit cell size can decrease as a result of dealumination, since the smaller SiO4tetrahedron replaces the larger AlO4— tetrahedron. The acidity of zeolites can also be affected by dealuminati on through the removal of framework aluminum and the formation of extra-framework aluminum species. Dealumination may affect the acidity of the zeolites by decreasing the total acidity and increasing the acid strength of the zeolite. The total acidity can decrease because of the removal of framework aluminum, which act as Brønsted acid sites. The acid strength of the zeolite may be increased because of the removal of paired acid sites or the removal of the second coordinate next nearest neighbor aluminum. The increase in the acid strength may be caused by the charge density on the proton of the OH group being highest when there is no framework aluminum in the second coordination sphere. In embodiments, the method does not include steaming to dealuminate the zeolite. In embodiments, the hydrothermally treated slurry, which can comprise at least the dealuminated zeolite, water, and boric acid, may not be actively dried or calcined before adjusting the pH to the intermediate pH. As used in this disclosure, “actively dried” refers to taking an active step, such as but not limited to applying heat, gas flow, or vacuum to the dealuminated zeolite, to increase a rate of mass transfer of solvents, such as water, out of the dealuminated zeolite. Without intending to be bound by any particular theory, it is believed that the lack of actively drying and calcining the hydrothermally treated slurry can reduce the economic cost of preparing the boronated zeolite catalyst. In embodiments, adjusting the pH of the hydrothermally treated slurry may include adding a base to the hydrothermally treated slurry to adjust the pH to an intermediate pH of from 8 to 9 to produce a basic slurry. In embodiments, the base can include any base capable of adjusting the pH to the intermediate pH of from 8 to 9. The base can be a hydroxide compound, such as but not limited to an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonium hydroxide, or combinations of these. In embodiments, the base can include ammonium hydroxide. Using ammonium hydroxide as the base can reduce or eliminate the presence of alkali or alkaline earth metal ions in the basic slurry, which can reduce the number of steps needed to prepare the boronated zeolite catalyst, increase the yield of the boronated zeolite catalyst, or both compared to using alkali or alkaline earth metal hydroxides. In embodiments, the base may be added stepwise to the hydrothermally treated slurry, and the pH of the hydrothermally treated slurry may be monitored during addition of the base until the pH is from 8 to 9, at which point addition of the base may be ceased. The methods disclosed herein can include hydrothermally treating the basic slurry at a temperature and for a duration sufficient to deposit boron within the framework and onto the surfaces of the dealuminated zeolite to produce a boronated zeolite. In embodiments, hydrothermally treating the basic slurry may include heating the basic slurry to a temperature of from 70° C. to 90° C. for a duration of time to produce a boronated zeolite slurry comprising the boronated zeolite. In embodiments, the basic slurry can be hydrothermally treated for a duration of time from 12 hours to 36 hours. In embodiments, the basic slurry can be hydrothermally treated for about 24 hours. In embodiments, hydrothermally treating the basic slurry can deposit boron in the dealuminated zeolite to produce the boronated zeolite slurry comprising boronated zeolite. In embodiments, the method can further comprise allowing the boronated zeolite slurry to return to room temperature after hydrothermally treating the basic slurry. In embodiments, removing liquids from the boronated zeolite slurry may include removing at least a portion of the liquids, such as water, from the boronated zeolite slurry to produce a boronated zeolite filtrate. Processes for removing the liquids from the boronated zeolite can include, but are not limited to filtration, decanting, centrifugation, other solid-liquid separation methods, or combinations of these. In embodiments, the boronated zeolite filtrate can be washed. The boronated zeolite filtrate can be washed with an aqueous solution, such as water, to remove at least a portion of ionic constituents in the boronated zeolite filtrate. In embodiments, the boronated zeolite filtrate can be washed with deionized water. The boronated zeolite filtrate can be washed with water a plurality of times to remove constituents of the boronated zeolite slurry and other contaminants from the surfaces of the boronated zeolite filtrate. Washing the boronated zeolite filtrate to remove reagents and other contaminants can reduce the pH of the boronated zeolite filtrate closer to neutral pH. Following washing the boronated zeolite filtrate with an aqueous solution, the methods of the present disclosure can further include removing residual liquids from the boronated zeolite filtrate. The residual liquids can include the water used to wash the boronated zeolite filtrate. In embodiments, removing liquids from the boronated zeolite filtrate can include evaporating the liquids from the boronated filtrate. In embodiments, the boronated zeolite filtrate can be heated, subjected to reduced pressure such as in a vacuum chamber, or both, to remove the liquids through evaporation. In embodiments, the boronated filtrate can be heated in an oven at an elevated temperature, such as about 90° C., for a duration of time sufficient to produce a solid powder. In embodiments, the drying time may be from 1 hour to 24 hours. Following drying, the boronated zeolite filtrate can be calcined to produce the boronated zeolite catalyst. In embodiments, calcining the boronated zeolite filtrate can include heating the filtrate to a temperature of from 550° C. to 700° C. for a duration of time sufficient to produce the boronated zeolite catalyst. In embodiments, the time of calcining can include a range of 30 minutes to 10 hours. In embodiments, the boronated zeolite catalyst can comprise greater than or equal to 3 wt. %, greater than or equal to 5 wt. %, or even greater than or equal to 10 wt. % boron based on the total weight of the boronated zeolite catalyst. In embodiments, the boronated zeolite catalyst can comprise boron in an amount of from 3 wt. % to 15 wt. %, from 3 wt. % to 10 wt. %, from 5 wt. % to 15 wt. %, or from 5 wt. % to 10 wt. % based on the total weight of the boronated zeolite catalyst. Without intending to be bound by any particular theory, it is believed that the inclusion of boron in the boronated zeolite catalyst in an amount of greater than or equal to 3 wt. % may reduce a hydride transfer reaction rate, lowering the aromatization activity of the catalyst, compared to zeolites with less than 3 wt. % boron. Decreasing the aromatization activity can increase yield and selectivity of light olefins, such as ethylene, propene, or both. Without intending to be bound by any particular theory, it is believed that greater than 15 wt. % boron in the boronated zeolite catalyst can significantly decrease the acidity of the catalyst, which can reduce the cracking activity of the catalyst. In embodiments, the boron can be disposed on the boronated zeolite catalyst in tetrahedral and trigonal planar sites within a framework of the zeolite. In embodiments, the boron can be disposed on the zeolite in trigonal planar extra-framework sites of the boronated zeolite catalyst. Without intending to be bound by any particular theory, it is believed that boron disposed on the zeolite in trigonal planar extra-framework sites can reduce coke formation on the boronated zeolite catalyst and reduce the hydride transfer reaction rate, both of which can increase the cracking activity of the catalyst. In embodiments, the molar ratio of silica to alumina in the boronated zeolite catalyst, after synthesizing the boronated zeolite catalyst, can be greater than or equal to 20, greater than or equal to 50, greater than or equal to 100, greater than or equal to 200, or even greater than or equal to 250. In embodiments, the molar ratio of silica to alumina in the boronated zeolite catalyst can be from 20 to 1600, from 20 to 800, from 20 to 400, from 20 to 300, from 20 to 200, from 20 to 100, from 20 to 50, from 50 to 1600, from 50 to 800, from 50 to 400, from 50 to 300, from 100 to 1600, from 100 to 800, from 100 to 400, from 100 to 300, from 200 to 1600, from 200 to 800, from 200 to 400, from 200 to 300, from 250 to 1600, from 250 to 800, from 250 to 400, from 250 to 300, from 300 to 1600, from 300 to 800, from 300 to 400, or from 350 to 400. Without intending to be bound by any particular theory, it is believed that a molar ratio of silica to alumina in the boronated zeolite catalyst of less than 20 may not result in an effective pore volume and thus may reduce the activity of the boronated zeolite catalyst in in cracking reactions. It is believed that a molar ratio of silica to alumina in the boronated zeolite catalyst greater than 1600 can cause a reduction in cracking activity due to a reduced number of solid acid sites. In embodiments, the boronated zeolite catalyst can have an average surface area of greater than or equal to 500 m2/g, or an average surface area of greater than or equal to 525 m2/g. In embodiments, the boronated zeolite catalyst can have an average surface area of from 500 m2/g to 800 m2/g, from 500 m2/g to 700 m2/g, or from 500 m2/g to 600 m2/g. In embodiments, the boronated zeolite catalyst can have an average microporous pore volume of greater than or equal to 0.15 cubic centimeters per gram (cm3/g). In embodiments, the boronated zeolite catalyst can have an average microporous pore volume of from 0.15 cm3/g to 0.600 cm3/g. In embodiments, the boronated zeolite catalyst can have a crystallinity of greater than or equal to 90%, greater than or equal to 92%, greater than or equal to 94%, or even greater than or equal to 95% of the crystallinity of the initial zeolite material from which the boronated zeolite catalyst may be formed. Greater crystallinity can impart increased stability to the zeolite, especially when exposed to elevated temperatures such as those in catalytic processes. The crystallinity may be measured with XRD (X-ray Diffraction). A commercialized and relatively well-crystallized ZSM-5 zeolite (for example, CBV-2804 from Zeolyst International) may be taken as the reference at 100% crystallinity. From XRD spectra, the five most intensive peaks are integrated. The sample relative crystallinity is calculated based on the following equation: X(%)=100%×ΣA/ΣA0, where A is the sum of the five peak total area of the fabricated samples; A0is the sum of the five peak total area of the reference sample (for example, CBV-2804). Without intending to be bound by any particular theory, it is believed that the mild acidic conditions during hydrothermally treating the initial slurry, and/or the mild basic conditions during hydrothermally treating the basic slurry, can produce the highly crystalline boronated zeolite catalyst. As previously discussed, the boronated zeolite catalyst of the present disclosure can be used in a process for catalytically cracking mixed butenes and other olefins to produce propylene, ethylene, or both. As previously discussed, the process for catalytically cracking olefins to produce propylene, ethylene, or both can include providing a butene-containing stream comprising at least mixed butenes as a feed stream and then contacting the feed stream with the boronated zeolite catalyst of the present disclosure under reaction conditions sufficient to catalytically crack at least a portion of the mixed butenes or other olefins in the feed stream to produce propylene, ethylene, or both. The feed stream can comprise one or more olefins, such as mixed butenes, mixed pentenes, mixed hexenes, or other olefins. The feed stream can comprise at least mixed butenes, such as but not limited to 1-butene, cis-2-butene, trans-2-butene, isobutene, or combinations of these. In embodiments, the feed stream can be a C4 stream, which can include mixed butenes as well as other C4 compounds, such as but not limited to butane, isobutane, 1,3-butadiene, or combinations of these. In embodiments, the feed stream can be a C4 stream recovered from a steam cracking process, from a fluidized catalytic cracking process, or from both. In embodiments, the feed stream can comprise, consist of, or consist essentially of 1-butene, 2-butenes, isobutane, and n-butane, where the 2-butenes comprise cis-2-butene, trans-2-butene, or both. In embodiments, the feed stream can comprise 1-butene. In embodiments, the feed stream can comprise from 12.5 wt. % to 50 wt. % 1-butene based on the total mass flow rate of the feed stream. In embodiments, the feed stream can comprise from 12.5 wt. % to 45 wt. %, from 12.5 wt. % to 40 wt. %, from 20 wt. % to 50 wt. %, from 20 wt. % to 45 wt. %, from 20 wt. % to 40 wt. %, from 25 wt. % to 50 wt. %, from 25 wt. % to 45 wt. %, from 25 wt. % to 40 wt. %, from 30 wt. % to 50 wt. %, from 30 wt. % to 45 wt. %, from 30 wt. % to 40 wt. %, or from 40 wt. % to 50 wt. % 1-butene based on the total mass flow rate of the feed stream. In embodiments, the feed stream can comprise 2-butenes, including cis-2-butene, trans-2-butene, or both. In embodiments, the feed stream can comprise from 12.5 wt. % to 30 wt. % 2-butenes based on the total mass flow rate of the feed stream. In embodiments, the feed stream can comprise from 12.5 wt. % to 25 wt. %, from 12.5 wt. % to 20 wt. %, from 12.5 wt. % to 15 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %, or from 20 wt. % to 25 wt. % 2-butenes based on the total mass flow rate of the feed stream. In embodiments, the feed stream can comprise isobutane. In embodiments, the feed stream can comprise from 15 wt. % to 30 wt. % isobutane based on the total mass flow rate of the feed stream. In embodiments, the feed stream can comprise from 15 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %, or from 20 wt. % to 25 wt. % isobutane based on the total mass flow rate of the feed stream. In embodiments, the feed stream can comprise n-butane. In embodiments, the feed stream can comprise from 5 wt. % to 55 wt. % n-butane based on the total mass flow rate of the feed stream. In embodiments, the feed stream can comprise from 5 wt. % to 50 wt. %, from 5 wt. % to 45 wt. %, from 5 wt. % to 40 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 55 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 45 wt. %, from 10 wt. % to 40 wt. %, from 20 wt. % to 55 wt. %, from 20 wt. % to 50 wt. %, from 20 wt. % to 45 wt. %, from 20 wt. % to 40 wt. %, from 30 wt. % to 55 wt. %, from 30 wt. % to 50 wt. %, from 30 wt. % to 45 wt. %, from 30 wt. % to 40 wt. %, or from 40 wt. % to 55 wt. % n-butane based on the total mass flow rate of the feed stream. The feed stream can also include other C4 constituents, such as but not limited to isobutene, 1,3-butadiene, or other C4 compounds. If present, the 1,3-butadiene concentration in the feed stream can be less than or equal to 0.1 wt. % 1,3-butadiene based on the total mass flow rate of the feed stream. In embodiments, the feed stream to the catalytic cracking process can be an effluent from a metathesis reactor for converting mixed butenes to propylene, ethylene, or both through one or more metathesis reactions. When the feed stream is an effluent from a metathesis reactor, the feed stream can further include greater molecular weight olefins, such as mixed pentenes, mixed hexenes, or other greater molecular weight olefins resulting from metathesis of mixed butenes. The feed stream can also include propylene, ethylene, or both produced from the metathesis reactions. When the feed stream is an effluent from a metathesis reactor, the feed stream can also include other reaction products resulting from the metathesis reactions. The feed stream generally does not include nitrogen or air. Without intending to be bound by any particular theory, it is believed that the presence of nitrogen, air, or both can cause side reactions in the cracking reactor resulting in reduced yield of propylene, ethylene, or both. In embodiment, the feed stream is substantially free of nitrogen, air, or both, such as having less than 0.1 wt. % or even less than 0.01 wt. % nitrogen, air, or both based on the total mass flow rate of the feed stream. Referring now toFIG.1, a reactor system10comprising a cracking reactor100for converting the feed stream102comprising at least mixed butenes to propylene, ethylene, or both is schematically depicted. The feed stream102is passed to the cracking reactor100, which comprises at least a cracking reaction zone110comprising the cracking catalyst112. In embodiments, the cracking reactor100can be a fixed bed reactor. Other types of reactors, such as but not limited to moving bed reactors, fluidized bed reactors, and the like can also be used to for the cracking reactor100. Although shown as a downflow reactor inFIG.1, the cracking reactor100can also be an upflow reactor, a horizontal flow reactor, or have any other suitable flow pattern suitable for contacting the feed stream102with the cracking catalyst112. In the cracking reactor100, the feed stream102comprising the mixed butenes can be contacted with the cracking catalyst112at reaction conditions sufficient to cause catalytic cracking of at least a portion of the mixed butenes or other olefins in the feed stream102to produce a cracking effluent120comprising propylene, ethylene, or both. Contact of the mixed butenes or other olefins in the feed stream102with the cracking catalyst112at the reaction conditions can cause at least a portion of the mixed butenes or other olefins to undergo cracking reactions to convert the olefins into propylene, ethylene, or both. The feed stream102can be contacted with the cracking catalyst112in the cracking reaction zone110at a temperature sufficient to cause cracking of the olefins to produce the cracking effluent120comprising propylene, ethylene, or both. In embodiments, the process can include contacting the feed stream102with the cracking catalyst112at a temperature of from 300° C. to 650° C., such as from 300° C. to 600° C., from 300° C. to 550° C., from 300° C. to 500° C., from 350° C. to 650° C., from 350° C. to 600° C., from 350° C. to 550° C., from 350° C. to 500° C., from 400° C. to 650° C., from 400° C. to 600° C., from 400° C. to 550° C., from 400° C. to 500° C., from 450° C. to 650° C., from 450° C. to 600° C., from 450° C. to 550° C., from 500° C. to 600° C., or about 550° C. In embodiments, the feed stream102can be contacted with the cracking catalyst112in the cracking reaction zone110at a pressure of from 1 bar (100 kPa) to 30 bar (3,000 kPa) or from 2 bar (200 kPa) to 20 bar (2,000 kPa). In embodiments, the feed stream102can be contacted with the cracking catalyst112in the cracking reaction zone110at atmospheric pressure. In embodiments, the feed stream102can be contacted with the cracking catalyst112in the cracking reaction zone110at a weight hourly space velocity (WHSV) of from 3 per hour (h−1) to 10,000 h−1, such as from 3 h−1to 5000 h−1, from 3 h−1to 2500 h−1, from 3 h−1to 1000 h−1, from 3 h−1to 100 h−1, from 3 h−1to 12 h−1, from 100 h−1to 5000 h−1, or from 300 h−1to 2500 h−1. The cracking catalyst112may be activated by passing a flow of nitrogen gas through the cracking catalyst112at elevated temperature prior to contacting the feed stream102with the cracking catalyst112in the cracking reaction zone110. In embodiments, the processes of the present disclosure can include, before contacting the feed stream102with the cracking catalyst112, activating the cracking catalyst112with a flow of nitrogen gas at a temperature of from 450° C. to 650° C., or about 550° C. for a period of from 8 hours to 24 hours. The butene-containing stream may be reacted by contact with the boronated zeolite catalyst in the cracking reaction zone, which can cause at least a portion of the butene-containing stream to undergo one or more catalytic cracking reactions to form one or more cracking reaction products, which may include ethylene, propylene, or both. The boronated zeolite catalyst, which may have a temperature equal to or greater than the reaction temperature of the cracking reaction zone, may transfer heat to the butene-containing stream to promote the endothermic cracking reaction. The boronated zeolite catalyst may be operable to crack at least a portion of the butene-containing stream to produce a greater amount of light olefins, such as ethylene and propylene, in comparison to a zeolite without boron. Without intending to be bound by any particular theory, it is believed that the inclusion of boron in the zeolite catalyst can reduce aromatization activity, which can improve the yield of light olefins. Further, the method of forming the boronated ZSM-5 zeolite catalyst described herein can reduce the number of drying and calcining steps required to prepare the catalyst in comparison to boronated ZSM-5 zeolite catalysts formed by conventional methods, which can reduce the economic cost of forming the catalyst. EXAMPLES The various aspects of the present disclosure will be further clarified by the following examples. The examples are illustrative in nature and should not be understood to limit the subject matter of the present disclosure. In the Examples, boronated ZSM-5 zeolite catalysts according to the present disclosure were prepared. The materials used in preparing the boronated ZSM-5 zeolite catalysts of the Examples are provided below in Table 1. TABLE 1ChemicalSupplierBoric acid (≥99%)Sigma AldrichOxalic acid dehydrate (≥99%)Sigma AldrichCitric acid anyhydrous (≥99%)Alfa AesarZSM-5 zeolite (CBV-2804)Zeolyst InternationalAmmonium hydroxide (28-30% NH3)Sigma Aldrich Example 1: Preparation of Boronated ZSM-5 Zeolite Catalysts Using Oxalic Acid To prepare the boronated ZSM-5 zeolite catalyst of Example 1, 4.528 grams (g) of boric acid and 4 g of oxalic acid dihydrate were dissolved in 200 mL of deionized water. 30 g of ZSM-5 zeolite (commercially available as CBV-2804 from Zeolyst International) having a silica-to-alumina ratio of 280 was added to the solution to form an initial slurry. The initial slurry was stirred gently at 80° C. for 24 hours to hydrothermally treat the initial slurry, producing a hydrothermally treated slurry that includes dealuminated ZSM-5 zeolite particles. The hydrothermally treated slurry was allowed to cool to room temperature. After cooling, the pH of the hydrothermally treated slurry was adjusted and monitored by adding a concentrated ammonium hydroxide solution (28-30% NH3) until a desired value of a pH of 8-9 was obtained to produce a basic slurry. The basic slurry was stirred gently at 80° C. for 24 hours to hydrothermally treat the basic slurry and produce a boronated ZSM-5 zeolite slurry. The zeolite was filtered from the boronated ZSM-5 zeolite slurry and washed with deionized water until the pH of the filtrate reached 7. The resulting zeolite was dried on the oven at 90° C. overnight to produce a solid powder. The solid powder was calcined in air at 600° C. for 4 hours at rate of 2° C./min to produce the boronated ZSM-5 zeolite catalyst of Example 1. Example 2: Preparation of Boronated ZSM-5 Zeolite Catalysts Using Citric Acid The boronated ZSM-5 zeolite catalyst of Example 2 was prepared according to the procedure of Example 1 using citric acid anhydrous instead of oxalic acid dehydrate. Specifically, Example 2 was prepared using 4 g of citric acid anhydrous and did not include oxalic acid dihydrate to produce the boronated ZSM-5 zeolite catalyst of Example 2. Example 3: Preparation of Boronated ZSM-5 Zeolite Catalysts Using Citric Acid and a Reduced Amount of Boric Acid The boronated ZSM-5 zeolite catalyst of Example 3 was prepared according to the procedure of Example 2, but the amount of boric acid used was reduced to 1 g to produce the boronated ZSM-5 zeolite catalyst of Example 3. Comparative Example 4: Parent ZSM-5 Zeolite Catalyst The ZSM-5 zeolite of Comparative Example 4 was the parent ZSM-5 zeolite (CBV-2804) used in Examples 1-3 without additional processing. Example 5: Characterization of Boronated ZSM-5 Zeolite Catalysts In Example 5, crystallinity and surface area, and microporous pore volume of the cracking catalysts of Examples 1-3 and Comparative Example 4 were evaluated. The crystallographic structures of the catalysts were obtained using X-ray diffraction (XRD). The relative crystallinity of Examples 1-3 in relation to the crystallinity of the initial zeolite material from which Examples 1-3 were formed was calculated based on the following equation: X(%)=100%×ΣA/ΣA0, where A is the sum of the five peak total area for each of Examples 1-3; and A0is the sum of the five peak total area of the reference sample (Comparative Example 4). The percent crystallinity of the catalysts of Examples 1-3 with respect to the parent zeolite (Comparative Example 4) is reported in Table 2. As shown by the crystallinity data in Table 2, the boronated zeolites of Examples 1-3 have similar crystallinity compared to the parent zeolite (Comparative Example 4). Surface area, pore volume, average pore size, and pore size distribution may be measured by N2adsorption isotherms performed at 77 Kelvin (K) (such as with a Micrometrics ASAP 2020 system). As would be understood by those skilled in the art, Brunauer, Emmett, and Teller (BET) analysis methods may be utilized to calculate the surface area, and the Barrett, Joyner and Halenda (BJH) calculation may be used to determine pore volume and pore size distribution. The surface area and microporous pore volume of the catalysts of Examples 1-3 and Comparative Example 4 are shown in Table 2. As shown in Table 2, the catalysts of Examples 1-3 demonstrated greater surface area and microporous more volume relative to the catalyst of Comparative Example 4. TABLE 2MicroporousSurface Areapore volumeCatalyst% Crystallinity(m2/g)(cc/g)Example 196.65300.155Example 295.35500.160Example 393.75450.158Comparative1004770.140Example 4 Example 6: Boron NMR Characterization of Boronated ZSM-5 Zeolite Catalysts In Example 6, the positions of the boron in the boronated ZSM-5 zeolite catalysts of Examples 1-3 were evaluated by measuring11B magic angle spinning (MAS) nuclear magnetic resonance (NMR) on a Varian 500 MHz nuclear magnetic resonance spectrometer, equipped with a 4 mm solids HX probe. To obtain11B MAS NMR spectra were obtained using a one pulse experiment, a relaxation delay of 3 seconds and a spinning frequency of 13 kHz. The11B chemical shifts were referenced externally to 0.1 M aqueous solution of H3BO3(19.6 ppm). The peak characterizations from11B MAS NMR are shown in Table 3. TABLE 311B MAS11B MAS11B MAS11B MASNMR peak 1NMR peak 2NMR peak 3NMR peak 4(tetrahedral(trigonal(trigonal(trigonalframework)planarplanarplanar extra-shiftframework)framework)framework)Catalyst(ppm)shift (ppm)shift (ppm)shift (ppm)Example 1−3.010.747.0417.45Example 2−2.970.786.8217.24Example 3−2.940.657.0417.34 As can be seen in Table 3, the Examples 1-3 have a first peak of about −3.0 attributed to boron being deposited in the tetrahedral framework position of the ZSM-5 zeolite catalyst. The examples have a second peak of about 0.70 and a third peak of about 7.0, both of which are attributed to boron being deposited within the trigonal planar framework position of the ZSM-5 zeolite catalyst. Further, Examples 1-3 have a fourth peak of about 17.0 attributed to boron being deposited within the trigonal planar extra-framework position of the ZSM-5 zeolite catalyst. Example 7: Catalytic Evaluation of Boronated ZSM-5 Zeolite Catalysts In Example 7, the cracking catalysts of Examples 1-3 and Comparative Example 4 were evaluated by conducting catalyst performance tests using a high-throughput screen reactor system manufactured by the HTE Company. The screen reactor system included 4 individual reactors that are grouped together and isothermally heated so that all the cracking catalysts are tested at the same reaction temperature of 550° C. The cracking catalysts were pressed and then sieved to a particle size of from 210 micrometers to 300 micrometers. Referring now toFIG.2, one reactor300of the screen reactor system for conducting the cracking catalyst evaluation is schematically depicted. Each reactor300includes a reaction chamber302having an inlet304and an outlet306. The cracking catalyst310is placed in the reaction chamber302between two layers of silicon carbide320. For a weight hourly space velocity of 7, the amount of cracking catalyst310for each evaluation was 0.14 grams. The reactor temperature was monitored by thermocouple330placed at three difference locations to ensure isothermal heating across the reactors300. To conduct the evaluation, the reactor was heated to a temperature of 120° C. and maintained at that temperature under a flow of nitrogen and argon for a period of 24 hours to ensure slow moisture desorption from the catalysts. The flowrate of argon was 6 mL/min and the flowrate of the nitrogen was 120 mL/min. The inlet and outlet were monitored to ensure no gas leakage from the system. The cracking catalysts were then activated under a nitrogen flow of 120 mL/min, a temperature of 550° C., and for an activation period of 24 hours. Then, the nitrogen was turned off and a feed stream comprising mixed butenes was fed to the reactor for a period of a few days. The composition of the feed stream comprising mixed butenes is provided in Table 4. The same feed stream was used for all 4 cracking catalysts. The flow rate of the feed stream to each reactor of the screen reactor system was 0.267 grams per minute (g/min). TABLE 4ComponentWt. %1-Butene45Cis-2-butene12.5Trans-2-butene12.5Iso-butane20n-butane10 An Agilent 7890B online gas chromatograph with helium as a carrier gas was used to analyze the products with a thermal conductivity detector (TCD) for light gases and two flame ionization detectors (FID) to identify C1-C6 hydrocarbons. The total olefins yield was determined from the measured compositions. In Example 7, the light olefins yield refers to the yield of propylene and ethylene. The light olefins yield does not include the amount of unreacted butenes. The results from the cracking of the butene-containing stream over the cracking catalysts of Examples 1-3 and Comparative Example 4 over time are shown inFIG.3, which shows the light olefins yield of Comparative Example 4 (ref. no. 350), Example 1 (ref. no. 360), Example 2 (ref no. 370), and Example 3 (ref no. 380), andFIG.4, which shows the light olefins selectivity of Comparative Example 4 (ref no. 450), Example 1 (ref. no. 460), Example 2 (ref. no. 470), and Example 3 (ref. no. 480). The average light olefins yield, average light olefins selectivity, and average percent improvement of light olefins selectivity for each of the cracking catalysts of Examples 1-3 and Comparative Example 4 are provided in Table 5. As can be seen in Table 5, the average light olefins selectivity using the cracking catalysts of Examples 1-3 was greater than the parent ZSM-5 zeolite (Comparative Example 4). TABLE 5Average LightAverage %Average LightOlefinsImprovementOlefins YieldSelectivity(Light OlefinsMaterial(wt. %)(wt. %)Selectivity)Example 143.557.415.7Example 241.351.33.4Example 342.854.08.9Comparative Example 443.049.6— A first aspect of the present disclosure is directed to a method of making a boronated zeolite catalyst, the method comprising preparing an initial slurry comprising water, a shape selective zeolite, boric acid, and a weak acid selected from the group consisting of oxalic acid, citric acid, and oxalic acid and citric acid, where the initial slurry may have an initial pH of from 1 to 5, hydrothermally treating the initial slurry at a temperature of from 70° C. to 90° C. to produce a hydrothermally treated slurry comprising dealuminated zeolite particles, adjusting the pH of the hydrothermally treated slurry to an intermediate pH of from 8 to 9 to produce a basic slurry, after adjusting the pH to the intermediate pH, hydrothermally treating the basic slurry at a temperature of from 70° C. to 90° C. to produce a boronated zeolite slurry, removing liquids from the boronated zeolite slurry to produce a boronated zeolite filtrate, and drying and calcining the boronated zeolite filtrate to produce the boronated zeolite catalyst. A second aspect of the present disclosure may include the first aspect, where hydrothermally treating the initial slurry may comprise stirring the slurry and heating the slurry for a time of from 12 hours to 36 hours. A third aspect of the present disclosure may include either one of the first or second aspects, where hydrothermally treating the initial slurry may remove at least a portion of aluminum from the shape selective zeolite. A fourth aspect of the present disclosure may include any one of the first through third aspects, where the hydrothermally treated slurry is not actively dried or calcined before adjusting the pH to the intermediate pH. A fifth aspect of the present disclosure may include any one of the first through fourth aspects, further comprising, after hydrothermally treating the initial slurry, allowing the hydrothermally treated slurry to return to room temperature. A sixth aspect of the present disclosure may include any one of the first through fifth aspects, where adjusting the pH of the hydrothermally treated slurry may comprise adding ammonium hydroxide to the hydrothermally treated slurry and monitoring the pH of the hydrothermally treated slurry until the pH is from 8 to 9. A seventh aspect of the present disclosure may include any one of the first through sixth aspects, where hydrothermally treating the basic slurry may comprise stirring the basic slurry and heating the basic slurry for a time of from 12 to 36 hours. An eighth aspect of the present disclosure may include any one of the first through seventh aspects, where the boronated zeolite filtrate may be washed before the drying and calcining. A ninth aspect of the present disclosure may include any one of the first through eighth aspects, where calcining the solid powder may comprise heating the solid powder to a temperature of from 500° C. to 700° C. A tenth aspect of the present disclosure may include any one of the first through ninth aspects, where the shape selective zeolite of the initial slurry may have an average silica to alumina molar ratio of from 15 to 800. An eleventh aspect of the present disclosure may include any one of the first through tenth aspects, where the initial slurry may comprise from 5 weight percent to 20 weight percent of the shape selective zeolite, based on the total weight of the initial slurry. A twelfth aspect of the present disclosure may include any one of the first through eleventh aspects, where the shape selective zeolite may be ZSM-5 zeolite. A thirteenth aspect of the present disclosure may include any one of the first through twelfth aspects, where the initial slurry may comprise from 0.01 weight percent to 1 weight percent of the boric acid, based on the total weight of the initial slurry. A fourteenth aspect of the present disclosure may include any one of the first through thirteenth aspects, where the initial slurry may comprise from 0.01 weight percent to 1 weight percent of the weak acid, based on the total weight of the initial slurry. A fifteenth aspect of the present disclosure may include any one of the first through fourteenth aspects, where the method does not include steaming to dealuminate the shape selective zeolite. A sixteenth aspect of the present disclosure may include a boronated zeolite catalyst made by the method of any one of the first through fifteenth aspects, where boron may be disposed at tetrahedral and trigonal planar sites within a framework of the boronated zeolite catalyst, and boron may disposed on the zeolite in trigonal planar extra-framework sites of the boronated zeolite catalyst. A seventeenth aspect of the present disclosure may include the sixteenth aspect, where the boronated zeolite catalyst may comprise from 3 weight percent to 15 weight percent boron, based on the total weight of the boronated zeolite catalyst. An eighteenth aspect of the present disclosure may include any one of the sixteenth or seventeenth aspects, where the boronated zeolite catalyst may have a silica to alumina molar ratio of from 20 to 1600. A nineteenth aspect of the present disclosure may include any one of the sixteenth through eighteenth aspects, where the boronated zeolite catalyst may have an average surface area of greater than or equal to 500 m2/g. A twentieth aspect of the present disclosure may include any one of the sixteenth through nineteenth aspects, where the boronated zeolite catalyst may have an average microporous pore volume of greater than or equal to 0.15 centimeters cubed per gram. A twenty-first aspect of the present disclosure may be directed to a process for cracking a butene-containing stream, the process comprising contacting the butene-containing stream with the boronated zeolite catalyst of any one of the sixteenth through twentieth aspects in a reactor, where contacting may cause at least a portion of butene to undergo cracking reactions to form a product stream comprising ethylene and propylene. A twenty-second aspect of the present disclosure may include the twenty-first aspect, where the butene-containing stream may comprise greater than or equal to 40 wt. % mixed butenes based on the total weight of the butene-containing stream. A twenty-third aspect of the present disclosure may include either the twenty-first or twenty second aspect, where the butene-containing stream may comprise 40 wt. % to 50 wt. % 1-butene, 10 wt. % to 20 wt. % cis-2-butene, 10 wt. % to 20 wt. % trans-2-butene, and 15 wt. % to 30 wt. % isobutane, based on the total weight of the butene-containing stream. A twenty-fourth aspect of the present disclosure may include any one of the twenty-first through twenty-third aspects, where a temperature of the reactor during the contacting may be from 300° C. to 650° C. It is noted that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. It is noted that one or more of the following claims utilize the term “where” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.” Having described the subject matter of the present disclosure in detail and by reference to specific aspects, it is noted that the various details of such aspects should not be taken to imply that these details are essential components of the aspects. Rather, the claims appended hereto should be taken as the sole representation of the breadth of the present disclosure and the corresponding scope of the various aspects described in this disclosure. Further, it will be apparent that modifications and variations are possible without departing from the scope of the appended claims.
54,409
11857954
DETAILED DESCRIPTION In this disclosure, a process is described as comprising at least one “step.” It should be understood that each step is an action or operation that may be carried out once or multiple times in the process, in a continuous or discontinuous fashion. Unless specified to the contrary or the context clearly indicates otherwise, multiple steps in a process may be conducted sequentially in the order as they are listed, with or without overlapping with one or more other step, or in any other order, as the case may be. In addition, one or more or even all steps may be conducted simultaneously with regard to the same or different batch of material. For example, in a continuous process, while a first step in a process is being conducted with respect to a raw material just fed into the beginning of the process, a second step may be carried out simultaneously with respect to an intermediate material resulting from treating the raw materials fed into the process at an earlier time in the first step. Preferably, the steps are conducted in the order described. Unless otherwise indicated, all numbers indicating quantities in this disclosure are to be understood as being modified by the term “about” in all instances. It should also be understood that the numerical values used in the specification and claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that any measured data inherently contain a certain level of error due to the limitation of the technique and equipment used for making the measurement. As used herein, the indefinite article “a” or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise. Thus, embodiments comprising “a metal” include embodiments comprising one, two, or more metals, unless specified to the contrary or the context clearly indicates only one metal is included. For the purposes of this disclosure, the nomenclature of elements is pursuant to the version of Periodic Table of Elements as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985). Abbreviations for atoms are as given in the periodic table (Li=lithium, for example). The following abbreviations may be used herein for the sake of brevity: RT is room temperature (and is 23° C. unless otherwise indicated), kPag is kilopascal gauge, psig is pound-force per square inch gauge, psia is pound-force per square inch absolute, and WHSV is weight hourly space velocity, and GHSV is gas hourly space velocity. Abbreviations for atoms are as given in the periodic table (Co=cobalt, for example). The phrases, unless otherwise specified, “consists essentially of” and “consisting essentially of” do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of this disclosure. Additionally, they do not exclude impurities and variances normally associated with the elements and materials used. “Consisting essentially of” a component in this disclosure can mean, e.g., comprising, by weight, at least 80 wt %, of the given material, based on the total weight of the composition comprising the component. For purposes of this disclosure and claims thereto, the term “substituted” means that a hydrogen atom in the compound or group in question has been replaced with a group or atom other than hydrogen. The replacing group or atom is called a substituent. Substituents can be, e.g., a substituted or unsubstituted hydrocarbyl group, a heteroatom, a heteroatom-containing group, and the like. For example, a “substituted hydrocarbyl” is a group derived from a hydrocarbyl group made of carbon and hydrogen by substituting at least one hydrogen in the hydrocarbyl group with a non-hydrogen atom or group. A heteroatom can be nitrogen, sulfur, oxygen, halogen, etc. The terms “hydrocarbyl,” “hydrocarbyl group,” or “hydrocarbyl radical” interchangeably mean a group consisting of carbon and hydrogen atoms. For purposes of this disclosure, “hydrocarbyl radical” is defined to be C1-C100 radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. The term melting point (mp) refers to the temperature at which solid and liquid forms of a substance can exist in equilibrium at 760 mmHg. The term boiling point (bp) refers to the temperature at which liquid and gas forms of a substance can exist in equilibrium at 760 mmHg. “Soluble” means, with respect to a given solute in a given solvent at a given temperature, at most 100 mass parts of the solvent is required to dissolve 1 mass part of the solute under a pressure of 1 atmosphere. “Insoluble” means, with respect to a given solute in a given solvent at a given temperature, more than 100 mass parts of the solvent is required to dissolve 1 mass part of the solute under a pressure of 1 atmosphere. The term “branched hydrocarbon” means a hydrocarbon comprising at least 4 carbon atoms and at least one carbon atom connecting to three carbon atoms. The term “olefinicity” refers to the molar ratio of the sum of olefins to the sum of paraffins detected. The olefinicity increases when the olefin/paraffin molar ratio increases. The olefinicity decreases when the olefin/paraffin molar ratio decreases. The terms “alkyl,” “alkyl group,” and “alkyl radical” interchangeably mean a saturated monovalent hydrocarbyl group. A “cyclic alkyl” is an alkyl comprising at least one cyclic carbon chain. An “acyclic alkyl” is an alkyl free of any cyclic carbon chain therein. A “linear alkyl” is an acyclic alkyl having a single unsubstituted straight carbon chain. A “branched alkyl” is an acyclic alkyl comprising at least two carbon chains and at least one carbon atom connecting to three carbon atoms. Alkyl groups can comprise, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues. The term “Cn” compound or group, where n is a positive integer, means a compound or a group comprising carbon atoms therein at the number of n. Thus, a “Cm to Cn” alkyl means an alkyl group comprising carbon atoms therein at a number in a range from m to n, or a mixture of such alkyl groups. Thus, a C1-C3 alkyl means methyl, ethyl, n-propyl, or 1-methylethyl-. The term “Cn+” compound or group, where n is a positive integer, means a compound or a group comprising carbon atoms therein at the number of equal to or greater than n. The term “Cn-” compound or group, where n is a positive integer, means a compound or a group comprising carbon atoms therein at the number of equal to or lower than n. The term “conversion” refers to the degree to which a given reactant in a particular reaction (e.g., dehydrogenation, hydrogenation, etc.) is converted to products. Thus 100% conversion of carbon monoxide means complete consumption of carbon monoxide, and 0% conversion of carbon monoxide means no measurable reaction of carbon monoxide. The term “selectivity” refers to the degree to which a particular reaction forms a specific product, rather than another product. For example, for the conversion of syngas, 50% selectivity for C1-C4 alcohols means that 50% of the products formed are C1-C4 alcohols, and 100% selectivity for C1-C4 alcohols means that 100% of the products formed are C1-C4 alcohols. The selectivity is based on the product formed, regardless of the conversion of the particular reaction. The term “nanoparticle” means a particle having a largest dimension in the range from 0.1 to 500 nanometers. The term “long-chain” means comprising a straight carbon chain having at least 8 carbon atoms excluding any carbon atoms in any branch that may be connected to the straight carbon chain. Thus, n-octane and 2-octain are long-chain alkanes, but 2-methylheptane is not. A long-chain organic acid is an organic acid comprising a straight carbon chain having at least 8 carbon atoms excluding any carbon atoms in any branch that may be connected to the straight carbon chain. Thus, octanoic acid is a long-chain organic acid, but 6-methylheptanoic acid is not. The term “organic acid” means an organic Bronsted acid capable of donating a proton. Organic acids include, carboxylic acids of any suitable chain length; carbon containing sulfinic, sulfonic, phosphinic, and phosphonic acids; hydroxamic acids, and in some embodiments, amidines, amides, imides, alcohols, and thiols. The term “surfactant” means a material capable of reducing the surface tension of a liquid in which it is dissolved. Surfactants can find use in, for example, detergents, emulsifiers, foaming agents, and dispersants. Detailed description of the nanoparticles and catalyst compositions of this disclosure, including the composition comprising nanoparticles of the first aspect, the process for producing nanoparticles of the second aspect, and the catalyst composition of the third aspect of this disclosure, is provided below. Kernel Characteristics A nanoparticle may be present as a discreet particle dispersed in a media such as a solvent, e.g., a hydrophobic solvent such as toluene in certain embodiments. Alternatively, a nanoparticle may be stacked next to a plurality of other nanoparticles in the composition of this disclosure. A nanoparticle in the nanoparticle composition of this disclosure comprises a kernel which are observable under a transmission electron microscope. The nanoparticle may in certain embodiments further comprises one or more long-chain groups attached to the surface thereof. Alternatively, a nanoparticle may consist essentially of, or consist entirely of a kernel only. A kernel in a nanoparticle can have a largest dimension in a range of from 4 nanometers to 100 nanometers. Kernels may have a near spherical or elongated shape (e.g. rod-shaped). Kernels that are elongated may have an aspect ratio of from 1 to 50, such as from 1.5 to 30, from 2 to 20, from 2 to 10, or from 3 to 8. The aspect ratio is the length of a longer side of the kernel divided by the length of a shorter side of the kernel. For example, a rod-shaped kernel of diameter 4 nm and length of 44 nanometers has an aspect ratio of 11. The kernels of the nanoparticles in the nanoparticle compositions of this disclosure may have a particle size distribution of 20% or less. The particle size distribution is expressed as a percentage of the standard deviation of the particle size relative to the average particle size. For example, a plurality of kernels that have an average size of 10 nanometers and a standard deviation of 1.5 nanometers has a particle size distribution of 15%. The kernels of the nanoparticles in the nanoparticle compositions of this disclosure may have an average particle size of from 4 to 100 nm, such as 4 to 35 nm, or 4 to 20 nm. Particle size distribution is determined by Transmission Electron Microscopy (“TEM”) measurement of nanoparticles deposited on a flat solid surface. The kernels of the nanoparticles in the nanoparticle compositions of this disclosure may be crystalline, semi-crystalline, or amorphous in nature. Kernels are composed of at least one metal element. The at least one metal may be selected from groups Mn, Fe, Co, Zn, Cu, Mo, W, Ag, Y, Sc, alkaline metals, the lanthanide series, group 13, 14, and 15, and combinations thereof. Where the at least one metal element comprises two or more metals, the metals may be designated as M1, M2, and M3, according to the number of metal elements. M1 may be selected from manganese, iron, cobalt, combinations of iron and cobalt at any proportion, combinations of iron and manganese at any proportion, combinations of cobalt with manganese at any proportion, and combinations of iron, cobalt, and manganese at any proportion. In specific embodiments, M1 is a single metal of manganese, cobalt, or iron. Where M1 comprises a binary mixture/combination of cobalt and manganese, cobalt may be present at a higher molar proportion than manganese. Where M1 comprises a binary mixture/combination of iron and manganese, iron may be present at a higher molar proportion than manganese. Without intending to be bound by a particular theory, it is believed that the presence of M1 provides at least a portion of the catalytic effect of the catalyst composition of the third aspect of this disclosure. M2 may be selected from nickel, zinc, copper, molybdenum, tungsten, silver, and combinations thereof. Without intending to be bound by a particular theory, it is believed that the presence of M2 promotes the catalytic effect of M1 in the supported nanoparticle compositions of the first aspect of this disclosure. The presence of M3 in the compositions of this disclosure is optional. If present, M3 may be selected from Y, Sc, lanthanides, and metal elements of Groups 1, 13, 14, or 15, and any combination(s) and mixture(s) of two or more thereof at any proportion. In certain embodiments, M3 is selected from aluminum, gallium, indium, thallium, scandium, yttrium, and the lanthanide series, and combination thereof. In some embodiments, M3 is selected from gallium, indium, scandium, yttrium, and lanthanides, and combinations thereof. Preferred lanthanide are: La, Ce, Pr, Nd, Gb, Dy, Ho, Er, and combinations thereof. Without intending to be bound by a particular theory, it is believed the presence of metal M3 can promote the catalyst effect of the catalyst compositions of the third aspect of this disclosure. The kernels can further comprise oxygen in the form of, e.g., a metal oxide. The presence of a metal oxide can be indicated by the XRD graph of the catalyst composition. By a “metal oxide,” it is meant to include oxide of a single metal, or a combination of two or more metals M1, M2, and/or M3. Suitably the kernel may comprise an oxide of a single metal, or a combination of two or more metals of M1, and/or M2. Suitably the kernel may comprise an oxide of a single metal, or a combination of two or more metals of M1. In at least one embodiment, the catalytic component may comprise one or more of iron oxide, cobalt oxide, manganese oxide, (mixed iron cobalt) oxide, (mixed iron manganese) oxide, mixed (cobalt manganese) oxide, and mixed (cobalt, iron, and manganese) oxide. In at least one embodiment, the kernel may comprise an oxide of a single metal, or a combination of two or more metals of M2 (e.g., yttrium and the lanthanides). The kernel may comprise an oxide of a metal mixture comprising an M1 metal and an M2 metal. The identification of the presence of an oxide phase in a nanoparticle can be conducted by comparing the XRD data of the nanoparticle against an XRD peak database of oxides, such as those available from International Center for Diffraction Data (“ICDD”). The kernel compositions of this disclosure may optionally comprise sulfur. Without intending to be bound by a particular theory, in certain embodiments, the presence of sulfur can promote the catalytic effect of the catalyst composition created from the nanoparticle compositions comprising kernels. The sulfur may be present as a sulfide, sulfate, or other sulfur-containing compound of one or more metals of M1, M2, and/or M3. The kernel compositions of this disclosure may optionally comprise phosphorus. Without intending to be bound by a particular theory, in certain embodiments, the presence of phosphorus can promote the catalytic effect of the catalyst composition created from the nanoparticle compositions comprising kernels. The phosphorus may be present as a phosphide of one or more metals of M1, M2, and/or M3. In specific embodiments, the kernel of a nanoparticle composition of this disclosure consists essentially of M1, M2, M3, oxygen, optionally sulfur, and optionally phosphorus e.g., comprising ≥85, or ≥90, or ≥95, or ≥98, or even ≥99 wt % of M1, M2, M3, oxygen, optionally sulfur, and optionally phosphorus based on the total weight of the kernel. The molar ratios of M2 to M1 (“r1”), M3 to M1 (“r2”), oxygen to M1 (“r3”), sulfur to M1 (“r4”), and phosphorus to M1 (“r5”), in the kernel of a nanoparticle composition of this disclosure are calculated from the aggregate molar amounts of the elements in question. Thus, if M1 is a combination/mixture of two or more metals, the aggregate molar amount of all metals of M1 is used for calculating the ratios. If M2 is a combination/mixture of two or more metals, the aggregate molar amounts of all metals M2 is used for calculating the ratio r1. If M3 is a combination/mixture of two or more metals, the aggregate molar amounts of all metals M3 is used for calculating the ratio r2. The molar ratio of M2 to M1 in the kernel of a nanoparticle composition of this disclosure, r1, can be from r1a to r1b, where r1a and r1b can be, independently, e.g., 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4 or 1.5, as long as r1a<r1b. In some embodiments, r1a=0, r1b=2; such as r1a=0, r1b=0.5; or r1a=0.05, r1b=0.5. In at least one embodiment, r1 is in the vicinity of 0.5 (e.g., from 0.45 to 0.55), meaning that M1 is present in the kernel at substantially twice the molar amount of M2. The molar ratio of M3 to M1 in the kernel of a nanoparticle compositions of this disclosure, r2, can be from r2a to r2b, where r2a and r2b can be, independently, e.g., 0, 0.005, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, or 0.5, as long as r2a≤r2b. In some embodiments, r2a=0, r2b=5; such as r2a=0.005, r2b=0.5. Thus M3, if present, is at a substantially lower molar amount than M1. The molar ratio of oxygen to M1 in the kernel of a nanoparticle composition of this disclosure, r3, can be from r3a to r3b, where r3a and r3b can be, independently, e.g., 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5, as long as r3a≤r3b. In some embodiments, r3a=0.05, r3b=5; such as r3a=0.5, r3b=4; or r3a=1, r3b=3. The molar ratio of sulfur to M1 in the kernel of a nanoparticle composition of this disclosure, r4, can be from r4a to r4b, where r4a and r4b can be, independently, e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5, as long as r4a≤r4b. In some embodiments, r4a=0, r4b=5; such as r4a=0, r4b=2. The molar ratio of phosphorus to M1 in the kernel of a nanoparticle composition of this disclosure, r5, can be from r5a to r5b, where r5a and r5b can be, independently, e.g., 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5, as long as r5a≤r5b. In some embodiments, r5a=0, and r5b=5; such as r5a=0 and r5b=2. In specific embodiments, the metal(s) M1 can be distributed substantially homogeneously in the kernel. Additionally and/or alternatively, the metal(s) M2 can be distributed substantially homogeneously in the kernel. Additionally and/or alternatively, the metal(s) M3 can be distributed substantially homogeneously in the kernel. Additionally and/or alternatively, oxygen can be distributed substantially homogeneously in the kernel. Still additionally and/or alternatively, sulfur can be distributed substantially homogeneously in the kernel. Additionally and/or alternatively, phosphorus can be distributed substantially homogeneously in the kernel. It is highly advantageous that the metal oxide(s) are highly dispersed in the kernel. The metal oxide(s) can be substantially homogeneously distributed in the kernel, resulting in a highly dispersed distribution, which can contribute to a high catalytic activity of the catalyst composition comprising nanoparticle compositions that comprise kernels. The nanoparticle composition of this disclosure may comprise or consist essentially of the kernel of this disclosure, e.g., comprising ≥85, or ≥90, or ≥95, or ≥98, or even ≥99 wt % of the kernel, based on the total weight of the nanoparticle composition. The nanoparticle composition of the present disclosure may comprise long-chain hydrocarbyl groups disposed on (e.g. attached to) the kernel. Nanoparticle Formation The nanoparticle composition, of this disclosure may be produced from a first dispersion system at a first temperature (T1). A first dispersion system comprises a long-chain hydrocarbon solvent, a salt of at least one long-chain organic acid and the at least one metal element, optionally sulfur or an organic sulfur compound (which can be soluble in the long-chain hydrocarbon solvent), and optionally an organic phosphorus compound (which can be soluble in the long-chain hydrocarbon solvent). The salt of at least one long-chain organic acid and the at least one metal element may be formed in situ with a salt of a second organic acid and the at least one metal element, and a long-chain organic acid The T1 may comprise temperatures from T1a to T1b, where T1a and T1b can be, independently, e.g., 0, RT, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, or 300° C., as long as T1a<T1b, such as T1a=RT, T1b=250° C.; or T1a=35° C., T1b=150° C. The first temperature may be maintained for from 10 min to 100 hours, such as from 10 min to 10 hours, 10 minutes to 5 hours, 10 minutes to 3 hours, or 10 minutes to 2 hours. The first dispersion system may be held under inert atmosphere or under pressure reduced below atmospheric pressure. For example, the first dispersion system may be maintained under flow of nitrogen or argon, and alternatively, may be attached to a vacuum reducing the pressure to less than 760 mmHg, such as less than 400 mmHg, less than 100 mmHg, less than 50 mmHg, less than 30 mmHg, less than 20 mmHg, less than 10 mmHg, or less than 5 mmHg. The choice of maintaining the first dispersion system under flow of inert gas versus reduced pressure may affect the size of the nanoparticles produced. Without being limited by theory, it is possible that a first dispersion system under reduced pressure has fewer contaminants and byproducts than if it was maintained under flow of inert gas and the fewer contaminants may allow for formation of smaller nanoparticles. In some embodiments, maintaining the first dispersion system under reduced pressure may decrease nanoparticle size without affecting particle size distribution as compared to maintaining the first dispersion system under flow of inert gas. In other embodiments, maintaining the first dispersion system under flow of inert gas may increase nanoparticle size without affecting particle size distribution as compared to maintaining the first dispersion system under reduced pressure. The long-chain hydrocarbon solvent may comprise saturated and unsaturated hydrocarbons, aromatic hydrocarbons, and hydrocarbon mixture(s). Some example saturated hydrocarbons suitable for use as the long-chain hydrocarbon solvent are C12+ hydrocarbons, such as C12 to C24, C14 to C24, C16 to C22, C16 to C20, C16 to C18 hydrocarbons, such as n-dodecane (mp −10° C., bp 214° C. to 218° C.), n-tridecane (mp −6° C., bp 232° C. to 236° C.), n-tetradecane (mp 4° C. to 6° C., bp 253° C. to 257° C.), n-pentadecane (mp 10° C. to 17° C., bp 270° C.), n-hexadecane (mp 18° C., bp 287° C.), n-heptadecane (mp 21° C. to 23° C., bp 302° C.), n-octadecane (mp 28° C. to 30° C., bp 317° C.), n-nonadecane (mp 32° C., bp 330° C.), n-icosane (mp 36° C. to 38° C., bp 343° C.), n-henicosane (mp 41° C., bp 357° C.), n-docosane (mp 42° C., bp 370° C.), n-tricosane (mp 48° C. to 50° C., bp 380° C.), n-tetracosane (mp 52° C., bp 391° C.), or mixture(s) thereof. Some example unsaturated hydrocarbons suitable for use as the long-chain hydrocarbon solvent include C12+ unsaturated unbranched hydrocarbons, such as C12 to C24, C14 to C24, C16 to C22, C16 to C20, C16 to C18 unsaturated unbranched hydrocarbons (the double-bond may be cis or trans and located in any of the 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 positions), such as 1-dodecene (mp −35° C., bp 214° C.), 1-tridecene (mp −23° C., bp 232° C. to 233° C.), 1-tetradecene (mp −12° C., bp 252° C.), 1-pentadecene (mp −4° C., bp 268° C. to 239° C.), 1-hexadecene (mp 3° C. to 5° C., bp 274° C.), 1-heptadecene (mp 10° C. to 11° C., bp 297° C. to 300° C.), 1-octadecene (mp 14° C. to 16° C., bp 315° C.), 1-nonadecene (mp 236° C., bp 329° C.), 1-icosene (mp 26° C. to 30° C., bp 341° C.), 1-henicosene (mp 33° C., bp 353° C. to 354° C.), 1-docosene (mp 36° C. to 39° C., bp 367° C.), 1-tricosene (bp 375° C. to 376° C.), 1-tetracosene (bp 380° C. to 389° C.), trans-2-dodecene (mp −22° C., bp 211° C. to 217° C.), trans-6-tridecene (mp −11° C., bp 230° C. to 233° C.), cis-5-tridecene (mp −11° C. to −10° C., bp 230° C. to 233° C.), trans-2-tetradecene (mp 1° C. to 3° C., bp 250° C. to 253° C.), trans-9-octadecene (mp 23° C. to 25° C., bp 311° C. to 318° C.), cis-12-tetracosene (mp 96° C. to 97° C., bp 385° C. to 410° C.), or mixture(s) thereof. In some embodiments, the long-chain hydrocarbon solvent is 1-octadecene. Aromatic hydrocarbons suitable for use as the long-chain hydrocarbon may comprise any of the above alkanes and alkenes where a hydrogen atom is substituted for a phenyl, naphthyl, anthracenyl, pyrrolyl, pyridyl, pyrazyl, pyrimidyl, imidazolyl, furanyl, or thiophenyl substituent. Hydrocarbon mixtures suitable for use as the long-chain hydrocarbon may comprise mixtures with sufficiently high boiling points such that at least partial decomposition of the metal salts may occur upon heating below or at the boiling point of the mixture. Suitable mixtures may include: kerosene, lamp oil, gas oil, diesel, jet fuel, or marine fuel. The long-chain organic acid may comprise any suitable organic acid with a long-chain, such as saturated carboxylic acids, mono unsaturated carboxylic acids, polyunsaturated carboxylic acids, saturated or unsaturated sulfonic acids, saturated or unsaturated sulfinic acids, saturated or unsaturated phosphonic acids, saturated or unsaturated phosphinic acids. The long-chain organic acid may be selected from C12+ organic acids, such as C12 to C24, C14 to C24, C16 to C22, C16 to C20, or C16 to C18 organic acids. In some embodiments, the organic acid is a fatty acid, for example: caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, petroselenic acid, linoleic acid, linoelaidic acid, α-linolenic acid, γ-linolenic acid, stearidonic acid, gondoic acid, paullinic acid, gondoic acid, gadoleic acid, arachidonic acid, eicosenoic acid, eicosapentaenoic acid, brassidic acid, erucic acid, adrenic acid, osbond acid, clupanodonic acid, docosahexaenoic acid, nervonic acid, colneleic acid, colnelenic acid, etheroleic acid, or etherolenic acid. The long-chain organic acid may be selected from C12+ unsaturated acids, such as C12 to C24, C14 to C24, C16 to C22, C16 to C20, C16 to C18 unsaturated acids, such as myristoleic acid, palmitoleic acid, sapienic acid, vaccenic acid, petroselenic acid, oleic acid, elaidic acid, paullinic acid, gondoic acid, gadoleic acid, eicosenoic acid, brassidic acid, erucic acid, nervonic acid. The long-chain organic acid may be selected from myristoleic acid, palmitoleic acid, cis-vaccenic acid, paullinic acid, oleic acid, gondoic acid, or gadoleic acid. In some embodiments, the long-chain organic acid is oleic acid. The long-chain organic acids used to prepare the metal salts may be similar in chain length to the long-chain hydrocarbon solvent, such as where the long-chain organic acid and the long-chain hydrocarbon do not differ in numbers of carbon atoms by more than 4, such as 3 or less, or 2 or less. For example, if metal oleate salts are used, then suitable long-chain hydrocarbon solvents may include: 1-heptadecene, 1-octadecene, 1-nonadecene, trans-2-octadecene, cis-9-octadecene or mixture(s) thereof. Metal salts of the long-chain organic acid comprise the salt of (i) at least one metal selected from groups 1, 2, 3, 4, 5, 6, 11, 12, 13, 14, and 15, Mn, Fe, Co, Ni, or W, and combinations thereof; and (ii) a long-chain organic acid. As salts, the metals may be in a 2+, 3+, 4+, or 5+ oxidation state forming Metal (II), Metal (III), Metal (IV), and Metal (V) complexes with the long-chain organic acid. If an oxidation state is not specified the metal salt may comprise Metal (II), Metal (III), Metal (IV), and Metal (V) complexes. The metal salts of long-chain organic acids may be M1 metal salts comprising the salt of an M1 metal and a long-chain organic acid. The metal salts of long-chain organic acids may be M2 metal salts comprising the salt of an M2 metal and a long-chain organic acid. The metal salts of long-chain organic acids may be M3 metal salts comprising the salt of an M3 metal and a long-chain organic acid. M1 metal salts, M2 metal salts, and M3 metal salts need not contain the same long-chain organic acid. Furthermore, M1 metal salts, M2 metal salts, and M3 metal salts may be formed in situ with a salt of a second organic acid and the M1, M2, or M3 metal element, and a long-chain organic acid. In at least one embodiments, the M1 metal salt is selected from cobalt myristoleate, cobalt palmitoleate, cobalt cis-vaccenate, cobalt paullinate, cobalt oleate, cobalt gondoate, cobalt gadoleate, iron myristoleate, iron palmitoleate, iron cis-vaccenate, iron paullinate, iron oleate, iron gondoate, iron gadoleate, manganese myristoleate, manganese palmitoleate, manganese cis-vaccenate, manganese paullinate, manganese oleate, manganese gondoate, or manganese gadoleate. In at least one embodiments, the M2 metal salt is selected from nickel myristoleate, nickel palmitoleate, nickel cis-vaccenate, nickel paullinate, nickel oleate, nickel gondoate, nickel gadoleate, zinc myristoleate, zinc palmitoleate, zinc cis-vaccenate, zinc paullinate, zinc oleate, zinc gondoate, zinc gadoleate, copper myristoleate, copper palmitoleate, copper cis-vaccenate, copper paullinate, copper oleate, copper gondoate, copper gadoleate, molybdenum myristoleate, molybdenum palmitoleate, molybdenum cis-vaccenate, molybdenum paullinate, molybdenum oleate, molybdenum gondoate, molybdenum gadoleate, tungsten myristoleate, tungsten palmitoleate, tungsten cis-vaccenate, tungsten paullinate, tungsten oleate, tungsten gondoate, tungsten gadoleate, silver myristoleate, silver palmitoleate, silver cis-vaccenate, silver paullinate, silver oleate, silver gondoate, or silver gadoleate. In at least one embodiment, the M3 metal salt is selected from gallium myristoleate, gallium palmitoleate, gallium cis-vaccenate, gallium paullinate, gallium oleate, gallium gondoate, gallium gadoleate, indium myristoleate, indium palmitoleate, indium cis-vaccenate, indium paullinate, indium oleate, indium gondoate, indium gadoleate, scandium myristoleate, scandium palmitoleate, scandium cis-vaccenate, scandium paullinate, scandium oleate, scandium gondoate, scandium gadoleate, yttrium myristoleate, yttrium palmitoleate, yttrium cis-vaccenate, yttrium paullinate, yttrium oleate, yttrium gondoate, yttrium gadoleate, lanthanum myristoleate, lanthanum palmitoleate, lanthanum cis-vaccenate, lanthanum paullinate, lanthanum oleate, lanthanum gondoate, lanthanum gadoleate, cerium myristoleate, cerium palmitoleate, cerium cis-vaccenate, cerium paullinate, cerium oleate, cerium gondoate, cerium gadoleate, praseodymium myristoleate, praseodymium palmitoleate, praseodymium cis-vaccenate, praseodymium paullinate, praseodymium oleate, praseodymium gondoate, praseodymium gadoleate, neodymium myristoleate, neodymium palmitoleate, neodymium cis-vaccenate, neodymium paullinate, neodymium oleate, neodymium gondoate, neodymium gadoleate, gadolinium myristoleate, gadolinium palmitoleate, gadolinium cis-vaccenate, gadolinium paullinate, gadolinium oleate, gadolinium gondoate, gadolinium gadoleate, dysprosium myristoleate, dysprosium palmitoleate, dysprosium cis-vaccenate, dysprosium paullinate, dysprosium oleate, dysprosium gondoate, dysprosium gadoleate, holmium myristoleate, holmium palmitoleate, holmium cis-vaccenate, holmium paullinate, holmium oleate, holmium gondoate, holmium gadoleate, erbium myristoleate, erbium palmitoleate, erbium cis-vaccenate, erbium paullinate, erbium oleate, erbium gondoate, or erbium gadoleate. The first dispersion system may also be formed by heating a mixture of a long-chain organic acid, a hydrocarbon solvent, and one or more metal salts of one or more second organic acids; and heating that mixture to T1. T1 may be a temperature at or higher than the lower of (i) the boiling point of the second organic acid or (ii) the decomposition temperature of the second organic acid. In some embodiments, the boiling point of the second organic acid is lower than T1. T1 may comprise temperatures from 50° C. to 350° C., such as 70° C. to 200° C., or 70° C. to 150° C. Heating at T1 may last from 10 min to 100 hours, such as from 10 min to 10 hours, 10 minutes to 5 hours, 10 minutes to 3 hours, or 10 minutes to 2 hours. The second organic acid may comprise organic acids with a molecular weight lower than the molecular weight of the long-chain organic acids such as C8-organic acids, C1 to C7, C1 to C5, or C2 to C4 organic acids. Furthermore, the second organic acid may be more volatile than the long-chain organic acids. Some examples of suitable second acids are formic acid (bp 101° C.), acetic acid (bp 118° C.), propionic acid (bp 141° C.), butyric acid (bp 164° C.), lactic acid (bp 122° C.), citric acid (310° C.), ascorbic acid (decomp 190° C.), benzoic acid (249° C.), phenol (182° C.), acetylacetone (bp 140° C.), and acetoacetic acid (decomposition 80° C. to 90° C.). The second organic acid metal salts may comprise, for example, metal acetate, metal propionate, metal butyrate, metal lactate, metal acetylacetonate, or metal acetylacetate. Without being limited by theory, the second organic acid disposed on the metal may be released from the metal by exchange with the long-chain organic acid and the second organic acid may be removed under decreased pressure or flow of inert gas. The greater volatility of the second organic acid may allow for efficient exchange as the second organic acid is removed from solution. Removal of the second organic acid may also allow for formation of the first dispersion system in a single reaction vessel and may further allow for direct use in nanoparticle formation in the same reaction vessel. In some embodiments, the long-chain organic solvent and the long-chain organic acid are mixed prior to addition of metals, sulfur, organosulfur, or organophosphorus forming a liquid pre-mixture. To the liquid pre-mixture may be added one or more metal salts of one or more second organic acids, and optionally elemental sulfur, organosulfur, organophosphorus, or combinations thereof. The optional sulfur or organic sulfur compounds may comprise elemental sulfur, alkyl thiols, aromatic thiols, dialkyl thioethers, diaryl thioether, alkyl disulfides, aryldisulfides, or mixture(s) thereof, such as 1-dodecanethiol (bp 266° C. to 283° C.), 1-tridecanethiol (bp 291° C.), 1-tetradecanethiol (bp 310° C.), 1-pentadecanethiol (bp 325° C.), 1-hexadecanethiol (bp 343° C. to 352° C.), 1-heptadecanethiol (bp 348° C.), 1-octadecanethiol (bp 355° C. to 362° C.), 1-icosanethiol (mp bp 383° C.), 1-docosanethiol (bp 404° C.), 1-tetracosanethiol (bp 423° C.), decyl sulfide (bp 217° C. to 218° C.), dodecyl sulfide (bp 260° C. to 263° C.), thiophenol (bp 169° C.), diphenyl sulfide (bp 296° C.), diphenyl disulfide (bp 310° C.), or mixture(s) thereof. The sulfur or organic sulfur compounds may be soluble in the long-chain organic solvent. The amount of sulfur or organic sulfur included in the first dispersion system is set by the mole ratio to the metal(s) in the first dispersion system. The optional organophosphorus compounds may comprise alkylphosphines, dialkyl phosphines, trialkylphosphines, alkylphosphineoxides, dialkyphosphineoxides, trialkylphosphineoxides, tetraalkylphosphonium salts, and mixtures thereof. For example, suitable organophosphorus compounds may include: tributylphosphine (bp 240° C.), tripentylphosphine (bp 310° C.), trihexylphosphine (bp 352° C.), diphneylphsophine (bp 280° C.), trioctylphosphine (bp 284° C. to 291° C.), triphenylphosphine (bp 377° C.), or mixture(s) thereof. The organic phosphorus compounds may be soluble in the long-chain organic solvent. The amount of organic phosphorus included in the first dispersion system is set by the mole ratio to the metal(s) in the first dispersion system. The first dispersion system may be substantially free of surfactants other than salts of the long-chain organic acid. The processes of producing nanoparticle compositions of this disclosure may comprise heating the first dispersion system to a second temperature (T2), where T2 is greater than T1 and no higher than the boiling point of the long-chain hydrocarbon solvent. T2 can promote at least a portion of the first dispersion system to decompose and form a second dispersion system comprising nanoparticles described in this disclosure dispersed in the long-chain hydrocarbon solvent. The second temperature may comprise temperatures from T2a to T2b, where T2a and T2b can be, independently, e.g., 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450° C., as long as T2a<T2b. In some embodiments, T2a is 210° C. or greater, such as where T2a=210 and T1b=450; or where T1a=250 and T1b=350. The M1 metal salt(s), M2 metal salt(s) (if any), and M3 metal salt(s) (if any) can decompose at the second temperature to form the kernels. The kernels may be solid particles comprising the metal and oxygen atoms. The long-chain organic acids or a portion thereof may partly remain attached to the kernel's surface. Without being limited by theory, oxygen atoms from the long-chain organic acids, may be included in the kernel as a portion of the surface oxygen atoms. Such partial attachments may be sufficient to withstand washing, centrifuging, and handling of the nanoparticles. Therefore, the nanoparticle composition may comprise kernels with long-chain hydrocarbyls attached to the surface of the kernels. Without being limited by theory, the long-chain hydrocarbyls attached to the kernel may allow for uniform dispersion in the second dispersion system and complete colloidal dissolution in hydrophobic solvents. Furthermore, some portion of the long-chain organic acid salt may decompose to form an unsaturated compound (e.g. long-chain olefins) becoming a portion of the second dispersion system. The unsaturated compound may be identical to the long-chain hydrocarbon solvent if the solvent chosen is an alpha-olefin one carbon length shorter than the long-chain organic acid. The decomposition of the metal salts forms kernels where two or three dimensions are from 4 nm to 100 nm in length, such as from 4 nm to 20 nm in length. The kernels can have a size distribution of 30% or less, 20% or less, 10% or less, or 5% or less, such as from 1% to 30%, from 5% to 20%, or from 5% to 10%. The size and size distribution are determined by TEM and SAXS. The processes may take place in one or more reaction vessels under an inert atmosphere. The processes may comprise separating the nanoparticle composition from the long-chain hydrocarbon solvent. A suitable method of separating the nanoparticles from the long-chain hydrocarbon solvent may comprise addition of a counter-solvent causing precipitation of the nanoparticles. Suitable counter solvents may include: C1-C8 alcohols, such as C1-C6, C2-C4, or 1-butanol. Without being limited by theory, the increased polarity of the solution may cause the nanoparticles to precipitate out of solution where the counter solvent dissolves in the long-chain hydrocarbon solvent and long-chain organic acid mixture. Contaminants including unreacted metal salts, organic acids and corresponding salts may remain in the mixture of long-chain hydrocarbon solvent and counter-solvent and be removed in the process. The mixture of solvents and contaminants may be removed by centrifugation and decantation or filtration. The processes may also include further purification of the nanoparticles by a cleaning process. The cleaning may comprise (i) dispersing the nanoparticles in a hydrophobic solvent such as benzene, pentane, toluene, hexanes, or xylenes; (ii) adding a counter solvent to precipitate the nanoparticles; and (iii) collecting the precipitate by centrifugation or filtration. Cleaning, comprising steps (i) through (iii), may be repeated to further purify the nanoparticles. Nanoparticle Support Purified and/or unpurified nanoparticles may be dispersed in liquid media to form a nanoparticle dispersion. Suitable liquid media for forming a nanoparticle dispersion may include: benzene, pentane, toluene, hexanes, or xylenes. The nanoparticles may also be dispersed on a solid support by contacting the nanoparticle dispersion with the support. Suitable methods for contacting the nanoparticle dispersion with a solid support include: wet deposition, wet impregnation, or incipient wetness impregnation of the solid support. If the support is a large (greater than 100 nm) flat surface the nanoparticles may self-assemble into a monolayer on the support. The supported nanoparticle composition of this disclosure comprises a support material (which may be called a carrier or a binder). The support material may be included at any suitable quantity, e.g., ≥20, ≥30, ≥40, ≥50, ≥60, ≥70, ≥80, ≥90, or even ≥95 wt %, based on the total weight of the supported nanoparticle composition. In supported nanoparticle compositions, the nanoparticle component can be suitably disposed on the internal or external surfaces of the support material. Support materials may comprise porous materials that provide mechanical strength and a high surface area. Non-limiting examples of suitable support materials can include: oxides (e.g. silica, alumina, titania, zirconia, or mixture(s) thereof), treated oxides (e.g. sulfated), crystalline microporous materials (e.g. zeolites), non-crystalline microporous materials, cationic clays or anionic clays (e.g. saponite, bentonite, kaoline, sepiolite, or hydrotalcite), carbonaceous materials, or combination(s) and mixture(s) thereof. A support material can be sometimes called a binder in a supported nanoparticle composition. The supported nanoparticle composition of this disclosure may optionally comprise a solid diluent material. A solid diluent material is a solid material used to decrease nanoparticle to solid ratio and may be a material selected from conventional support materials. For example, a solid diluent material may be oxides (e.g. silica, alumina, titania, zirconia, or mixture(s) thereof), treated oxides (e.g. sulfated), crystalline microporous materials (e.g. zeolites), non-crystalline microporous materials, cationic clays or anionic clays (e.g. saponite, bentonite, kaoline, sepiolite, or hydrotalcite), carbonaceous materials, or combination(s) and mixture(s) thereof. The nanoparticles can be combined with a support material, an optional promoter, or an optional solid diluent material, to form a supported nanoparticle composition. The combination of the support material and the nanoparticles can be processed in any suitable forming processes, including but not limited to: grinding, milling, sifting, washing, drying, calcination, and the like. Drying or calcining the nanoparticles, optional promoter, and optional solid diluent material, on a support produces a catalyst composition. Drying and Calcining may take place at a third temperature (T3). The third temperature may comprise temperatures from T3a to T3b, where T3a and T3b can be, independently, e.g., 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650° C., as long as T2a<T2b. In some embodiments, T2a is 500° C. or greater, such as where T2a=500° C. and T1b=650° C.; or where T1a=550° C. and T1b=600° C. The catalyst composition may be then disposed in a conversion reactor to perform its intended function, such as a syngas converting reactor in a syngas converting process. It is also contemplated that the nanoparticles may be combined or formed with a precursor of a support material to obtain a catalyst composition precursor mixture. Suitable precursors of various support materials can include, e.g., alkali metal aluminates, water glass, a mixture of alkali metal aluminates and water glass, a mixture of sources of a di-, tri-, and/or tetravalent metal, such as a mixture of water-soluble salts of magnesium, aluminum, and/or silicon, chlorohydrol, aluminum sulfate, or mixture(s) thereof. The catalyst composition precursor mixture comprising the support and nanoparticles is subsequently subject to drying and calcining, resulting in the formation of the catalyst composition and the support material substantially in the same step. A promoter may be added to a supported nanoparticle composition or a catalyst composition forming a catalyst precursor composition. The catalyst precursor may be dried and/or calcined to form a catalyst composition comprising a promoter. Promoters may include sulfur, phosphorus, or salts of elements selected from Groups 1, 7, 11, or 12 of the periodic table, such as Li, Na, K, Rb, Cs, Re, Cu, Zn, Ag, and mixture(s) thereof. Typically, sulfide and sulfate salts are used. For example, a promoter may be added to a supported nanoparticle composition or a catalyst composition as part of a solution, the solvent can then be removed via evaporation (e.g. an aqueous solution where the water is later removed). Without being bound by a particular theory, it is believed that the metal oxide(s), and possibly the elemental phases of M1 in the kernel provide the catalytic activity for chemical conversion processes such as a Fischer-Tropsch synthesis. One or more of M2 and/or M3 can provide direct catalytic function as well. In addition, one or more of M2 and/or M3 can perform the function of a “promoter” in the supported nanoparticle composition. Furthermore, sulfur and or phosphorus, if present, can perform the function of a promoter in the catalyst composition as well. Promoters typically improve one or more performance properties of a catalyst. Example properties of catalytic performance enhanced by inclusion of a promoter in a catalyst over the catalyst composition without a promoter, may include: selectivity, activity, stability, lifetime, regenerability, reducibility, and resistance to potential poisoning by impurities such as sulfur, nitrogen, and oxygen. It may be advantageous for the nanoparticles to be uniformly dispersed on the support. The nanoparticles can be substantially homogeneously distributed in the supported nanoparticle composition, resulting in a highly dispersed distribution, which can contribute to a high catalytic activity of a catalyst composition. The synthesis methods disclosed may produce crystalline kernels with uniform particle shape and size. The kernels comprise metal oxide(s) that may be uniformly distributed throughout the kernel, which may improve catalysis when the kernel is included in a catalyst composition. The kernel may be part of a nanoparticle which may comprise long-chain hydrocarbons disposed on the kernel. The nanoparticles may be formed in a single reaction vessel from readily available precursors. The nanoparticle may be dispersed in liquid media, and thereby dispersed on a solid support. The nanoparticles dispersed on solid support may together be dried and or calcined to form a catalyst composition Processes for Converting Syngas The supported nanoparticle composition and/or the catalyst composition of this disclosure may be used in any process where the relevant metal(s) and/or the metal oxide(s) can perform a catalytic function. The supported nanoparticle composition and/or the catalyst composition of this disclosure can be particularly advantageously used in processes for converting syngas into various products such as alcohols and olefins, particularly C1-05 alcohols, such as C1-C4 alcohols, and C2-05 olefins (particularly C2-C4 olefins), such as the Fischer-Tropsch processes. The Fischer-Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into hydrocarbons and/or alcohols. The products formed are the “conversion product mixture.” These reactions occur in the presence of metal catalysts, typically at temperatures of 100 to 500° C. (212 to 932° F.) and pressures of one to several tens of atmospheres. The term “syngas” as used herein relates to a gaseous mixture consisting essentially of hydrogen (H2) and carbon monoxide (CO). The syngas, which is used as a feed stream, may comprise up to 10 mol % of other components such as CO2and lower hydrocarbons (lower HC), depending on the source and the intended conversion processes. Said other components may be side-products or unconverted products obtained in the process used for producing the syngas. The syngas may contain such a low amount of molecular oxygen (O2) so that the quantity of O2present does not interfere with the Fischer-Tropsch synthesis reactions and/or other conversion reactions. For example, the syngas may comprise not more than 1 mol % O2, not more than 0.5 mol % O2, or not more than 0.4 mol % O2. The syngas may have a hydrogen (H2) to carbon monoxide (CO) molar ratio of from 1:3 to 3:1. The partial pressures of H2and CO may be adjusted by introduction of inert gas to the reaction mixture. Syngas can be formed by reacting steam and/or oxygen with a carbonaceous material, for example, natural gas, coal, biomass, or a hydrocarbon feedstock through a reforming process in a syngas reformer. The reforming process can be based on any suitable reforming process, such as Steam Methane Reforming, Auto Thermal Reforming, or Partial Oxidation, Adiabatic Pre Reforming, or Gas Heated Reforming, or a combination thereof. Example steam and oxygen reforming processes are detailed in U.S. Pat. No. 7,485,767. The syngas formed from steam or oxygen reforming comprises hydrogen and one or more carbon oxides (CO and CO2). The hydrogen to carbon oxide ratio of the syngas produced will vary depending on the reforming conditions used. The syngas reformer product(s) should contain H2, CO and CO2in amounts and ratios which render the resulting syngas blend suitable for subsequent processing into either oxygenates, such as methanol/dimethyl ether or in Fischer-Tropsch synthesis. The syngas from reforming to be used in Fischer-Tropsch synthesis may have a molar ratio of H2to CO, unrelated to the quantity of CO2, of 1.9 or greater, such as from 2.0 to 2.8, or from 2.1 to 2.6. On a water-free basis, the CO2content of the syngas may be 10 mol % or less, such as 5.5 mol % or less, or from 2 mol % to 5 mol %, or from 2.5 mol % to 4.5 mol %. It is possible to alter the ratio of components within the syngas and the absolute CO2content of the syngas by removing, and optionally recycling, some of the CO2from the syngas produced in one or more reforming processes. Several commercial technologies are available (e.g. acid gas removal towers) to recover and recycle CO2from syngas as produced in the reforming process. In at least one embodiment, CO2can be recovered from the syngas effluent from a steam reforming unit, and the recovered CO2can be recycled to a syngas reformer. Suitable Fischer-Tropsch catalysis procedures may be found in: U.S. Pat. Nos. 7,485,767; 6,211,255; and 6,476,085; the relevant portions of their contents being incorporated by reference. The supported nanoparticle composition and/or the catalyst composition may be contained in a conversion reactor (a reactor for the conversion of syngas), such as a fixed bed reactor, a fluidized bed reactor, or any other suitable reactor. The conversion conditions may comprise contacting the catalyst composition and/or the supported nanoparticle composition with syngas, to provide a reaction mixture, at a pressure of 1 bar to 50 bar, at a temperature of 150° C. to 450° C., and/or a gas hourly space velocity of 1000 h−1to 10,000 h−1for a reaction period. The conversion conditions may comprise a wide range of temperatures. In at least one embodiment, the reaction temperature may be from 100° C. to 450° C., such as from 150° C. to 350° C., such as from 200° C. to 300° C. For certain catalyst compositions or supported nanoparticle compositions, lower temperature ranges might be preferred, but if the composition comprises cobalt metal, higher temperatures are tolerated. For example, a catalyst composition comprising cobalt metal may be used at reaction temperatures of 250° C. or greater, such as from 250° C. to 350° C., or from 250° C. to 300° C. The conversion conditions may comprise a wide range of reaction pressures. In at least one embodiment, the absolute reaction pressure ranges from p1 to p2 kilopascal (“kPa”), where p1 and p2 can be, independently, e.g., 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, or 5,000, as long as p1<p2. Gas hourly space velocities used for converting the syngas to olefins and/or alcohols can vary depending upon the type of reactor that is used. In one embodiment, gas hourly space velocity of the flow of gas through the catalyst bed is from 100 hr−1to 50,000 hr−1, such as from 500 hr−1to 25,000 hr−1, from 1000 hr−1to 20,000 hr−1, or from 100 hr−1to 10,000 hr−1. Conversion conditions may have an effect on the catalyst performance. For example, selectivity on a carbon basis is a function of the probability of chain growth. Factors affecting chain growth include reaction temperatures, the gas composition and the partial pressures of the various gases in contact with the catalyst composition or the supported nanoparticle composition. Altering these factors may lead to a high degree of flexibility in obtaining a type of product in a certain carbon range. Without being limited by theory, an increase in operating temperature shifts the selectivity to lower carbon number products. Desorption of growing surface species is one of the main chain termination steps and since desorption is an endothermic process so a higher temperature should increase the rate of desorption which will result in a shift to lower molecular mass products. Similarly, the higher the CO partial pressure, the more catalyst surface that is covered by adsorbed monomers. The lower the coverage by partially hydrogenated CO monomers, the higher the probability of chain growth. Accordingly, it is probable that the two key steps leading to chain termination are desorption of the chains yielding alkenes and hydrogenation of the chains to yield alkanes. EXAMPLES Example 1. Preparation of MnCoOxSpherical Nanoparticles A reaction solution was prepared by dissolving manganese (II) acetylacetonate (Mn(CH3COCHCOCH2)2) and Cobalt (II) acetate tetrahydrate (Co(CH3COO)2.4H2O) in a mixture of oleic acid (OLAC) and 1-octadecene. The reaction solution had a molar ratio of 4.5 mol OLAC: mol metal and a combined metal concentration of 0.164 mmol Mn/mL of 1-octadecene. The reaction solution was heated to a temperature of 130° C. under flow of nitrogen and held at 130° C. for 90 minutes. The mixture was then heated under an inert atmosphere of nitrogen at a rate of 10° C./min to reflux (320° C.). The reaction mixture was held at 320° C. for 30 min. The reaction mixture was cooled under an inert atmosphere using a flow of RT air to cool the exterior of the reaction vessel. The nanoparticles were collected and purified via repeated washing and decanting/centrifugation steps using hexane as a hydrophobic solvent, and isopropanol as a counter solvent. The purified nanoparticles were dispersed in toluene. TEM imagery shows that the nanoparticles are roughly spherical in shape, have an average diameter of 6.3 nanometers and a size distribution of 13%. Example 1a. Supporting MnCoOxSpherical Nanoparticles with Silica Eight grams of SiO2was dispersed in hexane. While under vigorous stirring, the nanoparticle solution prepared according to Example 1 was added to the support dispersion and the mixture was stirred at 25° C. for 180 minutes. The catalyst powder was recovered by centrifugation. The powder was washed three times with hexane via sonication and centrifugation. The supported nanoparticle composition was dried at 60° C. for 12 hours under vacuum (100 mmHg). The dried supported nanoparticle powder was then calcined in static air at 325° C. for 180 minutes using heating and cooling ramps of 3° C. per minute. Example Lb. Supporting MnCoOxSpherical Nanoparticles with Alumina Eight grams of Al2O3was dispersed in hexane. While under vigorous stirring, the nanoparticle solution prepared according to Example 1 was added to the support dispersion and the mixture was stirred at 25° C. for 180 minutes. The catalyst powder was recovered by centrifugation. The powder was washed three times with hexane via sonication and centrifugation. The supported nanoparticle composition was dried at 60° C. for 12 hours under vacuum (100 mmHg). The dried supported nanoparticle powder was then calcined in static air at 325° C. for 180 minutes using heating and cooling ramps of 3° C. per minute. Example 2. Preparation of Supported MnCoOxRod-Shaped Nanoparticles A reaction solution was prepared by dissolving manganese (II) acetylacetonate acetate (Mn(CH3COCHCOCH2)2) and Cobalt (II) acetate tetrahydrate (Co(CH3COO)2.4H2O) in a mixture of oleic acid (OLAC) and 1-octadecene. The reaction solution had a molar ratio of 4.5 mol OLAC: mol Metal (Mn+Co) and a combined metal concentration of 0.9 mmol Mn/mL of 1-octadecene. The reaction solution was heated to a temperature of 130° C. under flowing nitrogen and held at 130° C. for 60 minutes. The mixture was then heated under an inert atmosphere of nitrogen at a rate of 10° C./min to reflux (320° C.). The reaction mixture was held at 320° C. for 120 min. The reaction mixture was cooled under an inert atmosphere using a flow of RT air to cool the exterior of the reaction vessel. The nanoparticles were collected and purified via repeated washing and decanting/centrifugation steps using hexane as a hydrophobic solvent, and isopropanol as a counter solvent. The purified nanoparticles were dispersed in toluene. TEM images illustrated that the nanoparticles are rod-shaped, have an average length of 64.1 with a length distribution of 15% and an average width of 11.7 nanometers with a width distribution of 13%. Comparative Example 3. Bulk Co2MnO4 An aqueous solution was prepared containing 48.9 g of Co(NO3)2-6H2O and 24.1 g of Mn(NO3)-2.6H2O in 125 ml water. This was added to an aqueous solution of 48.4 g citric acid and 14.1 mi ethylene glycol in 25 ml water with stirring at 70° C. to 90° C. The mixture became thick after 1-2 hours, after which it was calcined in air at 350° C. for 30 minutes. FIG.1shows catalyst selectivity in production C2-C4 hydrocarbons versus percent CO conversion. Bulk cobalt/manganese mixed metal oxide catalyst is shown as triangles102and a catalyst composition with 6.3 nm spherical cobalt/manganese mixed metal oxide nanoparticles according to example 1a are shown as circles104. The comparison of the bulk and silica supported nanoparticle catalyst compositions shows that at higher conversion rates the selectivity towards C2 to C4 hydrocarbons is similar between102and104. FIG.2shows the percent of olefins contained in the C2-C4 hydrocarbons produced versus percent CO conversion. Bulk cobalt/manganese mixed metal oxide catalyst is shown as triangles202and a catalyst composition with 6.3 nm spherical cobalt/manganese mixed metal oxide nanoparticles according to example 1a are shown as circles204. The comparison of the bulk and silica supported nanoparticle catalyst compositions shows that the catalyst composition comprising silica supported nanoparticles has a greater percentage of olefins in the C2-C4 hydrocarbons produced at all conversion rates over the bulk mixed metal oxide catalyst. Both the bulk and nanoparticle catalysts demonstrate a downward trend of less olefin in the C2-C4 hydrocarbon as conversion increases. The downward trend line206is a linear regression of triangles202for the supported nanoparticle catalyst composition, and the downward trend line208is a linear regression of circles204for the bulk mixed metal oxide catalyst composition. FIG.3shows the olefinicity of the C2-C4 hydrocarbons produced versus percent CO conversion. A catalyst composition with 6.3 nm spherical cobalt/manganese mixed metal oxide nanoparticles according to example 1b were used at three temperature in Fischer-Tropsch synthesis: (i) the use of alumina supported nanoparticles at 250° C. is shown as dots302; (ii) the use of alumina supported nanoparticles at 270° C. is shown as stars304; and (i) the use of alumina supported nanoparticles at 290° C. is shown as crosses306. Bulk cobalt/manganese mixed metal oxide catalyst is shown as rings308. The comparison of the bulk catalyst composition and the alumina supported nanoparticle catalyst composition shows that the catalyst composition comprising alumina supported nanoparticles has a greater percentage of olefins in the C2-C4 hydrocarbons produced at various conversion rates and temperatures over the bulk mixed metal oxide catalyst. Both the bulk and nanoparticle catalysts demonstrate a downward trend of less olefin in the C2-C4 hydrocarbon as conversion increases. FIG.4shows the yield of olefins C2-C4 hydrocarbons produced versus percent CO conversion. Yield was calculated by multiplying the conversion and the selectivity. A catalyst composition with 6.3 nm spherical cobalt/manganese mixed metal oxide nanoparticles according to example 1b are shown as crosses402and bulk cobalt/manganese mixed metal oxide catalyst is shown as dots404. The comparison of the olefin yield of the bulk catalyst composition and the alumina supported nanoparticle catalyst composition shows that the catalyst composition comprising alumina supported nanoparticles has a greater yield of C2-C4 olefins at all conversion rates over the bulk mixed metal oxide catalyst. Other non-limiting aspects and/or embodiments of the present disclosure can include: A1. A supported nanoparticle composition comprising:a support; anda plurality of nanoparticles on the support, where:each nanoparticle comprises a kernel, the kernels have an average particle size from 4 to 100 nm and a particle size distribution, expressed as a percentage of the standard deviation of the particle size relative to the average particle size, of no greater than 20%, as determined by small angle X-ray scattering (“SAXS”) and transmission electron microscopy (“TEM”) image analysis; the kernels comprise oxygen, a metal element M1, optionally sulfur, optionally phosphorus, optionally a metal element M2, and optionally a third metal element M3, where M1 is selected from Mn, Fe, Co, and combination of two or more thereof in any proportion, M2 is selected from Ni, Zn, Cu, Mo, W, Ag, and combinations thereof, and M3 is selected from Y, Sc, alkaline metals, the lanthanides, group 13, 14, and 15 elements, and combinations thereof, and the molar ratios of M2, M3, S, and P, if any, to M1 is r1, r2, r3, and r4, respectively, 0≤r1≤2, 0≤r2≤2, 0≤r3≤5, and 0≤r4≤5. A2. The supported nanoparticle composition of A1, where 0≤r1≤0.5, and 0≤r2≤0.5. A3. The supported nanoparticle composition of A2, where 0.05≤r1≤0.5, and 0.005≤r2≤0.5. A4. The supported nanoparticle composition of any of A1 to A3, where the kernels comprise a crystalline phase of an oxide of the at least one metal element selected from M1, M2, and M3. A5. The supported nanoparticle composition of any of A1 to A4, where the nanoparticles have an average particle size from 4 to 35 nm. A6. The supported nanoparticle composition of any of A1 to A5, where the nanoparticles have a size distribution of from 5 to 15%. A7. The supported nanoparticle composition of any of A1 to A6, where the kernels comprise at least two metal elements. A8. The supported nanoparticle composition of A7, where the at least two metal elements are uniformly distributed in the nanoparticles. A9. The supported nanoparticle composition of any of embodiments A1 to A8, where the nanoparticles comprise a plurality of hydrophobic long-chain groups attached to the surface of the kernels. A10. The supported nanoparticle composition of A7, where the long-chain groups comprise a C14-C24 hydrocarbyl group. A11. The supported nanoparticle composition of any of A1 to A10, where the nanoparticles consist essentially of oxygen, M1, optionally M2, optionally M3, optionally sulfur, and optionally phosphorus. A12. The supported nanoparticle composition of A11, where the nanoparticles are substantially free of long-chain groups attached to the surface of the kernels. A13. The supported nanoparticle composition of A11 or A12, where the kernels consist essentially of oxygen, M1, optionally M2, optionally M3, optionally sulfur, and optionally phosphorus. A14. The supported nanoparticle composition of A13, where the kernels consist essentially of a promoter and a mixed oxide selected from Fe and Mn; Co and Mn; or Fe, Cu, and Zn. A15. The supported nanoparticle composition of any of A1 to A14, where the kernels are substantially spherical. A16. The supported nanoparticle composition of any of A1 to A15, where the kernels are rod-shaped. A17. The supported nanoparticle composition of A16, where the kernels have an aspect ratio of >1 to 10. B1. A process for making the composition of any of A1 to A12, comprising:(I) providing a nanoparticle dispersion comprising a liquid medium and a plurality of nanoparticles distributed therein, where each nanoparticle comprises a kernel, the kernels have an average particle size from 4 to 100 nm and a particle size distribution, expressed as a percentage of the standard deviation of the particle size relative to the average particle size, of no greater than 20%, as determined by small angle X-ray scattering (“SAXS”) and transmission electron microscopy (“TEM”) image analysis; the kernels comprise oxygen, a metal element M1, optionally sulfur, optionally phosphorus, optionally a second metal element M2, and optionally a third metal element M3, where M1 is selected from Mn, Fe, Co, and combination of two or more thereof in any proportion, M2 is selected from Ni, Zn, Cu, Mo, W, Ag, and combinations thereof, and M3 is selected from Y, Sc, alkaline metals, the lanthanides, group 13, 14, and 15 elements, and combinations thereof, and the molar ratios of M2, M3, S, and P, if any, to M1 is r1, r2, r3, and r4, respectively, 0≤r1≤2, 0≤r2≤2, 0≤r3≤5, and 0≤r4≤5; and (II) disposing a quantity of the nanoparticle dispersion on a support to obtain a supported nanoparticle composition. B2. The process of B1, further comprising:(III) removing at least a portion of the liquid medium from the supported nanoparticle composition. B3. The process of B1 or B2, further comprising:(IV) calcining the supported nanoparticle composition to obtain a catalyst composition. B3. The process of any of B1 to B3, further comprising:(V) impregnating the support, the supported nanoparticle composition, or catalyst composition with a precursor of an promoter to obtain a catalyst precursor; and(VI) drying and/or calcining the catalyst precursor to obtain a catalyst composition comprising a promoter. B4. The process of B1 to B4, where step (I) comprises:(Ia) providing a first dispersion system at a first temperature, the first dispersion system comprising a salt of a long-chain organic acid and M1, optionally a salt of the long-chain organic acid and M2, optionally a salt of the long-chain organic acid and M3, a long-chain hydrocarbon solvent, optionally a salt of a second organic acid and M1, optionally a salt of a third organic acid and M2, optionally a salt of a fourth organic acid and M3, optionally sulfur or an organic sulfur compound soluble in the long-chain hydrocarbon solvent, and optionally an organic phosphorous compound soluble in the long-chain hydrocarbon solvent; and(Ib) heating the first dispersion system to a second temperature higher than the first temperature but no higher than the boiling point of the long-chain hydrocarbon solvent, where at least a portion of the salt(s) of the long-chain organic acid and at least a portion of the salt(s) of the second organic acid, if present, decompose to form a second dispersion system comprising nanoparticles dispersed in the long-chain hydrocarbon solvent, and the nanoparticles comprise kernels, and the kernels comprise M1, optionally M2, optionally M3, oxygen, optionally sulfur, and optionally phosphorus;(Ic) separating the nanoparticles from the second dispersion system; and(Id) dispersing the nanoparticles separated in (Ic) in the liquid medium to form the nanoparticle dispersion. B5. The process of any of B1 to B4, where the nanoparticles further comprise long hydrocarbon chains attached to the surface of the kernels. B6. The process of any of B1 to B5, where the nanoparticles have an average particle size in a range from 4 to 100 nm, and a particle size distribution of no greater than 20%, expressed as the percentage of the standard deviation of the particle size relative to the average particle size, as determined by small angle X-ray scattering (“SAXS”) and transmission electron microscopy (“TEM”) image analysis. B7. The process of B6, where the nanoparticles have an average particle size in a range from 4 to 20 nm, as determined by SAXS and TEM image analysis. B8. The process of any of B4 to B7, where step (Ia) comprises:(Ia.1) providing a first liquid mixture of the long-chain organic acid, the long-chain hydrocarbon solvent, and the salt of the second organic acid and M1, the optional salt of the third organic acid and M2, and the optional salt of the fourth organic acid and M3;(Ia.2) heating the second mixture to the first temperature to obtain the first dispersion system. B9. The process of B8, where steps (Ia.1), (Ia.2), and (Ib) are all performed in the same vessel. B10. The process of B8 or B9, where in step (Ia.1), the first liquid mixture comprises (i) elemental sulfur and/or an organic-sulfur compound soluble in the long-chain hydrocarbon solvent, and/or (ii) a phosphorous-containing organic compound soluble in the long-chain hydrocarbon solvent at the first temperature. B11. The process of any of B8 to B10, where step (Ia.1) comprises:(Ia. 1a) mixing the long-chain organic acid with the long-chain hydrocarbon solvent to obtain a liquid pre-mixture;(Ia. 1b) adding, to the liquid pre-mixture obtained in (Ia. 1a), (i) the salt of the second organic acid and M1, optionally the salt of the third organic acid and M2, and optionally the salt of the fourth organic acid and M3; (ii) optionally elemental sulfur and/or an organic-sulfur compound soluble in the long-chain hydrocarbon solvent, and (iii) optionally a phosphorous-containing organic compound soluble in the long-chain hydrocarbon solvent at the first temperature. B12. The process of any of B4 to B11, where the first dispersion system is substantially free of a surfactant other than the salt(s) of the long-chain organic acid. B13. The process of embodiment B5, where in step (Ia.2), the first mixture is heated to a temperature no lower than the boiling points of the second organic acid, the third organic acid if the salt of the third organic acid and M2 is added to the first mixture, the fourth organic acid if the salt of the fourth organic acid and M3 is added to the first mixture, or the decomposition temperatures of the second organic acid, the third organic acid, and the fourth organic acid, whichever is lower. B14. The process of any of B11 to B13, where the second organic acid has a boiling point lower than the first temperature. B15. The process of embodiment B6, where the second organic acid is selected from: formic acid, acetic acid, citric acid, propionate acid, actylacetonic acid, ascorbic acid, benzylic acid, phenol, acetoacetone, and the like. B16. The process of embodiment B15, where the second organic acid is acetic acid. B17. The process of any of embodiments B11 to B16, where the second mixture is heated to a temperature in a range from 70° C. to 150° C. B18. The process of embodiment B17, where the second mixture is heated to a temperature in a range from 70° C. to 200° C. for a period of t minutes, where 10≤t≤120. B18. The process of any of B4 to B18, where the second temperature is at least 210° C. B19. The process of any of embodiments B4 to B18, where the second temperature is in a range from 210° C. to 450° C. B20. The process of any of embodiments B4 to B19, where the long-chain organic acid is selected from C14-C24 fatty acids and mixtures of two or more thereof, and the long-chain hydrocarbon solvent is selected from a C14-C24 hydrocarbons and mixtures of two or more thereof. B21. The process of embodiment B20, where the long-chain organic acid is selected from C14-C24 monounsaturated fatty acids, and mixtures of two or more thereof, and/or the long-chain hydrocarbon solvent is selected from a C14-C24 unsaturated hydrocarbons and mixtures of two or more thereof. B22. The process of any of embodiments B20 or B21, where the long-chain organic acid and the long-chain hydrocarbon solvent do not differ in number of average carbon atoms per molecule by more than 4. B23. The process of any of embodiments B4 to B22, where the long-chain organic acid is oleic acid, and the long-chain hydrocarbon solvent is 1-octadecene. B24. The process of any of embodiments B4 to B23, where step (I) and/or step (II) are performed in the presence of an inert atmosphere. B25. The process of any of embodiments B4 to B24 wherein in step (Ia) M1, M2, M3, and M4 are present in the long-chain hydrocarbon solvent at a concentration of ≥0.5 mmol/mL. C1. A process for converting syngas, the process comprising contacting a feed comprising syngas with a composition of any of A1 to A16 in a conversion reactor under conversion conditions to produce a conversion product mixture. C2. The process of C1, where the conversion product mixture comprises one more of a C1-05 alcohol and/or one or more of a C2-05 olefin. C3. The process of C1 or C2, where the nanoparticles in the supported nanoparticle composition consist essentially of oxygen, M1, optionally M2, optionally M3, optionally sulfur, and optionally phosphorus. C4. The process of C3, where the nanoparticles are substantially free of long-chain groups attached to the surface of the kernels. C5. The process of C3 or C4, where the nanoparticles in the composition consist essentially of oxygen, M1, optionally M2, optionally M3, optionally sulfur, and optionally phosphorus. C6. The process of C5, where the nanoparticles consist essentially of a promoter and a mixed oxide selected from Fe and Mn; Co and Mn; or Fe, Cu, and Zn. C7. The process of any of C1 to C6, where the conversion conditions comprise a temperature of from 150° C. to 350° C., an absolute pressure of from 1 bar to 50 bar, a H2:CO ratio of from 1:3 to 3:1, and a GHSV of from 1,000 h−1to 10,000 h−1. D1. A composition comprising a metal oxide represented by Formula (F-1): MaM′bOx(F-1) where:M is a first metal selected from manganese, iron, cobalt, or a combination thereof;M′ is a second metal selected from transition metals and main group elements other thanthe first metal;a and x are independently greater than 0 to 1; andb is from 0 to 1; where:the metal oxide has a particle size of from about 4 nm to about 35 nm; andthe metal oxide has a size distribution having a standard deviation of about 20% or less based on the particle size. D2. The composition of embodiment D1, where the first metal is manganese. D3. The composition of any of embodiments D1 to D2, where the second metal is selected from zinc, copper, or tin. D4. The composition of any of embodiments D1 to D3, where the ratio of a:b is from about 1:3 to about 2:1. D5. The composition of any of embodiments D1 to D4, where one or more long-chain organic acids are disposed on the metal oxide. D6. The composition of embodiment D5, where the one or more long-chain organic acids is oleic acid. E1. A process of producing a composition comprising: a metal oxide represented by Formula (F-1): MaM′bOx(F-1) where:M is a first metal selected from manganese, iron, cobalt, or a combination thereof;M′ is a second metal selected from transition metals, and main group elements other than the first metal;a and x are independently greater than 0 to 1; andb is from 0 to 1; where:the metal oxide has a particle size of from about 4 nm to about 20 nm; andthe metal oxide has a size distribution having a standard deviation of about 20% or less based on the particle size, the process comprising:introducing at least one organic metal salt, a long-chain organic acid, and a non-coordinating solvent to a reaction vessel to form a reaction mixture, where the non-coordinating solvent has a boiling point of about 200° C. or higher; andapplying heat to the first reaction mixture to form a product mixture. E2. The process of embodiment E1, further comprising heating the reaction mixture from about 70° C. to about 150° C. for from about 30 minutes to about 3 hours in an inert atmosphere. E3. The process of embodiment E1, further comprising heating the reaction mixture from about 70° C. to about 150° C. for from about 30 minutes to about 3 hours under pressure reduced below atmospheric pressure. E4. The process of any of embodiments E1 to E3, further comprising cooling the product mixture to form a cooled product mixture. E5. The process of embodiment E4, further comprising precipitating the cooled product mixture with a polar solvent selected from ethanol or isopropanol to form a precipitated composition. E6. The process of embodiment E5, further comprising: centrifuging the precipitated composition to form a supernatant and a pellet; and decanting the supernatant. E7. The process of embodiment E6, further comprising washing the pellet, where washing comprises:dissolving the pellet in a non-polar solvent to form a solution;precipitating a purified precipitated composition from the solution using a polar solvent;centrifuging the purified precipitated composition to form a supernatant; anddecanting the supernatant. E8. The process of any of embodiments E1 to E7, where the at least one organic metal salt comprises a mixture of organic salts of the first metal and the second metal. E9. The process of embodiment E8, where the ratio a:b is from about 1:3 to about 2:1. E10. The process of any of embodiments E1 to E9, where a molar ratio of metal salt to long-chain organic acid of the reaction mixture is from about 1:2 to about 1:8. E11. The process of any of embodiments E1 to E10, where the non-coordinating solvent is selected from C14+ straight-chain alkanes or alkenes. E12. The process of any of embodiments E1 to E11, where the non-coordinating solvent is 1-octadecene. E13. The process of any of embodiments E1 to E12, where the long-chain organic acid is oleic acid. E14. The process of any of embodiments E1 to E13, where the reaction time period is from about 5 minutes to about 3 hours. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited. All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this disclosure. As is apparent from the foregoing general description and the specific embodiments, while forms of this disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of this disclosure. Accordingly, it is not intended that this disclosure be limited thereby. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa. While this disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of this disclosure.
82,453
11857955
For the purpose of describing the simplified schematic illustration and description ofFIG.2, the numerous valves, temperature sensors, electronic controllers, and the like that may be employed and well known to those of ordinary skill in the art of certain chemical processing operations are not included. Further, accompanying components that are often included in chemical processing operations, such as, for example, air supplies, heat exchangers, surge tanks, catalyst hoppers, or other related systems are not depicted. It would be known that these components are within the spirit and scope of the present embodiments disclosed. However, operational components, such as those described in the present disclosure, may be added to the embodiments described in this disclosure. It should further be noted that arrows in the drawings refer to process streams. However, the arrows may equivalently refer to transfer lines that may serve to transfer process steams between two or more system components. Additionally, arrows that connect to system components define inlets or outlets in each given system component. The arrow direction corresponds generally with the major direction of movement of the materials of the stream contained within the physical transfer line signified by the arrow. Furthermore, arrows that do not connect two or more system components signify a product stream which exits the depicted system or a system inlet stream which enters the depicted system. Product streams may be further processed in accompanying chemical processing systems or may be commercialized as end products. System inlet streams may be streams transferred from accompanying chemical processing systems or may be non-processed feedstock streams. Some arrows may represent recycle streams, which are effluent streams of system components that are recycled back into the system. However, it should be understood that any represented recycle stream, in some embodiments, may be replaced by a system inlet stream of the same material, and that a portion of a recycle stream may exit the system as a system product. Additionally, arrows in the drawings may schematically depict process steps of transporting a stream from one system component to another system component. For example, an arrow from one system component pointing to another system component may represent “passing” a system component effluent to another system component, which may include the contents of a process stream “exiting” or being “removed” from one system component and “introducing” the contents of that product stream to another system component. It should be understood that two or more process streams are “mixed” or “combined” when two or more lines intersect in the schematic flow diagram ofFIG.3. Mixing or combining may also include mixing by directly introducing both streams into a like reactor, separation device, or other system component. For example, it should be understood that when two streams are depicted as being combined directly prior to entering a separator or reactor, that in some embodiments the streams could equivalently be introduced into the separator or reactor and be mixed in the reactor. Reference will now be made in greater detail to various embodiments of the present disclosure, some embodiments of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or similar parts. DETAILED DESCRIPTION Disclosed herein are processes for forming catalysts that, in some embodiments, may be useful in steam enhanced fluid catalytic cracking reactions of hydrocarbons. The processes may generally include forming mesoporous beta zeolites, impregnating the mesoporous beta zeolite particles, and incorporation with clay and alumina. Particular non-limiting embodiments of such processes are disclosed herein. As used in this disclosure, the term “catalyst” may refer to any substance that increases the rate of a specific chemical reaction. As used in this disclosure, the term “cracking” may refer to a chemical reaction where a molecule having carbon-carbon bonds is broken into more than one molecule by the breaking of one or more of the carbon-carbon bonds; where a compound including a cyclic moiety, such as an aromatic, is converted to a compound that does not include a cyclic moiety; or where a molecule having carbon-carbon double bonds are reduced to carbon-carbon single bonds. Some catalysts may have multiple forms of catalytic activity, and calling a catalyst by one particular function does not render that catalyst incapable of being catalytically active for other functionality. As used in this disclosure, the term “particle size” of crystalline beta zeolite or mesoporous beta zeolite may refer to a greatest distance between two points located on crystalline beta zeolite or mesoporous beta zeolite. For example, the particle size of a spherical particle would be its diameter. In other shapes, the particle size is measured as the distance between the two most distant points of the same particle, where these points may lie on outer surfaces of the particle. The particle size may be determined by scanning electron microscopy (SEM). As used in this disclosure, the term “crystal size” of crystalline beta zeolite or mesoporous beta zeolite may refer to be a length of the coherent scattering domain in a direction orthogonal to the set of lattice planes which give rise to the reflection. The crystal size may be calculated from XRD. As used in this disclosure, the term “pore size” of crystalline beta zeolite or mesoporous beta zeolite may refer to the pore size determined by Barrett-Joyner-Halenda (BJH) analysis. BJH analysis measures the amount of a gas (argon) that detaches from a material, such as the mesoporous beta zeolite, at 87 Kelvin over a range of pressures. Using the Kelvin equation, the amount of argon adsorbate removed from the pores of the material and the relative pressure of the system can be used to calculate the pore size of the material. As used in this disclosure, the term “microporous” may refer to a material, such as a beta zeolite, having pores with an average pore size of from 0.1 nanometers (nm) to 2 nm. As used in the present disclosure, the term “mesoporous” may refer to a material, such as a beta zeolite, having pores with an average pore size of from 2 nm to 50 nm. As used in this disclosure, the term “macroporous” may refer to a material, such as a catalyst, having pores with an average pore size of greater than 50 nm. As used in the present disclosure, the term “crude oil” may refer to a mixture of petroleum liquids and gases, including impurities, such as sulfur-containing compounds, nitrogen-containing compounds, and metal compounds, extracted directly from a subterranean formation or received from a desalting unit without having any fractions, such as naphtha, separated by distillation. As used in the present disclosure, the term “reactor” may refer to a vessel or series of vessels in which one or more chemical reactions may occur between one or more reactants in the presence of one or more catalysts. For example, a reactor may include a tank or tubular reactor configured to operate as a batch reactor, a continuous stirred-tank reactor (CSTR), or a plug flow reactor. Example reactors include packed bed reactors such as fixed bed reactors, and fluidized bed reactors. Embodiments of the present disclosure are directed to processes of producing a catalyst.FIG.1Adepicts a flowchart for a process of producing a catalyst, according to one or more embodiments shown and described in this disclosure.FIG.1Bdepicts a flowchart for a process of forming a mesoporous beta zeolite, according to one or more embodiments shown and described in this disclosure. Referring toFIGS.1A and1B, in step110, mesoporous beta zeolite particles are formed. Step110includes converting a crystalline beta zeolite to a non-crystalline material with reduced silica content relative to the crystalline beta zeolite. In one or more embodiments, step110includes steps111and112(ofFIG.1B). In step111, a crystalline beta zeolite is converted to a non-crystalline material. The crystalline beta zeolite may have an average crystal size of from 0.01 micrometers (μm) to 5.0 μm, from 0.01 μm to 3.0 μm, from 0.01 μm to 2.0 μm, from 0.01 μm to 1.5 μm, or from 0.01 μm to 1.4 μm. The particle size may be calculated from XRD. The particle of crystalline beta zeolite may comprise one or more crystals. The crystal may comprise one or more unit cells. The crystalline beta zeolite may have an average crystal size of 0.05 μm to 5.0 μm, from 0.05 μm to 3.0 μm, from 0.05 μm to 2.0 μm, from 0.05 μm to 1.5 μm, from 0.05 μm to 1.4 μm, 0.1 μm to 5.0 μm, from 0.1 μm to 3.0 μm, from 0.1 μm to 2.0 μm, from 0.1 μm to 1.5 μm, or from 0.1 μm to 1.4 μm. The crystal size may be calculated from XRD. The crystalline beta zeolite may have an average pore size of from 0.5 nanometers (nm) to 3.0 nm, from 0.5 nm to 2.0 nm, from 0.5 nm to 1.0 nm, from 0.5 nm to 0.75 nm, from 0.5 nm to 0.74 nm, from 0.56 nm to 3.0 nm, from 0.56 nm to 2.0 nm, from 0.56 nm to 1.0 nm, from 0.56 nm to 0.75 nm, or from 0.56 nm to 0.74 nm. The pore size may be determined using the Mercury Intrusion Porosimetry. The crystalline beta zeolite may have a molar ratio of silica (SiO2) to alumina (Al2O3) of greater than or equal to 10, greater than or equal to 20, or even greater than or equal to 30. The crystalline beta zeolite may have a molar ratio of SiO2to Al2O3of less than or equal to 400, such as less than or equal to 350, or even less than or equal to 300. The crystalline beta zeolite may have a molar ratio of SiO2to Al2O3of from 10 to 400, from 10 to 350, from 10 to 300, from 20 to 400, from 20 to 350, from 20 to 300, from 30 to 400, from 30 to 350, from 30 to 300, from 10 to 70, from 20 to 60, from 30 to 50, from 250 to 400, from 280 to 350, or from 300 to 320. In step111, the crystalline beta zeolite may be mixed with one or more solvents, cetyltrimethylammonium bromide (CTAB), and metal hydroxide to produce a solution. In some embodiments, the mixing step include mixing the crystalline beta zeolite with metal hydroxide, and then adding CTAB into a mixture of the crystalline beta zeolite with metal hydroxide. Without being limited by any particular theory, it is believed the mixing step may evenly disperse the crystalline beta zeolite, CTAB, and metal hydroxide. Mixing may include one or more of stirring, swirling, vortexing, shaking, sonicating, homogenizing, blending, or the like. The metal hydroxide may include a single metal hydroxide species, or a combination of two or more metal hydroxide chemical species. In embodiments, the metal hydroxide comprises at least one alkali metal hydroxide, at least one alkali earth metal hydroxide, or combinations thereof. The metal hydroxide may comprise lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), strontium hydroxide (Sr(OH)2), barium hydroxide (Ba(OH)2), or combinations thereof. In one or more embodiments, the metal hydroxide may be in a solution. The metal hydroxide solution may have a metal hydroxide concentration from 0.01 moles per liter (M) to 10 M, such as from 0.01 M to 5 M, from 0.01 M to 3 M, from 0.01 M to 1 M, from 0.05 M to 1 M, from 0.05 M to 0.8 M, from 0.05 M to 0.5 M, or from 0.1 M to 0.4 M. Still referring toFIGS.1A and1B, as described above, the crystalline beta zeolite and the metal hydroxide may be mixed with cetyltrimethylammonium bromide (CTAB) in step111. CTAB is a surfactant. In particular, when the solution including the crystalline beta zeolite, the metal hydroxide, and CTAB, the CTAB is heated to produce a non-crystalline material, the CTAB may reduce silica content of the crystalline beta zeolite. Thus, the non-crystalline material may have reduced silica content relative to the crystalline beta zeolite. CTAB may be included in a CTAB solution. The CTAB solution may have greater than or equal to 1 wt. %, greater than or equal to 2 wt. %, or greater than or equal to 3 wt. % of CTAB. The CTAB solution may have less than or equal to 10 wt. %, less than or equal to 8 wt. %, less than or equal to 7 wt. %, or less than or equal to 6 wt. % of CTAB. The CTAB solution may have from 1 wt. % to 10 wt. %, from 1 wt. % to 8 wt. %, from 1 wt. % to 7 wt. %, from 1 wt. % to 6 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 8 wt. %, from 2 wt. % to 7 wt. %, from 2 wt. % to 6 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 8 wt. %, from 3 wt. % to 7 wt. %, or from 3 wt. % to 6 wt. % of CTAB. Still referring toFIGS.1A and1B, in step111, the solution may be heated at a temperature of from 50° C. to 150° C. to convert the crystalline beta zeolite to a non-crystalline material with reduced silica content relative to the crystalline beta zeolite. In the heating step, the crystalline beta zeolite may be disintegrated. The term “disintegrated” may refer that the siloxane bonds (silicate groups) of the crystalline beta zeolite are broken. The solution may be heated at a temperature of greater than or equal to 50° C., greater than or equal to 60° C., greater than or equal to 70° C., or greater than or equal to 80° C. The solution may be heated at a temperature of less than or equal to 150° C., less than or equal to 140° C., less than or equal to 130° C., or less than or equal to 120° C. The solution may be heated at a temperature of from 50° C. to 150° C., from 50° C. to 140° C., from 50° C. to 130° C., from 50° C. to 120° C., from 60° C. to 150° C., from 60° C. to 140° C., from 60° C. to 130° C., from 60° C. to 120° C., from 70° C. to 150° C., from 70° C. to 140° C., from 70° C. to 130° C., from 70° C. to 120° C., from 80° C. to 150° C., from 80° C. to 140° C., from 80° C. to 130° C., or from 80° C. to 120° C. Still referring toFIGS.1A and1B, in step111, the heated solution may be cooled to a temperature of from 25° C. to 40° C. The solution may be cooled at a temperature of greater than or equal to 0° C., greater than or equal to 10° C., greater than or equal to 20° C., or greater than or equal to 25° C. The solution may be cooled at a temperature of less than or equal to 50° C., less than or equal to 45° C., less than or equal to 40° C., or less than or equal to 30° C. The solution may be cooled at a temperature of from 0° C. to 50° C., from 0° C. to 45° C., from 0° C. to 40° C., from 0° C. to 30° C., from 10° C. to 50° C., from 10° C. to 45° C., from 10° C. to 40° C., from 10° C. to 30° C., from 20° C. to 50° C., from 20° C. to 45° C., from 20° C. to 40° C., from 20° C. to 30° C., from 25° C. to 50° C., from 25° C. to 45° C., or from 25° C. to 40° C. Still referring toFIGS.1A and1B, step110of forming a mesoporous beta zeolite includes step112of crystalizing the non-crystalline material to produce mesoporous beta zeolite particles. In some embodiments, in step112, the pH of the solution may be adjusted to from 8 to 10 by adding an acid. In the step of adjusting a pH of the solution, CTAB, which is already present in the solution, takes a circular micellar form. The acid may include dilute sulfuric acid, nitric acid, acetic acid, citric acid, oxalic acid, or combinations thereof. In some embodiments, the acid may have from 0.1 Normality (N) to 5 N, from 0.1 N to 4 N, from 0.1 N to 3 N, from 0.5 N to 5 N, from 0.5 N to 4 N, from 0.5 N to 3 N, from 1 N to 5 N, from 1 N to 4 N, or from 1 N to 3 N. In some embodiments, the solution may have the pH of greater than or equal to 13. The pH of the solution may be adjusted to greater than or equal to 7, greater than or equal to 8, or greater than or equal to 9. The pH of the solution may be adjusted to less than or equal to 12, less than or equal to 11, or less than or equal to 10. The pH of the solution may be adjusted to from 7 to 12, from 7 to 11, from 7 to 10, from 8 to 12, from 8 to 11, from 8 to 10, from 9 to 12, from 9 to 11, or from 9 to 10. In some embodiments, the process of the present disclosure of producing a catalyst includes stirring the solution from 10 hour to 48 hours (not shown inFIGS.1A and1B). The solution may be stirred at a time period of greater than or equal to 10 hours, greater than or equal to 13 hours, greater than or equal to 17 hours, or greater than or equal to 20 hours. The solution may be stirred at a time period of less than or equal to 48 hours, less than or equal to 40 hours, less than or equal to 35 hours, or less than or equal to 30 hours. The solution may be stirred at a time period of from 10 hours to 48 hours, from 10 hours to 40 hours, from 10 hours to 35 hours, from 10 hours to 30 hours, from 13 hours to 48 hours, from 13 hours to 40 hours, from 13 hours to 35 hours, from 13 hours to 30 hours, from 17 hours to 48 hours, from 17 hours to 40 hours, from 17 hours to 35 hours, from 17 hours to 30 hours, from 20 hours to 48 hours, from 20 hours to 40 hours, from 20 hours to 35 hours, or from 20 hours to 30 hours. Still referring toFIGS.1A and1B, in step112, the solution is aged at a temperature of from 50° C. to 150° C. for a time period sufficient to crystalize the non-crystalline material to produce beta zeolite particles. When the non-crystalline material is crystalized, the silica broken from the crystalline beta zeolite helps to produce a mesoporous beta zeolite having uniform mesopores and micropores. In particular, a surfactant, CTAB, may act as a structure directing agent. Re-crystallisation of beta zeolite in the presence of CTAB may prevent the dissolution of the crystals and lead to almost complete recovery of the zeolite. After calcination, the surfactant moiety may be removed and the resulting voids constitute the mesopores of the mesoporous zeolite. The achievement of uniform mesoporosity is highly desirable because the mesopore quality, which encompasses size, distribution, and connectivity, helps improve stability against coke deactivation. Conventional microporous beta zeolite may inhibit access to catalytically active sites on the beta zeolite to larger molecules, which may have a molecular size equal to or greater than the average pore size of the microporous beta zeolite. The mesoporous beta zeolite produced by the presently described process may be hierarchical mesoporous beta zeolite having both uniform mesopores and micropores. With these uniform mesopores and micropores, the mesoporous beta zeolite may increase access to the large size molecules, and thereby suitable for hydrocarbon feedstocks including larger hydrocarbon molecules, such as crude oil. Also, the mesoporous beta zeolite may exhibit stability at elevated temperatures, such as temperatures greater than 500° C., and the acid sites of mesoporous beta zeolites may be compatible with hydrocracking reactions, which are helpful to break up a hydrocarbon feed or a hydrocarbon fraction into smaller molecules. The mesoporous beta zeolite, therefore, may facilitate the transport of the larger hydrocarbon molecules in crude oil to catalytic sites and reduce the diffusion limitations of these catalysts. The solution may be aged at a temperature of greater than or equal to 50° C., greater than or equal to 60° C., greater than or equal to 70° C., or greater than or equal to 80° C. The solution may be aged at a temperature of less than or equal to 150° C., less than or equal to 140° C., less than or equal to 130° C., or less than or equal to 120° C. The solution may be aged at a temperature of from 50° C. to 150° C., from 50° C. to 140° C., from 50° C. to 130° C., from 50° C. to 120° C., from 60° C. to 150° C., from 60° C. to 140° C., from 60° C. to 130° C., from 60° C. to 120° C., from 70° C. to 150° C., from 70° C. to 140° C., from 70° C. to 130° C., from 70° C. to 120° C., from 80° C. to 150° C., from 80° C. to 140° C., from 80° C. to 130° C., or from 80° C. to 120° C. The solution may be aged at a time period of greater than or equal to 10 hours, greater than or equal to 13 hours, greater than or equal to 17 hours, or greater than or equal to 20 hours. The solution may be aged at a time period of less than or equal to 48 hours, less than or equal to 40 hours, less than or equal to 35 hours, or less than or equal to 30 hours. The solution may be aged at a time period of from 10 hours to 48 hours, from 10 hours to 40 hours, from 10 hours to 35 hours, from 10 hours to 30 hours, from 13 hours to 48 hours, from 13 hours to 40 hours, from 13 hours to 35 hours, from 13 hours to 30 hours, from 17 hours to 48 hours, from 17 hours to 40 hours, from 17 hours to 35 hours, from 17 hours to 30 hours, from 20 hours to 48 hours, from 20 hours to 40 hours, from 20 hours to 35 hours, or from 20 hours to 30 hours. In some embodiments, the process of the present disclosure of producing the catalyst includes filtering the beta zeolite particles from the solution (not shown inFIGS.1A and1B). In some embodiments, the process of the present disclosure of producing the catalyst includes washing the beta zeolite particles through distilled water (not shown inFIGS.1A and1B). The beta zeolite particles may be washed through distilled water to remove excess metal hydroxide and CTAB from the beta zeolite particles. In some embodiments, the process of the present disclosure of producing the catalyst includes drying the beta zeolite particles at a temperature of from 50° C. to 150° C. (not shown inFIGS.1A and1B). The beta zeolite particles may be dried at a temperature of greater than or equal to 50° C., greater than or equal to 60° C., or greater than or equal to 70° C. The beta zeolite particles may be dried at a temperature of less than or equal to 200° C., less than or equal to 150° C., or less than or equal to 100° C. The beta zeolite particles may be dried at a temperature of from 50° C. to 200° C., from 50° C. to 150° C., from 50° C. to 100° C., from 60° C. to 200° C., from 60° C. to 150° C., from 60° C. to 100° C., from 70° C. to 200° C., from 70° C. to 150° C., or from 70° C. to 100° C. The solution may be dried at a time period of greater than or equal to 2 hours, greater than or equal to 4 hours, greater than or equal to 6 hours, or greater than or equal to 8 hours. The solution may be dried at a time period of less than or equal to 24 hours, less than or equal to 20 hours, less than or equal to 15 hours, or less than or equal to 12 hours. The solution may be dried at a time period of from 2 hours to 24 hours, from 2 hours to 20 hours, from 2 hours to 15 hours, from 2 hours to 12 hours, from 4 hours to 24 hours, from 4 hours to 20 hours, from 4 hours to 15 hours, from 4 hours to 12 hours, from 6 hours to 24 hours, from 6 hours to 20 hours, from 6 hours to 15 hours, from 6 hours to 12 hours, from 8 hours to 24 hours, from 8 hours to 20 hours, from 8 hours to 15 hours, or from 8 hours to 12 hours. In some embodiments, the process of the present disclosure of producing the catalyst includes calcining the beta zeolite particles at a temperature of from 400° C. to 800° C. for 1 to 12 hours to remove the surfactant, such as CTAB (not shown inFIGS.1A and1B). The beta zeolite particles may be calcined at a temperature of greater than or equal to 400° C., greater than or equal to 450° C., or greater than or equal to 500° C. The beta zeolite particles may be calcined at a temperature of less than or equal to 800° C., less than or equal to 700° C., or less than or equal to 600° C. The beta zeolite particles may be calcined at a temperature of from 400° C. to 800° C., from 400° C. to 700° C., from 400° C. to 600° C., from 450° C. to 800° C., from 450° C. to 700° C., from 450° C. to 600° C., from 500° C. to 800° C., from 500° C. to 700° C., or from 500° C. to 600° C. The solution may be calcined at a time period of greater than or equal to 1 hour, greater than or equal to 3 hours, or greater than or equal to 5 hours. The solution may be calcined at a time period of less than or equal to 15 hours, less than or equal to 12 hours, less than or equal to 10 hours, or less than or equal to 8 hours. The solution may be calcined at a time period of from 1 hour to 15 hours, from 1 hour to 12 hours, from 1 hour to 10 hours, from 1 hour to 8 hours, from 3 hours to 15 hours, from 3 hours to 12 hours, from 3 hours to 10 hours, from 3 hours to 8 hours, from 5 hour to 15 hours, from 5 hour to 12 hours, from 5 hour to 10 hours, or from 5 hour to 8 hours. Still referring toFIGS.1A and1B, in some embodiments, the process of the present disclosure of producing the catalyst includes treating the beta zeolite particles with ammonium salt a temperature of from 70° C. to 90° C. for 1 to 12 hours (not shown inFIGS.1A and1B). The treating the beta zeolite particles with the ammonium salt may cause sufficient ion exchange of sodium ions with ammonium ions present in the ammonium salt to produce the mesoporous beta zeolite. The beta zeolite particles may be treated with the ammonium salt at a temperature of greater than or equal to or equal to 40° C., greater than or equal to or equal to 50° C., or greater than or equal to or equal to 60° C. The beta zeolite particles may be treated with the ammonium salt at a temperature of less than or equal to 200° C., less than or equal to 150° C., or less than or equal to 100° C. The beta zeolite particles may be treated with the ammonium salt at a temperature of from 40° C. to 200° C., from 40° C. to 150° C., from 40° C. to 100° C., from 50° C. to 200° C., from 50° C. to 150° C., from 50° C. to 100° C., from 60° C. to 200° C., from 60° C. to 150° C., or from 60° C. to 100° C. The solution may be treated with the ammonium salt at a time period of greater than or equal to or equal to 1 hour, greater than or equal to or equal to 2 hours, or greater than or equal to or equal to 3 hours. The solution may be treated with the ammonium salt at a time period of less than or equal to 12 hours, less than or equal to 10 hours, less than or equal to 9 hours, or less than or equal to 8 hours. The solution may be treated with the ammonium salt at a time period of from 1 hour to 12 hours, from 1 hour to 10 hours, from 1 hour to 9 hours, from 1 hour to 8 hours, from 2 hours to 12 hours, from 2 hours to 10 hours, from 2 hours to 9 hours, from 2 hours to 8 hours, from 3 hour to 12 hours, from 3 hour to 10 hours, from 3 hour to 9 hours, or from 3 hour to 8 hours. In some embodiments, the treating step may include first treating the beta zeolite particles with the ammonium salt at a temperature of from 70° C. to 90° C. for 1 to 12 hours, and second treating the beta zeolite particles with the ammonium salt at a temperature of from 70° C. to 90° C. for 1 to 12 hours to produce the mesoporous beta zeolite (not shown inFIGS.1A and1B). The beta zeolite particles may be first treated with the ammonium salt at a temperature of greater than or equal to 40° C., greater than or equal to 50° C., or greater than or equal to 60° C. The beta zeolite particles may be first treated with the ammonium salt at a temperature of less than or equal to 200° C., less than or equal to 150° C., or less than or equal to 100° C. The beta zeolite particles may be first treated with the ammonium salt at a temperature of from 40° C. to 200° C., from 40° C. to 150° C., from 40° C. to 100° C., from 50° C. to 200° C., from 50° C. to 150° C., from 50° C. to 100° C., from 60° C. to 200° C., from 60° C. to 150° C., or from 60° C. to 100° C. The solution may be first treated with the ammonium salt at a time period of greater than or equal to 1 hour, greater than or equal to 2 hours, or greater than or equal to 3 hours. The solution may be first treated with the ammonium salt at a time period of less than or equal to 12 hours, less than or equal to 10 hours, less than or equal to 9 hours, or less than or equal to 8 hours. The solution may be first treated with the ammonium salt at a time period of from 1 hour to 12 hours, from 1 hour to 10 hours, from 1 hour to 9 hours, from 1 hour to 8 hours, from 2 hours to 12 hours, from 2 hours to 10 hours, from 2 hours to 9 hours, from 2 hours to 8 hours, from 3 hour to 12 hours, from 3 hour to 10 hours, from 3 hour to 9 hours, or from 3 hour to 8 hours. The beta zeolite particles may be second treated with the ammonium salt at a temperature of greater than or equal to 40° C., greater than or equal to 50° C., or greater than or equal to 60° C. The beta zeolite particles may be second treated with the ammonium salt at a temperature of less than or equal to 200° C., less than or equal to 150° C., or less than or equal to 100° C. The beta zeolite particles may be second treated with the ammonium salt at a temperature of from 40° C. to 200° C., from 40° C. to 150° C., from 40° C. to 100° C., from 50° C. to 200° C., from 50° C. to 150° C., from 50° C. to 100° C., from 60° C. to 200° C., from 60° C. to 150° C., or from 60° C. to 100° C. The solution may be second treated with the ammonium salt at a time period of greater than or equal to 1 hour, greater than or equal to 2 hours, or greater than or equal to 3 hours. The solution may be second treated with the ammonium salt at a time period of less than or equal to 12 hours, less than or equal to 10 hours, less than or equal to 9 hours, or less than or equal to 8 hours. The solution may be second treated with the ammonium salt at a time period of from 1 hour to 12 hours, from 1 hour to 10 hours, from 1 hour to 9 hours, from 1 hour to 8 hours, from 2 hours to 12 hours, from 2 hours to 10 hours, from 2 hours to 9 hours, from 2 hours to 8 hours, from 3 hour to 12 hours, from 3 hour to 10 hours, from 3 hour to 9 hours, or from 3 hour to 8 hours. The ammonium salt may include salts that include an ammonium cation and at least one anion, such as but not limited to nitrate, chloride, carbonate, sulfate, or combinations of these. In some embodiments, the ammonium salt may include ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, or combinations thereof. The ammonium salt may be included in an ammonium salt solution. The ammonium salt solution may have a concentration of ammonium salts of from 0.05 moles per liter (M) to 0.5 M, such as from 0.05 M to 0.4 M, from 0.05 M to 0.3 M, from 0.1 M to 0.5 M, from 0.1 M to 0.4 M, from 0.1 M to 0.3 M, from 0.2 M to 0.5 M, from 0.2 M to 0.4 M, or from 0.2 M to 0.3 M. In step120, the mesoporous beta zeolite particles are produced. The mesoporous beta zeolite particles may have an average particle size of from 0.1 μm to 3.0 μm, from 0.1 μm to 2.0 μm, from 0.1 μm to 1.1 μm, 0.2 μm to 3.0 μm, from 0.2 μm to 2.0 μm, from 0.2 μm to 1.1 μm, 0.4 μm to 3.0 μm, from 0.4 μm to 2.0 μm, or from 0.4 μm to 1.1 μm. The particle size may be calculated from XRD. The mesoporous beta zeolite produced according to the previously described processes may have both mesopores and micropores. In some embodiments, the average mesopore size of the mesoporous beta zeolite may be from 2 nm to 20 nm, from 2 nm to 15 nm, from 2 nm to 10 nm, from 2 nm to 5 nm, from 2 nm to 4.5 nm, from 3 nm to 20 nm, from 3 nm to 15 nm, from 3 nm to 10 nm, from 3 nm to 5 nm, or 3 nm to 4.5 nm. In some embodiments, the average micropore size of the mesoporous beta zeolite may be from 0.01 nm to 3 nm, from 0.01 nm to 2.5 nm, from 0.01 nm to 2.0 nm, from 0.05 nm to 3 nm, from 0.05 nm to 2.5 nm, from 0.05 nm to 2.0 nm, from 0.1 nm to 3 nm, from 0.1 nm to 2.5 nm, from 0.1 nm to 2.0 nm, from 0.5 nm to 3 nm, from 0.5 nm to 2.5 nm, or from 0.5 nm to 2.0 nm. In some embodiments, the mesoporous beta zeolite may have a total pore volume of from 0.1 cm3/g to 1.0 cm3/g, from 0.1 cm3/g to 0.85 cm3/g, from 0.1 cm3/g to 0.8 cm3/g, from 0.5 cm3/g to 1.0 cm3/g, from 0.5 cm3/g to 0.85 cm3/g, or from 0.5 cm3/g to 0.8 cm3/g as determined by Brunauer-Emmett-Teller (BET) analysis. The total pore volume of the mesoporous beta zeolite may represent the total sum of the volume of micropores and mesopores in the mesoporous beta zeolite. The mesoporous beta zeolite may have a Brunauer-Emmett-Teller (BET) surface area of from 400 square meters per gram (m2/g) to 800 m2/g, from 400 m2/g to 750 m2/g, from 400 m2/g to 700 m2/g, from 450 m2/g to 800 m2/g, from 450 m2/g to 750 m2/g, from 450 m2/g to 700 m2/g, from 500 m2/g to 800 m2/g, from 500 m2/g to 750 m2/g, or from 500 m2/g to 700 m2/g. The mesoporous beta zeolite may have a mesopore volume of from 300 cm3/g to 500 cm3/g, from 300 cm3/g to 450 cm3/g, from 300 cm3/g to 400 cm3/g, from 350 cm3/g to 500 cm3/g, from 350 cm3/g to 450 cm3/g, or from 350 cm3/g to 400 cm3/g. Still referring toFIGS.1A and1B, in step120, the mesoporous beta zeolite particles are impregnated with a metal and phosphorus to produce a metal and phosphorus impregnated zeolite. For the impregnation method, the mesoporous beta zeolite particles may be mixed with water to form a dough that can be extruded using an extruder. The extrudate may be impregnated with an aqueous solution including the metal and phosphorus. In some embodiments, the metal includes Ce, La, Fe, or combinations thereof. In some embodiments, the metal and phosphorus impregnated zeolite include the metal in amount of from 0.1 wt. % to 10 wt. %, from 0.1 wt. % to 8 wt. %, from 0.1 wt. % to 5 wt. %, from 0.5 wt. % to 10 wt. %, from 0.5 wt. % to 8 wt. %, from 0.5 wt. % to 5 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 8 wt. %, from 1 wt. % to 5 wt. % the total weight of the metal and phosphorus impregnated zeolite, or any combination of these ranges. In some embodiments, the metal and phosphorus impregnated zeolite includes Ce, La, and Fe. In some embodiments, the metal and phosphorus impregnated zeolite includes from 0.1 wt. % to 5 wt. %, from 0.1 wt. % to 3 wt. %, from 0.1 wt. % to 2 wt. %, from 0.5 wt. % to 5 wt. %, from 0.5 wt. % to 3 wt. %, or from 0.5 wt. % to 2 wt. % of Ce based on the total weight of the metal and phosphorus impregnated zeolite, from 0.1 wt. % to 5 wt. %, from 0.1 wt. % to 3 wt. %, from 0.1 wt. % to 2 wt. %, from 0.5 wt. % to 5 wt. %, from 0.5 wt. % to 3 wt. %, or from 0.5 wt. % to 2 wt. % of La based on the total weight of the metal and phosphorus impregnated zeolite, from 0.1 wt. % to 5 wt. %, from 0.1 wt. % to 3 wt. %, from 0.1 wt. % to 2 wt. %, from 0.5 wt. % to 5 wt. %, from 0.5 wt. % to 3 wt. %, or from 0.5 wt. % to 2 wt. % of Fe based on the total weight of the metal and phosphorus impregnated zeolite. In some embodiments, the metal and phosphorus impregnated zeolite includes phosphorus. In some embodiments, the metal and phosphorus impregnated zeolite includes P2O5. In some embodiments, the metal and phosphorus impregnated zeolite include P2O5in amount of from 1 wt. % to 10 wt. %, from 1 wt. % to 8 wt. %, from 1 wt. % to 5 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 8 wt. %, from 2 wt. % to 5 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 8 wt. %, from 3 wt. % to 5 wt. % the total weight of the metal and phosphorus impregnated zeolite, or any combination of these ranges. In some embodiments, the metal and phosphorus impregnated zeolite include 0.1 wt. % to 5 wt. % of Ce based on the total weight of the metal and phosphorus impregnated zeolite, 0.1 wt. % to 5 wt. % of La based on the total weight of the metal and phosphorus impregnated zeolite, 0.1 wt. % to 5 wt. % of Fe based on the total weight of the metal and phosphorus impregnated zeolite, and 2 wt. % to 10 wt. % of P2O5based on the total weight of the metal and phosphorus impregnated zeolite. Still referring toFIGS.1A and1B, in step130, the metal and phosphorus impregnated zeolite is incorporated with clay and alumina to produce the catalyst. In some embodiments, the catalyst may include the metal and phosphorus impregnated zeolite in an amount of from 25 wt. % to 60 wt. % of the total weight of the catalyst. For example, the catalyst may include the metal and phosphorus impregnated zeolite in an amount of from 25 wt. % to 55 wt. %, from 25 wt. % to 50 wt. %, from 30 wt. % to 60 wt. %, from 30 wt. % to 55 wt. %, from 30 wt. % to 50 wt. %, from 35 wt. % to 60 wt. %, from 35 wt. % to 55 wt. %, from 35 wt. % to 50 wt. % the total weight of the catalyst, or any combination of these ranges. The clay may act as matrix materials. Without being bound by theory, it is believed that the matrix materials of the catalyst serve both physical and catalytic functions. Physical functions include providing particle integrity and attrition resistance, acting as a heat transfer medium, and providing a porous structure to allow diffusion of hydrocarbons into and out of the catalyst microspheres. The matrix materials can also affect catalyst selectivity, product quality and resistance to poisons. The matrix materials may tend to exert its strongest influence on overall catalytic properties for those reactions which directly involve relatively large molecules. In some embodiments, the clay may include kaolin clay. As used in this disclosure, the term “kaolin” may refer to a clay material that has a relatively large amount (such as at least about 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, or even at least 95 wt. %) of kaolinite, which can be represented by the chemical formula Al2Si2O5(OH)4. In some embodiments, the catalyst may include the clay in an amount of from 25 wt. % to 60 wt. % of the total weight of the catalyst. For example, the catalyst may include the clay in an amount of from 25 wt. % to 55 wt. %, from 25 wt. % to 50 wt. %, from 30 wt. % to 60 wt. %, from 30 wt. % to 55 wt. %, from 30 wt. % to 50 wt. %, from 35 wt. % to 60 wt. %, from 35 wt. % to 55 wt. %, from 35 wt. % to 50 wt. % the total weight of the catalyst, or any combination of these ranges. The alumina may act as a binder. As used in this disclosure, the term “binder” may refer to materials which may serve to “glue” or otherwise hold zeolite and the matrix together in the microsphere. It may improve the attrition resistance of the catalyst. In some embodiments, the catalyst may include alumina in an amount of from 10 wt. % to 40 wt. % of the total weight of the catalyst. For example, the catalyst may include alumina in an amount of from 10 wt. % to 35 wt. %, from 10 wt. % to 30 wt. %, from 12 wt. % to 40 wt. %, from 12 wt. % to 35 wt. %, from 12 wt. % to 30 wt. %, from 15 wt. % to 40 wt. %, from 15 wt. % to 35 wt. %, from 15 wt. % to 30 wt. % the total weight of the catalyst, or any combination of these ranges. The catalyst may be formed by a variety of processes. In some embodiments, the clay may be mixed with a fluid such as water to form a slurry, and the mesoporous beta zeolites may be separately mixed with a fluid such as water to form a slurry. The clay slurry and the mesoporous beta zeolite slurry may be combined under stirring. Separately, another slurry may be formed by combining the alumina with a fluid such as water. The alumina slurry may then be combined with the slurry containing the mesoporous beta zeolites and clay to form an all-ingredients slurry. The all-ingredients slurry may be dried, for example by spraying, and then calcined, to produce the catalyst. In step130, the catalysts are produced. The catalysts may include mesopores, micropores, and macropores. The mesoporous beta zeolite in the catalyst may provide mesopores and micropores. As described above, the mesoporous beta zeolite has uniform mesopores and micropores compared to conventional zeolites. With these uniform mesopores and micropores, the mesoporous beta zeolite may have longer catalytic cracking activity and increase access to the large size molecules, and thereby suitable for hydrocarbon feedstocks including larger hydrocarbon molecules, such as crude oil. Also, the mesoporous beta zeolite may exhibit improved hydrothermal stability at elevated temperatures, such as temperatures greater than 500° C., and the acid sites of mesoporous beta zeolites may be compatible with hydrocracking reactions, which are helpful to break up a hydrocarbon feed or a hydrocarbon fraction into smaller molecules. The mesoporous beta zeolite, therefore, may facilitate the transport of the larger hydrocarbon molecules in crude oil to catalytic sites and reduce the diffusion limitations of these catalysts. Moreover, alumina and the clay included in the catalyst may provide macropores in the catalyst. The macropores in the catalyst may break down large molecules in crude oil to make it easier for them to diffuse into the mesopores and micropores of the mesoporous beta zeolites. Further these macropores in the catalyst may trap contaminant metals. With these mesopores, micropores, and macropores, the catalyst produced by the presently described process may be capable of increasing the light olefin yield from steam enhanced fluidized catalytic cracking of the crude oil while having excellent hydrothermal stability and longer catalytic cracking activity. The catalysts produced by previously described processes may be used as a catalyst in fluidized catalytic cracking (FCC) processes. The catalysts may be contacted with the crude oil in the presence of steam to produce light olefin in a reactor, such as fluidized catalytic cracking (FCC) reactor. As used in this disclosure, a “fluidized catalytic cracking (FCC) reactor” refers to a reactor that can be operable to contact a fluidized reactant with a solid material (usually in particulate form), such as a catalyst. The reactor may be a fluidized bed reactor. As described in this disclosure, a fluidized bed reactor which cracks a reactant stream with a fluidized solid catalyst may be referred to as a fluidized catalytic FCC reactor. Examples of suitable processes for catalytically cracking crude oil in the presence of steam are disclosed in U.S. patent application Ser. Nos. 17/009,008, 17/009,012, 17/009,020, 17/009,022, 17/009,039, 17/009,048, and 17/009,073, all of which are incorporated by reference in their entireties. The catalyst may be deactivated by contact with steam prior to use in a reactor to convert crude oil. The purpose of steam treatment is to accelerate the hydrothermal aging which occurs in an operational FCC regenerator to obtain an equilibrium catalyst. Steam treatment may lead to the removal of aluminum from the framework leading to a decrease in the number of sites where framework hydrolysis can occur under hydrothermal and thermal conditions. This removal of aluminum results in an increased thermal and hydrothermal stability in dealuminated mesoporous beta zeolites. The unit cell size may decrease as a result of dealumination since the smaller SiO4tetrahedron replaces the larger AlO4-tetrahedron. The acidity of mesoporous beta zeolite s may also be affected by dealumination through the removal of framework aluminum and the formation of extra-framework aluminum species. Dealumination may affect the acidity of the mesoporous beta zeolite by decreasing the total acidity and increasing the acid strength of the mesoporous beta zeolite. The total acidity may decrease because of the removal of framework aluminum, which act as Bronsted acid sites. The acid strength of the mesoporous beta zeolite may be increased because of the removal of paired acid sites or the removal of the second coordinate next nearest neighbor aluminum. The increase in the acid strength may be caused by the charge density on the proton of the OH group being highest when there is no framework aluminum in the second coordination sphere. In some embodiments, the crude oil may have a relatively great API gravity, such as at least 30 degrees, and often greater than 50 degrees. In some embodiments, the crude oil may have an API gravity of at least about 30 degrees, at least 35 degrees, at least 40 degrees, at least 45 degrees, at least 50 degrees, at least 55 degrees, or even at least 60 degrees. In some embodiments, the crude oil may have a boiling point profile as described by the 5 wt. % boiling temperature, the 25 wt. % boiling temperature, the 50 wt. % boiling temperature, the 75 wt. % boiling temperature, and the 95 wt. % boiling temperature. These respective boiling temperatures correspond to the temperature at which a given weight percentage of the hydrocarbon feed stream boils. In some embodiments, the crude oil may have one or more of a 5 wt. % boiling temperature of less than 150° C., a 25 wt. % boiling temperature of less than 225° C., a 50 wt. % boiling temperature of less than 300° C., a 75 wt. % boiling temperature of less than 400° C., and a 95 wt. % boiling temperature of less than 600° C. In some embodiments, the crude oil may have one or more of a 5 wt. % boiling temperature of from 0° C. to 100° C., a 25 wt. % boiling temperature of from 75° C. to 175° C., a 50 wt. % boiling temperature of from 150° C. to 250° C., a 75 wt. % boiling temperature of from 250° C. to 350° C., and a 95 wt. % boiling temperature of from 450° C. to 550° C. In some embodiments, the reactor may be operated at a temperature of at least about 500° C. In some embodiments, the reactor may be operated at a temperature of from 500° C. to 800° C., from 550° C. to 800° C., from 600° C. to 800° C., from 650° C. to 800° C., from 500° C. to 750° C., from 550° C. to 750° C., from 600° C. to 750° C., from 650° C. to 750° C., from 500° C. to 700° C., from 550° C. to 700° C., from 600° C. to 700° C., or from 650° C. to 700° C. In some embodiments, steam may be injected to the reactor. The crude oil may be catalytically cracked in the presence of the steam with the catalyst. Steam may act as a diluent to reduce a partial pressure of the hydrocarbons in the crude oil. The steam to the crude oil mass ratio may be from 0.2 to 1.0, from 0.3 to 1.0, from 0.4 to 1.0, from 0.5 to 1.0, from 0.2 to 0.8, from 0.3 to 0.8, from 0.4 to 0.8, from 0.5 to 0.8, from 0.2 to 0.7, from 0.3 to 0.7, from 0.4 to 0.7, from 0.5 to 0.7, from 0.2 to 0.6, from 0.3 to 0.6, from 0.4 to 0.6, or from 0.5 to 0.6. Steam may refer to all H2O in the steam. In some embodiments, the residence time of the crude oil and the steam may be from 1 second to 20 seconds, from 2 seconds to 20 seconds, from 5 seconds to 20 seconds, from 8 seconds to 20 seconds, from 1 second to 18 seconds, from 2 seconds to 18 seconds, from 5 seconds to 18 seconds, from 8 seconds to 18 seconds, from 1 second to 16 seconds, from 2 seconds to 16 seconds, from 5 seconds to 16 seconds, from 8 seconds to 16 seconds, from 1 second to 14 seconds, from 2 seconds to 14 seconds, from 5 seconds to 14 seconds, from 8 seconds to 14 seconds, from 1 second to 12 seconds, from 2 seconds to 12 seconds, from 5 seconds to 12 seconds, or from 8 seconds to 12 seconds. In some embodiments, the catalyst to crude oil weight ratio may be from 7 to 50, from 7.5 to 50, from 8 to 50, from 7 to 45, from 7.5 to 45, from 8 to 45, from 7 to 40, from 7.5 to 40, or from 8 to 40. In some embodiments, the contacting of the crude oil with the catalyst in the presence of the steam produces a product stream that may comprise at least 30 wt. % of light olefins selected from ethylene, propylene, and butene. For example, in embodiments, the product stream may comprise at least 35 wt. % of light olefins, at least 38 wt. % of light olefins, or at least 40 wt. % of light olefins. In some embodiments, the product stream may comprise at least 12 wt. % of ethylene, at least 15 wt. % of ethylene, at least 18 wt. % of ethylene, or even at least 20 wt. % of ethylene, at least 12 wt. % of propylene, at least 14 wt. % of propylene, or even at least 15 wt. % of propylene, at least 4 wt. % of butene, at least 5 wt. % of butene, or even at least 6 wt. % of butene. EXAMPLES The various embodiments of methods for producing hierarchical mesoporous beta zeolites will be further clarified by the following examples. The examples are illustrative in nature, and should not be understood to limit the subject matter of the present disclosure. Example 1: Produce Catalyst In a glass reactor, 7 grams of a crystalline beta zeolite (HSZ-940 NHA) having the molar ratio of silicon to aluminum of 40 was mixed with 0.40 M sodium hydroxide (NaOH) solution. 4.45 wt. % of cetyltrimethylammonium bromide (CTAB) was also mixed with the crystalline beta zeolite and NaOH solution to produce a solution. The solution was heated with stirring at 100° C. for 24 hours to convert the crystalline beta zeolite to a non-crystalline material with reduced silica content. The heated solution was cooled down to a temperature of from 25° C. to 40° C. A pH of the cooled solution was adjusted to 9.0 through the addition of dilute sulfuric acid (2N). The solution was stirred for 24 hours and then aged at 100° C. for 24 hour to crystalize the non-crystalline material to produce beta zeolite particles. The beta zeolite particles were filtered, washed thoroughly using distilled water, and then dried at 80° C. overnight. The dried beta zeolite particles were calcined at 570° C. for 6 hours to remove CTAB. The calcined beta zeolite particle s were treated with 0.25 N ammonium nitrate (NH4NO3) solution twice at 80° C. for 5 hours to produce mesoporous beta zeolite. Mesoporous beta zeolite was first impregnated with phosphorus and metals with a targeted phosphorus content of 3.5 wt. % P2O5while the metal content (Ce, La and Fe) were 1 wt. % each of the total zeolite weight. The metal and phosphorus impregnated zeolite was then used to formulate a catalyst by spray drying. The formulated catalyst was prepared by blending 200 g (dry basis) kaolin clay powder with 431.92 g of deionized water (DI water) to make a kaolin slurry. In a separate step, 200 g (dry basis) of metal and phosphorus impregnated mesoporous beta zeolite was made into a slurry with 462.59 g of DI water and stirred for 10 mins. The zeolite slurry was added to the kaolin slurry and stirred for 5 mins. Separately, a slurry of Catapal B alumina was prepared by mixing 100.0 g (dry basis) kaolin clay powder with 194.92 g distilled water and peptized by adding 7.22 g concentrated formic acid (70 wt. %) and stirring for 30 mins. The resulting peptized Catapal B slurry was added to the zeolite-kaolin slurry and blended for 10 mins producing a slurry with high viscosity where the individual particles remain suspended. The resulting slurry made up of 30 wt. % solids was spray dried to produce particles of 20-100 microns, followed by calcination at 550° C. for 6 hours to produce the catalyst. The obtained catalyst was steam deactivated and tested in a fixed bed reactor for catalytic cracking. Comparative Example 1 A mixture including 75 wt. % of Equilibrium Catalyst (ECAT) and 25 wt. % of ZSM-5 (commercially available as OlefinsUltra® from W.R. Grace and Company) (referred to as “UMIX75”) was prepared. Example 2: Steam Enhanced Fluidized Catalytic Cracking Testing Example 2 provides data related to the cracking of crude oil in the presence of steam with Example 1 and Comparative Example 1. Experiments were carried out at atmospheric pressure in a fixed-bed reaction (FBR) system in the presence of steam and the absence of steam with Arabian Extra Light (AXL) crude oil as feed. Referring toFIG.3, AXL crude oil301was fed to a fixed-bed reactor30using a metering pump311. A constant feed rate of 2 g/h of AXL crude oil301was used. Water302was fed to the reactor30using a metering pump312. Water302was preheated using a preheater321. A constant feed rate of 1 g/h of water302was used. Nitrogen303was used as a carrier gas at 65 mL/min. Nitrogen303was fed to the reactor30using a Mass Flow Controller (MFC)313. Nitrogen303was preheated using a preheater322. Water302and Nitrogen303were mixed using a mixer330and the mixture was introduced to the reactor30. Prior to entering the reactor tube, oil, water, and nitrogen were preheated up to 250° C. in the pre-heating zone342. The pre-heating zone342was pre-heated using line heaters331. Crude oil301was introduced from the top of the reactor30through the injector341and mixed with steam in the top two-third of the reactor tube340before reaching the catalyst bed344. The mass ratio of steam:crude oil was 0.5. The crude oil was cracked at a cracking temperature of 675° C. and a weight ratio of catalyst to oil of 1:2. The residence time of the crude oil and the steam in the reactor was 10 seconds. Each of Example 1 and Comparative Example 1 was used as a cracking catalyst. 1 g of cracking catalyst of 30-40 mesh size was placed at the center of the reactor tube340, supported by quartz wool343,346and a reactor insert345. Quartz wool343,346were placed both at the bottom and top of the catalyst bed344to keep it in position. The height of the catalyst bed344was 1-2 cm. The reaction was allowed to take place for 45-60 min, until steady state was reached. Reaction conditions of the fixed-bed flow reactor30are listed in Table 1. The cracking reaction product stream was introduced to a gas-liquid separator351. A Wet Test Meter352was placed downstream of the gas-liquid separator351. The cracked gaseous products361and liquid products362were characterized by off-line gas chromatographic (GC) analysis using simulated distillation and naphtha analysis techniques. The reaction product streams from the cracking reaction were analyzed for yields of ethylene, propylene, and butylene. The yield analyses for Example 2 are depicted inFIG.3. TABLE 1ConditionsFeed UsedAXL Whole CrudeSpecific gravity of feedstock0.829API39.3Reaction apparatusFixed Bed ReactorWeight hourly space velocity3Reaction temperature, ° C.675Reaction temperature Range, ° C.600-700 As shown inFIG.3, the yield of ethylene of Example 1 (20.7 wt. %) was greater than those of Comparative Example 1 (16.3 wt. %). Further, the yield of ethylene and propylene of Example 1 (37.0 wt. %) was greater than those of Comparative Example 1 (33.3 wt. %). These results show that the catalyst in Example 1 is much more selective towards ethylene, and ethylene and propylene compared to Comparative Example 1. Also, the catalyst in Example 1 showed abilities to withstand high hydrothermal conditions, while retaining its activity and selectivity. In addition, the yield of light olefin of Example 1 (43.3 wt. %) was greater than those of Comparative Example 1 (43.2 wt. %). A first aspect of the present disclosure may be directed to a process of producing a catalyst comprising forming mesoporous beta zeolite particles, the forming step comprising converting a crystalline beta zeolite to a non-crystalline material with reduced silica content relative to the crystalline beta zeolite, and crystalizing the non-crystalline material to produce mesoporous beta zeolite particles, impregnating the mesoporous beta zeolite particles with a metal and phosphorus to produce a metal and phosphorus impregnated zeolite, and incorporating the metal and phosphorus impregnated zeolite with clay and alumina to produce the catalyst. A second aspect of the present disclosure may include the first aspect, wherein the metal comprises Ce, La, Fe, or combinations thereof. A third aspect of the present disclosure may include either one of the first or second aspects, wherein the metal and phosphorus impregnated zeolite comprises 0.1 wt. % to 5 wt. % of Ce based on the total weight of the metal and phosphorus impregnated zeolite, 0.1 wt. % to 5 wt. % of La based on the total weight of the metal and phosphorus impregnated zeolite, 0.1 wt. % to 5 wt. % of Fe based on the total weight of the metal and phosphorus impregnated zeolite, and 2 wt. % to 10 wt. % of P2O5based on the total weight of the metal and phosphorus impregnated zeolite. A fourth aspect of the present disclosure may include any one of the first through third aspects, wherein the clay comprises kaolin clay. A fifth aspect of the present disclosure may include any one of the first through fourth aspects, wherein the metal and phosphorus impregnated zeolite to the clay mass ratio is from 0.5 to 2. A sixth aspect of the present disclosure may include any one of the first through fifth aspects, wherein the converting step comprises mixing a crystalline beta zeolite with one or more solvents, cetyltrimethylammonium bromide (CTAB), and metal hydroxide to form a solution, and heating the solution at a temperature of from 50° C. to 150° C. to convert the crystalline beta zeolite to the non-crystalline material with reduced silica content relative to the crystalline beta zeolite. A seventh aspect of the present disclosure may include any one of the first through sixth aspects, wherein the forming step further comprises cooling the solution to a temperature of from −25° C. to 50° C. An eighth aspect of the present disclosure may include any one of the first through seventh aspects, wherein the crystalizing step comprises adjusting a pH of the solution to from 8 to 10 by adding an acid, and aging the solution at a temperature of from 50° C. to 150° C. for a time period sufficient to crystalize the non-crystalline material to produce the beta zeolite particles. A ninth aspect of the present disclosure may include any one of the first through eighth aspects, wherein the forming step further comprises treating the beta zeolite particles with ammonium salt a temperature of from 70° C. to 90° C. for 1 to 12 hours. A tenth aspect of the present disclosure may include any one of the first through ninth aspects, wherein the crystalline beta zeolite comprises an average crystal size of from 0.1 micrometer (μm) to 1.4 μm. An eleventh aspect of the present disclosure may include any one of the first through tenth aspects, wherein the crystalline beta zeolite comprises a molar ratio of silica to alumina of from 30 to 350. A twelfth aspect of the present disclosure may include any one of the first through eleventh aspects, wherein the metal hydroxide is in a solution and comprises a concentration from 0.01 moles per liter (M) to 5 M. A thirteenth aspect of the present disclosure may include any one of the first through twelfth aspects, wherein the metal hydroxide comprises lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), strontium hydroxide (Sr(OH)2), barium hydroxide (Ba(OH)2), or combinations thereof. A fourteenth aspect of the present disclosure may include any one of the first through thirteenth aspects, wherein the mesoporous beta zeolite comprises an average particle size of from 0.4 μm to 1.1 μm. A fifteenth aspect of the present disclosure may include any one of the first through fourteenth aspects, wherein the mesoporous beta zeolite comprises a total pore volume of from 0.5 cubic centimeters per gram (cm3/g) to 0.8 cm3/g. A sixteenth aspect of the present disclosure may include any one of the first through fifteenth aspects, wherein the mesoporous beta zeolite comprises a Brunauer-Emmett-Teller (BET) surface area of 450 square meters per gram (m2/g) to 700 m2/g. A seventeenth aspect of the present disclosure may include any one of the first through sixteenth aspects, wherein the mesoporous beta zeolite comprises an average mesopore size of from 2 nm to 5 nm and an average micropore size of from 0.5 nm to 2.0 nm. An eighteenth aspect of the present disclosure may be directed to a process of cracking crude oil comprising contacting the crude oil with a catalyst in a fluidized bed reactor, wherein the catalyst is produced by the process of any one of the first through seventeenth aspects. A nineteenth aspect of the present disclosure may include any one of the first through eighteenth aspects, further comprising injecting steam in to the reactor, wherein the steam to the crude oil mass ratio of from 0.2 to 1.0. A twentieth aspect of the present disclosure may include any one of the first through nineteenth aspects, wherein the catalyst to the crude oil weight ratio is from 7 to 40. It is noted that one or more of the following claims utilize the term “wherein” or “in which” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.” For the purposes of defining the present technology, the transitional phrase “consisting of” may be introduced in the claims as a closed preamble term limiting the scope of the claims to the recited components or steps and any naturally occurring impurities. For the purposes of defining the present technology, the transitional phrase “consisting essentially of” may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non-recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transitional phrases “consisting of” and “consisting essentially of” may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of” and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of” components A, B, and C as well as a composition “consisting essentially of” components A, B, and C. Any quantitative value expressed in the present application may be considered to include open-ended embodiments consistent with the transitional phrases “comprising” or “including” as well as closed or partially closed embodiments consistent with the transitional phrases “consisting of” and “consisting essentially of.” As used in the Specification and appended Claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly indicates otherwise. The verb “comprises” and its conjugated forms should be interpreted as referring to elements, components or steps in a non-exclusive manner. The referenced elements, components or steps may be present, utilized or combined with other elements, components or steps not expressly referenced. It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. The subject matter of the present disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.
63,551
11857956
DETAILED DESCRIPTION OF THE EMBODIMENTS The technical solutions of the present disclosure are described in further detail below with reference to specific examples. Example 1 A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps: S1. Synthesis of a skeleton carrier S11. Preparation of a sodium aluminate solution and an organic template solution Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution, where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 9 times a total mass of the sodium aluminate and sodium hydroxide; and a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution, where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 9 times a total mass of the TPAB and the concentrated sulfuric acid. S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution, where a mass ratio of the sodium aluminate to the organic template was 1:9. S13. A zirconium source was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 85:150. S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO2/Al2O3, where the reaction system was placed in a polytetrafluoroethylene (PTFE) reactor and subjected to the hydrothermal reaction at 105° C. for 10 h to obtain the mixed crystal ZrO2/Al2O3. S15. The mixed crystal ZrO2/Al2O3obtained in S14was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO2/Al2O3, where the organic template was heated at a heating rate of 10° C./min to 500° C. and ashed at this temperature for 3 min. S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid, where the ZrO2/Al2O3solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO2/Al2O3being 1:2, and the solid was soaked in the concentrated sulfuric acid at 120° C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO2/Al2O3—SO3. Example 2 A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps: S1. Synthesis of a skeleton carrier S11. Preparation of a sodium aluminate solution and an organic template solution Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution, where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 11 times a total mass of the sodium aluminate and sodium hydroxide; and a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution, where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 11 times a total mass of the TPAB and the concentrated sulfuric acid. S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution, where a mass ratio of the sodium aluminate to the organic template was 1:9. S13. Zirconium sulfate was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 95:150. S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO2/Al2O3, where the reaction system was placed in a PTFE reactor and subjected to the hydrothermal reaction at 115° C. for 10 h to obtain the mixed crystal ZrO2/Al2O3. S15. The mixed crystal ZrO2/Al2O3obtained in S14 was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO2/Al2O3, where the organic template was heated at a heating rate of 10° C./min to 500° C. and ashed at this temperature for 3 min. S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid, where the ZrO2/Al2O3solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO2/Al2O3being 1:2, and the solid was soaked in the concentrated sulfuric acid at 120° C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO2/Al2O3—SO3. Example 3 A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps: S1. Synthesis of a skeleton carrier S11. Preparation of a sodium aluminate solution and an organic template solution Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution, where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 13 times a total mass of the sodium aluminate and sodium hydroxide; and a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution, where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 13 times a total mass of the TPAB and the concentrated sulfuric acid. S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution, where a mass ratio of the sodium aluminate to the organic template was 1:9. S13. Zirconium sulfate was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 100:150. S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO2/Al2O3, where the reaction system was placed in a polytetrafluoroethylene (PTFE) reactor and subjected to the hydrothermal reaction at 125° C. for 10 h to obtain the mixed crystal ZrO2/Al2O3. S15. The mixed crystal ZrO2/Al2O3obtained in S14 was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO2/Al2O3, where the organic template was heated at a heating rate of 10° C./min to 500° C. and ashed at this temperature for 3 min. S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid, where the ZrO2/Al2O3solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO2/Al2O3being 1:2, and the solid was soaked in the concentrated sulfuric acid at 120° C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO2/Al2O3—SO3. Example 4 A preparation method of a solid acid catalyst for preparing D-galactose was disclosed in this example, including the following steps: S1. Synthesis of a skeleton carrier S11. Preparation of a sodium aluminate solution and an organic template solution Sodium aluminate and sodium hydroxide were dissolved in water to obtain the sodium aluminate solution, where a mass ratio of sodium aluminate to sodium hydroxide was 1:7 and a mass of the water was 15 times a total mass of the sodium aluminate and sodium hydroxide; and a compound as an organic template and concentrated sulfuric acid were dissolved in water to obtain the organic template solution, where the organic template was TPAB, a mass ratio of the TPAB to the concentrated sulfuric acid (mass fraction: 98%) was 1:8, and a mass of the water was 15 times a total mass of the TPAB and the concentrated sulfuric acid. S12. The sodium aluminate solution and the organic template solution were mixed and thoroughly shaken to obtain a mixed solution, where a mass ratio of the sodium aluminate to the organic template was 1:9. S13. Zirconium sulfate was added to the mixed solution obtained in S12, and a resulting mixture was thoroughly mixed, where a molar ratio of zirconium to aluminum was 115:150. S14. A reaction system obtained in S13 was subjected to a hydrothermal reaction to obtain a mixed crystal ZrO2/Al2O3, where the reaction system was placed in a polytetrafluoroethylene (PTFE) reactor and subjected to the hydrothermal reaction at 130° C. for 10 h to obtain the mixed crystal ZrO2/Al2O3. S15. The mixed crystal ZrO2/Al2O3obtained in S14 was rapidly heated until the organic template was completely ashed, and then washed with absolute ethanol to obtain a white solid ZrO2/Al2O3, where the organic template was heated at a heating rate of 10° C./min to 500° C. and ashed at this temperature for 3 min. S2. The skeleton carrier obtained in S1 was soaked in concentrated sulfuric acid such that sulfonyl was loaded on the skeleton carrier to obtain the target solid acid, where the ZrO2/Al2O3solid was added to the concentrated sulfuric acid (mass fraction: 98%) with a mass ratio of concentrated sulfuric acid to ZrO2/Al2O3being 1:2, and the solid was soaked in the concentrated sulfuric acid at 120° C. for 3 h under stirring, then filtered out, and thoroughly washed with absolute ethanol to obtain the target solid acid ZrO2/Al2O3—SO3. Comparative Example 1 A liquid sulfuric acid catalyst was prepared in this comparative example. Comparative Example 2 In this comparative example, a solid acid catalyst Al2O3—SO3was prepared as follows: aluminum hydroxide was soaked in H2SO4with a mass fraction of 98% at 120° C. for 3 h under stirring, and a resulting solid was filtered out and washed with absolute ethanol to obtain the solid acid catalyst Al2O3—SO3, where a mass ratio of H2SO4to Al2O3was 1:2. Comparative Example 3 In this comparative example, a solid acid catalyst ZrO2—SO3was prepared as follows: zirconium hydroxide was soaked in 98% H2SO4at 120° C. for 3 h under stirring, and a resulting solid was filtered out and washed with absolute ethanol to obtain the solid acid catalyst ZrO2—SO3, where a mass ratio of H2SO4to ZrO2was 1:2. The solid acids obtained in Examples 1 to 4 and Comparative Examples 2 and 3 each were tested for SSA with an SSA tester, and test results were shown in Table 1. The SSA of the solid acid prepared with the zirconium dioxide-modified aluminum oxide as a skeleton carrier in the present disclosure was significantly increased compared with that of the zirconium dioxide solid acid and the aluminum oxide solid acid, and the SSA of the product increased with the increase of the zirconium dioxide content. The solid acid in Example 4 had an SSA of 380 m2/g, which was 2.24 times an SSA of the pure aluminum oxide solid acid catalyst in Comparative Example 2. TABLE 1SSA data of the solid acids obtained in Examples1 to 4 and Comparative Examples 2 and 3GroupSSA (m2/g)Comparative Example 2169Comparative Example 3342Example 1345Example 2367Example 3371Example 4380 The catalytic efficiency of the catalyst obtained in each of Examples 1 to 4 and Comparative Examples 1 to 3 was tested, and specific test data were shown in Table 2. Lactose and a catalyst were added in a mass ratio of 1:0.1 to a reactor to allow a reaction under catalysis for 3 h, and a residual lactose content in a resulting reaction solution was tested according to the liquid chromatography (LC) method in the 2015 Chinese Pharmacopoeia: With amino-bonded silica gel as a filler, acetonitrile-water (70:30) as a mobile phase, and a column temperature of 45° C., 10 μL of a solution was allowed to pass through a chromatographic column at a flow rate of 1.0 mL/min, and a lactose content was tested at a wavelength of 238 nm; and a residual lactose content in each reaction solution was tested. Catalytic efficiency=(original lactose content−residual lactose content)/original lactose content*100%. TABLE 2Catalytic efficiency of the catalysts in Examples 1 to 4and Comparative Examples 1 to 3GroupCatalytic efficiency/%Comparative Example 178Comparative Example 261Comparative Example 355Example 179Example 281Example 383Example 486 In Comparative Example 2, aluminum oxide alone is used as a carrier for a solid acid, and a limited number of acidic groups are linked due to small SSA, resulting in low catalytic efficiency of the corresponding catalyst. In Comparative Example 3, zirconium dioxide itself exhibits poor linking performance for acidic groups, resulting in undesirable catalytic efficiency. Zirconium has an atomic volume of 14.1 cm3/mol and aluminum has an atomic volume of 10.0 cm3/mol. In the present disclosure, a molar ratio of zirconium to aluminum is controlled actually to increase an SSA of a product through the combination of zirconium dioxide and aluminum oxide, increase an exposed surface of active sites of aluminum, and increase a number of acidic groups linked to aluminum. It can be known from the comparison between Comparative Examples 2 and 3 and Examples 1 to 4 that the present disclosure controls a molar ratio of zirconium to aluminum to improve the catalytic efficiency.FIG.1shows an infrared (IR) spectrum of a sheet sample of the ZrO2/Al2O3prepared in Example 1 of the present disclosure in an IR spectrometer. Specific spectrum analysis is as follows: an absorption peak of hydroxyl appears at 2,900, an IR characteristic peak of zirconium dioxide (Zr—O—Zr bond) appears at 674 cm−1, and L acid characteristic peaks of aluminum oxide appear at 1,448 and 1,512. It can be known from the above results that characteristic peaks of zirconium dioxide and aluminum oxide appear during the test of the sample, indicating that ZrO2/Al2O3is prepared in Example 1. The catalytic efficiency of the solid acid catalyst provided in the present disclosure is comparable to or even better than the catalytic efficiency of the liquid acid catalyst, indicating significant improvement of the catalytic efficiency. The recycling effects of the solid acid catalysts obtained in Examples 1 to 4 and Comparative Examples 2 and 3 each were tested, and a specific operation method was as follows: Ethanol was added to a mixed solution obtained after a catalytic reaction, a resulting mixture was stirred to precipitate unisomerized lactose and a part of the solid acid catalyst in the mixed solution, and a precipitated substance was filtered out to obtain a solution x, where a volume of the ethanol was ⅓ of a volume of the mixed solution obtained after the catalytic reaction; and ethanol was added to the solution x with a volume of the ethanol being twice a volume of the solution x to obtain a pure solid acid catalyst and an isomerized lactose solution y, and the isomerized lactose solution y was subjected to distillation to remove ethanol (ethanol could be reused) to obtain a monosaccharide-containing mixed solution. In the present disclosure, unisomerized lactose in the isomerized mixed solution was selectively precipitated and the solid acid was further separated through different concentrations. A pure solid acid catalyst recovered after each catalysis of the solid acid catalyst of the present disclosure was reused five times to test a recycling effect of the solid acid catalyst, and specific test results were shown in Table 3. TABLE 3Catalytic efficiency of the solid acid catalysts obtained inExamples 1 to 4 and Comparative Examples 2 and 3during five times of catalysisFirstSecondThirdFourthFifthGroupcycle/%cycle/%cycle/%cycle/%cycle/%Comparative6155494234Example 2Comparative6966656461Example 3Example 17977767471Example 28178777574Example 38382807775Example 48684817877 It can be seen from the data in Table 3 that the solid acid catalyst provided by the present disclosure can be recycled; and after zirconium dioxide is added to the carrier, the stability of the overall structure of the solid acid catalyst is increased, and when the solid acid catalyst is repeatedly used, the catalytic efficiency of the solid acid catalyst decreases slowly. Therefore, it can be concluded that, because the composite skeleton of zirconium dioxide and aluminum oxide has high stability, the solid acid catalyst can be repeatedly used many times, which is conducive to industrial production.
16,809
11857957
DETAILED DESCRIPTION OF THE INVENTION Disclosed herein are fluidic devices that use relative channel configurations and in some aspects a passive air control valve for droplet formation and manipulation, fluidic systems containing multiple fluidic devices adjoined to one another, and methods for droplet formation and manipulation in a fluidic device or system. The passive air control valve disclosed herein allows different reagents to be loaded into different reaction wells in a series such that the fluidic devices and systems presented herein can be used without the need for large, complex instrumentation, thus providing devices that can be used outside of a laboratory or hospital environment, for example for point of care or laboratory testing. It has been discovered that by controlling certain physical properties, such as surface tension and resistance, and by the physical configuration and connections of different elements of a microfluidic device, many of the shortcomings of prior art devices can be overcome without the need for complex and costly instrumentation. A “fluidic device” of this disclosure is a device through which one or more fluids can be transported and/or moved through the same. The movement of the one or more fluids can be, for instance, through passages formed within and/or upon such a device. An exemplary fluidic device of this disclosure is illustrated inFIGS.1,5,7, and/or10-14. In some embodiments, the fluidic device can be a millifluidic, microfluidic or nanofluidic device in which the amount of fluids within, stored within or moving within said device can be in milliliter, microliter, nanoliter, and/or picoliter amounts. Thus, in some embodiments, the reaction well is configured to hold milliliters of a fluid. In other embodiments, the reaction well is configured to hold microliters of a fluid. In other embodiments, the reaction well is configured to hold nanoliters of a fluid. In other embodiments, the reaction well is configured to hold picoliters of a fluid. As such, a fluidic device presented herein can be a millifluidic, microfluidic, nanofluidic, or picofluidic device. In illustrative embodiments, the fluidic device is a microfluidic device. The fluidic devices described herein typically comprise multiple parts or regions therein through which fluids can move and/or in which fluids can be stored and/or manipulated. Such parts and/or regions can include, for example, one or more ports, one or more air valves (e.g., associated with or connected to a port), one or more channels that can form a fluidic connection, one or more high resistance air valve constriction channels, one or more reaction wells, one or more overflow channels, and one or more fluid transport channels. Where a high resistance air valve constriction channel is present in the fluidic device, it is typically positioned upstream (relative to movement of air or fluid through the fluidic device) of the fluidic connection. In some embodiments, the fluidic device also includes one or more inlets and/or outlets (e.g., ports) that may perform as an inlet, an outlet, or both. The different parts and/or regions typically communicate with one another either directly or indirectly with respect to fluids moving through the same (e.g., the parts or regions are in “fluidic communication” with one another (e.g., the parts or regions “fluidly communicate” with one another)). Direct communication between parts and/or regions means that a fluid moves directly from one part or region to another without passing through an intermediary part or region, which can be referred to herein as “direct fluidic communication”. For instance, as shown inFIGS.1A and1B, fluidic connection4is in direct fluidic communication with air control valve5, reaction well2, and fluid transport channel7A. Indirect communication, in contrast, means that fluid moves from one part or region to another through an intermediary part or region, referred to herein as “indirect fluidic communication”. For example, referring toFIGS.1A and1B, air control valve5is in indirect fluidic communication with reaction well2as the two parts or regions are each directly connected to fluidic connection4but not to one another. Similarly, the parts of the fluidic devices illustrated inFIGS.13and14may also be arranged to be in fluidic communication with one or more other parts of such fluidic devices (e.g., a first fluid transport channel (1A) in fluid connection with the first port (1), a reaction well (2) and an overflow channel (3) (FIG.13); a serpentine mixing channel (5) in fluidic communication with a second fluid transport channel). Individual fluidic devices can also be connected to one another as in series as, referred to herein as a “fluidic system”. Examples of multiple fluidic devices connected to one another in series are shown inFIGS.5,10and12. In such embodiments, each fluidic device can be attached to one another though a fluid transport channel. For instance,FIG.5shows a first fluidic device connected to a second fluidic device through fluid transport channels3A and1B, which collectively can be referred to as “intradevice fluid transport channel”. In such embodiments, the fluid transport channel of the first fluidic device (e.g.,3A inFIG.5) can be considered “continuous with” the fluid transport channel of the second fluidic device (e.g.,1B ofFIG.5). In such embodiments, the fluid transport channels are typically in direct fluidic communication with one another. The fluidic device described herein in certain illustrative embodiments comprise an “air control valve” which is a valve through which air can enter or leave the fluidic device. In some embodiments, such a valve can allow air to move into, or alternatively out of, the fluidic device when open to the surrounding atmosphere. As mentioned above, in some embodiments, the air control valve is configured such that the hydrodynamic resistance therein is greater than the hydrodynamic resistance in the fluidic connection and the overflow channel, thereby hindering the flow of fluid into the air control valve. The hydrodynamic resistance may be calculated using standard techniques in the art. For example, hydrodynamic resistance R for a rectangular channel of sufficiently small aspect ratio (e.g., h/w<0.1) can be found using the formula: R=12 μL/wh3where μ is the viscosity of the fluid, L is the length of the channel, w is the width and h is the height of the channel. The air control valve can also be configured to further increase hydrodynamic resistance by increasing the length of the air control valve. In some embodiments, the length of the air control valve is increased by changing the geometric structure. In illustrative embodiments, the air control valve has a geometric structure other than straight that increases the length of the air control valve and thus, its hydrodynamic resistance. In certain embodiments, the air control valve has a serpentine shape. Exemplary air control valves can include those having a structure and/or arrangement as illustrated as, for instance, without limitation,4or5inFIGS.1A and1B;5inFIG.5; and/or1A inFIGS.7and/or10-12. In some embodiments, the air control valve can form a straight path between a port and a fluidic connection (e.g.,5inFIG.1A and/or1AinFIG.7). In some embodiments, the air control valve can form geometric structure other than a straight path such as a serpentine shape as shown inFIG.1B(5). Such an air control form having a geometric structure other than a straight path (e.g., a serpentine geometry as in5ofFIG.1B) is typically one providing increased hydrodynamic resistance to a fluid moving through the same as compared to an air control valve forming a straight path (5inFIG.1A). The air control valve can also be fluidly connected to a port through which fluid can enter or exit the air control valve. An exemplary air control valve port is shown as6inFIGS.1A and1B. The fluidic devices described herein can also comprise a “fluidic connection” in direct fluidic communication with reaction well and a fluid transport channel (4inFIGS.1A and1B;4inFIG.13) or between a reaction well and/or a high resistance air valve constriction channel (4inFIG.7). As used herein, a “fluidic connection” is a channel that fills with fluid, thereby preventing fluid from escaping the reaction well and allowing passing air to bypass the reaction well and remove any excess fluid in the channel. For instance,FIGS.1A and1Billustrate “fluidic connection” as part (4). In some embodiments, a fluidic connection can be in direct communication with a high resistance air valve constriction channel via air (e.g.,4ofFIG.7). Such a high resistance air valve constriction channel will be understood by those of ordinary skill in the art as providing higher resistance (e.g., by presenting a greater surface area) to any fluids or air moving through the same as compared to the fluidic connection (e.g., part (4) ofFIGS.1A and1B) such that a selected fluid can be prevented from entering the high resistance air valve constriction channel. The “reaction well” is typically a compartment or region (e.g., a depression) of the fluidic device into which an initial reagent such as a primary/capture antibody solution can be trapped for a period of time to coat the surface with antibody or specified reagent, after which a test sample (e.g., a bodily fluid such as blood, urine, tissue extracts, and cellular extract) can reside and/or be trapped. Further, other assay reagents e.g. secondary antibody, wash buffer, detection substrates, stop reagents etc. can be passed through the same reaction well to complete the reaction before readouts. The reaction well is typically composed of a material allowing for sample components and/or reagents to be fixably attached thereto (removably or not), such as at the surface of the material forming the reaction well. In some embodiments, the shape of the reaction well is configured for an operation or assay of interest. In some embodiments, a reaction well is rectangular for purposes of dilution or washing out of fluid samples in a reaction well. In other embodiments, the reaction well is rounded in shape (e.g., semi-circular) but may also have hexagonal, rectangular, or other suitable shape. Exemplary reaction wells include part2inFIGS.1A and1B; part2inFIG.13; and part3inFIGS.7and11. In some embodiments, a reaction well can be coated with a substance such as poly-L lysine, known to promote cell adhesion, and living cells can be present on and adhere to a reaction well. An “overflow channel” of any of the fluidic devices described herein can provide a path through which fluid that can exceed the capacity of a “reaction well” thereof such that the fluid “overflows” into said overflow channel. The overflow channel(s) are typically connected to a fluid transport channel and/or reaction well as shown inFIGS.1A and1B(e.g., overflow channel3) orFIG.13(overflow channel3). A fluid transport channel such as1A and7A ofFIGS.1A and1B;1A and/or5A inFIG.13; or1A,2A, or3inFIG.14; can be used to introduce and/or extract fluids from the fluidic device. Such fluid transport channels can be in direct fluidic communication with, for instance, a reaction well and/or an overflow channel (e.g.,1A,2and3, respectively, ofFIGS.1A and1B;1A,2, and3ofFIG.13). Such fluid transport channels can alternatively and/or also be in direct fluidic communication with, for instance, an overflow channel and a fluidic connection (e.g.,7a,3and4, respectively, ofFIGS.1A and1B;3,4, and5A ofFIG.13). Such fluid transport channels can also be connected to one or more ports through which fluid can enter or exit the fluid transport channel. Exemplary ports include, for instance,1and7ofFIGS.1A and1B;1and5ofFIGS.13; or1and2ofFIG.14). An “intradevice transport channel” can be a fluid transport channel formed between devices that are connected to one another (e.g., in fluidic communication with one another) and/or connected in series (e.g.,3A/1B ofFIG.5). In some embodiments, such as when multiple fluidic devices are connected with one another in series (as in, e.g.,FIGS.5,10and12), the reaction well of one fluidic device is able to hold or maintain a fluid, sample component(s), and/or reagent(s) such that the same is not able to move into another fluidic device (e.g., a reaction well thereof) in the series (e.g., that reaction well can hold a fluid without contaminating fluids contained in adjoining fluidic devices). In some embodiments of the fluidic system disclosed herein, cross contamination between individual fluidic devices is minimal, such that less than, for example, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, or 0.1% of the contents of a first reaction well carry over into a second reaction well during a wash step. The ports of the fluidic devices described herein can be individually open or closed at any given time while the fluidic devices are in use to enable operations to be performed (e.g., to carry out an immunoassay). Such ports can be opened or closed (e.g., blocked or unblocked) using any available method, such as using the operators finger, one or more pipettors, one or more syringe pumps, and/or an automated system (e.g., using a solenoid control valve, pneumatic control channels, or other system available to those of ordinary skill in the art). For instance, when an air control valve port (e.g.,6inFIGS.1A and1B) is open (e.g., open to the atmosphere such that a fluid such as air can enter the same), a fluid can enter the fluidic connection (e.g.,4inFIGS.1A and1B) through the air control valve (e.g.,5inFIGS.1A and1B) and fill the reaction well. In this way, the “fluidic connection” can prevent fluid from escaping the reaction well. Similarly, a fluid can be introduced into the fluidic device through a port connected to a fluid transport channel (e.g.,7/7A or1/1A inFIGS.1A and1B). Excess fluids (e.g., a volume of fluid beyond what is required for a particular assay and/or can be contained within the fluidic device) can be removed from the fluidic device through the ports. Thus, in some embodiments, a fluid is introduced into a fluidic device having a passive air control valve using a pipette, syringe pump, or any other fluid driving mechanism (referred to herein as “fluid introduction devices”). In illustrative embodiments, fluids are introduced using standard micropipettes (about any of 0.001-30 microliters). In some embodiments, operation of a fluidic device having a passive air control valve for purposes of generating a droplet involves opening the port of the air control valve and then introducing a fluid followed by passing air into the first port of a first fluid transport channel. In this embodiment, the fluid enters the overflow region, increasing the hydrodynamic resistance therein, which causes the fluid to flow into the reaction well, forming a droplet. The passage of air immediately following fluid introduction forces excess fluid out of the overflow channel, into the second fluid transport channel, and out the second port. Alternatively, excess fluid can be aspirated back into the fluid introduction device. The port of the air control valve can be kept open to cause formation of the fluidic connection between the reaction well and the second fluid transport channel, thereby preventing the escape of fluid from the reaction well. Fluid can enter the reaction well when the port of the air control valve is open to the atmosphere. In some embodiments, operation of a fluidic device having a passive air control valve and a high resistance air valve constriction channel involves opening the port of the air control valve and then introducing a fluid followed by passing air into a port of a fluid transport channel. However, in some embodiments, fluid is introduced through the air control valve. In this embodiment, the fluid is introduced into the air control valve port, wherein the fluid enters the reaction well; and air is then introduced into the port of the air control valve, wherein the air enters the high resistance air valve constriction channel, causing excess fluid to be pushed through the fluid transport channel and out the port of the fluid transport channel. Alternatively, excess fluid can be aspirated back into the fluid introduction device. In some embodiments, the fluid can initially enter into the overflow channel and be rerouted, as resistance due to the fluid viscosity in the overflow channel is increased. The fluids in the fluidic devices can be any suitable fluid including but not limited an aqueous solution, a sample (e.g., comprising components such as cells and/or antibodies, nucleic acids, or plasma), one or more buffers, water, and/or one or more wash solutions. In some embodiments, the fluid may be air but the term fluid is typically used herein to indicate a type of aqueous solution. Air is therefore typically referred to as such. Those of ordinary skill in the art will understand that many different types of fluids can be suitable for use with the fluidic devices described herein. For instance, to carry out an immunoassay, suitable fluids can include those comprising one or more sample(s) (e.g., a blood sample), one or more reagents (e.g., antibodies, primary and/or secondary), one or more wash buffers (e.g., phosphate-buffered saline), one or more detection agents (e.g., a fluorescently-labeled secondary antibody), and the like. As mentioned above, a fluid can also be and/or comprise air. In some embodiments, a pocket of air can be introduced between a fluid or fluids, producing an “air plug”. In some embodiments, the fluid between air plugs can be referred to as a “fluidic slug”. The same or different fluids can also be introduced into the same or different ports during operation of the fluidic device. In some embodiments, a first fluid can be introduced into a first port followed by a second fluid at a flow rate and volume that causes dilution or the washing out of a first fluid in the reaction well (but not necessarily components of a sample fixably attached to the surface of the reaction well) such that the second fluid can be contained or “trapped” within the reaction well with (e.g., coalesced with) or in place of the first fluid such that an assay such as an immunoassay can be performed. In some embodiments, an air plug can separate the first and second fluids during operation of the fluidic device. In some embodiments, the fluid stored in the reaction well is manipulated by introducing a second fluidic slug into the first port or the second port, with the air control valve in the open position. The first port or the second port can be used interchangeably for introduction of fluids or for removal of excess fluid. In some embodiments in which the second port is used, fluid passes through the second fluid transport channel and the fluidic connection and into the reaction well, reversing the flow direction. In such embodiments, any excess fluid exits through the first port. For instance, in some embodiments, the second fluid is a sample, a buffer, a water, or a wash solution and the second fluid can be introduced at a flow rate of between 0.7 nanoliters/sec to 5 microliters/sec. In some embodiments, the second fluid can be introduced at a flow rate and volume that causes dilution of the first fluid in the reaction. In some embodiments, the concentration of the first fluid after introduction of the second fluid can be less than about any of, for example, 50%, 40%, 30%, 20%, 10%, 5% 1%, 0.5%, or 0.1% of the concentration of the first fluid prior to the introduction of the second fluid. In some embodiments, the second fluid can introduced at a flow rate and volume that causes the first fluid to be washed out of the reaction well and/or replaced with the second fluid. Washing out of the reaction well can occur when the washing buffer or replacement fluid is introduced at a flow rate of between 0.7, 1.2, 1.7, 2.2, 2.7, and 3.2 microliters/sec on the lower end of the range to 2.7, 3.2, 3.7, 4.2, 4.7, and 5 microliters/sec on the upper end of the range. In illustrative embodiments, washing of the reaction vessel occurs when the washing buffer or replacement fluid is introduced at a flow rate of between 0.7 microliters/sec and 5 microliters/sec. The fluidic devices can be fabricated using, for example, but not limited by, various soft lithographic micro-embossing techniques. A variety of fabrication micro-forming methods that utilize, for example, but are not limited to, micro-milling, micro-stamping, and micro-molding, can be matched to substrate material properties. In various embodiments of a device according to the present teachings, a substrate can be an optically transmissive polymer, providing good optical transmission from, for example at least about 85% to 90% optical transmission over a wavelength range of about 400 nm to about 800 nm. Examples of polymeric materials having good optical transmission properties for the fabrication of various embodiments of a fluidic circuit include organosilicon polymers. In some embodiments, a fluidic device presented herein is composed of hydrophobic materials. In some embodiments, the fluidic device is composed of hydrophobic materials such as polystyrene, polycarbonate, poly(methyl methacrylate) (PMMA), and/or polydimethylsiloxane (PDMS), polypropylene, cyclic-olefin polymers (COP), cyclic-olefin copolymers (COC), polystyrene polymers, polycarbonate polymers, acrylate polymers, and the like. Other hydrophobic materials may also be used as would be understood by those of ordinary skill in the art. In some embodiments, the fluidic device has a height between about any of 100, 125, 150, 175, 200, and 225 microns on the low end of the range and about any of 200, 225, 250, 275, and 300 microns on the high end of the range. In illustrative embodiments, the fluidic device has a height of about any of 100-300 microns (e.g., about any of 100, 150, 200, 250 or 300 microns). In some embodiments, the first fluid transport channel and the second fluid transport channel are each about 400 microns in length. In other embodiments, the overflow channel has a length between about any of 400, 425, 450, 475, 500, and 525 microns on the low end of the range and about any of 500, 525, 550, 575, 600, and 625 microns on the high end of the range. In illustrative embodiments, the overflow channel has a length between about any of 400 and 625 microns. In other embodiments, the high resistance air valve constriction channel is about 80 microns in length. In some embodiments, the air control valve has a width between about any of 60, 65, and 70 on the low end of the range and about any of 70, 75, and 80 on the high end of the range. In other embodiments, the air control valve is about any of 60-80 microns in length. InFIG.1A, for instance, air control valve5has a width of about 80 microns while the serpentine-shaped air control valve5ofFIG.1Bhas a width of about 60-80 microns. Other sizes may also be suitable as may be derived from this specification or the examples, and/or otherwise determined by those of ordinary skill in the art. In some embodiments, manipulation of a fluid (e.g., as a droplet) occurs as part of an assay. Any suitable assay (e.g. an immunoassay, a biochemical assay, a drug discovery assay, a nucleic acid binding assay, and other that will be known by a skilled artisan) can be carried out using the fluidic devices described herein. Any number of fluidic slugs/reagents can be introduced using the fluidic device presented herein until all steps of an assay are completed. In some embodiments, the assay detects binding pair members using the fluidic device presented herein. In embodiments of the methods, a sample is introduced into a fluidic device having a passive air control valve as described previously. In some embodiments, on-device liquid handling can be externally actuated in manual or automated mode using standard laboratory liquid handling equipment. According to various embodiments of components, devices and methods of this disclosure, a pressure applied at or between ports can be used as a motive force for moving liquids, for example, from part of a fluidic device to another part of that or another fluidic device. For example, a motive force for on-device liquid handling can be externally actuated by applying a decreased or negative pressure at a port or between ports or by applying an increased or a positive pressure at a port or between ports. Given that a full vacuum by definition is the absence of pressure, for example, 0 torr, and given that 1 standard atmosphere of pressure is, for example 760 torr, then a negative pressure is a decreased pressure less than 760 torr, for example, and a positive pressure is an increased pressure greater than 760 torr, for example. In that regard, on-device liquid handling for various embodiments of components, devices and methods of this disclosure can be externally actuated using any manual or automated standard laboratory liquid handling equipment, such as by manual or automated pipetting systems utilizing solid or liquid displacement, that can provide a pressure from between about 720 torr to about 800 torr, which is about +/−40 torr from 1 standard atmosphere of pressure. Fluidic devices provided herein can be used in any biological or biochemical method in which one or more samples are loaded into one or more reaction wells and one or more solutions are exchanged within the reaction well(s). A skilled artisan will recognize that a large number of such methods exist. Accordingly, a large number of samples can be delivered into a a fluidic device provided herein. Such samples can include cells, nucleic acid samples, protein samples, carbohydrate samples, buffers, reagents, organic compounds such as small organic candidate drug compounds, or combinations thereof, such as biological samples that are mixtures of these and other biochemicals, for example. Such biological samples can include, as non-limiting examples, blood, or a portion thereof, such as for example plasma or sera, tissue, tumor biopsy, sputum, cerebrospinal fluid, cells, and/or cell culture supernatant. In addition, any reagent that is used in such biological or biochemical methods may also be included. Such biological or biochemical methods can include, for example, immunological methods such as immunoassays (e.g. ELISAs), including but not limited to sandwich immunoassays, sample preparation methods, nucleic acid isolation and/or purification, cell culturing and imaging, nucleic acid assays, pharmaceutical drug candidate testing, or anti-drug antibody (ADA) assays. In certain embodiments, for performance of biological assays using a fluidic device provided herein, a detection system, such as an optical detection system can be in optical communication with the fluidic device. For such embodiments, the device cover through which an optical detection system is in optical communication is ideally transparent, for example transparent glass or transparent plastic. In some embodiments, the sample can be tested for the presence of a member of a binding pair complex (e.g., an antibody and an antigen to which the antibody binds), or for the presence of the complex, by introducing a second fluid containing a binding pair member (e.g., an antibody) and/or a detection agent. In some embodiments, the binding pair member (e.g., the antibody) is labelled to allow for detection. In some embodiments, the assay is an immunoassay (e.g., an ELISA) and the binding pair complex comprises an antigen and an antibody directed toward the antigen. In other embodiments, the assay is a nucleic acid based assay or an assay to assess DNA-protein interactions e.g. single nucleotide polymorphism (SNP) detection. For SNP detection, the reaction wells, either in single-/multi-plex device, can be coated with streptavidin, followed by introduction of specific biotin labeled DNA oligos into each reaction well. Each well would receive a different, but known oligo. The oligos would bind to the streptavidin followed by washing out the unbound oligos. DNA (optionally digested DNA) from a sample, mixed with fluorophore labeled nucleotides, buffer and enzyme can then be introduced into each well. DNA sequences complementary to the oligos would hybridize to the oligos and serve as templates for single-nucleotide base extension with labeled nucleotides or for amplification of a region of the bound DNA. The identity of the nucleotide added can be detected based on the fluorophore labels on the nucleotides by fluorescence emission using a camera. If the purpose is to amplify specific regions of the DNA for other purposes, the set up described above can also be used. The amplified DNA can be retrieved from each well and used for downstream applications. Other assays may also be carried out using the fluidic devices described herein, as may be determined by those of ordinary skill in the art. For example, in embodiments involving an immunoassay, an antigen of interest (a binding pair member), is immobilized by direct adsorption to the reaction well of the fluidic device or via a capture antibody that has been attached to the reaction well of the fluidic device. A sample is tested for the presence of the antigen by introducing the sample (e.g., a blood sample) into the reaction well of the fluidic device as disclosed herein and detecting the antigen by contacting the sample with a second fluid containing a labelled primary antibody or a labelled secondary antibody. Detection can be, for example, colorimetric or fluorescence-based and can utilize a camera or plate reader. For instance, in certain non-limiting embodiments, a target antibody or antigen if present in such first test sample or second test sample, for example, can coat the surface of a reaction well. The coated reaction well can then optionally be rinsed with a buffer, such as PBS or any buffer used in an immunoassay and then the surface of the reaction well blocked with an immunoassay blocking reagent, which are known in the art. Then a first test sample, such as a blood (or fraction thereof e.g. plasma or sera) from a first subject and a second test sample, which can be a blood sample from a second subject, or in non-limiting examples can be a control sample, can be delivered to the coated reaction well and incubated. Optionally, another antibody can be delivered to the reaction well and incubated. Then antibodies or antigens that bind components (if present) in the test samples that bound the coated antibody or antigen are delivered to the reaction well. This fluidic processing within the reaction well can be achieved by delivering samples into the reaction wells through, for instance, the ports shown inFIGS.13and/or14, for example, according to one or more of the steps provided in Example 9 for introducing a sample into a reaction well and replacing fluids within the reaction well, and for mixing two solutions before introducing them into the reaction well. In another non-limiting embodiment, an ADA assay can be performed using a fluidic device provided herein. A skilled artisan will realize that a fluidic device provided herein can be used in different ways to perform an ADA assay. As a non-limiting example, a biotherapeutic drug such as a biotherapeutic antibody can be delivered to a reaction well using methods provided herein for filling a reaction well of a microfluidic device. The biotherapeutic antibody and control antibody (if used) can be incubated in reaction wells to allow the biotherapeutic antibody and control antibody to coat the surface of the reaction wells. As a further step of the ADA assay, sera samples from subjects to whom the biotherapeutic antibody has been administered are each mixed with an acidic reagent as will be understood for ADA assays, and the acidified sera samples are each delivered to reaction wells using methods and microfluidic devices provided herein. A pH neutralizing reagent with a fluorescently-labeled antibody that recognizes the biopharmaceutical antibody, which will be referred to as a detection reagent, is applied to each of the reaction wells by delivery of the detection reagent thereto through one or more ports. Eventually, a detection system is used to identify wells containing fluorescent antibodies. Positive fluorescence from a biotherapeutic-coated sample reaction well but not a control antibody-coated reaction well is indicative of the presence of an anti-drug antibody in the subject sample applied to that reaction well. In certain illustrative embodiments usingFIG.14herein, the acidified sample and the detection reagent can be delivered into ports1and2and mixed within the mixing channel (5), before being delivered to a reaction well. In another non-limiting embodiment, a microfluidic device provide herein can be used to perform one or more sample preparation steps in a next-generation (i.e. massively parallel) sequencing workflow. In some embodiments, isothermal amplification reactions can be performed in the reaction wells and then amplification products can be removed from the reaction wells using methods for exchanging fluidic contents of a reaction well provided herein, and collected for further processing in a next-generation (e.g. massively multiplex) sequencing workflow. Other embodiments of such methods are also contemplated as being suitable for use with the fluidic devices provided herein, as will be understood by those of ordinary skill in the art. As a non-limiting example of manual operation of a microfluidic device provided in herein, a biochemical assay may be performed by introducing a suitable amount (e.g., 0.1-5 microliters) of a blood sample from a subject into a first port of a microfluidic device (e.g.,1or7inFIG.1;6or7inFIG.7; or6inFIG.11;1inFIG.13; or air valve control port (e.g.,1A inFIG.11)), using a micro-pipettor. A user then pushes the sample into the reaction well through a fluid transport channel using the pipettor. The sample is then incubated within the reaction well to permit binding of target antigen molecules within the blood sample to the surface of the reaction well. After a suitable period of time allowing for the binding of the target antigen molecules to the surface of the reaction well, 100 ul of a wash buffer is injected into one or more ports (e.g.,1or7inFIG.1;6or7inFIG.7; or6inFIG.11;1or5inFIG.13;1or2inFIG.14; or air valve control port (e.g.,1A inFIG.11)) by a user using a pipettor. Following circulation of the wash buffer through the reaction well, another reagent (e.g., an antigen-binding agent such as an antibody having specificity for the target antigen molecule) is introduced into the device through one or more ports (e.g.,1or7inFIG.1;6or7inFIG.7; or6inFIG.11;1or5inFIG.13;1or2inFIG.14; or air valve control port (e.g.,1A inFIG.11)). After a suitable amount of time, another wash buffer is then introduced into the device through one or more ports (e.g.,1or7inFIG.1;6or7inFIG.7; or6inFIG.11;1or5inFIG.13;1or2inFIG.14; or air valve control port (e.g.,1A inFIG.11)). Thereafter a detection reagent can be introduced into the device through one or more ports (e.g.,1or7inFIG.1;6or7inFIG.7; or6inFIG.11;1or5inFIG.13;1or2inFIG.14; or air valve control port (e.g.,1A inFIG.11)), and the presence or absence of the binding agent and, therefore, the target antigen molecule of interest, in the reaction is determined. With respect to the fluidic devices such as but not limited to those illustrated inFIG.13, secondary reagents (including wash buffer and other reagents) are typically injected via part5(FIG.13). This fluidic device therefore is ideally, but not necessarily, devoid of fluid (e.g., emptied) outside the reaction well/fluidic connection channel. In some embodiments, then, after each application of a new liquid to the microfluidic device through a port in a fluidic device illustrated byFIG.13or14, the fluidic device is emptied of fluids outside the reaction well and the fluidic connection channel using techniques provided herein. In some embodiments of the fluidic systems disclosed herein, the fluidic devices and/or systems comprising the same can be used in point-of-care (POC) applications. Point-of-care testing refers to medical diagnostic testing at or near the point of care, i.e. at the time and place of patient care. This contrasts with testing that is performed wholly or in part in a medical laboratory. In POC settings, fluids or reagents can be preloaded into a cartridge separated by air plugs to allow loading of any number of fluids into reactions wells. One non-limiting example is a rapid diagnostic test, i.e. a biochemical and/or an immunoassay and/or involving nucleic acid amplification such as isothermic amplification, that detects antigens of interest. For instance, a single plug of sub-microliter sample volume can be introduced into reaction wells coated with different antibodies, for example, to identify the presence of antigen binding partners in the sample. With reference toFIGS.1A-1B, shown are embodiments of a fluidic device having a passive air control valve. The fluidic device consists of a first port1, a first fluid transport channel1A, a reaction well2, an overflow channel3, a fluidic connection4, an air control valve5, a port for the air control valve into the atmosphere6, a second port7, and a second fluid transport channel7A. In some embodiments, a plurality of fluidic devices in which at least one has a passive air control valve, are adjoined such that they are in direct fluidic communication with one another, forming a fluidic system that can be used for point of care testing or laboratory testing. In some embodiments, the fluidic devices are adjoined in series. With reference toFIG.5, the embodiments of a fluidic system can include a first port1of a first fluid transport channel1A; a second port7of a second fluid transport channel7A; and a plurality of fluidic devices positioned between the first fluid transport channel1A and the second fluid transport channel7A wherein each fluidic device includes a first intradevice fluid transport channel1B; a reaction well2; an overflow channel3; a fluidic connection4; an air control valve5; a port for the air control valve6; and a second intradevice fluid transport channel3A. In this embodiment, for each individual fluidic device in the system, the fluidic connection is in direct fluidic communication with the reaction well, the air control valve, the overflow channel, and the second intradevice fluid transport channel. Furthermore, the second intradevice fluid transport channel of each fluidic device is continuous with the first intradevice fluid transport channel of a subsequent fluidic device in the plurality of fluidic devices adjoined to one another; and the second intradevice fluid transport channel of the last fluidic device in the series is continuous with the second fluid transport channel. With reference toFIG.7, shown are embodiments of a fluidic device having a passive air control valve and a high resistance air flow constriction channel. The fluidic device consists of an air control valve port1, an air control valve1A, a fluidic connection2, a reaction well3, a high resistance air flow constriction channel4, an overflow channel5, a first port7, a first fluid transport channel7A, a second port6, and a second fluid transport channel6A. In some embodiments, a plurality of fluidic devices in which at least one has a passive air control valve and a high resistance air valve constriction channel, are adjoined such that they are in direct fluidic communication with one another, forming a fluidic system that can be used for point of care testing or laboratory testing. In some embodiments, the fluidic devices are adjoined in series. With reference toFIG.10, the embodiments of a fluidic system can include a first port7of a first fluid transport channel7A; a second port6of a second fluid transport channel6A; and a plurality of fluidic devices positioned between the first fluid transport channel7A and the second fluid transport channel6A wherein each fluidic device includes a first intradevice fluid transport channel7B; a reaction well3; a high resistance air valve constriction channel4; an overflow channel5; a fluidic connection2; an air control valve1A; a port for the air control valve1; and a second intradevice fluid transport channel6B. In this embodiment, the first fluid transport channel is continuous with the first intradevice fluid transport channel; the first intradevice fluid transport channel of each fluidic device is in direct fluidic communication with the reaction well and the overflow channel thereof; the fluidic connection of each fluidic device is in direct fluidic communication with the reaction well, the air control valve, and the high resistance air valve constriction channel thereof; the second intradevice fluid transport channel of each fluidic device is in direct fluidic communication with the overflow channel and the high resistance air valve constriction channel thereof; the second intradevice fluid transport channel of each fluidic device is continuous with the first intradevice fluid transport channel of a subsequent fluidic device in the plurality of fluidic devices adjoined to one another; and the second intradevice fluid transport channel of the last fluidic device in the series is continuous with the second fluid transport channel. In some embodiments, the fluidic device has only one port of a fluid transport channel as inFIG.11. The fluidic device consists of an air control valve port1, an air control valve1A, a fluidic connection2, a reaction well3, a high resistance air flow constriction channel4, an overflow channel5, a port6, and a fluid transport channel6A. As shown inFIG.11, the high resistance air flow constriction channel4may be in direct fluidic communication with overflow channel5(which, in this embodiment, does not comprise a port) and fluidic connection2. In some embodiments, the fluidic device comprises multiple subunit fluidic devices in fluid communication with one another as illustrated inFIG.12(including an exemplary, non-limiting eight subunit fluidic devices). In this embodiment, described from left to right as illustrated inFIG.12, the first subunit fluidic device comprises a first port (7) of a first fluid transport channel (7A) which is in direct fluidic communication with a second fluid transport channel (6A) and reaction well (3). In this embodiment, the end of fluid transport channel6A opposite first fluid transport channel7A terminates in port6. Reaction well3is in direct fluidic communication with overflow channel5and fluidic connection2. Fluidic connection2is in direct fluidic communication with air control valve1A and high resistance air flow constriction channel4. High resistance air flow constriction channel4is in direct fluidic communication with overflow channel5. Opposite its connection with reaction3, overflow channel5is in direct fluidic communication with the fluid transport channel of the second fluidic device (8A) which includes the same components as the first subunit fluidic device but not including the first fluid transport channel (e.g., not including7A of the first fluidic device). This arrangement of parts continues through the third, fourth, fifth, sixth, and seventh subunit fluidic devices. The last subunit fluidic device, inFIG.12being the eighth subunit fluidic device, terminates with a sample outlet port connected to the last fluid transport channel (8A inFIG.12). Other arrangements are also possible (e.g., more or less than eight subunit fluidic devices) as would be understood by those of ordinary skill in the art. This disclosure describes, in some embodiments, a fluidic device comprising an air control valve (e.g., a passive air control valve) in direct fluidic communication with a fluidic connection. In some embodiments, the fluidic device further comprises an overflow channel and a reaction well connected to one another by the fluidic connection. In some embodiments, the air control valve has a geometric structure other than straight that increases hydrodynamic resistance as compared to hydrodynamic resistance provided by a geometrically straight air control valve. In some embodiments, multiple such fluidic devices may be arranged in fluid communication with one another (e.g., linked in series). In some embodiments, this disclosure provides a fluidic device comprising a first port of a first fluid transport channel; a reaction well; an overflow channel; a fluidic connection; an air control valve (e.g., a passive air control valve); a port for the air control valve; and, a second port of a second fluid transport channel; wherein: the first fluid transport channel is in direct fluidic communication with the overflow channel and the reaction well; the overflow channel is further in direct fluidic communication with the second fluid transport channel and the fluidic connection; and, the fluidic connection is further in direct fluidic communication with the reaction well and the air control valve. In some such embodiments, the air control valve has a geometric structure other than straight that increases hydrodynamic resistance as compared to hydrodynamic resistance provided by a geometrically straight air control valve. In some embodiments, at least two such fluidic devices are adjoined to one another (e.g., in fluid communication with one another). In some embodiments, this disclosure provides a fluidic device comprising an air control valve (e.g., a passive air control valve); a fluidic connection; a reaction well; a high resistance air valve constriction channel; an overflow channel; a first port of a first fluid transport channel; and, a second port of a second fluid transport channel; wherein: the first fluid transport channel is in direct fluidic communication with the overflow channel and the reaction well; the overflow channel is further in direct fluidic communication with the reaction well, the high resistance air valve constriction channel, and the second fluid transport channel; the reaction well is further in direct fluidic communication with the fluidic connection; the fluidic connection is further in direct fluidic communication with the high resistance air valve constriction channel and the air control valve; and, the second fluid transport channel is further in direct fluidic communication with the high resistance air valve constriction channel. In some embodiments, the fluidic device further comprises an air control valve port connected to the air control valve. In some embodiments, at least two such fluidic devices are adjoined to one another (e.g., in fluid communication with one another). In some embodiments, this disclosure provides a fluidic device comprising an air control valve; a fluidic connection; a reaction well; a high resistance air valve constriction channel; an overflow channel; and, a port of a fluid transport channel; wherein: the fluid transport channel is in direct fluidic communication with the overflow channel and the reaction well; the overflow channel is further in direct fluidic communication with the reaction well and the high resistance air valve constriction channel; the reaction well is further in direct fluidic communication with the fluidic connection; and, the fluidic connection is further in direct communication with the high resistance air valve constriction channel and the air control valve. In some such embodiments, the fluidic device the air control valve port is connected to (e.g., in fluidic communication with) an air control valve (e.g., a passive air control valve). In preferred embodiments, the fluidic device, or at least the reaction well, is composed of hydrophobic materials. In some embodiments, the fluidic device is a millfluidic, microfluidic, nanofluidic, or picofluidic device. In some embodiments, this disclosure provides a fluidic system comprising a first port of a first fluid transport channel; a second port of a second fluid transport channel; a plurality of fluidic devices adjoined to one another in series, each fluidic device being positioned between the first fluid transport channel and the second fluid transport channel, wherein each fluidic device comprises: a first intradevice fluid transport channel; a reaction well; an overflow channel; a fluidic connection; an air control valve (e.g., a passive air control valve); a port for the air control valve; and, a second intradevice fluid transport channel; wherein: the fluidic connection of each fluidic device is in direct fluidic communication with the reaction well, the air control valve, the overflow channel, and the second intradevice fluid transport channel thereof; the second intradevice fluid transport channel of each fluidic device is continuous with the first fluid intradevice transport channel of a subsequent fluidic device in the plurality of fluidic devices adjoined to one another; and, the second intradevice fluid transport channel of the last fluidic device in the series is continuous with the second fluid transport channel. In some embodiments, this disclosure provides a fluidic system comprising a first port of a first fluid transport channel; a second port of a second fluid transport channel; a plurality of fluidic devices adjoined to one another in series, each fluidic device being positioned between the first fluid transport channel and the second fluid transport channel, wherein each fluidic device comprises: a first intradevice fluid transport channel; a reaction well; an overflow channel; a fluidic connection; an air control valve (e.g., a passive air control valve); a high resistance air valve constriction channel; a port for the air control valve; and, a second intradevice fluid transport channel; wherein: the first fluid transport channel is continuous with the first intradevice fluid transport channel; the first intradevice fluid transport channel of each fluidic device is in direct fluidic communication with the reaction well and the overflow channel thereof; the fluidic connection of each fluidic device is in direct fluidic communication with the reaction well, the air control valve, and the high resistance air valve constriction channel thereof; the second intradevice fluid transport channel of each fluidic device is in direct fluidic communication with the overflow channel and the high resistance air valve constriction channel thereof; the second intradevice fluid transport channel of each fluidic device is continuous with the first intradevice fluid transport channel of a subsequent fluidic device in the plurality of fluidic devices adjoined to one another; and, the second intradevice fluid transport channel of the last fluidic in the series is continuous with the second fluid transport channel. In some embodiments, this disclosure provides a fluidic system comprising a first port of a first fluid transport channel; a second port of a second fluid transport channel; a plurality of fluidic devices adjoined to one another in series, each fluidic device being positioned between the first fluid transport channel and the second fluid transport channel, wherein each fluidic device comprises: a first intradevice fluid transport channel; a reaction well; an overflow channel; a fluidic connection; an air control valve (e.g., a passive air control valve); a high resistance air valve constriction channel; a port for the air control valve; and a second intradevice fluid transport channel; as well as a sample port and sample channel for at least one of the plurality of fluidic devices wherein: the first fluid transport channel is in direct fluidic communication with the sample channel and the first intradevice fluid transport channel of the first fluidic device; the first intradevice fluid transport channel of each fluidic device is in direct fluidic communication with the reaction well and the overflow channel thereof; the fluidic connection of each fluidic device is in direct fluidic communication with the reaction well, the air control valve, and the high resistance air valve constriction channel thereof; the second intradevice fluid transport channel of each fluidic device is in direct fluidic communication with the overflow channel and the high resistance air valve constriction channel thereof; the second intradevice fluid transport channel of each fluidic device is continuous with the first intradevice fluid transport channel of a subsequent fluidic device in the plurality of fluidic devices adjoined to one another and the first intradevice fluid transport channel and the second intradevice fluid transport channel are in direct fluidic communication with the sample channel; and, the second intradevice fluid transport channel of the last fluidic device in the series is continuous with the second fluid transport channel. In some embodiments comprising a plurality of fluidic devices, at least one (e.g., all) of said plurality of fluidic devices has/have an air control valve with a geometric structure other than straight that increases hydrodynamic resistance as compared to hydrodynamic resistance provided by a geometrically straight air control valve. In some embodiments, each of the plurality of fluidic devices holds a fluid without contaminating fluids contained in adjoining fluidic devices. In some embodiments, the fluidic system enables operations to be performed in each fluidic device without contaminating fluid contained in adjoining fluidic devices. In some embodiments, this disclosure provides methods of operating a fluidic device, the method comprising: a) opening a port of an air control valve, wherein the air control valve is in direct fluidic communication with a fluidic connection that connects a reaction well to a second fluid transport channel comprising a second port; b) introducing a fluid into a first port of a first fluid transport channel, wherein said fluid enters an overflow channel in direct fluidic communication with a reaction well, causing the fluid to enter the reaction well; and, c) introducing air into the first port thereby forcing excess fluid to enter the second fluid transport channel by way of the overflow channel and exit through the second port; wherein said port of the air control valve is kept open during steps a), b) and c) to allow fluid to accumulate in the fluidic connection between the reaction well and second fluid transport channel, thereby preventing fluid from escaping the reaction well; and, wherein fluid only enters the reaction well when the port of the air control valve is open to atmosphere. In some embodiments, the port of the air control valve is closed upon completion of steps a), b) and c). In other embodiments, excess fluid is aspirated back into the fluid introduction device. In some embodiments, this disclosure provides methods for manipulating a first fluid stored in a reaction well of a fluidic device, wherein said fluidic device comprises an air control valve with a port, a first fluid transport channel having a first port, and a second fluid transport channel having a second port, said method comprising: a) opening the port of the air control valve, wherein the air control valve is in direct fluidic communication with a fluidic connection that connects a reaction well to the second fluid transport channel; and, b) introducing a second fluid into the second port, wherein said second fluid passes through the second fluid transport channel and the fluidic connection into the reaction well, resulting in a mixture of the first and second fluids in the reaction well. In some such embodiments, excess fluid flows out of the first port in direct fluidic communication with the reaction well. In some embodiments, the second fluid is a sample, buffer, water, or wash solution. In some embodiments, the second fluid is introduced at a flow rate and volume that causes dilution of the first fluid in the reaction well. In some embodiments, the second fluid is introduced at a flow rate and volume that causes the first fluid to be washed out of the reaction well. In some embodiments, the second fluid is trapped inside the reaction well with the first fluid to conduct an assay. In some embodiments, the assay is a biochemical and/or an immunoassay and/or involves isothermal amplification. In some embodiments, the assay is colorimetric or fluorescence-based. In some embodiments, such methods further comprise detection of assay results using a plate reader or camera. In some embodiments, this disclosure provides methods for operating a fluidic device, wherein said fluidic device comprises an air control valve with a port and a fluid transport channel having a port, said method comprising: a) introducing a fluid into a port of an air control valve, wherein said air control valve is in direct fluidic communication with a fluidic connection, which is further in direct fluidic communication with a high resistance air valve constriction channel and a reaction well and wherein the fluid enters the reaction well; and, b) introducing air into the port of the air control valve, wherein said air enters the high resistance air valve constriction channel, which is in direct fluidic communication with an overflow channel which is in direct fluidic communication with the fluid transport channel, causing excess fluid to be pushed through the overflow channel and the fluid transport channel and out the port of the fluid transport channel. In other embodiments, excess fluid is aspirated back into the fluid introduction device. In some embodiments, this disclosure provides methods for manipulating a first fluid stored in a reaction well of a fluidic device having a port of an air control valve and a port of a fluid transport channel, said method comprising introducing a second fluid into a port of an air control valve, wherein said air control valve is in direct fluidic communication with a fluidic connection which is in direct fluidic communication with a reaction well and a high resistance air valve constriction channel and wherein said second fluid enters the reaction well, coalescing with the first fluid. In some embodiments, this disclosure provides methods for introducing fluids into any one or more fluidic devices of a fluidic system wherein said system comprises a first port of a first fluid transport channel; multiple fluidic devices arranged in series, and a second port of a second fluid transport channel; wherein the fluidic devices are positioned between the first port and the second port and in direct fluidic communication with another and wherein at least one of the fluidic devices comprises an air control valve that can be opened or closed using an air control valve port; wherein the method comprises: a) introducing a first fluid into a second port, wherein said first fluid enters a reaction well of a fluidic device for which the associated air control valve is open; b) introducing a second fluid, different from the first fluid, into the second port, wherein said second fluid enters a reaction well of a fluidic device for which the associated air control valve is open, said fluidic devices being the same or different as those of step a); and, c) optionally repeating steps a) and b), using fluids the same or different from the first and second fluids. In some such embodiments, the first and second fluids are separated by one or more air plugs. In some embodiments, this disclosure provides methods for introducing fluids into a fluidic device comprising a reaction well in direct fluidic communication with an air control valve with a port and a second port of a second fluid transport channel; the method comprising introducing a first fluid into the reaction well through the air control valve port while the second port is blocked. In some such embodiments, the reaction well is further in direct fluidic communication with a first fluid transport channel having a first port, the method further comprising unblocking the second port and introducing a second fluid into the reaction well through the first port, thereby diluting the first fluid in the reaction well. In some embodiments, two or more fluidic devices are connected in series. In some embodiments, additional fluids, different from the first fluid and the same or different from the second fluid, are introduced through the first port separated from one another by air plugs. In some embodiments, said fluid and/or air is introduced using a pipette or syringe pump. In some embodiments, the opening or closing of the port of the air control valve is automated. In some embodiments, this disclosure provides a series of fluidic devices connected to one another (e.g., as shown inFIGS.5and6). In some embodiments, different fluids can be introduced into the second port of a series of fluidic devices by introducing a fluid plug followed by air, which pushes the fluid into the reaction wells for which the associated air control valve ports are open, thereby selectively filling reaction wells with the fluid. In such methods, reaction wells with closed air control valve ports do not fill with the fluid. Thus, in some embodiments, different fluids can be introduced through a second port to a series of connected fluidic devices, or a subset thereof. In some embodiments, this can be accomplished by opening air control valve port of the first reaction well (keeping those of the of the reaction wells of the other devices in the series closed) and introducing first fluid into the second port followed by air or aspirating the fluid back into the fluid introduction device, causing the first fluid to enter the reaction well of the first fluidic device in the series (and no other reaction wells), and then closing the air control valve port for that reaction well. The air control valve port of the second reaction well in the series can then opened (keeping those of other reaction wells in the series closed), and a second fluid can be introduced into the second port of the second reaction well followed by passing air or aspirating the fluid back into the fluid introduction device, causing the second fluid to enter reaction well of the second fluidic device in the series (and no other reaction wells), and then closing the air control valve port for that reaction well. Subsequent reaction wells in the series can then sequentially filled using the same process for each respective reaction well. In such embodiments, substantial mixing of the first and second fluids does not occur. In some embodiments, different fluids could be trapped in each respective well using these methods. In some embodiments, some of the reaction wells may be filled with the same fluids and some with different fluids. For instance, in some embodiments, such as in a device comprising eight fluidic devices connected to one another, the air control valve ports may be opened for reaction wells1,3,5and7, and a first fluid introduced into the second port followed by passing air or aspirating the fluid back into the fluid introduction device, causing that fluid to enter reaction wells1,3,5and7but not reaction wells2,4,6and8. The air control valve ports for reaction wells1,3,5and7can then be closed and the air control valve ports for reaction wells2,4,6and8opened. A second fluid can then be introduced into the second port followed by passing air or aspirating the fluid back into the fluid introduction device, thereby causing reaction wells2,4,6and8to fill with the second fluid. In such embodiments, substantial mixing of the first and second fluids does not occur. In some embodiments, this disclosure provides fluidics devices linked in series (e.g., as exemplified inFIGS.5and6) such that the same may be used in point of care applications (e.g., immunoassays). In some embodiments, fluids and/or reagents can be preloaded into a cartridge (e.g., a hydrophobic tubing, pipette tip or cartridge) separated by air plugs to allow loading of any number of fluids into the reaction wells. For example, with immunoassays, a sample can be introduced into a common port, either the first port or the second port, allowing it to be introduced into reaction wells, each coated with different antibodies. Detection of binding reactions between one or more components of such sample and the antibodies may then be detected using standard techniques. Other embodiments are also contemplated by this disclosure, as would be understood by those of ordinary skill in the art. In some embodiments, this disclosure provides a fluidic device comprising: a first port; a first fluid transport channel in fluid connection with the first port, a reaction well, and, an overflow channel; a second fluid transport channel in fluid communication with the overflow channel; a fluidic connection channel comprised of a hydrophobic material and being in fluid communication with the reaction well and the second fluid transport channel; and, a second port in fluid communication with the second fluid transport channel. In some embodiments, this disclosure provides a fluidic device comprising a first port in direct fluidic communication with a first fluid transport channel that is also in direct fluidic communication with a reaction well and an overflow channel. In some embodiments, the fluidic device also comprises a second fluid transport channel in direct fluid communication at one end with the overflow channel and with a second port at the other end. In some embodiments, the second fluid transport channel is also in direct fluidic communication with a fluidic connection channel (that may be comprised of a hydrophobic material) which is in direct fluid communication with the reaction well. An exemplary embodiment of such a fluidic device is illustrated inFIG.13. In some embodiments, this fluidic device comprises a device such as that illustrated inFIG.13and further comprises a fluidic mixer comprising a serpentine mixing channel in fluidic communication with the second fluid transport channel; a third fluid transport channel in fluidic communication with the serpentine mixing channel, the third fluid transport channel optionally comprising a mixing window; a fourth fluid transport channel in fluid communication with a second port; a fifth fluid transport channel in fluid communication with a third port; wherein the fourth and fifth transport channels are in fluidic communication with one another distal from their respective ports, and further in fluidic communication with the third fluid transport channel. In some embodiments, the fluidic mixer comprises a serpentine mixing channel that at one end is in fluidic communication with a fluid transport channel of a fluidic device (such as the second fluid transport channel of the fluidic device illustrated inFIG.13). In some embodiments, the fluidic mixer comprises a third fluid transport channel in direct fluidic communication with the end of the serpentine mixing channel opposite the fluid channel of the device such as that illustrated inFIG.13, where the third fluid transport channel optionally further comprising a mixing window. Opposite the end of the third fluid transport channel in direct fluidic communication with the serpentine mixing channel, the third fluid transport channel is in direct fluidic communication with: a fourth fluid transport channel that is in direct fluid communication with a port; and a fifth fluid transport channel in direct fluid communication with a port; where the fourth and fifth transport channels are in direct fluidic communication with one another distal from their respective ports. An exemplary embodiment of such a fluidic device is illustrated inFIG.14. In some embodiments, a fluidic device arranged essentially as illustrated inFIG.13and/orFIG.14may be designed and constructed with reference to the relative diameters (widths) of the various fluid transport channels, overflow channel(s), the reaction well(s), and/or the serpentine mixing channel(s). In certain illustrative embodiments such fluidic device does not include a passive air control valve. For instance, the various fluid transport channels may be of approximately the same diameter (and/or width) or within, e.g., 10-15% of one another. In some embodiments, the diameter of the reaction well is approximately four times that of the fluid connection channel, which is itself approximately 20-33% the diameter of the second fluid transport channel (e.g.,5A inFIG.13). In some embodiments, such as in the fluidic device ofFIG.14, the fourth and fifth fluid transport channels, and in some embodiments, the third fluid transport channel, may be of approximately the same diameter. In some embodiments, the third fluid transport channel may be of a smaller diameter than the fourth and/or fifth fluid transport channel(s), or the parts of each forming the junction at which these parts meet may be of the same diameter which may change (e.g., becoming larger or smaller) in the direction in which the fluid flows through the third fluid transport channel toward the serpentine mixing channel. The third fluid transport channel and the serpentine mixing channel may also be of the same diameter, or the third fluid transport channel may be of a smaller (in preferred embodiments) or larger diameter than the serpentine mixing channel. As the serpentine mixing channel comes into fluidic communication with a device such as that provided inFIG.13, e.g., at the second fluid transport channel (5A inFIG.13), the diameters may be approximately the same (e.g., at the junction thereof), or the diameter of the second fluid transport channel (5A inFIG.13) may be greater than that of the serpentine mixing channel. Other embodiments may incorporate different diameters as long as the flow of fluid through the device is maintained, as may be determined by those of ordinary skill in the art using standard design and manufacturing techniques. In some such embodiments, especially with respect to, but not limited to, those illustrated inFIGS.13and14, one or more of the following features is present: the first fluid transport channel comprises a diameter distal to the first port of about 2-8 times, 3-5 times, or in illustrative embodiments four times its diameter proximal to the first port; the diameter of the reaction well is 1.5-4 times, or in illustrative embodiments, approximately twice the diameter of the fluid transport channel proximal to the first port; the length of the reaction well is ⅕ to the same length as, and in illustrative embodiments, approximately one third the length of, the first fluid transport channel; the diameter of the overflow channel is 0.3 to 0.8 or in illustrative embodiments, or approximately 0.4 to 0.75 the diameter of the first fluid transport channel distal to the first port; the fluidic device is comprised of PDMS wherein the diameter of the overflow channel is 0.4 to 0.8 or in illustrative embodiments, approximately 0.6 the diameter of the first fluid transport channel distal to the first port; the device is comprised of COC wherein the diameter of the overflow channel is 0.3 to 0.7 times the diameter of, and in illustrative embodiments, approximately 0.5 the diameter of the first fluid transport channel distal to the first port; the length of the overflow channel is at least 0.5 to 1.5 times, or in illustrative embodiments about 0.9 times the length of the first fluid transport channel; the second fluid transport channel comprises a diameter distal to the second port of 1.5 to 3 or in illustrative embodiments about two times its diameter proximal to the second port; and/or, the length of the second fluid transport channel is 0.5 to 2 times, or in illustrative embodiments approximately equivalent to approximately 1.25 times the length of the first fluid transport channel. In some embodiments, a fluidic device provided herein (e.g., that illustrated inFIG.1orFIG.13) is in fluidic communication with a fluidic mixer such that two, three, four or more solutions can be mixed before being introduced into the fluidic device. In an illustrative embodiment, the fluidic mixture comprises a serpentine mixing channel in fluidic communication with the second fluid transport channel (7A) of a device such as that ofFIG.1or with the second fluid transport channel of a device such as that ofFIG.13; a third fluid transport channel in fluidic communication with the serpentine mixing channel, the third fluid transport channel optionally comprising a mixing window; a fourth fluid transport channel in fluid communication with a second port; a fifth fluid transport channel in fluid communication with a third port; wherein the fourth and fifth transport channels are in fluidic communication with one another distal from their respective ports, and further in fluidic communication with the third fluid transport channel. An exemplary embodiment of such a fluidic device is illustrated inFIG.14. In some such embodiments, one or more of the following features is present: a fluid within the mixing window is visible to a user; the serpentine mixing channel has a length of approximately 15 to approximately 25 times (e.g., 90.1 mm vs. 4.6 mm in an embodiment of the fluidic mixer ofFIG.14; e.g., approximately 20 times) the length of the third fluid transport channel; the serpentine mixing channel has a diameter of approximately twice the diameter of the third fluid transport channel; the fourth and fifth fluid transport channels are of approximately the same diameter and length; the length of the third fluid transport channel is approximately the same length of the fourth and/or fifth fluid transport channels; and/or, the diameter of the third fluid transport channel is approximately 0.4 the diameter of the fourth and/or fifth fluid transport channels. However, it is noted that the ratio of the diameter of the third fluid transport channel relative to the diameter of the fourth and/or fifth fluid transport channels is flexible and, e.g., the 0.4 value is only a preferred ratio. It is noted that, in some embodiments, when differences in diameters are discussed, it is the diameter at the junction of channels and/or reaction well(s) being discussed. It is also noted that the diameters of two parts that are in direct fluidic communication with one another will typically be approximately the same (e.g., the third, fourth and fifth fluid transport channels illustrated inFIG.14). While the serpentine mixing channel is typically arranged as shown inFIG.14, this is not necessarily so since, in some embodiments, the serpentine mixing channel can comprise or be configured in a form other than a straight channel, as long as it creates turbulence and therefore mixing of liquids that pass through it, such as where the serpentine channel comprises one or more complete serpentine coils (e.g., between two to twelve serpentine coils, alone or combined with straight channels). In some embodiments of the devices provided here, especially with respect to, but not limited to, those illustrated inFIGS.13and14, the diameter of the fluidic connection channel is any of: approximately 0.1 to 0.4 or in illustrative embodiments, preferably approximately 0.15 to approximately 0.30, the diameter of the reaction well; approximately 150-225 mu, optionally wherein the fluidic connection channel is comprised of PDMS; approximately 175-200 mu; approximately 160-215 mu, optionally wherein the fluidic connection channel is comprised of COC; approximately 0.15 to approximately 0.30 the diameter of the reaction well; approximately 0.2-0.25 the diameter of the reaction well; approximately 0.1-0.2 the diameter of the second fluid transport channel at the point at which the fluidic connection channel and the second fluid transport channel contact one another; and/or approximately 0.1-0.25 the length of the reaction well. In some embodiments of the devices described above such as those illustrated inFIGS.13and14, the length of the fluidic connection channel is approximately 0.1-0.175 the length of the reaction well; approximately 0.125-0.150 the length of the reaction well; approximately 0.1-0.175, optionally 0.125-0.150, the length of the reaction well where the fluidic connection channel is comprised of PDMS; and/or approximately 0.11-0.13 the length of the reaction well where the fluidic connection channel is comprised of COC. In certain embodiments provided herein, as a non-limiting example, the fluidic device illustrated inFIG.13, the relative diameters of channels within the device are one or more, or in illustrative embodiments all, of the following: the first fluid transport channel comprises a diameter distal to the first port of about 2-8 times, 3-5 times, or in illustrative embodiments four times its diameter proximal to the first port; the diameter of the reaction well is 1.5-4 times, or in illustrative embodiments, approximately twice the diameter of the fluid transport channel proximal to the first port; the diameter of the overflow channel is 0.3 to 0.8 times or in illustrative embodiments, or approximately 0.4 to 0.75 times the diameter of the first fluid transport channel distal to the first port; the second fluid transport channel comprises a diameter distal to the second port of 1.5 to 3 times or in illustrative embodiments about two times its diameter proximal to the second port; the diameter of the fluidic connection channel is any of: approximately 0.1 to 0.4 times or in illustrative embodiments, preferably approximately 0.15 to approximately 0.30 times the diameter of the reaction well; and the fluid connection channel is 20-33% the diameter of the second fluid transport channel. In certain embodiments provided herein, which can include those provide in the paragraph immediately above, during filling of the fluidic device, or in some embodiments when the overflow channel is partially filled with fluid and the reaction well is at least 75%, 80%, 85%, 90%, or 95% filled with fluid, and in illustrative embodiments 80% filled with fluid, or in some embodiments wherein the device comprises effective relative dimensions of channels and the reaction well(s) and/or effective relative dimensions at the junctions of channels and at the junctions of the reaction well(s) with adjacent channels:a) the ratio of capillary pressures within the fluidic connection channel and the first overflow channel is approximately 1.3 to 1.8;b) the ratio of capillary pressures within fluidic connection channel and the first overflow channel is approximately 1.438 to 1.726, optionally wherein the fluidic device is comprised of PDMS;c) the ratio of capillary pressures within fluidic connection channel and the first overflow channel is approximately 1.510-1.603, optionally wherein the fluidic device is comprised of PDMS; ord) the ratio of capillary pressures within fluidic connection channel and the first overflow channel is approximately 1.426 to 1.628, optionally wherein the fluidic device is comprised of COC. Capillary pressure is derived from the fluid air interface, such that when the channels of the device are full of fluid, the ratio of capillary pressures is not as important. Thus, capillary pressure is most important when the device comprises and/or is full of air, and fluid is being inputted into the device. In some embodiments of the devices provided herein, then, especially with respect to, but not limited to, those illustrated inFIGS.13and14, as the device is at least partially filled with fluid (e.g., such that when the overflow channel is partially filled with fluid and the reaction well is (or is approximately) at least 75%, 80%, 85%, 90%, or 95% filled with fluid, and in illustrative embodiments 80% filled with fluid), the ratio of capillary pressures within fluidic connection channel and the first overflow channel is preferably approximately 1.3 to 1.8. In some embodiments, during filling of the device with fluid, the ratio of capillary pressures within fluidic connection channel and the first overflow channel is approximately 1.438 to 1.726 (optionally wherein the fluidic device is comprised of PDMS). In some embodiments, during filling of the device with fluid, the ratio of capillary pressures within fluidic connection channel and the first overflow channel is approximately 1.510-1.603 (optionally wherein the fluidic device is comprised of PDMS). In some embodiments, during filling of the device with fluid, the ratio of capillary pressures within fluidic connection channel and the first overflow channel is approximately 1.426 to 1.628 (optionally wherein the fluidic device is comprised of COC). In some embodiments, upon filling of the device with fluid, or when the device is completely filled with fluid, the fluidic connection channel is completely filled with fluid and/or does not comprise air. In some embodiments, a fluid air interface is present at an end of the fluidic connection channel distal to the reaction well. In some embodiments, this disclosure provides methods for filling a reaction well using a microfluidic device provided herein, such as a mircofluidic device ofFIG.1orFIG.13. Accordingly, In another aspect, provided herein is a method for loading a sample into a reaction well of a fluidic device, the method comprising: A) introducing the sample through a first port of a microfluidic device into a first fluid transport channel to fill the reaction well, an overflow channel, a second fluid transport channel, and a fluidic connection channel, wherein the reaction well and the overflow channel are in fluid connection with the first fluid transport channel, the overflow channel is in fluid communication with the second fluid transport channel at an end opposite the end that is in fluid communication with the first fluid transport channel, and wherein the fluidic connection channel is in fluid communication with the reaction well and the second fluid transport channel, and wherein the second fluidic channel is in fluid communication with a second port; and, B) either applying negative pressure from the first port (e.g. part1ofFIG.13) or passing air into the second port (e.g. part5o fFIG.13), to remove the sample from the overflow channel, the first fluid transport channel and the second fluid transport channel, wherein the sample is retained in the reaction well and typically in the fluidic connection channel as well. When using a fluidic device such as but not limited to that illustrated byFIG.13, rinsing and loading of a secondary reagent is typically accomplished from the second port (part5inFIG.13). In most embodiments, the reaction well cannot be washed or have its contents replaced from fluid from the first port (part1inFIG.13) and this must be accomplished using the second port (part5inFIG.13). A solution such as wash buffer or a secondary reagent can be loaded into the reaction well from the first port (part1inFIG.13), but that is typically only where in the fist step where the reaction well is empty. If the reaction well is full of fluid (i.e., outside the first step of the device usage), then fluid must be applied from the second port (part5inFIG.13). In some embodiments, the method can include a step to replace the contents of the reaction well and the fluidic connection channel. For example by injecting a solution through the second port (e.g.,5inFIG.13) until the contents of the microfluidic device are filled with the second fluid and optionally, some second fluid flows out the first port (e.g.,1inFIG.13). In other embodiments, the method for loading the sample can be repeated with another solution such as a wash buffer, after the sample is loaded into the reaction well and removed from the microfluidic device other than the reaction well and the fluidic connection channel, to exchange the sample within the reaction well and fluidic connection channel with the other solution. Microfluidic devices provided herein are typically constructed such that when the sample is removed from the microfluidic device as provided in step B above, it remains in the reaction well and typically the fluidic connection channel as well. Accordingly, illustrative microfluidic devices provided herein are constructed such that either i) the overflow channel has an effective composition and dimensions, the second fluid transport channel has an effective composition and dimensions, and the fluidic connection channel has an effective composition and dimensions, to provide appropriate capillary pressure ratios to retain the sample in the reaction well and typically the fluidic connection channel as well, while removing the sample from other channels of the microfluidic device; or ii) the fluidic connection channel is in fluid communication with the reaction well and an air control valve that is opened and closed in such a manner so as to achieve this result, as provided herein. As explained in Example 9 herein, the fluidic device illustrated inFIG.13has two ports available for fluid entry or exit (1and5). In a first step of using this fluidic device in an exemplary embodiment, fluid is introduced into the fluidic device through the first port into the first fluid transport channel, where it begins to fill both the reaction well and the overflow channel, based in large part on the ratio of hydrodynamic resistance between these structures (the hydrodynamic resistance ratio). Fluid completely fills the reaction well before the overflow channel is full. After the reaction well is full, fluid begins to enter the fluidic connection channel, while fluid in the overflow channel continues to advance. Fluid fills the fluidic connection channel and continues around the overflow channel until both fluid streams meet. Fluid then begins to enter the second fluid transport channel. At this point, first port (1inFIG.13); a first fluid transport channel (1A inFIG.13); a reaction well (2inFIG.13); an overflow channel (3inFIG.13); a fluidic connection channel (4inFIG.13); are each entirely full of fluid. In the second step, at the initiation of which fluid is trapped solely in the reaction well and the connection channel, negative pressure is applied from the first port. Fluid retreats from the second transport channel in a direction opposite to its loading direction. As fluid recedes to the junction between the fluid connection channel and the overflow channel, fluid passes solely through the overflow channel (e.g., the fluid effectively “chooses” this channel). The smaller width of the fluid connection channel in comparison to the overflow channel, as provided in further detailed embodiments herein, produces a much stronger fluid-air interface, which prevents any fluidic recession through the connection channel or the reaction well. As fluid retreats around the overflow channel, it passes by the entrance to the reaction well and continues through the first fluid transport channel, leaving a fluid air interface at the opening of the reaction well. All excess fluid is removed from the first fluid transport channel and the first port, leaving fluid trapped only in the reaction well and fluid connection channel. In the third step, to partially or fully replace the contents of the reaction well and fluid connection bridge with a new fluid, the second fluid port is used. Fluid enters through the second fluid port via applied pressure and continues through the second fluid transport channel. As fluid reaches the junction between the fluid connection channel and the overflow channel, fluid continues through both paths. Fluid begins to push the fluid housed in the fluid connection bridge and begins to pass around the overflow channel. This process continues; fluid continues to move around the overflow channel (e.g., “bridge”) and continues to push fluid out of the fluid connection channel and the reaction well. Eventually, fluid from the overflow channel combines with fluid emerging from the opening of the reaction well. This combination of fluid continues through the first fluid transport channel and out of the first fluid port. At this point, the entire fluidic device is full of fluid. As more fluid is applied, the contents of the fluid connection bridge and reaction well are completely replaced by the new fluid. To “re-trap” this new fluid in the fluid connection bridge and reaction well, air is applied via positive pressure following the fluid from the second port (2inFIG.13). Similar to the phenomena described earlier, this air forces fluid around the overflow channel as opposed to through the fluid connection channel and reaction well (due to the strong fluid-air interface at the opening of the fluid connection channel). Fluid is continually driven around the overflow channel and through the first fluid channel and removed via the first fluid port. This leaves the new fluid only trapped in the fluidic connection channel and the reaction well. When used in conjunction with the fluidic mixer (e.g., as illustrated inFIG.14), two or more different fluids may be introduced into the fluidic mixer using the second and third ports connected to the fourth and fifth fluid transport channels. The fluids then enter the third fluid transport channel (optionally comprising the window) and then enters the serpentine mixing channel. The fluids are mixed within the third fluid transport channel, and especially the serpentine mixing channel, and then migrates into an attached fluidic device, such as that illustrated inFIG.13(which has already been loaded with fluid and/or cells (e.g., into the reaction well)). Fluids may be mixed in the fluidic mixer in equal parts (e.g., a 50/50 mixture) and/or unequal parts, by introducing equivalent or unequivalent amounts through the ports of the fluidic mixer, and/or introducing such fluids at different flow rates such that a greater amount of one fluid with respect to another fluid enters the third fluid transport channel and then the serpentine mixing channel, thereby producing a mixture comprising more of one fluid as compared to the other (e.g., and a great concentration of one active agent over another). In addition, multiple fluids or mixtures of fluids may be introduced into the fluidic mixer in series such that the fluidic device adjoined to the fluidic mixture (e.g.,6) receives different fluids and/or mixtures over time. Additional fluids, washing fluids, and the like may be loaded into and removed from the attached fluidic device, such as that illustrated inFIG.13(6inFIG.14), as described herein (e.g., using negative and/or positive pressures and the first port illustrated inFIG.13). In some embodiments, this disclosure provides methods for analysing the effect of a test compound on a cell population using the fluidic devices described herein. In such a method, a population of cells is introduced into a reaction well of a microfluidic device provided herein (e.g., that illustrated inFIG.13or shown as part6inFIG.14) using steps for loading a sample into a reaction well provided herein. Next, the contents of the microfluidic device other than the reaction well and a fluidic connection channel in fluidic connection with the reaction well, are removed from the microfluidic device using steps provided herein. The cells are then incubated in the reaction well such that they adhere to a surface of the reaction well, such as by pre-coating the reaction well with poly-L lysine, or another composition known in the art for promoting cell adhesion. Next, a solution comprising a test compound is introduced into the microfluidic device using steps provided herein, such that the solution comprising the test compound enters the reaction well and replaces the fluid contents therein. The contents of the microfluidic device other than the reaction well and the fluidic connection channel are then removed using steps provided herein. The solution comprising the test compound is then incubated in the reaction well with the cells adhered to a surface therein. A solution is then introduced into the microfluidic device to remove the solution comprising the test compound from the reaction well, which can be collected and analysed to identify, for example, biomarkers that are secreted by the cell population in response to exposure to the test compound. Some embodiments of the method for analysing provided immediately above, can utilize a microfluidic device herein that further comprises an upstream fluidic mixer component, for example as provided inFIG.14. As such, the methods can comprise introducing a first solution comprising a test compound and a second solution through a first and second port into the upstream fluidic mixer component, to mix the first solution comprising the test compound with the second solution to form a mixed solution comprising the test compound. This mixed solution comprising the test compound can then be introduced into the microfluidic device as provided immediately above through a channel that connects the upstream fluidic mixer component to the second fluid transport channel. In some embodiments, the method can be a dynamic cell analysis method that include real-time adjustments of a concentration of the test compound that is accomplished, for example, by changing the flow rate of the first solution comprising the test compound and/or the second solution, and continuous collecting of output from the port on the opposite end of the flow path from the ports into which the first solution comprising the test compound is introduced into the fluidic mixer component. The collected output can then be analysed, for example for the presence and optionally amount of one or more biomarkers. Unless otherwise indicated, the terms and phrases used herein are to be understood as the same would be understood by one of ordinary skill in the art. For instance, terms and phrases used herein can be used consistent with the definition provided by a standard dictionary such as, for example, the Tenth Edition of Merriam Webster's Collegiate Dictionary (1997). The terms “about”, “approximately”, and the like, when preceding a list of numerical values or range, refer to each individual value in the list or range independently as if each individual value in the list or range was immediately preceded by that term. The values to which the same refer are exactly, close to, or similar thereto (e.g., within about one to about 10 percent of one another). Ranges can be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent about or approximately, it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. Ranges (e.g., 90-100%) are meant to include the range per se as well as each independent value within the range as if each value was individually listed. All references cited within this disclosure are hereby incorporated by reference into this application in their entirety. A skilled artisan will appreciate that where the specification provides an approximate value or range, the exact value or range is within the scope of the current specification as well. Certain embodiments are further disclosed in the following examples. These embodiments are provided as examples only and are not intended to limit the scope of the claims in any way. EXAMPLES Example 1 Operation of a Fluidic Device Having a Passive Air Control Valve A fluid was introduced via pipette into the first port (1) of a fluidic device manufactured with hydrophobic materials and having a first port (1) of a first fluid transport channel (1A), a reaction well (2), an overflow channel (3), a fluidic connection (4), an air control valve (5), a port for the air control valve into the atmosphere (6), and a second port (7) of a second fluid transport channel (7A) (FIGS.1A and1B), with the port for the air control valve in the open condition. The fluid entered the overflow channel (3) as shown inFIG.2B, thereby increasing hydrodynamic resistance in the overflow channel and causing the fluid to fill the reaction well (FIG.2C). The open port of the air control valve allowed fluid to form a fluidic connection (4); however, fluid was prevented from entering the air control valve (5) by surface tension forces and hydrodynamic resistance. Air was then introduced into the first port (1), forcing excess fluid through the overflow channel (3) and out the second port (7) (FIG.2D). Once the fluid was trapped in the reaction well, the port of the air control valve (6), was closed. Example 2 Dilution or Washing Out of Fluid Held in a Fluidic Device Having a Passive Air Control Valve The reaction well of a fluidic device disclosed in Example 1 held a fluid as shown inFIG.3A. The port of the air control valve was opened, and a washing buffer was introduced into the second port (7) and passed through the fluidic connection (4) into the reaction well, diluting the fluid and pushing excess fluid out the first port (1) (FIGS.3B-3E). The first port and the second port can be used interchangeably for fluid introduction or removal of excess fluid. Furthermore, by increasing the flow rate and volume of the washing buffer, the washing buffer can be used to completely wash the fluid out of the reaction well. Example 3 Immunoassays A fluid sample containing no clenbuterol (“Negative sample”) and a fluid sample containing 8.1 ng/mL of clenbuterol (“Clenbuterol sample”) each were added to a fluidic device coated with anti-Clenbuterol antibody of Example 1 (FIG.4A) using the method disclosed in Example 1. A colorimetric ELISA (Clenbuterol ELISA kit, Neogen, Lexington, Ky., USA) was performed, and either the Ultra TMB substrate (chromogenic) or the QuantaBlu™ substrate (fluorogenic) was used for detection. The different reagents, i.e. the antibody solution, washing buffer, the enzyme conjugate, the Ultra TMB substrate or the QuantaBlu™ substrate, and the stop solution, were added to the reaction well according to the protocol set forth in the Clenbuterol ELISA kit. After the addition of each reagent, the flow direction was reversed so that the next reagent could be trapped in the reaction well for its respective role in the ELISA (Examples 1 and 2). The port for the air control valve was kept open for each step to allow fluid to enter the reaction well. Thus, during the initial filling step, the port valve is kept open but it does not need to remain open thereafter. Upon completion of the ELISA assay, the reaction wells were read using a camera (FIG.4A) or a plate reader (FIG.4B). The immunoassay was successfully performed using the fluidic device of Example 1 (FIG.4A). Moreover, the results obtained from the immunoassay conducted using the fluidic device were comparable to that of immunoassays performed in 96 well or 384 well plates (FIG.4B). Example 4 Storage of Multiple Fluids Without Cross-Contamination A series of fluidic devices of Example 1 were connected as shown inFIG.5. Different fluids can be added into the second port (7) of a series of fluidic devices by introducing a fluid plug followed by air, which pushes the fluid into the reaction wells for which the associated air control valve ports are open, thereby selectively filling reaction wells with the fluid. Filling of reaction wells can also be accomplished by introducing the fluid plug and aspirating it back into the fluid introduction device, e.g., a pipetting system such as pipette tip of manual/electronic/liquid-handling system or syringe pump tubing. Reaction wells with closed air control valve ports do not fill with the fluid. In this way, different fluids were introduced into a second port of a series of connected fluidic devices (FIGS.6A and6B). This was accomplished by opening air control valve port of the first reaction well (keeping those for reaction wells2-8closed) and introducing fluid A into the second port (7) followed by air or aspirating the fluid back into the fluid introduction device, causing the fluid A to enter reaction well1(and no other reaction wells) and then closing the air control valve port for that reaction well. The air control valve port of the second reaction well was then opened (keeping those of reaction wells1and3-8closed) and fluid B introduced into the second port of the second reaction well followed by passing air or aspirating the fluid back into the fluid introduction device, causing the fluid B to enter reaction well2(and no other reaction wells) and then closing the air control valve port for that reaction well. Reaction wells3-8were sequentially filled by using the same process for each respective reaction well. No mixing of fluids A and B was observed. While this example used only two types of fluids, a different fluid could be trapped in each respective well using this method. This may also be accomplished, for example, by opening the air control valve ports for reaction wells1,3,5and7, introducing fluid A can be introduced into the second port followed by passing air or aspirating the fluid back into the fluid introduction device, causing that fluid to enter reaction wells1,3,5and7but not reaction wells2,4,6and8. The air control valve ports for reaction wells1,3,5and7can then be closed and the air control valve ports for reaction wells2,4,6, and8opened. Fluid B can then be introduced into the second port followed by passing air or aspirating the fluid back into the fluid introduction device, thereby causing reaction wells2,4,6, and8to fill with the fluid B. No mixing of fluids A and B would be observed. InFIG.6B, multiple fluidic plugs of different types (fluids C-N) were used to show the filling of specific reaction wells with certain fluids, with a lack of cross contamination between reaction wells, that was accomplished by the opening and closing of air control valve ports essentially as described above for the device shown inFIG.6A. The use of fluidics devices in a series (e.g., as exemplified inFIGS.5and6) enables their use in point of care applications. Fluids or reagents can be preloaded into a cartridge (e.g. a hydrophobic tubing, pipette tip or cartridge) separated by air plugs to allow loading of any number of fluids into the reaction wells. For example, with immunoassays, a sample can be introduced into a common port, either the first port (1) or the second port (7), allowing it to be introduced into reaction wells, each coated with different antibodies. Example 5 Operation of Exemplary Fluidic Devices For a fluidic device manufactured with hydrophobic materials and having a port for an air control valve (1) a fluidic connection (2), a reaction well (3), a high resistance air valve constriction channel (4), an overflow channel (5), a second port (6), and a first port (7) (FIG.7), fluid can be introduced into either the second port, the first port, or the air control valve port. For example, inFIG.8, a solution of fluorescence beads and water was introduced into the port of the air control valve (1) using a pipettor. The second port (6) was blocked (seeFIG.11). The fluid preferentially entered the reaction well instead of the high resistance air valve constriction channel (FIG.8B). When air was subsequently introduced into the air control valve port (1), the surface tension of the liquid and air interface caused the air to bypass the reaction well (3) and pass through the high resistance air valve constriction channel (4) and into the overflow channel. Any excess fluid was forced out the first port (7) by the air (FIGS.8C and8D). Example 6 Dilution or Washing Out of Fluid Held in an Exemplary Fluidic Device A fluidic device disclosed in Example 5 was used to store a fluid (FIG.9A). To dilute or wash out the fluid held in the fluidics device, a washing buffer was introduced into the port of the air control valve (FIG.9A). The washing buffer coalesced (FIG.9A and9B) with the droplet in the reaction well and washed the fluid out of the reaction well, with the excess fluid leaving out the first port (7). The first port, the second port, and the port of the air control valve each can be used as the fluid introduction port or for removal of excess fluid. Furthermore, by altering the flow rate and/or volume of the washing buffer, the droplet can be diluted or completely washed out of the reaction well. Example 7 Connection of Fluidic Devices in Series A series of fluidic devices of Example 5 can be connected as shown inFIG.10. Different fluids can be added into the first port (1) of the series of fluidic devices by introducing a fluid plug followed by air to push the fluid into specific reaction wells. The fluid will only enter reaction wells for which the associated air control valves are open. In addition, a pipette can be programmed with preloaded reagents separated by air plugs to perform any number of steps of an immunoassay. Example 8 Parallel Multiplexed Operations The fluidic device presented in Example 5 (FIG.7) can be connected in series with each having an additional port (FIG.12). Fluidic operations can be as shown in previous Examples; however, overflow fluid can exit from the additional port following the terminal fluidic device subunit (8in the eighth subunit inFIG.12) without contaminating the other reaction wells that are connected in a series. Moreover, a single fluid plug can be passed through serially connected fluidic devices with the additional ports closed, allowing the fluid to enter all of the reaction wells, thereby enabling parallel multiplexed operations (FIG.12). Since the nearest atmospheric exit or zero pressure is the sample port and geometrically the distance to the next port is larger, the fluid would typically exit through the port closest to the reaction well. Example 9 Alternate Fluidic Device Another fluidic device is illustrated inFIG.13. This device comprises, in direct fluid connection with one another and in series: a first port (1); a first fluid transport channel (1A); a reaction well (2); an overflow channel (3); a fluidic connection channel (4); a second fluid transport channel (5A); and a second port (5). The device illustrated inFIG.13comprises many of the design features exhibited by the fluidic device portrayed inFIGS.1A and1B. The device inFIG.13has two ports available for fluid entry or exit (1and5). In the first step, fluid is initially loaded into the reaction well; this fluid must enter the device through the first port. Fluid passes from this port through the first fluid transport channel, where it begins to fill both the reaction well and the overflow channel, based in large part on the ratio of hydrodynamic resistance between these structures. Fluid completely fills the reaction well before the overflow channel is full. After the reaction well is full, fluid begins to enter the fluidic connection channel, while fluid in the overflow channel continues to advance. Fluid fills the connection channel and continues around the overflow channel until both fluid streams meet. Fluid then begins to enter the second fluid transport channel. At this point, first port (1); a first fluid transport channel (1A); a reaction well (2); an overflow channel (3); a fluidic connection channel (4); are each entirely full of fluid. In the second step, in which fluid is trapped solely in the reaction well and the connection channel, negative pressure is applied from the first port. Fluid retreats from the second transport channel in a direction opposite to its loading direction. As fluid recedes to the junction between the fluid connection channel and the overflow channel, fluid passes solely through the overflow channel (fluid effectively “chooses” this channel). The smaller width of the fluid connection channel in comparison to the overflow channel produces a much stronger fluid-air interface, which prevents any fluidic recession through the connection channel or the reaction well. As fluid retreats around the overflow channel, it passes by the entrance to the reaction well and continues through the first fluid transport channel, leaving a fluid air interface at the opening of the reaction well. All excess fluid is removed from the first fluid transport channel and the first port, leaving fluid trapped only in the reaction well and fluid connection channel. In the third step, to partially or fully replace the contents of the reaction well and fluid connection bridge with a new fluid, the second fluid port is used. Fluid enters through the second fluid port via applied pressure and continues through the second fluid transport channel. As fluid reaches the junction between the fluid connection channel and the overflow channel, fluid continues through both paths. Fluid begins to push the fluid housed in the fluid connection bridge and begins to pass around the overflow channel. This process continues; fluid continues to move around the overflow channel (e.g., “bridge”) and continues to push fluid out of the fluid connection channel and the reaction well. Eventually, fluid from the overflow channel combines with fluid emerging from the opening of the reaction well. This combination of fluid continues through the first fluid transport channel and out of the first fluid port. At this point, the entire fluidic device is full of fluid. As more fluid is applied, the contents of the fluid connection bridge and reaction well are completely replaced by the new fluid. To “re-trap” this new fluid in the fluid connection bridge and reaction well, air is applied via positive pressure following the fluid from fluid port2. Similar to the phenomena described earlier, this air forces fluid around the overflow channel as opposed to through the fluid connection channel and reaction well (due to the strong fluid-air interface at the opening of the fluid connection channel). Fluid is continually driven around the overflow channel and through the first fluid channel and removed via the first fluid port. This leaves the new fluid only trapped in the fluidic connection channel and the reaction well. The optimal dimensions (width or diameter) and length for the various parts of the device illustrated inFIG.13, when used in combination with one another, were determined for an illustrative embodiment. This height of this device ranged from 100 to 300 um and an optimal height determined to be be 300 um. The optimal width (diameter) and length of the first (1A) fluid transport channel was determined to include a tapering from the first port toward the overflow channel (3) of from 400 um (proximal to the first port) to 1600 um (distal from the first port and toward the reaction well (2) and the overflow channel). The optimal width (diameter) and length of the reaction well (2) was determined to be 800 um and 1000 um, respectively. The optimal width (diameter) and length of the overflow channel (3) was determined to be 945 um and 3185 um, respectively, when made of PDMS; and 790 um and 3065 um, respectively, when made of COC. The optimal width (diameter) and length of the fluidic connection channel (4) was determined to be 175 um and 140 um, respectively. And the optimal width (diameter) of the second (5A) fluid transport channel was determined to include a tapering from the overflow channel (3) and fluidic connection channel (4) toward the second port (5) of from 1240 um (proximal to the fluidic connection channel (4)) to 650 um (distal from the fluidic connection channel (4) and toward the second port (5)). The optimal length of the second (5A) fluid transport channel was determined to be 3350 um. As noted in the specification and claims, the relationships between these parts may also be expressed as a ratio, as would be understood by those of skill in the art from this example. Optimal dimensions for the fluid connection channel (4) were also determined. This varied slightly depending on the material from which the fluid connection channel was prepared. A fluid connection channel (4) prepared from PDMS was found to have an optimal width (diameter) of from 150-225 um, and an ideal range of 175-200 um; and an optimal length of from 100-175 um, with an ideal range of 125-150 um. A fluid connection channel (4) prepared from COC was found to have an optimal width (diameter) of from 160-215 um; and an optimal length of 110-130 um. The ratio of hydrodynamic resistance and capillary pressure within the fluid connection channel (4) and the the overflow channel (3) was also determined to be important to the proper function of the fluidic device. Capillary pressure in a hydrophobic channel (which includes all the materials we are using) serves as an opposing pressure or force to the flow of liquid. The higher this hydrophobic capillary pressure is, the more difficult it is to flow fluid through that channel (or the more pressure it takes to do so). In this case, the capillary pressure ratio between overflow channel (3) and fluid connection channel (4) is important. If overflow channel (3) has a very low capillary pressure compared to fluid connection channel (4), fluid will have much less opposing pressure when flowing through that path. This may lead to more fluid flow through overflow channel (3) as opposed to part4, and slower fluid flow into fluid connection channel (4). If the flow into fluid connection channel (4) is too weak, the capillary pressure of fluid connection channel (4) may be strong enough to prevent fluid from completely filling that channel, leaving some air trapped in fluid connection channel (4). If air is trapped in fluid connection channel (4), the subsequent washing steps will either be significantly less effective or completely ineffective. The capillary pressure of fluid connection channel (4) must be low enough to allow this fluid in initially (as mentioned above), but must also be high enough to hold the fluid—air interface in the subsequent washing steps (e.g., fluid and air passed from serpentine mixing channel (5inFIG.14described below). This is an important balance for the device to work correctly. A suitable range for the hydrodynamic resistance ratio of the fluid connection channel (4) and the the overflow channel (3) was determined to be about 0.13 to about 0.34 (ideally 0.185 to 0.254) when prepared using PDMS, or about 0.13 to about 0.21 when prepared using COC. A suitable range for the capillarly pressure ratio of the fluid connection channel (4) and the the overflow channel (3) was determined to be about 1.438 to about 1.726 (ideally 1.510 to 1.603) when prepared using PDMS, or about 1.426 to about 1.628 when prepared using COC. FIG.14depicts a fluidic device embodiment that incorporates a downstream fluidic device (designated part6, inFIG.14) similar to that shown inFIG.13but lacking the second port in combination with an upstream fluidic mixer component. The fluidic mixer component is comprised of parts1(second port),1A (fourth fluid transport channel),2(third port),2A (fifth fluid transport channel),3(third fluid transport channel),4(mixing window, an optional feature), and5(serpentine mixing channel). Before fluid is introduced into the upstream fluidic mixer (parts1-5), the downstream fluidic device (part6) can be loaded with an initial fluid as described in the description ofFIG.13above (i.e., steps1and2). After loading of part6, fluid may be introduced into the upstream fluidic mixer component. Fluid entry can occur in ports1or2, and each respective fluid initially travels through the fourth and fifth fluid transport channels (1A and2A, respectively). Fluids from the first and second transport channels then converge in the downstream (third) fluid transport channel (3). The initial fluid convergence in the beginning of the downstream fluid transport channel (i.e., near the junction of the fourth and fifth fluid transport channels (1A and2A, respectively)) which marks the beginning of fluid mixing. As fluid continues through the third fluid transport channel part3, it reaches the mixing “window” (4) when included in the device, where the interface between fluids can be visualized by the user. The fluid with a higher flow rate will occupy more of this mixing window than the fluid with the lower flow rate, with the ratio of window occupancy being directly related to the flow rate ratio between fluids. After fluid passes through the third fluid transport channel (3) and/or mixing window (4), it reaches the serpentine mixing channel (5). This serpentine mixing channel is designed specifically to ensure complete fluidic mixing before the downstream fluidic device (6). Mixing in this channel relies primarily on diffusion; channel length and channel width are two of the major dimensional factors that influence this diffusion. The channel width and length of the serpentine mixing channel are selected to ensure complete fluid mixing for the desired fluid input settings. After the fluid is mixed in the serpentine mixing channel, it flows into the downstream fluidic device (6). The incoming mixed fluid enters the downstream fluidic device (6) via the second fluid transport channel (part5A fromFIG.13). At this point, incoming fluid will interact with the initial fluid in the downstream fluidic device (6) as described in Step3in the description ofFIG.13. Fluid mixed in the upstream fluidic mixer component will then flow through and replace the fluid initially loaded in downstream fluidic device (6). With regards to fluid dispensed in ports1or2(FIG.14), there are a variety of different input parameters. A single port may be used for a single fluid, leaving the other port unused, and the mixing device may simply serve as a transport channel to the downstream fluidic device (6). Two different fluids may also be used where, e.g., one fluid has a higher or lower flow rate compared to the other fluid. For instance, one fluid may be a concentrated drug solution, while the other fluid may be a buffering solution. By modifying the flow rates of each inputted solution, varying drug or sample concentrations may be achieved in the mixed solution. The optimal dimensions (width or diameter) and length for the various parts of the device illustrated inFIG.14, when used in combination with one another, were determined. This height of this device ranged from 100 to 300 um and an optimal height determined to be be 300 um. The width (diameter) and length of the fourth and fifth fluid transport channels used in this exemplary device was 500 um and 5340 um, respectively, but can be of any suitable width (diameter) and length which should be approximately the same. The width (diameter) and length of the overflow channel (3) used in this embodiment was determined to be 200 um and 4600 um, but can be of a longer or shorter length as the majority of the mixing function is provided by the serpentine mixing channel (5). The optimal width (diameter) and length of the serpentine mixing channel (5) was determined to be 400 um and 90.1 mm, respectively. The serpentine mixing channel (5) of the embodiment illustrated inFIG.14also included seven switchbacks with the length of between each being approximately equivalent. The dimensions of the downstream fluidic device (6) in this embodiment was essentially as described above forFIG.13, except that the second port (7inFIG.13) was not included since the second fluid transport channel (5A ofFIG.13) is in fluidic connection with the serpentine mixing channel (5). As noted in the specification and claims, the relationships between these parts may also be expressed as a ratio, as would be understood by those of skill in the art from this example. The device detailed inFIG.14allows for dynamic control of solution composition. As mentioned before, this solution may contain a drug, the concentration of which in solution may need to be adjusted in real time. Multiple input ports and control of input parameters allow for precise control of drug (or other substance) concentration, and the serpentine mixing channel ensures the drug (or other substance) is adequately mixed in the desired diluting solution. Independent loading ability provided by the inclusion of the downstream fluidic device (6), combined with the dynamic and real-time solution composition control provided by upstream fluidic mixer component (1-5ofFIG.14), offers many benefits to the user. In one example, a cell population can be loaded into the reaction well of the downstream fluidic device (6). A drug solution of interest can be developed and mixed in the upstream fluidic mixer component, the concentration of which is adjustable by the user. Through a combination of the upstream fluidic mixer component and the downstream fluidic device, constant perfusion drug studies can be performed on cells, providing a much more tailored and realistic experience than standard static drug studies. The device pictured inFIG.14offers a dynamic cell study solution more closely related to in vivo situations than standard static cell studies. While certain embodiments have been described in terms of the preferred embodiments, it is understood that variations and modifications will occur to those skilled in the art. Therefore, it is intended that the appended claims cover all such equivalent variations that come within the scope of the following claims.
122,041
11857958
DETAILED DESCRIPTION Examples of Circular-Shaped Parts I, H and G According to a specific embodiment, said support part (I), said mould (H1, H2) and said perforated part (G1, G2) are circular-shaped, making it possible in particular to be adapted to the cell culture boxes with a diameter of 35 mm. FIG.67presents a specific embodiment of the process wherein said mould (H1) and said perforated part (G1) respectively comprise 100 moulded 3D nanostructures and 100 perforations. Such a process makes it possible to obtain a central unit with 100 protuberances. FIG.68presents a specific embodiment of the process wherein said mould (H2) and said perforated part (G2) respectively comprise 9 moulded 3D nanostructures and 9 perforations. Such a process makes it possible to obtain a central unit with 9 protuberances. These examples of numbers of perforations and moulded 3D nanostructures, are not limiting. Selecting the mould and the perforated part depends on the desired number of protuberances for the 3D nanostructured membrane of the central unit. In this specific embodiment, the central module consisting of the perforated part G with the protuberances obtained from the process detailed above, can be placed on a cell culture chamber, such as a cell culture box with a diameter of 35 mm containing the culture medium, by way of a part F, as shown inFIG.71. According to an embodiment of the invention, the central module obtained by the process described above, is placed on a lower module such as described in the present invention, comprising at least one duct to collect secretions from the at least one protuberance. The lower module is of identical shape and identical dimensions to said central module. The lower module is assembled to the central module in a reproducible and specific alignment which is guided by the flat section of the parts and the pin for aligning the part of the lower module which is inserted in the hole for aligning the central module. The lower module comprises a number of ducts, identical to the number of perforations, and therefore protuberances of the central module, such that the assembly of said central module with said lower module makes it possible to align the ducts with the perforations and therefore the protuberances, to collect the secretions from the cells via a microfluidic system. In this other specific embodiment according to the invention, the lower module is replaced by the part F. This part F, used as a support of the central module on the culture box such as represented inFIGS.67,68and71comprises square openings making it possible for the circulation of the culture medium to give nutrients to the growth cells on the inner face of said at least one protuberance. Examples of Square-Shaped Parts I, H and G According to a specific embodiment, said support part (i), said mould (h1, h2) and said perforated part (g1, g2) are square-shaped. FIG.72presents a specific embodiment of the process wherein said mould (h1) and said perforated part (g1) respectively comprise 100 moulded 3D nanostructures and 100 perforations. Such a process makes it possible to obtain a central unit with 100 protuberances. FIG.73presents a specific embodiment of the process wherein said mould (h2) and said perforated part (g2) respectively comprise 9 moulded 3D nanostructures and 9 perforations. Such a process makes it possible to obtain a central unit with 9 protuberances. These examples of numbers of perforations and moulded 3D nanostructures, are not limiting. Selecting the mould and the perforated part depends on the desired number of protuberances for the 3D nanostructured membrane of the central unit. The resorbable polymeric solution is preferably made with chitosan, agarose or alginate. According to a specific embodiment, the invention relates to a process for producing a microfluidic cell culture chip, wherein said resorbable polymer solution (22) is chitosan. When chitosan is used, the resorbable mould can be prepared by dissolving 2% chitosan in 2% acetic acid for one night, then by diluting 1.5% chitosan with ethanol. The chitosan solution is then polymerised in a 5M hot bath of NaOH: ethanol at a ratio 1:1. According to a specific embodiment, the invention relates to a process for producing a microfluidic cell culture chip, wherein the step of polymerising said resorbable polymer solution (22), said resorbable polymer solution (22) being chitosan, is made by an incubation with a 2% acetic acid solution. When chitosan is used as a resorbable polymeric material, the dissolution is done by an incubation overnight with a 2% acetic acid solution, according to a protocol that is well known to a person skilled in the art. According to a specific embodiment, the invention relates to a process for producing a microfluidic cell culture chip, wherein said resorbable polymer solution (22) is agarose. When agarose is used, the resorbable mould can be prepared by heating and by dissolving 40 μg/ml of agarose in PBS (phosphate buffered saline). Agarose is polymerised by placing the solution obtained at a temperature below the gelation point thereof. According to a specific embodiment, the invention relates to a process for producing a microfluidic cell culture chip, wherein the step of polymerising said resorbable polymer solution (22), said resorbable polymer solution (22) being agarose, is carried out by an incubation at a temperature greater than the gelation temperature of agarose. When agarose is used as a resorbable polymeric material, the dissolution is done by a slow heating from ambient temperature to a temperature of 70° C., for 120 minutes, then by letting the temperature of the agarose return to ambient temperature over one night. This heating can be done in a water bath. It is important that the temperature slowly increases to minimise thermal convection currents which could damage the 3D nanostructured porous membrane. Variants of this heating protocol, well known to a person skilled in the art, include the addition of DMSO in the water of the water bath to modify the gelation properties of agarose. According to a specific embodiment, the invention relates to a process for producing a microfluidic cell culture chip, wherein said resorbable polymer solution (22) is alginate. According to a specific embodiment, the invention relates to a process for producing a microfluidic cell culture chip, wherein the step of polymerising said resorbable polymer solution, said resorbable polymer solution (22) being alginate, is carried out by an incubation overnight with a solution with no Ca2+a Ca2+ion binding agent added, such as EDTA or EGTA. The polyelectrolyte multilayer film comprises, as variable parameters:the number of layers,the thickness of each of the layers,the charge of the polyelectrolyte(s) used. By varying the number of layers, the roughness, the thickness and the rigidity of the final multilayer film can be modified. Preferably, the film is composed of 15 layers, 2 nm thick, of polyelectrolytes. By varying the number of layers or the type of charge for the polyelectrolytes used, the hydrophobicity of the final multilayer film can also be modified. The extrusion of the 3D nanostructure can be subject to the following defects, due to the pumping system used for the extrusion:translation defect, when there is a translation of the protuberance with respect to leaving the site provided, directly aligned with the perforation of the support,extrusion defect, when there are defects in the shape of the protuberance, like for example a thickening of the base or other defects which will be known to a person skilled in the art. A protuberance thus formed from 3D nanostructures with a translation defect or an extrusion defect can continue exercising the technical function thereof provided initially within the device, however, as the protuberance thus formed has a less optimal shape, the performance thereof within the device is also less optimal. However, the device can continue to exercise the function thereof provided, but with a reduced performance. The protuberance can have different changes such as:a tilt with respect to an axis (y), passing through the centre of said opening and which is perpendicular to said support,a variation of the height thereof,a translation with respect to the perforation, due to the translation of the 3D nanostructured porous membrane on the support. These changes are due to the process for preparing the central module, and in particular at the phase of extruding the polymeric solution through the perforations of said support. Certain changes are also driven directly during the use of the protuberance in the device. I—Example of Using the Chip for a Co-Culture 1. Conditions for Maintaining Line Cultures of Prostate Epithelial Cells and Stromal Cells The culture medium used for all experiments is a Keratinocyte Serum Free Medium (KSFM) (Life Technologies, Carlsbad, CA, Ref. 17005-075) supplemented by 5 ng/mL of epidermal growth factor (EGF) and 50 μg/mL of bovine pituitary extract. The lines of prostate epithelial cells and stromal cells are maintained in the medium are cultured in an atmosphere at 37° C. and 5% CO2. The subculturing of the cells in a fresh medium is done every three days for epithelial cells and every two days for stromal cells. For this, the cells are washed with a phosphate buffered saline solution from Dulbecco (D-PBS) without calcium and without magnesium (Life Technologies, Ref. 14190), then incubated with 1 mL of Trypsine-EDTA at 0.25 mg/mL, at 37° C., (Lonza, Basel, CH, Ref. CC-5012) for around 7 minutes. For all experiments, the culture medium of the cells has been supplemented each day with the fresh culture medium. 2. Preparing Cells Before the Introduction in the Central Unit A chemical separation of the cells is done by an incubation of 5 minutes at 37° C. with 1 ml of trypsin-EDTA at 0.25 mg/ml (Life Technologies, Ref. 25300-054) in the PBS medium without calcium and without magnesium. Independently, a microfluidic chip according to the invention is sterilised by making a 70% ethanol (volume/volume) solution circulate through the ducts, then by drying all of the microfluidic system in a furnace at a temperature of between 35° C. and 45° C. for at least 30 minutes, then by exposing it to a U.V. radiation, and to ozone for 40 minutes. 3. Preparing the 3D Nanostructured Porous Membrane of the Central Unit The 3D nanostructured porous membrane consists of successive layers of polyelectrolytes alternating a positively charged polyelectrolyte layer and a negatively charged polyelectrolyte layer. According to the production process, this same membrane consists of protuberances. The outer face and the inner face of the protuberances, consisting of the polyelectrolyte porous membrane, are covered by an extracellular matrix (ECM) preparation composed of Matrigel® and/or collagen, fibronectin or hyaluronic acid. The Matrigel® matrix used here is a commercial product produced by the company Corning@. It is a reconstituted basal membrane preparation, which is extracted from Engelbreth-Holm-Swarm (EHS) mouse sarcoma, a tumour rich in extracellular matrix proteins. Once isolated, this material is composed of around 60% laminin, 30% collagen IV, and 8% entactin. Entactin is a bridging molecule which interacts with laminin and collagen IV, and contributes to the structural organisation of these molecules of the extracellular matrix. The Matrigel® matrix from Corning® also contains heparan sulphate proteoglycans (perlecan), of transforming growth factor β (TGF-β), of epidermal growth factor, of insulin type growth factor, of fibroblast growth factor, a plasminogen tissue activator and other growth factors which are naturally present in the EHS tumour. It also contains residual matrix metalloproteinases derived from tumour cells. Matrigel® can be used by itself to functionalise the porous membrane, at a concentration of 6 mg/ml, or as a mixture with type I collagen at a concentration of between 0.75 and 2.5 mg/ml. 4. Introducing Two Cell and Cell Co-Culture Types in the Central Unit 4.1. Introduction of Epithelial Cells Initially, the epithelial cells are introduced to form a cell joining layer, i.e. a cell culture at the stage of the confluence. According to a specific embodiment, the epithelial cells are introduced on the inner faces of the protuberances of the central unit. Three hours are required to obtain the adhesion of the cells, and 24 hours for the formation of a layer for joining cells, i.e. at a stage of cell confluence. These adherent and proliferative cells secrete their own extracellular matrix and thus establish a basal layer playing the role of a barrier. The inner face of the protuberances of the central unit is thus covered by a dense single layer of epithelial cells, which is used as a physiological support for the growth and differentiation of human cells, isolated from the patient's urine. The introduction of cells on the inner face of the protuberances can be done, according to 3 methods:returning the central module in order to have the lower sections of the perforations towards the top and manually pipette a cell suspension.returning the central module in order to have the lower sections of the perforations towards the top and use a robot for handling fluids to introduce a cell suspension.assembling the upper module, the central module and the lower module, and fill the central unit on the side of the inner face of the protuberances using microfluidic ducts of the lower unit. In the case of this pre-assembly of the three modules, the cells are therefore introduced via the ducts of the lower module. This method of introducing cells after a pre-assembly of the three modules is preferred to the two other methods, as it prevents any bacterial contamination, because the previously sterilised system is kept closed. According to a specific embodiment, the epithelial cells are introduced at a concentration of 3.106cells/mL in the central unit, either directly via the perforations (1stand 2ndmethod) with a syringe, or via the ducts of the lower unit (3rdmethod) by using a fluid system, automated and controlled by pressure and flow (Fluigent) or a syringe pump. Using a syringe pump with an adjustable flow is preferred, in order to provide a smooth and controlled introduction of cells. A stable and continuous flow is delivered by using pressure pumps (Fluigent, France). Pressurised containers containing the culture medium are kept in a chamber at a controlled temperature and CO2level. The flow is adjusted to around 5-10 mL/hour (10 mbar) and the adhesion and the proliferation of the cells is observed over time. All the samples are kept in an incubator, humidified at 37° C. and 5% CO2. In a specific embodiment, the central unit comprises protuberances of a height of 350 μm with a circular base of 150 μm in diameter. The area of the inner surface of the protuberance is thus 329700 μm2, on which around 50 epithelial cells are counted at the confluence stage (joining cell layer), that is around one cell every 66 μm2. 4.2. Introduction of Cells on the Outer Face of the Protuberances Secondly, once the layer of joining (or confluent) epithelial cells formed on the inner face of the protuberances, the stromal cells are dispensed on the porous membrane at the outer and inner faces of the protuberances. The introduction of cells on the inner face of the protuberances can be done according to two methods:returning the central module in order to have the tops of the protuberances towards the top and manually pipette a cell suspension.assembling the upper module, the central module and the lower module and fill the central unit on the side of the inner face of the protuberances using the microfluidic ducts of the lower unit. In the case of this pre-assembly of the three modules, the cells are therefore introduced via the inlet/outlet ducts of the upper unit. This method of introducing cells after a pre-assembly of the three modules, is preferred to the other methods, as it prevents any bacterial contamination because the previously sterilised system is kept closed. According to a specific embodiment, the stromal cells are introduced via the inlet/outlet ducts of the upper module at a concentration of 3.106cells/mL in the central unit directly using a syringe (1stmethod), that is via the ducts of the upper module (2ndmethod) by using a fluid system, automated and controlled by pressure and flow (Fluigent) or a syringe pump. The stromal cells adhere very quickly (less than one hour). It is not necessary that the stromal cells form a layer of confluent (or joining) cells, the simple adhesion thereof on the outer face in this example is enough. Generally, the ratio between the epithelial cells and the stromal cells is 1:2. Thus, according to a specific embodiment, for a co-culture on a surface of 0.7 cm2, the porous membrane at the outer and inner faces of the protuberances is functionalised with 90 μl of a Matrigel® solution diluted to 6 mg/ml, then seeded to obtain, in the end, 7000 epithelial cells/cm2and 14000 stromal cells (fibroblasts)/cm2. The culture medium, introduced via the inlet/outlet ducts of the upper module and via the ducts of the lower module to supply the cell cultures, is identical on either side of the protuberances, and consists of the KSFM culture medium supplemented by 5 ng/mL of epidermal growth factor (EGF) and by 50 μg/mL of bovine pituitary extract. 4.3. Examples of Epithelial Cells and Stromal Cells These epithelial cells can be non-tumorigenic commercial cell lines (prostate or bladder or kidney) or commercial primary cultures. These stromal cells can be:either fibroblasts (commercial primary cultures or lines),or mesenchymal cells (commercial cultures or lines),or other stromal cells (endothelial, etc.). The two cell types used to form these cellular single layers, are called “neutral” or “healthy”, they are non-tumorigenic and only play the role of a basal layer. These “neutral” cells form, at the stage of the confluence, a highly contiguous layer of cells on the inner and outer face of the protuberances, establishing tight seals, that it is possible to characterise by immunofluorescence and imaging (see E-cadherin part 5 marking). 4.4. Interchangeability of Cultures on the Inner and Outer Faces of the Protuberances According to a specific embodiment, the epithelial cells are introduced on the inner face of the protuberances and the stromal cells are introduced on the outer face of the protuberances. However, the co-culture can be established in an interchangeable manner, i.e. the stromal cells can also be introduced on the inner face of the protuberances, and the epithelial cells on the outer face of the protuberances. In both cases, the polyelectrolyte layer located between the two cell types, makes it possible to constitute a porous barrier, using the positively and negatively charged polyelectrolyte mesh thereof. 5. Visualisation of the Cells in the Central Unit (Proof of Concept of the Co-Culture on the Protuberances) In order to validate the method of co-culture on the protuberances of the central unit, an immunomarking is carried out. This immunomarking is therefore carried out on dead cells (attached by PFA) and this visualisation has the sole aim of controlling the co-culture being correctly in place, and that the methodology of introducing cells in correct. The cells are visualised in the central module by immunomarking.Phalloidin is used to identify cortical actin filaments, which follow the edges of the plasma membrane and, consequently provide a means to delimit the extent of the cell and the membrane thereof.E-cadherin is used to detect the cell-cell junctions.Immunostaining is carried out by introducing E-cadherin with a syringe pump via the ducts at ambient temperature.After the formation of a confluent layer of epithelial cells, around 24 hours after the introduction thereof, they are attached for 20 minutes with 4% Perfluoroalkoxy (PFA) (volume to volume) in a solution composed of 10% sucrose in a cytoskeleton buffer (solution A).The cells are then washed with solution A and permeabilised for 3 minutes with a solution A added with 0.1% Triton TX-100. A washing with a TBS solution is carried out for 10 minutes, followed by a second washing with a PBS solution for 30 minutes. The autofluorescence of the PFA is inactivated by the NH4Cl contained in the TBS solution. The non-specific sites are blocked by an incubation with a PBS solution with 10% goat serum and 3% BSA. The cells are then incubated with a primary antibody for one hour. The primary antibody used is an anti-E-cadherin antibody (Abcam, Ref. ab1416) diluted to 1/50 in a PBS solution with 0.1% Tween-20 and 1% BSA. The cultures are then washed for 30 minutes with a PBS solution, then incubated with a secondary anti-mouse antibody coupled with the cytochrome Cy3 (Jackson, Ref. 115-162-062), diluted to 1/1000 of Phalloidin FITC (Sigma, Ref. P5282) diluted to 1:1000 in a PBS solution with 0.1% Tween-20 and 1% BSA, for 20 minutes.After a washing of 30 minutes with a PBS solution, the rings are counter-stained with Hoechst colourant (Life Technologies, Ref. H-1399), diluted to 1:7000, for 5 minutes. The cells are then washed for 10 minutes and the Dako fluorescent medium is manually introduced.The binding focal points have been detected by marking by using Vinculine. For counter-marking with Vinculine, the cells are pre-permeabilised for 40 seconds with Triton X-100 and attached with a PBS solution with 4% PFA (v/v), for 20 minutes, then washed once with a PBS solution.To avoid any non-specific antibody adsorption, the cells are incubated with a 0.1% BSA and 10% goat serum solution for one hour.The cells are then incubated for one hour with a primary antibody directed against Vinculine (Sigma, Ref. V9131) diluted to 1:700 in a PBS solution with 0.05% Tween 20 and 5% goat serum, then washed 4 consecutive times for 45 minutes with a PBS SolutionThe cells are then incubated with an anti-mouse antibody, coupled with the cytochrome Cy5, diluted to 1/500 in a PBS solution with 0.05% Tween 20 and with 5% goat serum (Jackson). The central module is then washed 4 times for 15 minutes with a PBS solutions. The rings and the actin are stained as described above. The co-culture is observed by fluorescence microscopy or can be observed by other microscopy methods such as phase contrast microscopy, lensless imaging, confocal microscopy, light sheet microscopy. The images are captured during the cell culture. To provide a view of the whole of the total width of the device, cell images are recorded using a lensless sensor. SEM analyses are also carried out. In a specific embodiment, the fluorescence images of the central module containing the co-culture of cells, are obtained using a Zeiss Axiolmager Z1 microscope with a 20× lens equipped with the right Apotome module for acquisitions with a z-stack field depth, with the shot every 3 mm in the axis z, for a tube, 150 mm in diameter. The images are recorded using a digital AxioCam MRm digital camera mounted on the microscope. 6. Visualisation of the Cells in the Central Unit in Real Time The cell cultures in the central unit can be monitored in real time by a phase contract microscope observation which makes it possible to visualise the non-marked and living cells, because of the transparency of the materials consisting of the modules. II—Example of Using the Chip for the Diagnosis 1. Introduction of Cells Coming from the Patient According to a specific embodiment, the epithelial cells are introduced on the inner face of the protuberances and the stromal cells are introduced on the outer face of the protuberances. Once a single layer of cells obtained on each of the faces, that is after 24 hours, the microfluidic chip, thus provided with cells, can be used for the diagnosis of a patient. For this, the cells are isolated from a urine sample of a patient of at least 50 ml, in particular from 50 to 100 ml. The isolation is done by centrifuging the urine sample at a low speed, in particular 800 g for 5 minutes, making it possible for the sedimentation of the cells contained in the urine sample. This centrifugation step is well known to a person skilled in the art. The lower part of sedimented cells is then resuspended in the culture medium and the cell suspension is directly introduced in the microfluidic chip according to the invention, which means that the cells do not require any pre-culture before the introduction thereof in the chip. The concentration of the cells obtained from the urine sample is or varies by a few hundred cells to several thousand. The isolated urine cells of the patient can be introduced on the side of the face of the protuberance which supports the culture of epithelial cells, or on the side of the face of the protuberance which supports the culture of stromal cells. In other words, these cultures, being interchangeable on either side of the protuberance, the isolated cells of the urine of the patient can be introduced both on the inner face, and on the outer face of the protuberances. According to a specific embodiment, the isolated cells of the urine of the patient are introduced on the side of the face of the protuberance which supports the culture of epithelial cells. Thus, they are introduced via the ducts of the lower unit, when the single layer of epithelial cells is formed on the side of the inner face of the protuberances, that is via the inlet/outlet ducts of the upper module when the single layer of epithelial cells is formed on the side of the outer face of the protuberances. The cells isolated from the urine of the patient are exfoliated uroepithelial (or urothelial) cells, including all bladder, prostate and kidney epithelial cells. In a specific embodiment, the inner face of the protuberances is covered by a layer, pre-formed of previously cultured epithelial cells, the outer face of the protuberances is covered by a layer, pre-formed of fibroblasts (stromal cells), and the isolated cells are dispensed via the ducts of the lower module. These isolated cells are inserted in this layer, pre-formed of healthy epithelial cells on the side of the inner face of the protuberances, and which is supported by a layer of healthy fibroblasts. 2. Observation of the Proliferation of Cells Coming from the Patient The proliferation of isolated cells is thus monitored, in order to observe the progression of the proliferation of the isolated cells in the device and to examine if this proliferation results in replacing healthy basal cells and affects the overall secretory profile of the tissue. 3. Recovery of Secretions Once the introduction of cells isolated from the urine of the patient is done, the epithelial cells of patients are stimulated by adding 0.1 ng/ml of DHT (Dihydrotestosterone) on the outer or inner face of the protuberance. This stimulation of cells by DHT lasts between 24 hours and 48 hours. The membrane consisting of the outer and inner faces of the protuberances being porous, this stimulation can be made equally on either side of the protuberances. The epithelial cells can also be stimulated by adding mibolerone (non-metabolised hormone). The stimulation of the epithelial cells is thus, made after the binding of two cell types on either side of the protuberances, and after the growth thereof until the confluence stage. The secretions can be recovered when the isolated cells of the patient bind and are inserted in this layer, pre-formed of healthy epithelial cells on the side of the inner face of the protuberances, and which is supported by a layer of healthy fibroblasts on the side of the outer face of the protuberances. The binding of the isolated cells of the patients lasts around 3 hours and the integration thereof lasts around 6 hours. The accumulation of a sufficient volume of secretions progressively occurs. The final recovery of the secretions for the analysis of secretome is carried out after having left at least 12 hours pass. More specifically, the secretions are recovered at the end of the 24 to 48 hours of stimulation with DHT. They are then analysed by a device making it possible for the analysis of compounds in the solution. According to a specific embodiment, the secretome is analysed by mass spectrometry. The secretions can be analysed in line by sensors incorporated in said chip. It must be noted, that the different modules composing said chip are not affected when the secretions are recovered or when the secretions are continuously analysed by the sensors in line. Searching for specific markers by immunological methods can also be done in the recovered secretions. For example, the detection of PSA (prostate-specific antigen), reference biomarker of prostate cancer, can be made. For a protuberance of a height of 350 μm and a circular base with a diameter of 150 μm, the volume of secretions recovered at the end of 24 hours is around 2 nL. The detection and the quantification of PSA is done by an ELISA test. For this, around 50 μl of medium inside several protuberances are collected then deposited in a 96-well plate, placed at 37° C. for 45 minutes. Five successive washes with distilled water are necessary, in order to remove proteins not attached to the anti-PSA primary antibody. 100 μL of free anti-PSA secondary antibody coupled with HRP (Horseradish peroxidase) are then added in each well before 45 minutes of incubation at 37° C. of the ELISA plate. Finally, 100 μL of substrate (TMB) are added, giving rise to a substrate enzyme colorimetric reaction. After 15 minutes at 37° C., the reaction is stopped by adding 100 μL of sulphuric acid and the absorbance is detected using an ELISA plate reader at 450 nm. III—Example of Using the Chip for Screening Molecules In a specific embodiment, the microfluidic cell culture chip according to the invention, is used for screening molecules. IV—Example of Using the Chip to Determine the Effect of a Treatment of Urological Cancers in a Patient In a specific embodiment, the microfluidic cell culture chip according to the invention, is used to determine the effect of a treatment for a urological cancer in a patient suffering from a urological cancer. In this embodiment, the analysis of the secretome of isolated cells of the urine of the patient, inserted in the culture of epithelial cells on the protuberance, is done before and after the treatment of the patient, and/or during the treatment. The comparison of the secretome obtained before the treatment with that obtained after the treatment, and/or that obtained during the treatment, makes it possible to determine the effect of the treatment on the urological cancer of which the patient is suffering from. BRIEF DESCRIPTION OF THE DRAWINGS 1support consisting of a non-resorbable membrane (central unit)2upper face of the support consisting of a non-resorbable membrane (central unit)3lower face of the support consisting of a non-resorbable membrane (central unit)4perforation of the support consisting of a non-resorbable membrane (central unit)53D nanostructured porous membrane (central unit)6upper face of 3D nanostructured porous membrane (central unit)7lower face of 3D nanostructured porous membrane (central unit)8protuberance (central unit)9outer face of protuberance (central unit)10inner face of protuberance (central unit)11section of the perforation at the upper face of the support (central unit)12section of the perforation at the lower face of the support (central unit)13circular base of the protuberance (central unit)14duct (lower unit)15upper orifice of the duct (lower unit)16lower orifice of the duct (lower unit)17reservoir (lower unit)18duct of the reservoir (lower unit)19orifices of the upper unit leading to the inlet/outlet ducts (upper unit)20upper orifice of the duct (lower module)21lower orifice of the duct (lower module)22resorbable polymer233D nanostructure24epithelial cell101upper module102upper unit103base of the upper module104central module105central unit106base of the central module107lower module108lower unit109base of the lower module201attachment elements202inlet/outlet ducts (upper module)203chamber (upper unit)204attachment elements205set of lower orifices of the ducts (lower module)206set of upper orifices of the ducts (lower module)207set of protuberances (central module)208moulded 3D nanostructure209upper face of the mould210resorbable polymer matrix211negative mould of a 3D nanostructure212lower face of the matrixF support part of the central module213side frame of the support part214open upper face of the support part215solid lower face of the support part216cut of the solid face of the support part217alignment pin218alignment holeH, H1, H2, h1, h2mouldI, i support partG, G1, G2, g1, g2perforated part FIG.1: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is in whole, facing the perforation. FIG.2: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is less than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is in whole, facing the perforation. FIG.3: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and to the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is partially facing the perforation. FIG.4: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is less than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is partially facing the perforation. FIG.5: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is less than the value of the diameter d2of the lower section of said perforation, and is less than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is partially facing the perforation. FIG.6: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is less than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is partially facing the perforation. FIG.7: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is in whole, facing the perforation. FIG.8: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is in whole, facing the perforation. FIG.9: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is less than the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is in whole, facing the perforation. FIG.10: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is less than the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is partially facing the perforation. FIG.11: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is less than the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, and wherein the protuberance is in whole, facing the perforation. FIG.12: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the protuberance is tilted along an axis (z) with respect to the vertical axis (y). FIG.13: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the inner face of the protuberance is covered by an assembly of a first cell type at the stage of the confluence, and the outer face of the protuberance is covered by an assembly of a second cell type at the stage of the confluence. FIG.14: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is in whole, facing the duct. FIG.15: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d5of the lower orifice, and wherein the protuberance is in whole, facing the duct. FIG.16: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is in whole, facing the duct. FIG.17: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is in whole, facing the duct. FIG.18: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is in whole, facing the duct. FIG.19: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is in whole, facing the duct. FIG.20: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.21: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is less than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.22: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is less than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.23: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is less than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.24: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.25: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.26: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.27: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.28: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is greater than the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.29: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.30: Schematic, cross-sectional view of a central unit comprising a protuberance in the 3D nanostructured membrane, and a perforation in the support, and wherein the value of the diameter d1of the upper section of said perforation is equal to the value of the diameter d2of the lower section of said perforation, and is greater than the value of the diameter d3of the circular base of said protuberance, said central unit being positioned on a lower unit comprising a duct, of which the value of the diameter d4of the upper orifice is equal to the value of the diameter d2of the lower section of said perforation, and is equal to the value of the diameter d5of the lower orifice, and wherein the protuberance is partially facing the duct. FIG.31: Schematic, cross-sectional view of a central unit comprising two protuberances in the 3D nanostructured membrane, and two perforations in the support, and wherein the value of the diameter d1of the upper section of each of the perforations is equal to the value of the diameter d2of the lower section of each of the perforations, and is equal to the value of the diameter d3of the circular base of each of the protuberances, said central unit being positioned on a lower unit comprising two ducts, of which the value of the diameter d4of the upper orifice of each of the ducts is equal to the value of the diameter d2of the lower section of each of the perforations and is equal to the value of the diameter d5of the lower orifice, and the two lower orifices of the two ducts respectively leading to a reservoir, leading to the outside of the lower module via an outlet duct (protuberance in whole, facing the duct). FIG.32: Schematic, cross-sectional view of a central unit comprising two protuberances in the 3D nanostructured membrane, and two perforations in the support, and wherein the value of the diameter d1of the upper section of each of the perforations is equal to the value of the diameter d2of the lower section of each of the perforations, and is equal to the value of the diameter d3of the circular base of each of the protuberances, said central unit being positioned on a lower unit comprising two ducts, of which the value of the diameter d4of the upper orifice of each of the ducts is equal to the value of the diameter d2of the lower section of each of the perforations and is equal to the value of the diameter d5of the lower orifice, and the two lower orifices of the two ducts leading to the outside of the lower module in two distinct sites (protuberance in whole, facing the duct). FIG.33: Schematic, cross-sectional view of a central unit comprising two protuberances in the 3D nanostructured membrane, and two perforations in the support, and wherein the value of the diameter d1of the upper section of each of the perforations is equal to the value of the diameter d2of the lower section of each of the perforations, and is equal to the value of the diameter d3of the circular base of each of the protuberances, said central unit being positioned on a lower unit comprising two ducts, of which the value of the diameter d4of the upper orifice of each of the ducts is equal to the value of the diameter d2of the lower section of each of the perforations and is equal to the value of the diameter d5of the lower orifice, and the two ducts are connected to one another such that the two lower orifices of the two ducts lead to the outside of the lower module in the same site (protuberance in whole, facing the duct). FIG.34: Schematic, cross-sectional view of a central unit comprising two protuberances in the 3D nanostructured membrane, and two perforations in the support, and wherein the value of the diameter d1of the upper section of each of the perforations is equal to the value of the diameter d2of the lower section of each of the perforations, and is equal to the value of the diameter d3of the circular base of each of the protuberances, said central unit being positioned on a lower unit comprising two ducts, of which the value of the diameter d4of the upper orifice of each of the ducts is equal to the value of the diameter d2of the lower section of each of the perforations and is equal to the value of the diameter d5of the lower orifice, and the two lower orifices of the two ducts respectively leading to a reservoir, each of the reservoirs leading to the outside of the lower module in the same site, via the outlet ducts connected to one another (protuberance in whole, facing the duct). FIG.35: Schematic, cross-sectional view of a central unit comprising two protuberances in the 3D nanostructured membrane, and two perforations in the support, and wherein the value of the diameter d1of the upper section of each of the perforations is equal to the value of the diameter d2of the lower section of each of the perforations, and is equal to the value of the diameter d3of the circular base of each of the protuberances, said central unit being positioned on a lower unit comprising two ducts, of which the value of the diameter d4of the upper orifice of each of the ducts is equal to the value of the diameter d2of the lower section of each of the perforations and is greater than the value of the diameter d5of the lower orifice, and the two ducts are connected to one another such that the two lower orifices of the two ducts lead to the same site on a reservoir, which leads to the outside of the lower module via an outlet duct (protuberance in whole, facing the duct). FIG.36: Schematic, cross-sectional view of a central unit comprising two protuberances in the 3D nanostructured membrane, and two perforations in the support, and wherein the value of the diameter d1of the upper section of each of the perforations is equal to the value of the diameter d2of the lower section of each of the perforations, and is equal to the value of the diameter d3of the circular base of each of the protuberances, said central unit being positioned on a lower unit comprising two ducts, of which the value of the diameter d4of the upper orifice of each of the ducts is equal to the value of the diameter d2of the lower section of each of the perforations and is greater than the value of the diameter d5of the lower orifice, and the two lower orifices of the two ducts respectively lead to two distinct sites on one same reservoir, which leads to the outside of the lower module via an outlet duct (protuberance in whole, facing the duct). FIG.37: Schematic, cross-sectional view of a central unit comprising four protuberances in the 3D nanostructured membrane, and four perforations in the support, and wherein the value of the diameter d1of the upper section of each of the perforations is equal to the value of the diameter d2of the lower section of each of the perforations, and is equal to the value of the diameter d3of the circular base of each of the protuberances, said central unit being positioned on a lower unit comprising four ducts, of which the value of the diameter d4of the upper orifice of each of the ducts is equal to the value of the diameter d2of the lower section of each of the perforations and the two lower orifices of a first set of two ducts respectively lead to two distinct sites on a first reservoir, and the two lower orifices of a second set of two ducts respectively lead to two distinct sites on a second reservoir, the first and the second reservoir respectively leading to the outside of the lower module in distinct sites (protuberance in whole, facing the duct). FIG.38: Schematic, perspective view of the upper module. FIG.39: Schematic, perspective view of the central module. FIG.40: Schematic, perspective view taken from above the upper face of the 3D nanostructured porous membrane, of a central unit comprising a set of protuberances. FIG.41: Schematic, perspective view of the lower module. FIG.42: Schematic, perspective view of the microfluidic chip comprising the assembly of the upper module, of the central module and of the lower module. FIG.43: Photo of the upper module (side view of the opening of the chamber). FIG.44: Photo of the central module. Top view of the upper face of the 3D nanostructured porous membrane comprising a set of protuberances. FIG.45: Photo of the lower module. Top view of the upper face of the lower unit comprising the set of upper orifices of the ducts. FIG.46: Photo of the upper module and of the lower module. FIG.47: Photo of the disassembled upper module, of the disassembled central module and of the disassembled lower module. FIG.48: Schematic, cross-sectional view of the support consisting of a non-resorbable membrane, of the central unit, comprising a perforation. FIG.49: Schematic, cross-sectional view of the support consisting of a non-resorbable membrane, of the central unit, comprising a perforation, through which a resorbable polymer has been extruded to form a 3D nanostructure on the side of the upper face of said support. FIG.50: Schematic, cross-sectional view of the support consisting of a non-resorbable membrane, of the central unit, comprising a perforation, through which a resorbable polymer has been extruded to form a 3D nanostructure on the side of the upper face of said support on which a polyelectrolyte layer has been applied to obtain the 3D nanostructured porous membrane comprising a moulded protuberance on said 3D nanostructure. FIG.51: Schematic, cross-sectional view of the support consisting of a non-resorbable membrane and comprising a perforation, of the central unit, on which is positioned secured to the 3D nanostructured membrane comprising a hollow protuberance. FIG.52: Photo using a confocal microscope of the inner face of a protuberance supporting a culture of epithelial cells at the stage of the confluence. FIG.53: Schematic, cross-sectional view of a mould comprising at least one moulded 3D nanostructure on the side of the upper face thereof. FIG.54: Schematic, cross-sectional view of a mould covered with resorbable polymer on the side of the upper face of said mould. FIG.55: Schematic, cross-sectional view of a resorbable polymer matrix comprising at least one negative mould of at least one moulded 3D nanostructure. FIG.56: Schematic, cross-sectional view of a resorbable polymer matrix comprising at least one negative mould of at least one moulded 3D nanostructure, the lower face of said matrix being covered by a polyelectrolyte layer. FIG.57: Schematic, cross-sectional view of a resorbable polymer matrix comprising at least one negative mould of at least one moulded 3D nanostructure assembled with a perforated part comprising a support consisting of a non-resorbable membrane perforated by at least one perforation, said matrix being assembled on the side of the lower face thereof with the upper face of said support, such that the negative mould of the 3D nanostructure is aligned with said perforation of the support. FIG.58: Schematic, cross-sectional view of a resorbable polymer matrix comprising at least one negative mould of at least one moulded 3D nanostructure assembled with a perforated part comprising a support consisting of a non-resorbable membrane perforated by at least one perforation, said matrix being assembled on the side of the lower face thereof with the upper face of said support, such that the negative mould of the 3D nanostructure is aligned with said perforation of the support, wherein the continuous surface constituted by the lower face of said support and the lower face of said resorbable polymer matrix comprising at least one negative mould at said at least one perforation of said support, is covered by a polyelectrolyte layer to form a 3D nanostructured membrane comprising at least one protuberance. FIG.59: Schematic, cross-sectional view of the central module corresponding to the perforated part comprising, on the side of the lower face of the support, a 3D nanostructured porous membrane and on the side of the upper face of the support, at least one protuberance in the extension of the at least one perforation of the support of the perforated part. FIG.60: Schematic, cross-sectional view of a mould comprising at least one moulded 3D nanostructure on the side of the upper face thereof, assembled on the side of the upper face thereof with a support part comprising a cut in the lower face thereof. FIG.61: Schematic, cross-sectional view of a mould comprising at least one moulded 3D nanostructure on the side of the upper face thereof, assembled on the side of the upper face thereof with a support part comprising a cut in the lower face thereof, where said mould is covered by resorbable polymer on the side of the upper face thereof. FIG.62: Schematic, cross-sectional view of a resorbable polymer matrix comprising at least one negative mould of at least one moulded 3D nanostructure, said matrix being formed at the cut of the support part. FIG.63: Schematic, cross-sectional view of a support part containing at the cut of the solid lower face thereof, a resorbable polymer matrix comprising at least one negative mould of at least one moulded 3D nanostructure, said support part being assembled to a perforated part comprising a support with at least one perforation, such that said negative mould of at least one moulded 3D nanostructure is aligned with said perforation. FIG.64: Schematic, cross-sectional view of a support part containing at the cut of the solid lower face thereof, a resorbable polymer matrix comprising at least one negative mould of at least one moulded 3D nanostructure, said support part being assembled to a perforated part comprising a support with at least one perforation, such that said negative mould of at least one moulded 3D nanostructure is aligned with said perforation, the continuous surface constituted by the lower face of said support and the lower face of said resorbable polymer matrix comprising at least one negative mould at the said at least one perforation of said support, being covered by a polyelectrolyte layer to form a 3D nanostructured membrane comprising at least one protuberance. FIG.65: Schematic, cross-sectional view of the support of the perforated part comprising, on the side of the lower face thereof, a 3D nanostructured porous membrane and on the side of the upper face thereof, at least one polyelectrolyte protuberance in the extension of the at least one perforation of the support of the perforated part, and the support part I. FIG.66: Schematic, cross-sectional view of the central module corresponding to the perforated part comprising, on the side of the lower face of the support, a 3D nanostructured porous membrane, and on the side of the upper face of the support, at least one protuberance in the extension of the at least one perforation of the support of the perforated part. FIG.67: Schematic, perspective view of a circular-shaped support part I, of a circular-shaped mould H and comprising 100 moulded 3D nanostructures (H1), of a circular-shaped perforated part G and comprising 100 perforations (G1) and of a support part F of the central module. FIG.68: Schematic, perspective view of a circular-shaped support part I, of a circular-shaped mould H and comprising 9 moulded 3D nanostructures (H2), of a circular-shaped perforated part G and comprising 9 perforations (G2) and of a support part F of the central module. FIG.69: Schematic, perspective views of the assembly of a circular-shaped support part I on a circular-shaped mould H and comprising 100 moulded 3D nanostructures (H1), via the alignment pin of I and the alignment hole of H1. A: Top view when the two elements are assembled. B: Top view when the elements are disassembled. C: Profile view when the two elements are assembled. D: Profile view when the two elements are disassembled. FIG.70: Schematic, perspective views of the assembly of a circular-shaped support part I on a circular-shaped perforated part G and comprising 100 perforations (G1) via the alignment pin I and the alignment hole of G1. A: Top view when the two elements are assembled. B: Top view when the elements are disassembled. C: Bottom view when the two elements are assembled. D: Bottom view when the two elements are disassembled. E: Profile view when the two assembled elements are returned such that G1is oriented towards the top and I is oriented towards the bottom. FIG.71: Schematic, perspective views of the assembly of a circular-shaped perforated part G and comprising 100 perforations (G1) on a support part F of the central module. A: Bottom view of the two assembled elements. B: Bottom view when the two elements are disassembled. C: Profile view when the two elements are assembled. D: Profile view when the two elements are assembled. FIG.72: Schematic, perspective view of a square-shaped support part i, of a square-shaped mould H and comprising 100 moulded 3D nanostructures (h1), of a square-shaped perforated part G comprising 100 perforations (g1). FIG.73: Schematic, perspective view of a square-shaped support part i, of a square-shaped mould H and comprising 9 moulded 3D nanostructures (h2), of a square-shaped perforated part G and comprising 9 perforations (g2).
68,015
11857959
DETAILED DESCRIPTION Microfabrication for most microchemical (or microfluidic) systems (MCSs) has matured around material made of silicon or polymeric materials, which are not suitable for harsh environments such as high pressure, high temperature, and corrosive reactants. Disclosed herein is a powder-based fabrication framework that suitably withstands harsh operating environments and minimizes processing efforts while integrating various components through new processing techniques. Various MCS components can be made, for example micro-reactionware, microchannels, heat exchangers, pack-bed reactors (e.g., a micro-biomass reformer consisting of a pack-bed microreactor for filtration), combustion chambers, high-temperature gas clean-up separators, and high-temperature heat exchangers in addition to a micro flame ionization detector (μFID) serving as an on-chip diagnosis tool. Individual MCS components can be subsequently assembled in a modular fashion for system-level integration. The disclosed methods provide several advantages, both in terms of processing and the final formed apparatus. A one-pot fabrication method can be used to make an apparatus with open and/or fully enclosed cavities (e.g., as internal channels for the MCS devices). Nearly full-density apparatus can be formed after fully sintering, and without the need for other phases such as binders or fillers. An intermediate, partially sintered structure is suitable for machining additional structure/cavities into the apparatus before final/full sintering. Control of the process permits formation of cavities with desirably small sizes and smooth interior finishes. Ceramic-based MCSs are more suitable for operation under harsh environments such as high temperature and corrosive reactants compared to the more conventional MCS materials such as silicon and polymers. With the recent renewed interests in chemical manufacturing and process intensification, simple, inexpensive, and reliable ceramic manufacturing technologies are needed. The disclosed powder-based fabrication framework is a one-pot, cost-effective, and versatile process for ceramic MCS component fabrication. The process includes the compaction of metal-oxide nanopowders with a graphite or other fugitive phase that is burned out to create internal cavities and microchannels before full sintering. In illustrative embodiments, pure alumina powder has been used without any binder phase to form a micro-burner/combustion chamber, enabling more precise dimensional control and less structure deformation upon sintering. Process steps such as powder compaction, graphite burnout during partial sintering, machining in a conventional machine tool, and final densification have been examined to characterize the process and impact on the resulting MCS component. This near-full density ceramic structure with the combustion chamber and various internal channels was fabricated to be used as a micro-burner for a gas sensing application. Miniaturization of chemical system has garnered significant attentions in chemistry and biology due to many advantages such as enhancement in heat/mass transfer rates at small scale, reduction in expensive reagents and hazardous wastes, and facilitation of massive parallelization in reaction/catalyst screening and optimization. The significant technological advancements for MCSs have been focused on chemical reactions, separation, and sensing in a low-to-medium temperature range (20° C. to 600° C.). One notable example is a lab-on-a-chip or micro total analytical system, in which the total sequence of laboratory processes is integrated to perform chemical synthesis, transport, and analysis, and it has profound influence in chemistry and biomedical areas. In some cases, the microreactors and heat exchangers in MCSs need to be operated at high temperatures (>600° C.) and/or under highly corrosive environments like solid-oxide fuel cells, fuel reformers, combustion burners, and gasifiers. However, high-temperature μCSs with sophisticated design and similar level of integration found in low-temperature counterpart have rarely been realized mainly because the conventional MCS materials such as silicon, glass, polymers, metals and conventional metal alloys are not stable at these high operating temperatures. Ceramic materials offer excellent high-temperature compatibility and corrosion resistances, but pose significant manufacturing challenges due to their hardness and brittleness. Several groups have demonstrated the promise of ceramic-based microreactors for medium-to-high temperature reactions such as hydrogen production from continuous reforming of propane, oxidative coupling of methane, catalytic combustion, and nanoparticle synthesis. Despite these efforts and as discussed below, the current ceramic fabrication techniques still have some or all of the following challenges: (1) These structures are fabricated as open channel/reactors, requiring a joining process to create a fully enclosed system; (2) It is difficult to join or bond ceramic structures—high temperature adhesive typically used may create thermal mismatch, therefore with temperature cycling the joining areas are susceptible to failure; (3) It is difficult to establish a robust fluidic connection using conventional fitting to ceramic structures; and/or (4) It is difficult to monolithically integrate functionally diverse structures. For example, one of the paramount challenges in fabricating ceramic MCSs is that the microfabrication techniques borrowed from well-established microelectronics and microelectromechanical system (MEMS), which are very effective for silicon- or polymer-based MCSs, are not compatible with ceramic materials. Instead, the conventional and non-conventional ceramic processing techniques have been utilized to create ceramic microreactors and other components of MCSs. These techniques include rapid prototyping using low-pressure injection molding, micromachining, sol-gel/nanoparticle casting, and tape casting. In the rapid prototyping process, a negative silicone mold is first created from the original polymer mold fabricated by micro-steoreolithography, which is used directly for low-pressure injection molding. The resolution and surface quality of the ceramic components depend on the stereolithography quality of the original polymer mold, and the critical dimension of hundreds of microns (which is a relevant length scale in most MCSs) can be easily obtained. More recently, the smallest feature size on the order of a few microns in ceramic structures has been fabricated using the soft-lithographic molding technique like micromolding in capillaries combined with sol-gel casting. However, these molding/casting-based techniques can create only the open channel or chamber structures due to the demolding requirement. To utilize them in MCS applications, the fabricated structures need to be bonded with or packaged in another high-temperature material to form sealed microchannels or microreactors. Tape casting with low-temperature co-fired ceramic (LTCC) is perhaps the most widely used technique when it comes to the fabrication of the ceramic microreactors and microchannels. While low co-firing/sintering temperature (<900° C.) is beneficial for integrating metal electrodes and other applications, the operation temperature is typically limited due to the presence of the glass phase. Unlike the various molding techniques, tape casting is capable of producing suspended structures, enclosed cavity or microchannels for MCSs. However, the suspended structures tend to deform and sag due to high lamination pressures and the softening of the glass component in the ceramic composite during sintering. Multilayer lamination with fugitive materials such as waxes, polymeric materials, and carbon materials was used to support the embedded structures during lamination and sintering. Wax- and polymer-based fugitive materials, however, were completely burnt out even before the sintering of LTCC, and therefore sagging of the suspended region cannot be prevented during sintering. Moreover, in tape casting, each machined layer needs to be aligned to the previous layers before lamination, entailing some special equipment for alignment and lamination. The disclosed methods and apparatus address the problems associated with ceramic MCSs and are directed to a simple, inexpensive, reliable, and reproducible ceramic manufacturing technology for high-temperature μCSs and microdevice application. The disclosed methods employ the cold compaction of metal-oxide powders with a graphite or other fugitive phase for the embedded features. In embodiments without a binder phase in the powder mix, the final chemistry and dimension of the sintered ceramic structures can be more precisely tuned. The advantages of the disclosed powder-based technique include one or more of (1) a one-pot, cost-effective process to create either open or fully-enclosed ceramic microreactors and microchannels, (2) near-full density ceramic structures without any other phases (e.g., organic or glass materials) in the final devices, (3) partially-sintered ceramic structures facilitating machining, and (4) abilities to control the surface finish of the internal cavity walls and easily incorporate additional features on the cavity surface. Process steps such as powder compaction, graphite burn-out during partial sintering, machining of partially sintered ceramics, and final densification can be selected/controlled to optimize the process and the properties of the resulting apparatus. As described in the examples below, a fully-enclosed ceramic structure with sub-millimeter internal cavities was formed according to the disclosure to provide an MCS component for micro-burner and micro flame ionization detector (μFID) applications. FIG.1illustrates a microchemical apparatus10according to the disclosure and in the form of a microburner including a combustion chamber. The microchemical apparatus10includes a fully sintered microchemical apparatus400, which has a generally solid or continuous (e.g., non-porous) body420defining an interior cavity410corresponding to the desired structural features of the apparatus10(e.g., including a flame or combustion area410A as indicated). The apparatus10can include one or more inlets and/or outlets430to the interior cavity. The inlets/outlets430can result from machined orifices or other structures in in a partially sintered compact and/or from a fugitive phase material having an exposed edge at an external boundary of the apparatus10structure prior to fugitive phase removal (e.g., both being formed as described in more detail below). As illustrated, the inlets/outlets430can include ports for (gaseous) analytes, hydrogen (H2) gas, other gases, and exhaust (outlet) gases. EXAMPLES The examples illustrate the disclosed apparatus, processes, and compositions, but are not intended to limit the scope of any claims thereto. In particular, the examples include illustrative embodiments of the disclosed methods for forming a ceramic microchemical apparatus in the specific context of a ceramic micro-burner. This example illustrates the disclosed powder processing processes and related apparatus for a micro-burner whose critical dimension is below 1 mm. The micro-burner structural design in the examples was adopted from Kim et al. (2012) without major modifications. Unlike most ceramic processing techniques that start with ceramic powders or sols mixed with polymeric binder phases, however, the disclosed processes employ cold compaction of raw powders while utilizing a graphite fugitive phase to create internal cavities and channels. The processes allow the fabrication of open and fully-enclosed cavities/microchannels, and both configurations were formed in the examples. A micro-burner device with an open ceramic structure covered with a transparent quartz top was employed to visualize and optimize the flame in the micro-burner before the fabrication of the micro-burner with the fully-enclosed combustion chamber. A flat circular disc with a small thickness-to-diameter ratio (˜0.1) was selected for the micro-burner apparatus overall geometry, because the thin circular disc is one of the simplest shapes known to successfully compact the powder in a uniform density under a uniaxial load. Fabrication Procedure: The overall fabrication protocols for the two open and closed configurations are depicted inFIG.2. The open-channel configuration is denoted as ‘1’ (e.g., b1, c1, . . . ) while the fully-enclosed configuration as ‘2’ (e.g. b2, c2, . . . ). The fabrication of the first configuration (open-channel configuration) is only slightly different from the second one (fully-enclosed configuration). Thus, the fabrication protocol for the fully-enclosed micro-burner configuration is described in more detail. Alpha-phase alumina (AKP-50, Sumitomo in Japan) powder with the purity higher than 99.99% and the particle size between 0.1 and 0.3 micrometer was purchased for fabricating the proposed micro-burners. The common first step is to cut the 0.9 mm thick graphite sheet (EDM-3, Saturn Industries) in a CNC machine into the integrated shape of the combustion chamber and the internal channels. This graphite piece served as a fugitive phase200(e.g., first fugitive phase material210with a specific shape/geometry212) that would later burn out during partial sintering and leave the interior cavities310for the combustion chamber and the internal channels. Once the graphite fugitive phase200was machined, half of the alumina powder to be used (about 2 grams) as the metal oxide powder100was poured into a die20to serve as the first metal oxide powder110(FIG.2, panel a). Prior to depositing the alumina powder100, the interior of the die20, whose inner diameter is 22.2 mm, was lubricated by zinc stearate (C36H70O4Zn) with 12.5-14% of ZnO (Alfa Aesar). This solid lubricant mixture facilitates the release of the powder compact. In addition, it also helps to reduce the frictional force that may be exerted to the powder compact with the graphite fugitive phase. After the first half of the alumina powder100was deposited, the die20stage was shaken with mild vibration and the punch gently pressed the powder with its own weight (˜200 grams) to flatten the powder surface. Subsequently, the machined graphite fugitive phase material210was placed onto the powder surface of the first metal oxide powder110(FIG.2, panels b1 and b2). As illustrated, the first fugitive phase material210has a surface area210A which is small (e.g., 50% or less) relative to the surface area110A of a layer of the first metal oxide powder110in a plane P on which the first fugitive phase material210is placed. (FIG.2, panels a and b1). The placement and orientation of the graphite piece210with respect to the die reference point is crucial because it is difficult to identify the location of the cavity once the fully-enclosed cavity is formed. The other half of alumina powder100was poured into the die20to serve as the second metal oxide powder120(FIG.2, panel b2), followed by the full compaction of the powder and the embedded graphite using MTS Insight300(MTS Systems Corp.) with the compaction pressure of 50 MPa at a speed of 1 mm·min−1(FIG.2, panels c1 and c2 showing compression within the die20, and panels d1 and d2 showing a compressed, non-sintered compact150removed from the die20). The powder compact150was then partially sintered in a furnace30(Carbolite-HTF1700, UK) at 800° C. for 2 hours to burn out the graphite fugitive phase210and form a partially sintered compact300(FIG.2, panels e, f1, and f2). The graphite reacts with oxygen in the furnace and becomes CO2gas which escapes through the porous wall/body320of the partially-sintered alumina compact300, thus leaving an interior cavity310within the compact300and generally having a cavity geometry312corresponding to the original geometry212of the first fugitive phase material210(FIG.2, panels f1 and f2). This partially-sintered compact300with the formed interior cavity310was drilled to make connecting channels330as inlets/outlets for fuel and oxidant sources for the micro-burner applications (FIG.2, panels g1 and g2). The portion corresponding to the burner exhaust was milled to reveal the embedded channel310. Finally, the partially-sintered compact300was fully sintered in the furnace30at 1350° C. to provide the mechanical integrity of the micro-burner in the final microchemical apparatus10having a fully sintered body400(FIG.2, panels h, i1 and i2). Material Characterization: In order to determine an appropriate partial-sintering temperature and graphite burn-out behavior, a thermogravimetric analysis (TGA Q500, TA Instruments, USA) was conducted at a constant ramping rate (15° C.·min−1), which is the same as the temperature ramping rate used in the fabrication process for the examples. TGA measures a change in weight of the sample as a function of temperature, revealing the kinetics of graphite vaporization. During the TGA experiments, air was constantly flowing at 60 mL·min−1to ensure complete oxidation of graphite. The densification process of alumina powder compact during sintering was investigated using a thermomechanical analyzer (TMA, Setaram 95, France). TMA results present the correlation between sintering temperature and sample densification kinetics in real time. A flat compacted sample was placed in between an alumina plate as a base and an alumina probe. The probe was then adjusted to zero. A change in dimension of the sample was measured by recording the movement of the alumina probe. Scanning electron microscopy (SEM) was used to evaluate the microstructures of the partially-sintered alumina samples that were sintered at different temperatures. The presence of the cavity and channels embedded in the fully-enclosed alumina sample was visualized by a computerized tomography (CT) scan (GE eXplore Locus RS micro CT) that has the highest resolution up to 27 μm. Micro-burner Testing Setup: Both configurations of the micro-burners (as schematically shown inFIG.2) were prepared for the flame testing. A micro-burner with a transparent window was used to characterize the flame shape and optimize the flow rates of fuel and oxidant streams. A quartz disc (25-mm in diameter, Quartz Scientific Inc.) was bonded to the open channel device of the sintered alumina using a medium-temperature adhesive (1531 DURASEL™, maximum service temperature of 343° C.). Through the quartz window attached on the channel side, an oxy-hydrogen flame can be visually observed to determine the presence and location of the flame within the chamber. The holes on the surface of the alumina micro-burner was made to insert the stainless steel (SS) tubing (0.46 mm I.D., 0.90 mm O.D.) for the fluidic connections and fixed with RESBOND™ 907GF, which can endure up to 1260° C. Once the adhesives to bond the quartz window and the SS tubing were cured at room temperature for 24 hours, the micro-burner was completed for testing. Hydrogen and oxygen were created using a commercial electrolyzer (E-65 from h-tec) coupled to the custom-made flow manifold to control the flow rates of each stream. Because the electrolyzer produces hydrogen and oxygen at a fixed stoichiometric ratio (H2:O2=2:1), a miniature pump was added to deliver air to the oxygen line to independently control the fuel-to-oxidant ratio. A flame image was taken using a Nikon camera (D50, shutter speed: 30 second, ISO 2.8) in a dark room. Under the normal circumstances, an oxy-hydrogen flame is not visible to bare eyes or regular cameras, and therefore the special UV intensifier would be required to image the flame. A trace amount of organic contaminants (diffusion oil) was introduced to the combustion system to visualize the flame. Fabrication Results:FIG.3shows photograph images of the micro-burner apparatus in both open and closed configurations in each process stage as described above and schematically illustrated inFIG.2. The 0.9-mm-thick graphite layer fugitive phase210was CNC-machined (FIG.3, panel a) and sandwiched/cold-pressed into the alumina powder/first metal oxide powder110without damage (FIG.3, panel b). The fabrication result for the open-channel micro-burner with the quartz top is shown in the top row ofFIG.3(panels c1, d1, e1) while the fully-embedded micro-burner in the bottom row ofFIG.3(panels c2, d2, e2). For the fully-embedded sample, the other half of the alumina powder/second metal oxide powder120was deposited and compacted to what is shown onFIG.3, panel b.FIG.3, panel c1 indicates that the graphite layer was completely burned out during the partial sintering at 800° C. as the decomposition temperature of the graphite phase is lower than 800° C. In case of the fully-enclosed sample, whether or not the graphite layer was completely removed was not clear by the visual inspection. The partially-sintered state of the alumina for the compact300permits the use of conventional machining (e.g. milling, drilling, etc.) for further modification as illustrated by the holes330which were drilled in the partially-sintered alumina burner300for fluidic connection (FIG.3, panels d1 and d2). A medium-temperature epoxy was used to seal the open-channel micro-burner between the 25-mm diameter transparent quartz disc and the 22-mm diameter alumina disc (FIG.3, panel e1). Stainless Steel (SS) tubing fixed with the high-temperature epoxy provides gas-tight delivery of fuel (e.g. hydrogen) and oxidant (e.g. oxygen and/or air) to the burner cavity (FIG.3, panels e1 and e2). FIG.4shows the cross-section views of the fully-sintered micro-burner400with the embedded interior cavity/channel410configuration. X-ray micro-computed tomography (micro-CT) technology was used to noninvasively image the internal channels, which include the interior cavity410resulting from the eliminated fugitive phase as well as the inlet/outlet structures330machined into the pre-sintered compact300(FIG.4, panel a). This technique can be particularly useful to orient and position the interior cavity and channels410of the fully-enclosed structure for drilling or other machining process of external features. The interior cavity410took the exact shape of the graphite fugitive phase material210, and the machined holes330were well aligned to the internal channels of the interior cavity410. The photograph of the crosscut sample reveals that no noticeable cracks or defects were found (FIG.4, panel b). Performing the micro-CT scan each time to locate the internal feature can be costly. As an alternative, the design was modified by extending the end exhaust part/edge214of the graphite fugitive phase material210and exposing it to the exterior surface of the micro-burner400(i.e., by appropriate original placement in the first metal oxide powder110), which correspondingly enabled identification of the location of the interior cavity410and corresponding channels for machining. This technique also provides additional structures on the channel wall without adding a process step. For example,FIG.4, panel c shows two protruded lines of the trapezoidal cross-section at the bottom of the sub-millimeter channel embedded in the alumina device, which structures were incorporated by simply making two grooves in the graphite fugitive phase before compaction. This type of the structure would be difficult to be fabricated within the cavity walls using any other conventional ceramic processing techniques. FIGS.5and6illustrate that the surface finish quality of interior cavity410can be tuned as it is directly related to the surface finish of the fugitive phase210. Ceramic processing techniques that can create embedded sub-millimeter channels or cavities (e.g. LTCC or 3D printing) in general have difficulties in controlling the surface finish of the internal features. The fugitive phase210according to the disclosure permits control the surface quality required for each application. The final surface quality of the interior cavity410is directly dependent on the smoothness of the graphite fugitive phase210and the size of metal oxide powder100. To attain the smooth surface, the graphite fugitive phase sheet210is polished before being placed into the alumina powder110having a powder size between 0.1 and 0.3 micrometer. The resulting surface of interior cavity410channel walls is significantly smoother. After sintering, the internal surface of open micro-burners was measured by Confocal Laser Scanning Microscope (Zeiss LSM 210, German). The wavelet-based filtering scheme written in MATLAB was used to eliminate the artifacts.FIG.5, panel a shows the topography of the sample made with the unpolished graphite fugitive phase210, where the peaks range between 10 μm to 40 μm on the surface. In contrast, hardly any peak above 10 μm was observed on the surface of the sample made by polished graphite fugitive phase210(FIG.5, panel b). Three random cross-sectional profiles on the measured area were taken to quantify the surface roughness of the resulting ceramic surface.FIG.6further shows the improvement in surface finish of the sample with the polished graphite. Three topological profiles of the three random locations were used to evaluate the average surface roughness of the interior cavity410by taking the average values of the distances between the adjacent peaks and valleys, resulting in an average surface roughness of 2.9 μm for the alumina surface made from the unpolished graphite fugitive phase210and 0.7 μm for that made from the polished graphite fugitive phase210. Processing Characterization: The fully-enclosed design of the alumina micro-burner was used for process characterization including powder compaction, optimization of the sintering temperature profile, and thermogravimetric analysis (TGA) experiments for graphite burn-out. Control of powder compaction during fabrication is important, because the presence of stiff graphite with a complex shape impedes the powder flow, frequently causing non-uniform stress distribution and resulting in cracks in the final component. One simple remedy is to remove sharp edges and geometric complexities in the machined graphite layer. The rounded edges and corners facilitate the powder to flow around them, preventing undesirable cracks due to the non-uniform density distribution. The edges of the graphite after cut in a CNC machine were smoothened by manual grinding. In addition, the sharp protrusion or the feature of graphite with a high aspect ratio makes the resulting powder structure susceptible to crack formation during fully sintering because of the non-uniform density distribution. For example, the region intersecting two gas channels to the combustion chamber was found to be prone to the crack formation (see circled region ofFIG.3, panel d1). Moreover, if the size of the graphite fugitive phase is too large in comparison to the overall ceramic sample, the ceramic sample may become collapsed or fractured. Since the powder holds its shape after compaction with the friction among the powder, the sufficient powder area is needed in terms of both thickness and planform area. In a typical LTCC process, the burning of fugitive materials requires large openings because ceramic tapes consisting of the ceramic matrix infiltrated with polymeric or glassy phases are non-porous, leaving little room for gas diffusion. When the pure alumina powder is compacted without any binder phase, the powder compact is still substantially porous, allowing gases (e.g., O2and CO/CO2) to diffuse in and out. Among many materials serving as fugitive phases, graphite was selected for two reasons. First, graphite has a very low coefficient of the thermal expansion (2˜6 μm·m−1·K−1), which minimizes the stress exerted onto the powder compact during partial sintering. This is important because the ceramic powders are in an extremely fragile state when the graphite is burnt out. Also the dimension of the integrated cavity can be predicted with better accuracy compared to other polymer-based fugitive phases. Secondly, the graphite burns out before the alumina powder starts to consolidate. Adequate interstitial spaces are provided for the byproducts of graphite oxidation, mainly CO and CO2, to escape. However, each graphite grade is slightly different in its oxidation temperature, and appropriate temperature ramp rate, soaking temperature, and soaking duration values can be determined/modified as desired.FIG.7shows the two different sintering temperature profiles (oven temperature vs. time) and the resulting alumina micro-burners. When a full sintering temperature was reached at a constant ramp rate (15° C.·min−1) without any soaking step, a crack was observed at the side or corner of the final structure (FIG.7, panel a photograph). A similar crack was observed even at lower ramp rates. Compacted green ceramic samples were visually inspected using a microscope, and samples with observable cracks due to the improper die pressing were removed from further analysis, and the macroscopic cracked structure inFIG.7, panel a was not a result of poor powder compaction, but rather by stress developed during sintering. Crack formation, crack propagation, and structural integrity of the sintered ceramic structure could affected by the sintering temperature profile for several reasons. On one hand, a higher ramp rate would induce a higher temperature gradient within the structure and in turn cause internal stresses to be developed, leading to crack propagation. On the other hand, an insufficient amount of time for graphite to completely burn out would generate a pressure build-up in the internal cavity as the consolidation of alumina powders progresses. The former factor is believed to be less important since no crack was observed in the open-channel configuration regardless of the ramp rate. In the open-channel sample, the graphite phase is fully exposed to outer environment, and therefore there is no restriction for CO/CO2to be released. Conversely, a competition between graphite volatilization and powder consolidation exists in the fully-enclosed sample. If the alumina powders become consolidated before all graphite phases are burnt out, CO/CO2has little interstitial space to escape and the pressure will build up until the structure bursts open. This net increase in pressure within the cavity can be attributed to the different gas permeabilities of O2and CO2in porous metal oxide structures (see Supplementary Information). To facilitate graphite volatilization, a soaking step holding at a constant temperature of 800° C. was added—the temperature high enough for graphite to burn out while low enough for alumina powders not to sinter (or consolidate) significantly. The modified sintering cycle resulted in crack-free ceramic structures with the internal cavities (FIG.7, panel b photograph). To understand the kinetics of the graphite burn-out with and without the presence of alumina powders, thermogravimetric analysis (TGA) was performed on a small piece of graphite and a graphite piece embedded in the alumina powder compact. First, a pure graphite sample was tested to determine the onset temperature of decomposition (or oxidation) for the graphite materials used in this study.FIG.8, panel a shows a percent weight change as a function of temperature for the pure graphite sample (˜10 mg). The temperature was increased from room temperature to 850° C. at a constant ramp rate of 10° C.·min−1with air flowing through the sample chamber. The weight loss started to take place at around 650° C. The onset temperature (Td) of intense thermal decomposition can be determined by the intersection point of tangents to two branches of the TGA curve and be estimated to be approximately 760° C. (FIG.8, panel a). This observation served as a basis for determining the soaking temperature of 800° C. inFIG.7. Next, the TGA experiment for the graphite piece embedded in the alumina powder compact was performed to model the graphite decomposition process in the fabrication of the micro-burner. A small (˜7 mm diameter) alumina compact encapsulating a graphite piece was fabricated in the same way that the micro-burner was made. The size of the graphite piece was scaled proportional to the alumina structure such that the mass and volume ratio of graphite to alumina remained the same as the original burner structure. The temperature profile used in the experiment was similar to the partial sintering step of the alumina micro-burner and consisted of (i) temperature rise from room temperature to 800° C. at the ramp rate of 15° C.·min−1, (ii) soaking at 800° C. for 2 hours, and (iii) ramping again to 900° C. at the ramp rate of 15° C.·min−1. The weight loss as a function of temperature is shown for the “graphite with alumina” sample inFIG.8, panel b. A noticeable decrease in weight was observed around 760° C., corresponding to the onset temperature of the graphite decomposition. In the final ramping step (from 800° C. to 900° C.), no apparent weight loss was witnessed, suggesting that the entire graphite phase was completely burnt out during the 2-hour soaking step at 800° C. After cooling down, the graphite/alumina sample was retrieved and inspected under the optical microscope. No crack was visible in the sample. Therefore, it was concluded that the modified sintering schedule was capable of completely removing the graphite phase without damaging the ceramic structure. Further, a small yet measurable (˜0.5%) decline in weight in the initial ramping step (from room temperature to 650° C.) was observed. Since no weight loss was seen in the pure graphite sample up to 650° C., the alumina powder should be responsible for this initial weight loss. To understand this trend, further testing of only the alumina powder was performed for the same mass with the same operating condition and a similar initial decrease in weight was observed (FIG.8, panel b dotted line). The loss in mass was attributed water loss based on the hygroscopic nature of alumina powder—consisting of high-surface-area sub-micron-particles that absorbed moisture from the ambient environment. Upon heating, bound water was desorbed, leading to the initial weight loss. The linear shrinkage of alumina in air was measured by thermomechanical analysis (TMA) and is shown as a function of time and temperature inFIG.9, panels a and b, respectively. The sintering temperature profile used in the TMA experiment was the same as the micro-burner sintering process. After an initial dip (which is related to the translation deformation induced by the load), there is a constant increase in displacement up to 800° C., representing the thermal expansion of alumina powders. Because sintering had not occurred significantly below 800° C., thermal expansion dominates over particle consolidation. In the 2-hour soaking period at 800° C., the dimension of the sample did not change—the isothermal condition causing neither thermal expansion nor particle consolidation. Lack of shrinkage in the alumina sample at that temperature also indicates that the pores in the sample were still interconnected, allowing CO/CO2emitted from graphite oxidation to escape without much barrier. The densification rate, a time derivative of displacement, is also plotted with temperature inFIG.9, panel b, showing that the temperatures for the onset of densification and the maximum densification rate are around 965° C. and 1306° C., respectively. It also suggests that sintering and densification essentially stopped at the temperature above 1350° C. Finally, during the cool-down process, the sample shrunk due to thermal contraction. The TMA results were compared to the dimensional change of the micro-burner measured from the cross-sectional image (FIG.4). Table 1 shows the overall size and internal channel dimension of the alumina micro-burner at each process stage. The green state (after compaction) of the sample had the diameter of 22.2 mm and the thickness of 4.98 mm. Just as the TMA shrinkage indicated, the sample size barely changed after the partial sintering at 800° C. However, dimensional changes over 18% were made at the end of the full sintering process around 1350° C. The similar dimensional reduction was observed for the internal channel. Dimensional shrinkage also can be inferred from the density (or volume) ratio of the green and sintered sample. As a result of the disclosed process in these examples, the relative densities of the green and sintered ceramics were estimated about 52% and 96%, respectively. The volume ratio is then: Vsintered/Vgreen=(1−S)(1−S)(1−S)=52/96=54%, where S is a dimensionless shrinkage (assumed to be the same in all three directions). This leads to S≈18.6%, which is consistent with the TMA results (maximum shrinkage rate of 18.3%) and the other reported values. The volume ratio of 54% also suggests that the green-state ceramics (after compaction) are 40˜50% porous. Since the TMA result indicates no significant shrinkage up to 1000° C., the partially sintered alumina possesses the same level of high porosity, providing sufficient gas permeability for the graphite removal through the fully-enclosed structure. TABLE 1Change in overall size and internal channeldimensions of alumina micro-burnerAlumina Sample Dimension (all units in mm)Green state800° C.1350° C.(after(partial(% Shrinkage)compaction)sintering)(full sintering)Overall Diameter22.2222.1418.11(18.5%)Overall Thickness4.984.904.02(19.2%)Channel Height0.90.890.74(17.7%)Channel Width2.192.151.79(18.2%) Machining of Partially Sintered Ceramic (PSC): Fully sintered ceramics including alumina are known to have poor machinability due to their stiffness and brittleness. Machining green or white ceramic compacts would be easier if the final tolerance is not strict. Green machining is referred to as the machining of a ceramic in the unfired state, i.e., a powder compact before exposing to high temperature. In green machining, the powder is usually mixed with a binder phase (typically organic polymer or wax) to achieve the sufficient strength for machining. In these examples according to the disclosure, pure alumina powder was utilized without any binder phase. Therefore, the compacted powder was too difficult to handle and prone to fragment during machining, preventing performance of green machining. On the other hand, white machining is an approach to machining on partially sintered ceramics (PSC). The powder compacts can be partially sintered by firing at a temperature substantially below their typical sintering temperature. The formation of necks among the individual powder particles during partial sintering provides PSCs with the strength to withstand machining. These examples use a white machining technique to create fluidic connections to the enclosed channels in the micro-burner. The extent of neck formation in PSCs, which determines the strength of the powder compact, highly depends on partial sintering temperature. For this reason, the partial sintering condition such as pre-sintering temperature and its duration has been shown to significantly affect the quality of the machined features. To understand the effect of partial sintering temperature on the machined features on PSCs, four alumina samples were prepared that were partially sintered at four different temperatures (600° C., 800° C., 1000° C., and 1200° C.). The conventional machining processes such as drilling and milling were performed on these PSC samples using a small bench-top CNC machine. The quality of the machined features was correlated to the amount of chips and cracks generated around holes during machining. The optimal machining parameters for the PSCs included a feed rate of 1 mm·min−1and cutting speed of 1500 rpm for these examples. FIG.10shows the effect of the partial sintering temperature on the machined features of alumina PSCs. The alumina sample partially sintered at 800° C. exhibited no pronounced surface chipping or cracks around the edges of the holes and grooves (FIG.10, panels b and f). Minor cracks and chips were observed in the sample partially sintered at 600° C. (FIG.10, panels a and e) while more noticeable defects were seen for the 1000° C. sample (FIG.10, panels c and g). The sample partially sintered at 1200° C. exhibited the extensive chipping damages around the edges of the machined features (FIG.10, panels d and h). X-ray diffraction (XRD) analysis (not shown) on the green (unfired) ceramic and these four PSCs suggests that the starting alumina powder is in the a-phase and there is no phase change during partial or full sintering. Therefore, the marked differences in the machined features of the alumina PSCs partially sintered at the different temperatures are not likely coming from the phase change of alumina. Unlike metals whose major removal mechanism is a local shear deformation, the underlying mechanism of machining PSCs is related to the breakage of necks between particles. When the partial sintering temperature increased from 600 to 800° C. (i.e., initial stage of partial sintering), more neck formation occurred, providing stronger connections among individual particles and more resistance to chipping or cracks. However, once the partial sintering temperature increased to 1000° C. or above, the consolidation taking place beyond the neck formation was too extensive such that brittle fracture became a dominant material removal mechanism. The high-resolution scanning electron microscopy (SEM) images inFIG.10, panels j-l show the extent of the neck formation and particle consolidation (or lack of porosity) for these four samples. Extensive neck formation on the powder compact can be clearly observed for the samples with higher partial sintering temperatures. To further characterize the mechanical properties of the PSCs sintered at different temperatures and correlate them to the observed machining behaviors, a 3-point bending test was conducted to measure the flexural strength of the PSCs. The bending test demonstrated the higher flexural strength with the increasing partial sintering temperature. Combined with the results shown inFIG.10, it is concluded that the PSC sample partially sintered at 600° C. was too fragile to machine, while the sample partially sintered at 1200° C. was strong but too brittle to machine. Micro-burner Testing: The fully-sintered alumina sample was tested for micro-burner applications. Both open-channel and embedded-channel configurations were tested.FIG.11, panel a shows how the fuel (H2) and oxidant (O2or air) streams are connected to the micro-burner as well as the location of the exhaust. Hydrogen generated by an electrolyzer and air from a miniature gas pump were fed to the open-channel micro-burner (bonded with a quartz window;FIG.3, panel e1). Under the laminar flow condition, these two streams create a stable hydrodynamic boundary layer in the flame region where a folded diffusion flame would be formed. When the H2flow rate was high (˜100 sccm), the flame was ignited at the outside of the exhaust channel (FIG.11, panel b). As the H2flow rate (controlled by the electrical power applied to the electrolyzer) was reduced to 30˜50 sccm, the flame started to move into the exhaust channel and eventually became anchored in the cavity. In order to reduce the amount of air that needed to be pumped, an O2flow co-generated by the electrolyzer was added to the oxidant stream. The oxidant flow rate (O2plus air) was determined to keep the fuel-to-oxidant ratio stoichiometrically correct or under lean-burn condition. A stable folded flame was observed for the range of the hydrogen flow rates (40˜55 sccm) and oxidant flow rates (20˜27 sccm for oxygen and 20˜80 sccm for air). After identifying the H2and air flow rates that anchored the flame inside the combustion chamber, the enclosed micro-burner was tested with the similar flow conditions. The flame generated within the enclosed micro-burner cannot be observed due to the opaque nature of the alumina walls. Therefore, the presence and approximate location of the flame was indirectly determined by recording the outer wall temperature of the micro-burner.FIG.11, panel c depicts the temperature distribution of the burner's exterior surface measured by the thermocouple from 7 by 7 points (49 total measurements with each point 1.5 mm apart). The region of the highest temperature indicates the location of the flame, which resembles the flame location of the quartz/alumina micro-burner. The maximum steady-state temperature of the alumina outer surface was measured to be around 170° C. (for flow rate conditions: H235 sccm and O217.5 sccm/air 20 sccm). This temperature is much lower than the adiabatic flame temperature of the oxy-hydrogen flame, which is between 2210 and 3200° C. depending on the fuel-to-oxidant ratio and oxygen-to-air ratio in the oxidant stream. The low thermal conductivity of alumina (12˜38 W·m−1·K−1) therefore provided reasonable thermal isolation compared to the other common micro-burner materials like metals or silicon. The enclosed micro-burner was continuously operated for more than 6 hours with the stable flame throughout. More than 10 micro-burners have been tested over a 10-month period, and no structural damage has been observed due to the high operation temperature or repeated heating/cooling (i.e. thermal stresses) from each run. Finally, the alumina micro-burner was tested as a micro flame ionization detector (μFID). Two tungsten wires (0.5 mm diameter) were inserted into the exhaust to serve as electrodes. A flame was ignited and anchored into the micro-burner cavity with the flow rate conditions of H245 sccm and O222.5 sccm/air 20 sccm. This oxy-hydrogen flame ionizes hydrocarbon molecules, and the produced ions are driven by the applied electric field and collected by the electrodes. Without further optimization, train of 0.1 mL of natural gas was injected through the analyte port using a gas-tight syringe at times shown by the arrows inFIG.11, panel d. With the applied voltage of 160 V between the electrodes, a generated current was converted to an amplified voltage via a transimpedance amplifier (gain=105). Each peak inFIG.11, panel d corresponds to each event of natural gas injection. Due to large dead volumes associated with the injection port and the manual syringe injection setup, the obtained signals were short and broad. The electrode design and operation conditions were far from being optimal, and therefore the further characterization of the μFID would significantly improve the device performance. Though the performance of the μFID does not quite match that of the state-of-the-art system, this testing demonstrates a practical use of the micro-burner created by the proposed ceramic processing. Summary: These examples illustrate methods and apparatus according to the disclosure for processing ceramic metal oxide powders to fabricate ceramic structures with internal cavities and channels for microchemical system applications. High-purity, binder-free alumina micron-powder was compacted with a graphite fugitive phase embedded in the powder bed. The graphite was later burnt out during partial sintering, leaving the cavity and channels. The sintering schedule used in partial (and full) sintering critically influenced the structural integrity of the final alumina structure. Instead of the continuous temperature ramping to the full sintering temperature, the compacted alumina was partially sintered at 800° C. for two hours, which not only facilitated the removal of the graphite fugitive phase but also promoted the optimal neck formation for the subsequent machining processes. The TGA and TMA results showing graphite oxidation and alumina densification kinetics supported the competing nature of graphite burn-out and powder consolidation. The quality of the machined features on the partially sintered alumina was investigated using various imaging techniques, revealing that the partial sintering temperature is an important parameter for machining. Finally, the fabricated open-channel and fully-enclosed alumina micro-burners were tested in various flow rate conditions of hydrogen and oxygen/air, demonstrating that the fully-enclosed device functioned as designed without failing over long-term and cyclic operations. Because other modifications and changes varied to fit particular operating requirements and environments will be apparent to those skilled in the art, the disclosure is not considered limited to the example chosen for purposes of illustration, and covers all changes and modifications which do not constitute departures from the true spirit and scope of this disclosure. Accordingly, the foregoing description is given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications within the scope of the disclosure may be apparent to those having ordinary skill in the art. All patents, patent applications, government publications, government regulations, and literature references cited in this specification are hereby incorporated herein by reference in their entirety. In case of conflict, the present description, including definitions, will control. Throughout the specification, where the compounds, compositions, methods, apparatus, and processes are described as including components, steps, or materials, it is contemplated that the compositions, processes, or apparatus can also comprise, consist essentially of, or consist of, any combination of the recited components or materials, unless described otherwise. Component concentrations can be expressed in terms of weight concentrations, unless specifically indicated otherwise. Combinations of components are contemplated to include homogeneous and/or heterogeneous mixtures, as would be understood by a person of ordinary skill in the art in view of the foregoing disclosure. PARTS LIST 10microchemical apparatus20filling/compression die30furnace100metal oxide powder(s)110first metal oxide powder110A first metal oxide powder area (e.g., cross-sectional/surface area)120second metal oxide powder150non-sintered compact including fugitive phase200fugitive phase(s)210first fugitive phase material210A first fugitive phase material area (e.g., cross-sectional/surface area)212geometry of first fugitive phase material214end/edge of first fugitive phase material at external boundary300partially sintered compact310interior cavity within partially sintered compact312geometry of interior cavity320porous wall/body of partially sintered compact330machined structures within partially sintered compact (e.g., holes, channels, inlet/outlet orifices, etc.)400fully sintered microchemical apparatus410interior cavity within fully sintered microchemical apparatus410A combustion area420solid (e.g., continuous or non-porous) body of fully sintered microchemical apparatus430inlets/outlets to interior cavityP plane of first metal oxide powder into which first fugitive phase material is placed REFERENCES 1. McMullen, J. P. & Jensen, K. F. Integrated microreactors for reaction automation: New approaches to reaction development.Annu. Rev. Anal. Chem.3, 19-42 (2010).2. Jensen, K. F. Microreaction engineering—is small better?.Chem. Eng. Sci.56, 293-303 (2001).3. Marre, S., Adamo, A., Basak, S., Aymonier, C. & Jensen, K. F. Design and packaging of microreactors for high pressure and high temperature applications.Ind. Eng. Chem. Res.49, 11310-11320 (2010).4. deMello, A. J. Control and detection of chemical reactions in microfluidic systems.Nature442, 394-402 (2006).5. Jensen, K. F., Reizman, B. J. & Newman, S. G. Tools for chemical synthesis in microsystems.Lab on a Chip14, 3206-3212 (2014).6. Suzuki, T., Yamaguchi, T., Fujishiro, Y., Awano, M. & Funahashi, Y. Recent development of microceramic reactors for advanced ceramic reactor system.J. Fuel Cell Sci. Technol.7, 31005-31009 (2010).7. Garbayo, I. et al. Full ceramic micro solid oxide fuel cells: towards more reliable MEMS power generators operating at high temperatures.Energy Environ. Sci.7, 3617-3629 (2014).8. Suzuki, T., Yamaguchi, T., Sumi, H., Hamamoto, K. & Fujishiro, Y. Microtubular solid-oxide fuel cells for low-temperature operation.MRS Bull.39, 805-809 (2014).9. Beckel, D. J. et al. Thin films for micro solid oxide fuel cells.J. Power Sources173, 325-345 (2007).10. Jiang, B. et al. Design and packaging of a highly integrated microreactor system for high-temperature on-board hydrogen production.Chem. Eng. J.275, 206-219 (2015).11. Cocco, D. & Tola, V. Externally reformed solid oxide fuel cell-micro-gas turbine (SOFC-MGT) hybrid systems fueled by methanol and di-methyl-ether (DME).Energy34, 2124-2130 (2009).12. LindstrÖm, B. et al. Diesel fuel reformer for automotive fuel cell applications.Int. J. Hyd. Energy34, 3367-3381 (2009).13. Miesse, C. M., Masel, R. I., Jensen, C. D., Shannon, M. A. & Short, M. Submillimeter-scale combustion.AlChE J.50, 3206-3214 (2004).14. Keramiotis, C., Stelzner, B., Trimis, D. & Founti, M. Porous burners for low emission combustion: An experimental investigation.Energy45, 213-219 (2012).15. Di Carlo, A., Bocci, E. & Dell'Era, A. Comparison by the use of numerical simulation of a MCFC-IR and a MCFC-ER when used with syngas obtained by atmospheric pressure biomass gasification,Int. J. Hyd. Energy36, 7976-7984 (2011).16. Mandl, C., Obernberger, I. & Biedermann, F. Modelling of an updraft fixed-bed gasifier operated with softwood pellets.Fuel89, 3795-3806 (2010).17. Christian, Mitchell, M., Kim, D.-P. & Kenis, P. J. A. Ceramic microreactors for on-site hydrogen production.J. Catal.241, 235-242 (2006).18. Christian, Mitchell, M. & Kenis, P. J. A. Ceramic microreactors for on-site hydrogen production from high temperature steam reforming of propane.Lab Chip6, 1328-1337 (2006).19. Knitter, R. & Liauw, M. A. Ceramic microreactors for heterogeneously catalysed gas-phase reactions.Lab Chip4, 378-383 (2004).20. Arana, L. R., Schaevitz, S. B., Franz, A. J., Schmidt, M. A. & Jensen, K. F. A microfabricated suspended-tube chemical reactor for thermally efficient fuel processing.J. Microelectromech. Syst.12, 600-612 (2003).21. Guan, G., Kusakabe, K., Taneda, M., Uehara, M. & Maeda, H. Catalytic combustion of methane over pd-based catalyst supported on a macroporous alumina layer in a microchannel reactor.Chem. Eng. J.144, 270-276 (2008).22. Jain, K. et al. Synthesis of nanoparticles in high temperature ceramic microreactors: design, fabrication and testing.Int. J. Appl. Ceram. Technol.6, 410-419 (2009).23. Knitter, R., Bauer, W., Göhring, D. & Haußelt, J. Manufacturing of ceramic microcomponents by a rapid prototyping process chain.Adv. Eng. Mater.3, 49-54 (2001).24. Tiggelaar, R. M. et al. Fabrication and characterization of high-temperature microreactors with thin film heater and sensor patterns in silicon nitride tubes.Lab Chip5, 326-336 (2005).25. Morales, A. M., Pitchumani, R., Garino, T. J., Gutmann, A. K. & Domeier, L. A. Fabrication of ceramic microstructures via microcasting of nanoparticulate slurry.J. Am. Ceram. Soc.88, 570-578 (2005).26. Christian & Kenis, P. J. A. Fabrication of ceramic microscale structures.J. Am. Ceram. Soc.90, 2779-2783 (2007).27. Schmitt, C. et al. Ceramic plate heat exchanger for heterogeneous gas phase reactionsChem. Eng. Technol.28, 337-343 (2005).28. Jurków, D. et al. Overview on low temperature co-fired ceramic sensors.Sensor. Actuat. A: Phys.233, 125-146 (2015).29. Bauer, W. & Knitter, R. Development of a rapid prototyping process chain for the production of ceramic microcomponents.J. Mater. Sci.37, 3127-3140 (2002).30. Bauer, W. et al. Design and prototyping of a ceramic micro turbine: a case study.Microsyst. Technol.16, 607-615 (2010).31. Holthaus, M. G., Treccani, L. & Rezwan, K. Comparison of micropatterning methods for ceramic surfaces.J. Eur. Ceram. Soc.31, 2809-2817 (2011).32. Gongora-Rubio, M. R., Espinoza-Vallejos, P., Sola-Laguna, L. & Santiago-Avilés, J. J. Overview of low temperature co-fired ceramics tape technology for meso-system technology (MsST).Sensor. Actuat. A: Phys.89, 222-241 (2001).33. Peterson, K. A. et al. Novel microsystem applications with new techniques in low-temperature co-fired ceramics.Int. J. Appl. Ceram. Technol.2, 345-363 (2005).34. Ibáñez-García, N., Alonso, J., Martínez-Cisneros, C. S. & Valdés, F. Green-tape ceramics. New technological approach for integrating electronics and fluidics in microsystems.TrAC Trends Anal. Chem.27, 24-33 (2008).35. Khoong, L. E., Tan, Y. M. & Lam, Y. C. Overview on fabrication of three-dimensional structures in multi-layer ceramic substrate.J. Eur. Ceram. Soc.30, 1973-1987 (2010).36. Bienert, C. & Roosen, A. Characterization and improvement of {LTCC} composite materials for application at elevated temperatures.J. Eur. Ceram. Soc.30, 369-374 (2010).37. Khoong, L. E., Tan, Y. M. & Lam, Y. C. Carbon burnout and densification of self-constrained {LTCC} for fabrication of embedded structures in a multi-layer platform.J. Eur. Ceram. Soc.29, 457-463 (2009).38. Roosen, A. New lamination technique to join ceramic green tapes for the manufacturing of multilayer devices.J. Eur. Ceram. Soc.21, 1993-1996 (2001).39. Kim, J., Bae, B., Hammonds, J., Kang, T. & Shannon, M. A. Development of a micro-flame ionization detector using a diffusion flame.Sensor. Actuat. B: Chem.168, 111-117 (2012).40. Bae, B. et al. Development of a portable gas analyzer using a micro-gas chromatograph/flame ionization detector (micro-GC/FID) for NASA's environmental missions. 42nd International Conference on Environmental Systems;15-19 Jul. 2012; San Diego, CA, USA; (AIAA, 2012).41. Swain, S., Sharma, R. A. & Bhattacharya, S. Effects of nano-silica/nano-alumina on mechanical and physical properties of polyurethane composites and coatings.Trans. Electric. Electro. Mater.14, 1-8 (2013).42. Yeh, T.-S. & Sacks, M. D. Effect of particle size distribution on the sintering of alumina. J.Am. Ceram. Soc.71, 484-487 (1988).43. Hillman, S. H. & German, R. M. Constant heating rate analysis of simultaneous sintering mechanisms in alumina.J. Mater. Sci.27, 2641-2648 (1992).44. Fujiwara, S., Tamura, Y., Maki, H., Azuma, N. & Takeuchi, Y. Development of new high-purity alumina.Sumitomo Kagaku1-10 (2007).45. Shin, H., Kwon, P., Kok, C. K. & Case, E. Machining channels on mesoscale ceramic components.J. Manuf. Process.6, 15-23 (2004).46. Halcomb, L. D. & Rey, M. C. Ceramic cutting tools for machining unsintered compacts of oxide ceramics.Ceram. Bull.61, 1311-1314 (1982).47. Klocke, F., Gerent, O. & Schippers, C. Machining of advanced ceramics in the green state.Ceram. Forum Int.74, 288-290 (1997).48. Klocke, F., Gerent, O. & Schippers, C. inMachining Of Ceramics And Composites(eds Jahanmir, S. et al.) Ch. 1, 1-10 (Marcel Dekker, 1998).49. German, R. M.Sintering Theory And Practice. (Wiley, 1996).
59,136
11857960
DETAILED DESCRIPTION This invention relates to a microfluidic device for rapid point-of-care collection of a fluid analyte and multiplex analysis thereof. This invention also provides methods and systems for using a microfluidic device to provide rapid multiplexed analysis of a fluid analyte. The present disclosure generally provides methods for a microfluidic device for sample collection and testing. Some of the devices described herein comprise a sample collection cartridge. The sample collection cartridge can be used in combination with an assay reader for point-of-care (POC) diagnostics as described herein. One aspect of this invention is to provide a cartridge for collecting a target analyte for testing. The cartridge includes a metering stack configured to receive and distribute a target analyte along a first channel. The first channel has a bottom that includes a porous or mesh material and one or more venting holes located along the first channel. The cartridge further includes an assay stack comprising at least one assay component that includes one or more assay pad. Each assay pad comprises a reagent for performing an assay on the target analyte or a portion thereof. The cartridge also includes a spacer layer disposed between the metering stack and the assay stack. The spacer layer provides a gap between the metering stack and the assay stack that prevents the target analyte from flowing from the metering stack into the assay stack when the cartridge is in an uncompressed state. The porous or mesh material permits the target analyte to flow from the metering stack to the assay stack only when the cartridge is sufficiently compressed to bring the metering stack in contact with the assay stack. Another aspect of this invention is to provide an assay reader. The assay reader includes a chamber configured to receive a cartridge. The assay reader also features a compression mechanism configured to compress the cartridge when or after the cartridge is inserted into the chamber after collection of a target analyte. This causes one or more assay reactions to start within the cartridge. The assay reader also includes a detection system for measuring a signal change corresponding to the one or more assay reactions. The invention also provides a system for multiplexed analysis of a target analyte. The system comprises a cartridge which includes a metering stack configured to receive and distribute the target analyte along a first channel. The first channel has a bottom that comprises a porous or mesh material. The system also includes an assay stack comprising at least one assay component. Each assay component includes one or more assay pads that contain a reagent for performing an assay on the target analyte or a portion thereof. The cartridge in the system further includes a spacer layer disposed between the metering stack and the assay stack. The spacer layer provides a gap between the metering stack and the assay stack that prevents the target analyte from flowing from the metering stack into the assay stack when the cartridge is in an uncompressed state. In addition, the porous or mesh material permits the target analyte to flow from the metering stack to the assay stack only when the cartridge is sufficiently compressed to bring the metering stack in contact with the assay stack. The system further includes an assay reader that includes a chamber configured to receive the cartridge and a compression mechanism configured to compress the cartridge when or after the cartridge is inserted into the chamber after collection of the target analyte. This causes one or more assay reactions to start at the same time within the cartridge. The system further includes a detection system for detecting a signal change corresponding to the one or more assay reactions. In yet another aspect, the invention provides a method of performing a plurality of assays. The method includes receiving a target analyte into a first channel in a cartridge, and inserting the cartridge into an assay reader, thereby compressing the cartridge to expose at least one component of the target analyte stored in a first channel to one or more assay pads. This causes the assay reactions to start. The method also includes the step of detecting one or more signal changes associated with the one or more assay reactions. The invention also provides a method of fabricating a cartridge. The method comprises obtaining a first layer comprising (1) a layer of polymeric material with a channel formed therein, wherein the channel comprises at least one venting hole disposed along the channel, (2) a porous or mesh material attached on a bottom surface of the polymeric material such that the channel is bounded on a bottom surface by the porous or mesh material. The method also comprises the steps of obtaining a second layer comprising one or more assay pads, each comprising a porous material capable of absorbing analyte from the bottom of the channel, and a reagent for performing an assay on the target analyte or a portion thereof. The method also includes the steps of obtaining a compressible intermediate layer and combining the first layer, compressible intermediate layer, and second layer in a cartridge housing such that the compressible intermediate layer separates the first layer and the second layer when the compressible intermediate layer is in an uncompressed state, and the channel is aligned with the one or more assay pads in a direction perpendicular to the first layer. The invention also provides a method of fabricating a cartridge that comprises combining a first layer, a compressible intermediate layer, and a second layer in a cartridge housing. The first layer comprises (1) a layer of polymeric material with a channel formed therein and (2) a porous or mesh material attached on a bottom surface of the polymeric material such that the channel is bounded on a bottom surface by the porous or mesh material. The second layer comprises one or more assay pads, each comprising a reagent for performing an assay on the target analyte or a portion thereof. The compressible intermediate layer comprises a compressible material that separates the first layer and the second layer when the compressible intermediate layer is in an uncompressed state. When the first layer, compressible intermediate layer, and second layer are stacked in the cartridge housing, the channel is aligned with the one or more assay pads in a direction perpendicular to the first layer. Any of the features, components, or details of any of the arrangements or embodiments disclosed in this application, including without limitation any of the cartridge embodiments and any of the testing or assay embodiments disclosed below, are interchangeably combinable with any other features, components, or details of any of the arrangements or embodiments disclosed herein to form new arrangements and embodiments. In one aspect, this invention provides an easy-to-use and fully integrated POC testing device that allowed for multiplexed analysis of a target analyte. As described herein, the POC testing device simplifies target analyte sample collection and obviates problems associated with conventional POC testing devices, including unwanted bubble formation, inaccuracy in collected sample volumes, and uncertainty in target analyte dispensing time when the assay is conducted. In addition, the POC testing devices according to the invention contain few moving parts and do not employ mechanical devices, such as plungers or valves, for collecting the target analyte samples. In this way, the POC testing devices of the invention are more mechanically robust and minimize the chance for user errors. FIG.1shows a POC testing device according to one exemplary embodiment of the invention. The POC testing device comprises a cartridge100and an assay reader110. As described herein, cartridge100is used to collect the target analyte. The collection process also distributes the target analyte within cartridge100. After the target analyte is collected in cartridge100, the user inserts cartridge100into assay reader110. As described herein, the act of inserting cartridge100into assay reader110results in the compression of cartridge100, thereby causing at least one component of the target analyte to be distributed to a plurality of assay pads. In this way, the act of inserting cartridge100into assay reader100commences a plurality of assay reactions that provide information regarding the contents of the target analyte. As described herein, assay reader110is equipped with a detection system that is used to detect the results of the assay reactions that occur at the assay pads of cartridge100. The detection system is not particularly limited and may be a detection system which causes a measurable signal change as the result of an assay reaction. Non-limiting examples of suitable detection systems include optical and electrochemical detection systems as described herein. FIG.2Aillustrates a top view of an embodiment of a cartridge200. InFIG.2A, cartridge200includes a housing201attached to a handle202. In general, cartridge200is designed to be easy to handle by the user and to provide a protective shell for the microfluidic distribution system and assay components housed within cartridge200. In general, suitable materials for housing201and handle202include polyolefinic compounds, such as polyethylene, polypropylene, and other polymeric resins or compounds that are amenable to sterilization procedures known in the medical device manufacturing art, e.g., exposure to ethylene oxide gas. During sample collection, cartridge200is brought into contact with a target analyte (e.g., blood). The target analyte is drawn into channel203and via channel opening204by capillary action. In some embodiments, channel203comprises a plurality of receiving chambers located along channel203. In preferred embodiments, each receiving chamber is positioned between two venting holes, which facilitate the division of the target analyte in the channel into multiple aliquots which flow to the assay pads in the assay stack. It should be recognized that the channel opening204can function as a venting hole and that neighboring receiving chambers can share a common venting hole between them. The venting holes, in combination with the porous or mesh material described herein, prevent unwanted bubble formation as the target analyte is drawn into the receiving chambers.FIG.2Billustrates a bottom view of an embodiment of the cartridge200. InFIG.2B, the bottom portion of housing201comprises a plurality of assay detection ports206aligned with channel opening204. The assay detection ports206permit the assay results to be interrogated, for example, by optical detection methods as described herein. In addition, the bottom portion of housing201may comprise plurality of holes207, which are additional assay detection ports that may be used with assay components and microfluidic channels that are arranged in a corresponding configuration. FIG.2Cprovides an exploded view of the components of the cartridge200, according to one embodiment of the invention. InFIG.2C, the outer shell of cartridge200comprises a handle202, bottom housing portion227, and a cap223that is equipped with a slot228. The bottom housing portion227can be a cuboid shape enclosure with one open side. The enclosure shape of the bottom housing portion227protects the components within the interior chamber and can avoid accidental actuation of the device. The cap223can fit to the open side of the bottom housing portion227and have a shape and size that corresponds to the open side of the bottom housing portion227. When the bottom housing portion227and cap223of the housing are assembled together, an interior chamber can be formed for enclosing other components of the cartridge within the interior chamber. In other embodiments, the cap223and bottom housing portion227do not form an enclosure with an interior chamber and can be rigid structures positioned on the top of a metering stack and bottom of an assay stack, which are described herein. In preferred embodiments, bottom housing portion227and cap223can be formed of a material to provide a rigid structure to the cartridge200. For example, the bottom housing portion227and the cap223can be a plastic material, as described herein. The bottom housing portion227and cap223can be moveable or non-moveable with relation to each other. In preferred embodiments, when cartridge200is inserted into an assay reader, the components within the interior chamber are compressed to cause at least one portion of the collected target analyte to be delivered to a plurality of assay components. In some embodiments, the cartridge does not comprise a cap and bottom housing portion. In such embodiments, the cartridge does not include the housing201(seeFIG.2A) and the metering stack and assay stack can be inserted into an assay reader without an enclosure around it. As shown inFIG.2C, cartridge200can include a metering stack224, a spacer material225, and an assay stack226. The metering stack224can be used to collect a sample of the target analyte (e.g., blood) and the assay stack226comprises assay components necessary for the test to be carried out as discussed in detail herein. As used herein, the term “metering” refers to collecting a liquid sample of a target analyte and delivering one or more predetermined volumes of at least a portion of the target analyte to the assay components for further analysis via the assay components contained in the assay stack. When assembled into a cartridge, the metering stack224, a spacer material225, and an assay stack226can arranged in a stack. The spacer material225is a compressible layer that may be positioned between the metering stack224and assay stack226as shown inFIG.2C. In an embodiment, the spacer layer225may be a flexible material that can be compressed in the vertical direction when the cartridge is inserted into the assay reader and the metering stack224is moved into contact with or close proximity to the assay stack226. In some embodiments, the spacer layer225can be a flexible material, such as foam, rubber, porous polymer, metal, cotton, or other bending, folding, or moving mechanisms such as a clamp or spring. In some embodiments, the metering and assay stacks are initially separated by an air gap maintained by the spacer layer225. In certain embodiments, spacer material225is physically affixed to another layer, such as metering stack224or assay stack226before the layers of the cartridge are brought together. Typically, the metering and assay stacks remain separated throughout the sample collection process. In such embodiments, the separation between the metering stack and the assay stack prevent a chemical reaction from starting during the target analyte collection step. When the spacer material225is compressed, the metering stack224and assay stack226can come into contact with or brought into close proximity to each other. In preferred embodiments, when the metering stack is fully filled with the target analyte, the cartridge is inserted into an assay reader. Preferably, the material that is used for the top surface of channel230is sufficiently transparent so that a user can determine by visual inspection when the channel230is filled and the cartridge is ready for insertion into the assay reader. The assay reader is configured to accept the assay reader and comprises a mechanism that compresses the spacer layer, thereby pushing the metering stack and assay stack together when the cartridge is inserted into the assay reader. The compression of the spacer layer causes a predetermined volume of at least a portion of the collected target analyte to flow to assay components in the assay stack. In this way, the act of compressing the metering and assay stacks together can, in certain embodiments, provide a well-defined point in time that marks the start of the assays of the assay components in the assay stack. In some embodiments, the metering stack and assay stack can be pushed together inside the assay reader by non-movable physical constraints as illustrated inFIGS.3A-B.FIGS.3A-Billustrate an embodiment in which physical compression of the metering stack304and assay stack306occurs when cartridge300is inserted into an assay reader307.FIG.3Aillustrates the cartridge300and assay reader307before the cartridge300is inserted into the assay reader307in the direction indicated the arrow inFIG.3A.FIG.3Billustrates the cartridge300after it has been inserted into a slot of the assay reader307. The positioning of a top portion301aof the assay reader slot with respect to a bottom portion301bof the slot causes the metering stack304to move vertically within the cartridge300, thereby compressing the spacer material305. If desired, the top portion301amay be sized to compress only the portion of the metering stack that is directly above the assay components in the assay stack. This may be achieved, for example, by sizing the top portion301asuch that it slides into a slot in the cap303of the cartridge (e.g., slot228inFIG.2C). If desired, the assay reader slot may be shaped to limit the degree to which cartridge300may be inserted into the assay reader307. For example, once bottom housing portion302is fully inserted, it may interact with lip308to prevent further insertion of cartridge300into assay reader307. Once the spacer material305is compressed from the insertion of cartridge300into assay reader307, the collected target analyte flows from the metering stack304to the assay components in the assay stack306. Alternatively, the metering stack304and assay stack306can be pushed together by one or more moving parts in the assay reader, non-limiting examples of which include pushing pins, or movable blocks actuated by a motor, servo, air pressure, magnetic force, electro-magnetic force, manual force exerted by the user, or other moving mechanisms. Combinations of these mechanisms are also expressly contemplated by the invention. In some embodiments, the metering stack304and assay stack306can be pushed together by one or more moving parts in the assay reader such as a plunger pressor using electromechanical forces in the assay reader. FIGS.3C-3Dillustrate an embodiment of moving pins used to compress the metering stack and assay stack when the cartridge is inserted into an assay reader. As illustrated inFIGS.3C-3D, moving pins can be used to compress the metering stack354onto the assay stack356.FIG.3Cillustrates the cartridge with the base352and cap353within the assay reader357. Moving pins372can be used within the assay reader357to compress the metering stack354and spacer material355so that the metering stack354can come into contact with the assay stack356. The moving pins357can move downward in the direction of arrow shown inFIG.3Cto compress the metering stack354onto the assay stack356. In some embodiments, the moving pins can pass through a portion of the cap353as shown inFIG.3D. As illustrated inFIGS.3C-3D, in some embodiments, the moving pins can move vertically within the assay reader357. In some embodiments, the target analyte is blood, and the cartridge can be used to collect a sample of blood from a skin prick and deliver the sample to the assay stack consistently with minimal user intervention. The user, with a regular pricking lancet, can elicit bleeding in a suitable body site such as a fingertip, palm, hand, forearm, belly etc. Once a drop of blood of sufficient volume is on the skin, the user can collect it by touching the tip of the cartridge to the blood drop. Once the metering stack is fully filled with blood, the user can insert the cartridge into the assay reader, which triggers the delivery of the blood sample to the assay stack. In some embodiments, this can be performed by a patient, administrator, or healthcare provider. The blood collection and testing as described herein does not have to be performed by a trained heath care professional. In addition, the cartridge design can allow for dispensing different pre-defined volumes of blood sample to multiple assay locations, without using any moving parts such as pumps or valves in the cartridge or in the assay reader. This increases the accuracy and flexibility of a multiplexed quantitative POC analysis, while reducing the complexity and cost of the cartridge and the assay reader. Typically, as illustrated inFIG.2C, the metering stack224comprises a channel230to contain the target analyte (e.g., blood sample). In certain embodiments, the channel can hold a volume of target analyte in the range of about 0.5 to about 100 about 5 μl to about 90 about 10 to about 80 about 20 μl to about 60 μl or about 30 μl to about 50 μl. The volume of the target analyte can be controlled by the dimensions of the channel, including the shape, width, length, and depth of the channel, as described herein. In some embodiments, the depth of the channel can be in the range of about 5 μm to about 3 mm, about 10 μm to about 2 mm, or about 250 μm to about 1 mm. In some embodiments, the width of the channel can be in the range of about 100 μm to about 10 mm, about 250 μm to about 5 mm, about 500 μm to about 3 mm, or about 750 μm to about 1 mm. In certain preferred embodiments, the dimensions of the channel are selected such that the target analyte is drawn into the channel by capillary action. The material of the metering stack224can, in some embodiments, form one or more fluid collecting chambers, or receiving chambers, along the length of the channel.FIGS.4A-5Billustrate embodiments of the channel(s)410within the metering stack. As shown inFIGS.4A-5B, the shape of the channel is not particularly limited and will vary based on the requirements of the assay components in the corresponding assay stack. In some embodiments, the longitudinal cross section of the channel, in a plane parallel to the layered components of the cartridge, can be a rectangle with a constant width or a combination of different rectangular, circular, oval, and/or other shapes.FIG.4Aillustrates one embodiment in which the channel410has a rounded rectangular longitudinal cross section.FIG.4Billustrates a channel410with a combination of rectangular portions and circular portions, the latter of which corresponds to receiving chambers located along the length of the channel. The channel410can have an inlet412where the target analyte sample can be inserted or drawn in (e.g., by capillary action) to fill the channel410. The channel may also comprise one or more venting holes411that connect the channel to the atmosphere. An example of such a configuration is illustrated inFIG.4A, which shows channel410with a plurality of venting holes411arranged along the length of channel410and a channel inlet412. In addition, as indicated inFIG.4B, channel410may comprise one or more receiving chambers413for collecting and temporarily storing one or more predetermined volumes of the target analyte prior to introducing the target analyte to the assay components in the assay stack. In certain embodiments, the predetermined volumes of the receiving chambers are such that they permit temporary storage and subsequent delivery of a greater volume of the target analyte than a channel without such receiving chambers (cf.FIGS.4A and4B). When channel410comprises one or more receiving chambers413, such venting holes411may be disposed along the portions of the channel410between the receiving chambers413, as illustrated inFIG.4B. However, in other embodiments, the venting holes may be coincident with the receiving chambers. In general, the venting holes release air bubbles that may be trapped in the channel during collection of the target analyte (e.g., blood) thereby helping to distribute the target analyte sample in the channel and facilitating subsequent distribution of the target analyte (or a portion thereof) to the assay components in the assay stack. If desired, the metering stack can include one channel or multiple channels sharing a same channel inlet412.FIG.4Cillustrates an embodiment with multiple channels410in a metering stack, each equipped with venting holes411. The multiple channels410are fluidly connected and can be filled with the target analyte via common channel inlet412. FIGS.5A-Billustrate two exemplary embodiments of channels according to the invention. InFIG.5A, channel510has venting holes511which are arranged along the length of channel510at uneven intervals513,514, and515. When the target analyte is admitted into channel510via channel inlet512, this configuration permits different volumes of the target analyte to be delivered to the respective assay components. If desired, the segment between venting holes511can hold a volume of target analyte in the range of 0.5-25 μl for each assay. Alternatively, as shown inFIG.5B, channel510may be equipped with a plurality of receiving chambers513,514, and515which have different predetermined volumes to permit delivery of different volumes of the target analyte to the respective assay components. Preferably, the metering stack is designed to direct the target analyte fluid to flow into the channel and into any receiving chamber(s) that may be present. In some embodiments, the channel can be formed of or coated with a hydrophilic material, non-limiting examples of which include 93210 hydrophilic PET (Adhesives Research, Glen Rock PA) or 9984 Diagnostic Microfluidic Surfactant Free Fluid Transport Film, 9960 Diagnostic Microfluidic Hydrophilic Film, or 9962 Diagnostic Microfluidic Hydrophilic Film (3M Oakdale, MN). The channel can also have one or more porous or mesh material along at least some portions of the channel that allows at least a portion of the target analyte to be dispensed from the channel of the metering stack to contact assay components in the assay stack. One non-limiting embodiment is shown inFIG.6.FIG.6shows a plan view of metering stack layer650that comprises porous or mesh material655which is positioned such that it is aligned with the channel portion on its top surface and the assay distribution ports and assay components on its bottom surface. In some embodiments, the porous or mesh material is selected such that the pores in such material separate the target analyte into a portion that is to be delivered to the assay components and a portion that is not delivered to the assay components. For example, when the target analyte is blood, the pores of the porous or mesh material may be of a size that is suitable for separating erythrocytes from other blood components, such as plasma. In this way, when the cartridge is inserted into the assay reader to perform the assays, only plasma is delivered to the assay components for analysis. Of course, combinations of porous or mesh materials may be used such that the entire target analyte is delivered to some of the assay components, while only portions of the target analyte may be delivered to other assay components. For example, the combination of porous or mesh materials may allow only plasma to reach some assay components, but allow for the delivery of all blood components to other assay components. In certain embodiments, the channel can include a porous or mesh material at the bottom of the channel. The porous or mesh material at the bottom of the channel can be a hydrophilic material or a material coated with a hydrophilic coating. In some embodiments, the porous or mesh material can have a pore size between about 1 μm to about 500 μm. Advantageously, when the target analyte is blood, the pores of the porous or mesh material can be sized to allow the porous or mesh material to hold the blood sample in the channel without dripping during blood collection and to be absorbed by the assay stack during the blood dispensing step which occurs upon insertion of the cartridge into the assay reader. In some embodiments, the porous or mesh material can also be used to release air and prevent bubble formation during the time that channel is filled with the target analyte. In some embodiments, the channel has a round or octagonal transverse cross-section, as illustrated inFIG.7A, and in such embodiments, the upper-most layer may have venting holes that are off-set to the side. InFIG.7A, the venting hole711can be disposed at a 45-degree angle relative to the top surface of the cartridge and the mesh or porous material703can be positioned on the bottom of the channel. In such a configuration, air may escape from venting hole711or through porous mesh703as the channel becomes filled with the target analyte. In some embodiments, as illustrated inFIG.7B, the venting holes711can be positioned on the bottom of the metering stack704within or near a mesh or porous material703. As illustrated inFIG.7B, the channel of the metering stack may have one side open to receive the target analyte. In some embodiments, the channel inlet itself can be one of the venting holes of the channel and, optionally, the end of the channel opposite the channel inlet can be open to the environment and serve as a venting hole for additional air to escape. In some embodiments, as illustrated inFIG.7C, the venting holes711can be positioned on the top the channel710and the mesh or porous material703can be positioned on the bottom of the channel710. FIG.8illustrates an exploded view of a metering stack according to one exemplary embodiment of the invention. InFIG.8, the metering stack804is formed by assembling multiple layers. The first layer841can be a plastic sheet with a first side842in communication with the surrounding environment when the cartridge is located outside the assay reader and a second side843that faces the assay stack. In some embodiments, the first layer841may be a cover layer or top layer of the metering stack. In preferred embodiments, first layer841may have a hydrophilic surface or coating on second side843. Non-limiting examples of suitable hydrophilic surfaces coatings include polyvinylpyrrolidone-polyurethane interpolymer, poly(meth)acrylamide, maleic anhydride polymers, cellulosic polymers, polyethylene oxide polymers, and water-soluble nylons or derivatives thereof, to name just a few. The presence of the hydrophilic surface or coating on second side843helps to draw the target analyte into the channel, since most, if not all, of the target analytes are aqueous mixtures, such as blood. The first layer841may include vent holes811positioned to align with the channel810defined by the layers below. InFIG.8A, for example, the vent holes811are aligned with the receiving chambers of channel810to allow air that otherwise would be trapped as an air bubble in the receiving chamber during channel filling to escape efficiently into the surrounding environment. It should be noted that the channel opening can also serve as a vent hole, if desired. In certain preferred embodiments, the first layer841comprises polyethylene terephthalate (PET) with a hydrophilic coating on the second side843and with venting holes811. The second layer844is positioned below the first layer841on the second side or assay facing side of the first layer841. The second layer844itself can be a combination of one or more layers as illustrated inFIG.8. Regardless of whether second layer is comprised of one layer or more than one layer, the second layer essentially defines the shape and size of channel in the metering stack, including any receiving chambers that may be part of the channel. For example, the second layer844can be formed from one or more layers of polymeric material cut to define the volume and shape of the channel810that can contain the target analyte. Other non-limiting methods of forming the channel810include injection-molding, stamping, machining, casting, laminating, and 3-D printing. Combinations of such fabrication techniques are also expressly contemplated by the invention. In the embodiment shown inFIG.8, second layer844has a first side847facing the first layer841and an opposite second side848that faces the assay stack. Furthermore, second layer844comprises adhesive layer845and plastic layer846. Adhesive layer845fastens first layer841to plastic layer846. In some embodiments, the second layer844can be a combination of one or more layers of plastic sheet(s)846and adhesive layers845. Preferably, adhesive layer845or plastic layer846or both are fabricated from materials which present a hydrophilic surface to the interior surfaces of the channel810in order to facilitate the distribution of the target analyte within channel810. In some embodiments, the hydrophilic plastic sheet(s) can include a PET material with a channel810cut into it. If desired, channel810may include one or more receiving chambers as shown inFIG.8. Thus, the thickness and geometry of channel810can control the volume of sample to be collected. The hydrophilic interior surfaces of the channel810allow the metering stack to collect blood sample by capillary force. In some embodiments, the first layer841and the second layer844can be one integrated layer used in the metering stack. InFIG.8, third layer849can be formed from a hydrophobic adhesive layer. Non-limiting examples of suitable materials for fabricating third layer849include 3M 200MP adhesive or 3M 300MP adhesive (3M, Oakdale, Minn.). In preferred embodiments, the same channel geometry as channel810is cut into the third layer to match channel810cut in the second layer. In some embodiments, the third layer849can have a first side851facing the second layer844and an opposite side852. In some embodiments, the third layer849can define the hydrophilic region in a fourth layer850positioned below or on the second side852of the third layer. In some embodiments, the fourth layer850can be a hydrophilic mesh or porous material. In some embodiments, substantially all of the fourth layer850can include the mesh or porous material as shown inFIG.8. In other embodiments, the hydrophilic mesh or porous material can be a portion of the fourth layer850as shown inFIG.6. More specifically,FIG.6illustrates an embodiment of a fourth layer of the metering stack that includes a mesh or porous material within the portion of the fourth layer that aligns with the channel formed from the second and third layers. In some embodiments, such as the example shown inFIG.8, the fourth layer850can have a first side853facing the third layer849and an opposite assay stack facing second side854. The hydrophobic third layer849can be positioned above the fourth layer850. The hydrophobic third layer849can be a hydrophobic adhesive layer to define a wettable region of the mesh or porous material of the fourth layer850. The method used to fabricate the metering stack is not particularly limited, so long as it is compatible with the general manufacturing requirements for medical devices. In certain embodiments, the layers that constitute the metering stack are first fastened together as large multilayer sheet or strip which is then subjected to stamping or cutting processes to form the metering stack, including the channel and any receiving chambers that may be present. In some embodiments, the first layer841and second layer844can be combined in one piece of plastic material with a hydrophilic surface forming the channel. In some embodiments, the third layer849and fourth layer850can be combined in one piece of patterned mesh made by printing or other method to define the hydrophilic porous area. In some embodiments, the third layer is not used in the metering stack. Various other combinations of two or more layers, as well as additional layers, are contemplated by various embodiments. In the assay systems of the invention, the assay reactions occur in the assay stack. In general, an assay stack comprises one or more “assay components.” As used herein, the term “assay component” refers to one or more of the active component and a passive supporting element or mask, including but not limited to the multiplexed assay pads. The number assay pads in a particular assay component is not particularly limited and is scalable to meet the assay requirements needed to diagnose the condition of the patients for whom the assay stack is designed. In preferred embodiments, the top layers of the assay pads of a given assay component align vertically with the appropriate regions of the channel in the metering stack above to ensure that a predetermined volume of target analyte, sufficient to perform the assay associated the particular assay, is delivered to the assay pad. The assay pad can act as a sponge that draws the sample through the mesh of the metering stack into the assay stack, for example through capillary action, gravity, etc. Therefore, once the metering stack and the assay stack are in contact with or within close proximity to each other, the fluid from the target analyte sample to be analyzed is directed to move into the assay pad, where it may encounter one or more chemical reagents required to perform the assay associated with the particular assay component. If desired, the assay stack may comprise additional layers that contain the chemicals required for the completion of the assay. The number of layers required can depend on the number of chemical reactions that need to take place to complete the assay. For instance, some assays require a single layer while others may require multiple layers. In various embodiments, layers of the assay stack can be made of variously-shaped and variously-sized pads of different porous membrane materials, non-limiting examples of which include nylon, polyethersulphone (PES), nitrocellulose, cellulose filter paper, and glass fiber. The type of assays that may be formed using the assay systems of the invention are not particularly limited and can be any assay for which the required reagents can be stably incorporated into one or more assay pads and which can cause a change that can be detected by the assay reader. In preferred embodiments, the assay reactions cause a color change, which may be detected using the colorimetric detection methods as described herein. In certain embodiments, the assays may be porous material-based lateral flow assays, vertical flow assays, and/or a combination of lateral and vertical flow assays. In general, the target analyte is a biological fluid, non-limiting examples of which include blood, saliva, sweat, urine, lymph, tears, synovial fluid, breast milk, and bile, or a component thereof, to name just a few. In certain preferred embodiments, the target analyte is blood or a component thereof (e.g., blood plasma). For example, in one embodiment, the assay systems of the invention are useful for providing diabetic patients with point-of-care information regarding their blood composition, including glucose level, hemoglobin A1C with eAG, C-peptide levels, creatinine levels, and the like. By way of example, glucose levels may be measured by reaction with dinitrosalicylic acid, which results in a color change that is proportional to the amount of glucose present. Alternatively, glucose levels in a target analyte may be analyzed by monitoring the degree of change in yellow color characteristic of ferricyanide. As another example, the presence of creatinine can be detected by reacting creatinine with a picrate, which results in a colored complex. In yet another example, the assay systems may be used to evaluate the immune reactivity of blood platelets using a colorimetric assay chemistry based on the reduction of tetrazolium salts. See, e.g., Vanhée D., et al, “A colorimetric assay to evaluate the immune reactivity of blood platelets based on the reduction of a tetrazolium salt,” J. Immunological Methods, Vol. 159, Issues 1-2, February 1993 pp. 253-259. In other embodiments, when the target analyte is urine, the assay stack may comprise assay components for measuring glucose, detecting uric acid, detecting hematuria, or detecting metabolites of illicit drugs, using assay chemistries as known in the art. For instance, when the target analyte is uric acid, an assay monitoring the reduction of cupric copper to cuprous copper, which may in turn complex with the neocuproine to form a colored material that is proportional in density to the concentration of uric acid in the analyzed liquid. See, e.g., U.S. Pat. No. 3,992,158, which is incorporated by reference in its entirety. In certain embodiments, one or more assay pads in an assay component do not contain any reagents for performing assays on the target analyte, but instead simply absorbs or adsorbs the target analyte to present it for direct analysis using the assay reader of the invention. For example, in certain embodiments, the assay pad absorbs blood plasma that has been separated from the red blood cells of the original blood sample, using the methods described herein, and presents the blood plasma for optical analysis by the assay reader to determine the extent to which hemolysis has occurred. FIG.9illustrates an exemplary assay stack906according to one embodiment of the invention. InFIG.9, the assay stack906is formed of multiple layers, including one or more of the layers with active components and a passive supporting element or mask. More specifically, inFIG.9, assay stack906comprises assay stack cover layer910that features cut-out portion911that is aligned with the channel in the overlying assay stack. Generally, assay stack cover layer910is fabricated from a polymeric material that provides rigidity to the assay stack and provides ease of handling during manufacturing of the cartridge. Furthermore, cut-out portion911allows the target analyte to flow past assay cover layer910towards the under assay components when the cartridge is inserted into the assay reader, as described herein. In some embodiments, the assay stack906comprises a separation layer961in the top most layer facing the metering stack, although this invention also expressly contemplates embodiments in which an assay stack comprises a plasma separation layer which is not in the top most layer of the assay stack. It should be noted that the separation layer is optional, and that in certain embodiments, the assay stack does not comprise any separation layer. When present, separation layer961may be used to separate components of the target analyte to prevent undesirable components of the target analyte from reaching the underlying assay components. For example, when the target analyte is blood, the separation layer961may be a plasma separation membrane that prevents erythrocytes from reaching the assay components after the cartridge has been inserted into the assay reader. This is advantageous because the strong spectral absorption by the hemoglobin present in erythrocytes may overwhelm the color changes that occur at the assay pad after the assay is performed. Such a plasma separation membrane can be made of a variety of materials, non-limiting examples of which include an asymmetric polysulphone membrane, glass fiber, or cellulose. In some embodiments, the fabrication of the plasma separation membrane can include surface treatments for improved wettability and/or other properties. The plasma separation layer can be one continuous piece of membrane for all of the assay components, or multiple pieces of membrane material that may be same or different (or some combination thereof) for each of the assay pads in the assay component in the assay stackFIG.9. In some embodiments, some of the assay pads of an assay component have a corresponding plasma separation layer, while other assay pads do not have such a layer. InFIG.9, assay stack906includes assay component920, which features mask support layer930with a plurality of cut-outs931that are configured to receive and immobilize assay pads940when the assay stack906is assembled. Preferably, cut-outs931are positioned laterally in mask support layer930such that each of the assay pads940are aligned with both the channel and the porous or mesh material of the metering stack above in order to receive predetermined volumes of target analyte sufficient to perform the assay reaction associated with the given assay pad. As shown inFIG.9, in some embodiments, the assay stack906can include a second assay component962positioned below the plasma separation layer961and first assay component920. The second assay component962comprises a mask support layer950with a plurality of cut-outs951that are configured to receive and immobilize assay pads963when the assay stack906is assembled. Preferably, cut-outs951are positioned to align assay pads963with assay pads940, such that the target analyte will flow from assay pads940into assay pads963. Assay pads963may comprise chemical reagents that are necessary to complete the assay reactions that are initiated when the target analyte flows through the assay pads940of assay component920. In other embodiments, one or more of assay pads963are non-functional pads that do not cause any further chemical reactions with the target analyte and merely transmit the completed assay products to the bottom of the assay stack for analysis by the assay reader. In some embodiments, assay pads963serve as a detection indicator layer that provides information corresponding to the results of the assay performed. For example, assay pads963can include a visual indicator, such as a color change, to indicate the results of the assays. Furthermore, while assay stack906inFIG.9contains only two assay components920and962, it should be understood that the assay stack906may contain additional assay components with assay pads that are impregnated with chemical reagents that are required to complete and/or report the results of a particular assay. For instance, the assay stack906can include any number of assay components necessary to perform the analysis of the blood sample. Because some assays require more chemical steps than others, assay components near the bottom of the assay stack may comprise more non-functional assay pads which only serve to draw the completed assay products to the bottom of the assay stack, where the results may be detected by the assay reader, as described herein. Assay stack906inFIG.9also includes an assay bottom layer970, which is typically fabricated from a polymeric material to provide mechanical strength and ease of handling of assay stack906during the manufacturing process. In addition, assay bottom layer970typically comprises a plurality of detection ports971which are aligned with the assay pads of the assay stack and sized to permit interrogation of the assay results by the assay reader. For example, as described herein, the assay reader may probe the assay results by shining light of a particular wavelength onto the assay pads of the bottommost assay component in the assay and detecting the intensity or wavelength of the light that is scattered from the assay pads. FIG.10comprises a cartridge1000and an assay reader1050according to another embodiment of the invention. Cartridge1000features a unitary outer shell that includes handle portion1005and housing portion1010. In this embodiment, handle portion1005is a long, thin tab that permits easy handling of the cartridge1000by user, even when the user is using only one hand. As shown inFIG.10, cartridge1000further comprises metering stack1020which is partially exposed when it is inserted into housing portion1010. In particular, channel inlet1021protrudes slightly from the housing portion1010, such that the mouth of the channel1021may be dipped into the target analyte, causing the target analyte to be drawn into the channel of metering stack1020. A plurality of venting holes1023are visible on the top layer of metering stack1020and are aligned with the underlying channel of the metering stack1020. The venting holes1023prevent the formation of undesirable air bubbles in the channel while the channel is being filled with the target analyte. Not shown is a corresponding assay stack, which is positioned underneath metering stack1020. After the channel of metering stack1020is filled with the target analyte, cartridge1000is inserted into assay reader1050(FIG.11). As shown inFIG.10, cartridge1000features a slot1015, which is configured to receive an internal tab that extends along the longitudinal direction of assay reader1050. The internal tab protrudes downward into the receiving chamber1052assay reader1050, creating a rudimentary “lock and key” mechanism that makes it impossible for the user to inadvertently insert cartridge1000upside down into assay reader1050. In addition, when the cartridge1000is inserted into assay reader1050after the target analyte has been collected, the internal tab provides a compressive force that compresses together the metering stack1020and the underlying assay stack, thereby initiating the assay reactions, as described herein. FIG.12shows an exploded view of metering stack1020corresponding to the embodiment of the cartridge shown inFIG.10. Top layer1201comprises a polymeric sheet with venting holes1203that are aligned with the underlying channel in the metering stack. In certain preferred embodiments, the surfaces of top layer1201may be subjected to chemical treatments that facilitate the collection of the target analyte. For instance, when the target analyte is blood, it is advantageous to apply a hydrophobic coating1205to the top surface of top layer1201and a hydrophilic coating1206to the bottom surface of top layer1201. In this way, during blood collection, the hydrophobic top coating1205on top layer1201prevents the blood from sticking to the exposed top surface of the metering stack in the cartridge. On the other hand, the hydrophilic bottom coating1206of the top surface1201helps to draw the blood into the metering stack when channel inlets1221and1231are brought into contact with the blood, because the hydrophilic coating allows the blood to wet the bottom surface of top layer1201as the channel fills. The metering stack inFIG.12further includes an upper channel layer1220and a lower channel layer1230. Upper channel layer1220includes channel1222which has channel inlet1221and three receiving chambers1223,1224, and1225. As shown inFIG.12, receiving chamber1225is larger than receiving chambers1223and1224and therefore capable of holding a larger volume of the target analyte when the chamber is filled. Lower channel layer1230comprises channel1232with channel inlet1231and three receiving chambers1233,1234, and1235. In certain preferred embodiments, the top surface of lower channel layer1230is coated with a hydrophilic coating, which helps to draw the target analyte (e.g., blood) into channels1222and1232by permitting the target analyte to wet the top surface of lower channel layer1230. In certain preferred embodiments, the bottom (assay stack facing) surface of lower channel layer1230is coated with a hydrophobic coating, which helps to localize the target analyte in receiving chambers1233,1234, and1235both during collection and when the metering stack is compressed by the assay reader to drive the target analyte into the underlying assay stack for analysis. At the bottom of the metering stack shown inFIG.12is porous hydrophilic layer1250, which prevents the target analyte from contacting the underlying assay stack until the metering stack and assay stack are compressed together as a result of insertion into the assay reader. In the “dual channel” configuration shown inFIG.12, upper channel layer1220and lower channel layer1230are aligned such that they are in fluid communication when the metering stack is assembled. Preferably, the receiving chambers of upper channel layer1220and lower channel layer1230coincide, as shown in theFIG.13A(top view) andFIG.13B(perspective view). Thus, the channel and1222receiving chambers1223,1224, and1225in upper channel layer1220serve as reservoirs of additional target analyte that can be delivered to corresponding receiving chambers1233,1234, and1235in lower channel layer1230. In this way, the additional target analyte in upper channel1222and corresponding receiving chambers1223,1224, and1225ensure that a sufficient amount of the target analyte is delivered to the underlying assay stack when the cartridge is inserted into the assay reader. The size of the receiving chambers1223,1224, and1225may be varied depending on the sample size requirements of the assay pads in the assay stack as described herein. For example, in the non-limiting embodiment shown inFIG.12, receiving chamber1225in upper channel layer1220is larger than corresponding receiving chamber1235in lower channel layer1230. This permits different volumes of the target analyte to be delivered as needed to the assay pads in the assay stack below, thereby providing additional flexibility as to the types of assays that may be incorporated in the cartridges of the invention. In addition, the bottom of lower channel1230defines the fluid communication region between the channel and the assay pad. In one embodiment, the fluid communication region is the same or smaller than the top surface area of the assay pad. FIG.14Ashows metering stack1400and corresponding assay stack1450before they are assembled together and inserted into the cartridge. In this non-limiting embodiment, metering stack1400has a dual-channel construction, with an upper channel layer and lower channel layer as shown inFIG.12. When metering stack1400is assembled, upper channel1422with receiving chambers1423,1424, and1425can be seen through top layer1415. Venting holes1440are aligned with channel1422and positioned between receiving chambers1423and1424, between receiving chambers1424and1425, and at the end of channel opposite the channel inlet1421. Furthermore, receiving chambers1423,1424, and1425are aligned with the receiving chambers in the lower channel, but only receiving chamber1435of the lower channel can be seen readily since receiving chambers1423and1424are the same size as and coincident with their corresponding receiving chambers in the lower channel. The receiving chambers in the lower channel layer are aligned with corresponding assay pads1452,1454, and1456in assay stack1450. This alignment is shown inFIG.14B, which is a transverse cross-sectional view of metering stack1400and assay stack1450through upper receiving chamber1425and lower receiving chamber1435after the metering stack and assay stack have been brought together. FIGS.15A-15Dillustrate the operation of the cartridge in four steps according to one exemplary implementation of the invention. For clarity, the embodiment shown inFIGS.15A-15Dcomprises a metering stack with only a single channel layer. It should be noted, however, that the basic principle of operation is similar for metering stacks with more than one channel, as exemplified inFIGS.12-14.FIG.15Aillustrates a schematic longitudinal cross sectional view of metering stack1504during sample collection. As shown inFIG.15A, target analyte is distributed on surface1501, which may be the surface of a patient's skin when the target analyte is blood. During sample collection, the channel1510in the metering stack1504can be filled with the target analyte (e.g., blood) by exposing channel inlet1505to the target analyte1502. The target analyte1502is drawn into channel1510by capillary action and/or by gravity, as indicated by arrow1508. In some embodiments, pointing channel inlet1505of the channel1510of the metering stack1504upwards can help blood flow into the channel1510. As channel1510begins to fill, the air in the channel1510is displaced by the target analyte1502and driven out of channel1510via vent holes1511, as indicated for one vent hole by the black arrow labeled1512. In addition, some of the air in channel1510may escape via the porous or mesh layer1550at the bottom of the metering stack. Furthermore, the presence of the venting holes1511and/or porous or mesh layer1550also permits any air bubbles introduced into the channel by user error to escape before the sample collection is completed. Such air bubbles may form, for example, if the user accidentally moves channel inlet1505outside of the drop of target analyte1502on surface1501during sample collection. In this way, the venting holes1511in metering stack1504help to ensure that a predetermined volume of target analyte is reliably delivered to the assay stack below. As shown inFIGS.15A-D, the metering stack and assay stack can have extra space to allow overdraw of the sample without dispensing the extra sample to the assay pad. In addition, the channel1510in the metering stack1504may extend beyond the last assay pad to act as a run-off area. If the user keeps filling the channel after the sample reaches the indicator location the excess sample can fill the extra volume in the channel beyond the last pad. As described herein, the size of the pores or mesh in porous or mesh layer1550is selected to ensure that the target analyte does not leak through the porous or mesh layer1550during target analyte collection. In some embodiments, channel1510comprises a plurality of receiving chambers1515located along the length of the channel. Due to the nature of the longitudinal cross section shown inFIG.15A, the positions of the receiving chambers1515are indistinguishable from the rest of channel1510and are therefore represented by the dotted lines, which also indicate that receiving chambers1515are positioned between vent holes1511. In the configuration shown inFIG.15A, metering stack1504is separated from assay stack1506by spacing1525, which may achieved by inserting a compressible spacing material (not shown for clarity) between the metering stack and the assay stack. The compressible spacing material is positioned in spacing1525such that it does not interfere with the transfer of the target analyte1502from the metering stack to the underlying assay stack1506. Assay stack1506includes a plurality of assay pads1530which contain reagents that interact with the target analyte1502to provide an assay result when the target analyte is transferred from metering stack1504to assay stack1506. In this exemplary embodiment, assay stack1506also features separation layer1531which may be used to prevent a portion of the target analyte from reaching the assay pads1530(e.g., red blood cells, if the target analyte is blood). Separation layer1531may also contain assay reagents that interact with the target analyte1502. In addition, for each assay pad1530, separation layer1531may be comprised of different materials with different thicknesses and/or reagents contained within, although in this illustrative embodiment, separation layer1531is one continuous piece. The assay stack includes one or a plurality of assay pads, which may be used for different functions, non-limiting examples of which include separation of analyte components, assay reactions, or a combination thereof. In some embodiments, the assay stack contains only one or more assay pad with assay reagents, and the assay pads do not function as a separation layer. In certain embodiments, one or more assay pads function as separation layers and do not contain any assay reagents. Of course, the invention also contemplates embodiments where the assay stack contains assay pads that contain reagents and also function as a separation layer. For the purposes of illustration, a gap1532is shown between the separation layer1531and the assay pads1530. However, in many (if not most) embodiments, assay pads1530will be in direct contact with separation layer1531, so that the target analyte will be wicked directly into the assay pads when the metering stack and the assay stack are brought together. The filling of the channel1510with target analyte can be judged by indicators on the metering stack1504. In some embodiments, the indicator can be a visual indicator. For example, the presence of the target analyte (e.g., blood) inside the channel may be visible through a transparent material above or surrounding the channel or at the end of the channel. In other embodiments, the visible indicator can be an indicator initiated when target analyte reaches a particular location in the channel. For example, the visible indicator can be initiated when target analyte reaches the end of the channel. For example, when the target analyte is blood, the top layer of the metering stack1504can be designed so that the blood is visible only through a slit at a given location of the channel1510. Once the blood reaches this location the user can see a “red slit,” a “red line,” or any other indicator which can be used as a visual cue for a user to know when to stop collecting the sample. In some embodiments, the indicator can be a light emitting diode (LED) that activates when the blood reaches a set point. In some embodiments, the indicator can be activated by electrodes. The electrodes can trigger or activate an alarm, light, or other indictor when the electrodes are in contact with blood in the channel. FIG.15Bshows metering stack1504and assay stack1506after the channel1510has been filled with target analyte1502and inserted into the assay reader, causing the compression of the spacer material between the metering stack1504and the assay stack1506the removal of gap1525. In this way, metering stack1504and the assay stack1506are brought together. At this point, target analyte1502is permeating through porous or mesh layer1550and separation layer1531, but has not reached assay pads1530, as shown by the absence of any target analyte in gap1532. In certain embodiments, due to the design of metering stack1504, target analyte1502reaches all of the assay pads at essentially the same time. This is illustrated schematically inFIG.15C, which shows target analyte portions1502a,1502b,1502c, and1502dpermeating porous or mesh layer1550and separation layer1531and contacting assay pads1530in parallel. The synchronization of the assays in the assay stack is advantageous, because many assays require the reagents to react for a certain time before valid assay results can be obtained. By providing a well-defined starting point for the assays, the invention provides a reliable, repeatable system assay system for performing different assays at the same time. It should be noted, however, that the invention also specifically contemplates embodiments where the start of the assays is not synchronized. For example, in certain embodiments, the assay reader comprises sensors which are capable of detecting the actual starting time and ending time by monitoring a signal change as described herein, a non-limiting example of which includes a change in color. When the target analyte1502contacts assay pads1530, the target analyte is drawn or wicked into the assay pads by capillary action and/or gravity, as indicated by the black arrows inFIG.15C. At this point, vent holes1511allow ambient air to enter channel1510, thereby preventing the formation of a partial vacuum that would otherwise be caused by the absorption of the target analyte1502from the channel1510into the assay pads1530below. InFIG.15D, a substantial portion of target analyte1502has been drawn out of channel1510toward the underlying assay pads1530below, resulting in the emptying of a substantial portion of channel1510. In certain embodiments, portions of the target analyte in the channel above the assay pads “break off” from the target analyte in the rest of the channel, due to the wicking action of the assay pads below. This may result in some target analyte1502being left behind in the channel1510in regions which are not directly over an assay pad, such as near the ends of the channel, between the end of the channel and the nearest venting hole (seeFIG.15D). Assay pads1530receive the portions of the target analyte1502that can pass through the separation layer1531. This portion of the target analyte then undergoes assay reactions in assay pads1530. In certain embodiments, the assay pads undergo a change (e.g., a color change) which can be detected by the assay reader, as described herein. FIG.16Ashows a schematic drawing of an assay reader, in longitudinal cross-section, according to one non-limiting embodiment of the invention. InFIG.16A, assay reader1600includes cartridge receiving chamber1610which houses the cartridge when it is inserted as indicated by arrow1605. Tab1615runs longitudinally along assay reader1600and extends into cartridge receiving chamber1610. Tab1615is configured to insert into a slot at the top of the cartridge, such as slot228inFIG.2Cor slot1015inFIG.10, when the cartridge is inserted into the assay reader. In addition, the spacing1625between the bottom edge of tab1615and support surface1620is set such that when the cartridge is inserted, tab1615compresses the metering stack and the assay stack together, thereby causing the target analyte to flow from the metering stack into the assay stack and initiating the assay reactions. In certain embodiments, the assay reader may comprise a snap-fit mechanism that locks the cartridge in place once it has been fully inserted into the assay reader. This is advantageous because it prevents the user from accidentally removing the cartridge from the assay reader before the assays are complete, which could adversely affect the accuracy of the assay results. In some embodiments, assay reader1600also comprises sensors1642aand1642b, which detect and time the insertion of the cartridge. For example, as the cartridge is inserted into cartridge receiving chamber1610and begins to engage with tab1615, the bottom surface of the cartridge may pass over sensor1642a, which is detected by appropriate electronics as the beginning of the insertion of the cartridge. The second sensor,1642b, is located further inside the assay reader1600and detects the presence of the cartridge when the cartridge is fully inserted as well as the time at which full insertion occurred. Assay reader1600may then compare the overall time for insertion of the cartridge to determine if the insertion of the cartridge was timely and proper. In this way, assay reader will not perform any assay readings in situations where (1) the cartridge was only partially inserted, or (2) the cartridge was partially inserted, removed, and inserted again. Either case could give inaccurate assay readings, due to incomplete compression of the metering stack and assay stack, resulting in incomplete delivery of the required amount of target analyte to the assay pads in the assay stack. In the exemplary embodiment shown inFIG.16A, assay reader1600detects the results of the assay by detecting the color change of the assay pad caused by the assay reactions. To achieve this, assay reader1600comprises a plurality of light sources (not shown in this cross-sectional drawing) and light detection elements1650arrayed within assay reader1600such that they align with the assay pads of the cartridge when the cartridge is fully inserted. In order for light detection elements1650to be able to detect the color of the assay pads, support surface1650may be equipped with one or more apertures or be fabricated from a transparent material that allows light to penetrate therethrough.FIG.16Bshows a schematic illustration of a longitudinal cross-section of assay reader1600with cartridge1602fully inserted. Cartridge1602includes metering stack1604and assay stack1606, which are compressed together by tab1615such that the target analyte is delivered from the metering stack1604to the assay pads1630. Assay pads1630are aligned with light detection elements1650. Note, however, that assay reader1600may comprise an additional light detection element1650awithout a corresponding assay pad1630. The presence of additional light detection elements, such as light detection element1650a, allow the assay reader to be used with different types of cartridges for different assays, particularly cartridges that may be designed to perform more assays, as well as to identify the different types of cartridges for the different assays. FIG.17Ashows a schematic drawing of a transverse cross-section of the assay reader shown inFIG.16. InFIG.17A, assay reader1700includes a tab1715that extends into cartridge receiving chamber1710to engage with a slot on the cartridge to compress the metering stack and the assay stack against support surface1720to initiate the assay reactions. Light sources1760aand1760bprovide light for detecting the assay results and are positioned near light detection device1750. As illustrated inFIG.17A, light sources1760aand1760bprovide light to analyze the assay pad corresponding to light detection element1750. In general, it is advantageous to dedicate one or more light sources to each light detection element in order to ensure that the photon flux onto the light detection element is sufficient to obtain an accurate reading. In some embodiments, the light sources dedicated to a particular light detection element have the same output spectrum. In other embodiments, however, the light sources corresponding to a given light detection element produce different output spectra. For instance, the light sources may be light emitting diodes (LEDs) that produce different colors of light. For example, when the target analyte is blood, it may be useful to use light sources that can generate bichromatic pairs (600 nm/570 nm) to detect the presence of undesirable hemolysis. In general, it is advantageous to include optical elements to direct the light and/or reduce the amount of light scattering in the assay reader. In some embodiments, the optical elements are apertures that only allow light emanating from the light source that is line-of-sight to the respective assay pad to reach the assay pad. For example, inFIG.17A, light source1760ais limited by aperture defining members1770aand1771asuch that only the light from light source1760athat passes through aperture1773awill reach the assay pad and subsequently be detected by light detection device1750. Similarly, light source1760bis limited by aperture defining members1770band1771b, such that only the light from light source1760bthat passes through aperture1773bwill reach the assay pad and subsequently be detected by light detection device1750. In preferred embodiments, aperture defining members1770a,1770b,1771a, and1771bare fabricated from a black matte material to reduce the amount of undesirable scattering when light sources1760aand1760bare turned on. Furthermore, in this embodiment, light detection device1750located in a housing that is comprised of aperture defining members1771aand1771bthat only permit light that passes through aperture1772to reach light detection device1750. If desired, the aperture1772may be fitted with a filter to admit only light of a predetermined wavelength or wavelength range for detection by light detection device1750. This may be useful, for example, when the light sources are equipped to provide only white light for colorimetric analysis. In addition the light from light sources1760aand1760band the light to be detected by light detection device1750may be directed or manipulated using optical elements such as lenses, filters, shutters, fiber optics, light guides, and the like without departing from the spirit and the scope of the invention. FIG.17Bshows a schematic illustration of the operation of the assay reader described inFIG.17A. InFIG.17B, a cartridge comprising metering stack1704and assay stack1706are inserted into cartridge receiving chamber1710of assay reader1700. Tab1715compresses metering stack1704and assay stack1706against support surface1720to cause the target analyte to flow from the channel1712into assay pad1730. As noted previously, assay reader1700may be fitted with sensors to confirm that the cartridge has been inserted correctly and in a timely manner. Assay reader1700may also be pre-programmed before sample collection, either by the user or during the manufacturing process, to illuminate the assay pads at the appropriate time based on the type of cartridge being used. In this way, assay reader1700collects assay data from assay pad1730only when the assay is completed. Alternatively, if desired, assay reader1700may be configured to collect assay data from assay pad1730during the entire assay reaction after the cartridge has been inserted. As shown inFIG.17B, light source1760aprovides light beam1780a, which impinges on the bottom face of assay pad1730. Similarly, light source1760bproduces light beam1780b, which may impinge on the bottom of the assay pad1730at the same time as light beam1760aor a different time, depending on the requirements of the assays being detected. FIG.18shows a block diagram of a sensor configuration inside an assay reader according to one exemplary embodiment of the invention. InFIG.18, four assay pads (identified by reference numerals1841,1842,1843, and1844) have completed their assay reactions with the target analyte, undergone the respective color changes, and are ready for colorimetric analysis. Note that, if desired, this configuration can also be used to collect data from the four assay pads to monitor the progress of the assay reactions. Input signal1801from a first microcontroller serial-peripheral interface bus (MCU SPI Bus) enters digital-to-analog converter unit1810, which comprises individual digital-to-analog converters1811,1812,1813, and1814that independently control current sources1821,1822,1823, and1824. These current sources, in turn, power light sources1831,1832,1833, and1834respectively. In some embodiments, input signal1801may be sent by a timing circuit at a predetermined time after the insertion of the cartridge into the assay reader. In such embodiments, the predetermined time corresponds to the known time or times for the assay reactions in the assay pads to reach completion. In some preferred embodiments, the light sources1831,1832,1833, and1834are activated at the same time to measure the assay-induced color change of assay pads1841,1842,1843, and1844simultaneously in a multiplexed mode. However, this invention also contemplates operating all of the light sources separately and sequentially, or some simultaneously and some separately, depending on the timing requirements of the assays in the cartridge. In this non-limiting example, each of light sources1831,1832,1833, and1834comprises individual three light emitting diodes (LEDs) which may be the same or different colors, depending on the requirements of the assay and any optical elements that may be present in the assay reader. For example, in certain embodiments, the three LEDs in a particular light source (e.g.,1831) may be red, green and blue (RGB LEDs), such that the light impinging on the assay pad is white light when all three LEDS are activated. Of course, the light sources are not limited to any particular number or type of LEDs or other light generating devices. More generally, the light sources that are useful in the assay readers of the invention are not particularly limited, so long as they provide light of suitable wavelength(s) and brightness for the light detection element to make an accurate reading of the colored light reflected from the assay pad. In certain non-limiting embodiments, the light sources are light emitting diodes (LEDs), organic light emitting diodes (OLEDs), active matrix organic light emitting diodes (AMOLEDs) or lasers. For example, the light source may be only one LED that has sufficient brightness and the proper wavelength to allow colorimetric analysis of an assay reaction in a given assay pad. In certain embodiments, the light sources may produce light of specific wavelengths. As one non-limiting example, when the target analyte is blood (with erythrocytes removed), a bichromatic light source that produces light at 570 nm and 600 nm may be used to detect the presence of heme on a non-functional (i.e., assay reagent-free) assay pad, which is indicative of undesirable hemolysis in the patient. Alternatively, the light source may be a broadband source that is paired with one or more narrow bandpass filters to select light of certain desired wavelength(s). Typically, the light sources produce light in the visible region of the electromagnetic spectrum (i.e., wavelength between 400-700 nm) although this invention also contemplates light sources that produce electromagnetic radiation in the infrared (700 nm to 106nm) or ultraviolet regions (10 nm-400 nm) of the electromagnetic spectrum, so long as they are paired with the appropriate light detection devices. Combinations of different light sources are also expressly contemplated by the invention. InFIG.18, element1840is a schematic representation of optical elements that optionally may be present in the optical path between the light sources1831,1832,1833, and1834and assay pads1841,1842,1843, and1844. When desired, one or more optical elements may be located between the light source and its corresponding assay pad to direct the light, focus the light, reduce undesirable scattering, select one or more wavelengths for assay detection, or some combination thereof. Non-limiting examples of such optical elements include apertures, lenses, light guides, bandpass filters, optical fibers, shutters, and the like. Similarly, element1842represents optical elements that optionally may be present in the optical path between assay pads1841,1842,1843, and1844and corresponding light detection devices1851,1852,1853, and1854. These optical elements may be used to manipulate the light upstream of the light detector devices in a manner similar to that described for element1840. It is to be understood that different types and numbers of optical elements may be used for each combination of light source, assay pad, and light detection device. Light detecting devices1851,1852,1853, and1854detect the light from the assay pads1841,1842,1843, and1844. In this non-limiting example, the light detecting devices are photodiodes. More generally, the type of light detection device is not particularly limited, provided that it is capable of detecting the light that is reflected from the assay pads used for colorimetric measurement of the assay results. Other examples of suitable light detection elements include photodiode arrays, CCD chips, and CMOS chips. The outputs from photodiodes1851,1852,1853, and1854are sent to transimpedance amplifier/low pass filter elements1861,1862,1863, and1864, which convert the current signal from the photodiodes to a voltage output, while filtering unwanted signal components. The output from elements1861,1862,1863, and1864are sent to analog-to-digital converter unit1870, which comprises multiplexer unit1871, gain1872, and analog-to-digital converter1873. The output of analog-to-digital converter unit1870may be sent to a component1880, which may be a second MCU SPI bus, a transmitter, or a processor. In certain embodiments, the transmitter allows for hardwired or wireless connectivity (e.g., Bluetooth or Wi-Fi) with a personal computer, mobile device, or computer network. In one particularly useful embodiment, the assay results are transmitted to the user's mobile device or personal computer, where they are displayed in a graphical user interface (GUI). If desired, the GUI may display prior assay results, in addition to the current results, in order to provide the user with information regarding the overall trends in the results of the assays. For example, if the user is diabetic, the GUI may plot the glucose levels measured by the assay reader as a function of time to allow the user to determine whether blood glucose level is being properly controlled. In addition, the assay results may be transmitted from the user's mobile device or computer to a computer network, such as one belonging to the user's physician. In this way, the assay systems of the invention can allow a user's physician to monitor a patient closely, by providing up-to-date medical information from the assay results obtained by the assay reader. It should be noted that the optical detection systems described in the foregoing correspond to some exemplary embodiments of the system, but that the invention expressly contemplates other types of detection systems as well. In general, any detection system which corresponds to a signal change caused by an assay reaction may be used in connection with the assay reader of the invention. Thus, for example, in certain embodiments, the detection system is an optical detection system that is based on chemiluminescence. In such embodiments, light sources such as LEDS and OLEDS are not required to detect a color change caused by the assay reaction in the assay pads. Rather, the signal change may be caused by the reaction of an oxidative enzyme, such as luciferase, with a substrate which results in light being generated by a bioluminescent reaction. In another exemplary embodiment, the signal change caused by the assay reaction may be detected by electrochemical reaction. As one non-limiting example, the presence of glucose in a biological sample may be tested using an electrochemical enzymatic sensor, which consists of a platinum electrode coated with a glucose oxidase layer that is separated from the biological sample by a semipermeable membrane. Such sensors have been reported, for example, by Mor et al., in an article entitled “Assay of glucose using an electrochemical enzymatic sensor” Analytic Biochemistry, Vol. 79, Issues 1-2, May 1977 pp. 319-328, which is hereby incorporated by reference in its entirety. FIG.19shows a flowchart that illustrates a method of using of the assay system according to one embodiment of the invention to perform a plurality of assays. The method includes step1910, which involves receiving a target analyte into a first channel in a cartridge. Step1920involves inserting the cartridge into an assay reader, thereby compressing the cartridge to expose at least one component of the target analyte stored in a first channel to a plurality of assay pads in the cartridge simultaneously to cause a plurality of assay reactions. Step1930involves detecting one or more signal changes associated with the plurality of assay reactions. FIG.20shows a flowchart that illustrates a method of fabricating a cartridge according to one embodiment of the invention. The method includes the steps of obtaining a first layer comprising (1) a layer of polymeric material with a channel formed therein and (2) a porous or mesh material attached on a bottom surface of the polymeric material such that the channel is bounded on a bottom surface by the porous or mesh material; (step2010) and obtaining a second layer comprising two or more assay pads, each comprising a reagent for performing an assay on the target analyte or a portion thereof (step2020). The method also includes the step of obtaining a compressible intermediate layer comprising a compressible material (step2030). It is to be understood that steps2010,2020, and2030can occur independently, and not necessarily stepwise or sequentially. In addition, in certain embodiments, the compressible intermediate layer can be attached to, or be a part of the first or second layer. The method also includes the step of combining the first layer, compressible intermediate layer, and second layer in a cartridge housing such that the compressible intermediate layer separates the first layer and the second layer when the compressible intermediate layer is in an uncompressed state, and the channel is aligned with the two or more assay pads in a direction perpendicular to the first layer (step2040). While various embodiments of the invention have been described above, it should be understood that they have been presented by way of example only, and not by way of limitation. Likewise, the various diagrams may depict an example architectural or other configuration for the disclosure, which is done to aid in understanding the features and functionality that can be included in the disclosure. The disclosure is not restricted to the illustrated example architectures or configurations, but can be implemented using a variety of alternative architectures and configurations. Additionally, although the disclosure is described above in terms of various exemplary embodiments and implementations, it should be understood that the various features and functionality described in one or more of the individual embodiments are not limited in their applicability to the particular embodiment with which they are described. They instead can be applied, alone or in some combination, to one or more of the other embodiments of the disclosure, whether or not such embodiments are described, and whether or not such features are presented as being a part of a described embodiment. Thus the breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments. Unless otherwise defined, all terms (including technical and scientific terms) are to be given their ordinary and customary meaning to a person of ordinary skill in the art, and are not to be limited to a special or customized meaning unless expressly so defined herein. It should be noted that the use of particular terminology when describing certain features or aspects of the disclosure should not be taken to imply that the terminology is being re-defined herein to be restricted to include any specific characteristics of the features or aspects of the disclosure with which that terminology is associated. Terms and phrases used in this application, and variations thereof, especially in the appended claims, unless otherwise expressly stated, should be construed as open ended as opposed to limiting. As examples of the foregoing, the term ‘including’ should be read to mean ‘including, without limitation,’ ‘including but not limited to,’ or the like; the term ‘comprising’ as used herein is synonymous with ‘including,’ containing,′ or ‘characterized by,’ and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps; the term ‘having’ should be interpreted as ‘having at least;’ the term ‘includes’ should be interpreted as ‘includes but is not limited to;’ the term ‘example’ is used to provide exemplary instances of the item in discussion, not an exhaustive or limiting list thereof; adjectives such as ‘known’, ‘normal’, ‘standard’, and terms of similar meaning should not be construed as limiting the item described to a given time period or to an item available as of a given time, but instead should be read to encompass known, normal, or standard technologies that may be available or known now or at any time in the future; and use of terms like ‘preferably,’ preferred,′ ‘desired,’ or ‘desirable,’ and words of similar meaning should not be understood as implying that certain features are critical, essential, or even important to the structure or function of the invention, but instead as merely intended to highlight alternative or additional features that may or may not be utilized in a particular embodiment of the invention. Likewise, a group of items linked with the conjunction ‘and’ should not be read as requiring that each and every one of those items be present in the grouping, but rather should be read as ‘and/or’ unless expressly stated otherwise. Similarly, a group of items linked with the conjunction ‘or’ should not be read as requiring mutual exclusivity among that group, but rather should be read as ‘and/or’ unless expressly stated otherwise. Where a range of values is provided, it is understood that the upper and lower limit, and each intervening value between the upper and lower limit of the range is encompassed within the embodiments. With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity. The indefinite article “a” or “an” does not exclude a plurality. A single processor or other unit may fulfill the functions of several items recited in the claims. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope. It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.” All numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification are to be understood as being modified in all instances by the term ‘about.’ Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of any claims in any application claiming priority to the present application, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches. All of the features disclosed in this specification (including any accompanying exhibits, claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The disclosure is not restricted to the details of any foregoing embodiments. The disclosure extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed. Various modifications to the implementations described in this disclosure may be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other implementations without departing from the spirit or scope of this disclosure. Thus, the disclosure is not intended to be limited to the implementations shown herein, but is to be accorded the widest scope consistent with the principles and features disclosed herein. Certain embodiments of the disclosure are encompassed in the claim set listed below or presented in the future.
93,277
11857961
DETAILED DESCRIPTION A microfluidic apparatus (e.g., device, system or the like) for controlled liquid manipulation may include a two-dimensional (planar) fluidic chamber. The chamber may include a first sheet and a second sheet separated by a gap therebetween. The gap may separate the first and second sheets by any feasible distance. The first and second sheets may be hydrophobic or may include hydrophobic coatings. In some examples the first and second sheet are hydrophobic and oleophobic and/or include a hydrophobic and oleophobic coating. Microfluidic droplets may be manipulated through mechanical manipulation that applies forces directly or indirectly to the first sheet or second sheet selectively reducing the gap. This process may sometimes be referred to as mechanical actuation on the surface (MAOS), also described as the use of mechanical compression to change the capillary force. The applied forces, which may include compressive forces, may be applied near or adjacent to droplets within the gap. In some aspects, reducing the gap may cause the droplets to move, separate, combine, mix, incubate, or the like. In some examples, the forces may be applied by a stylus. The stylus may include an electrode and/or a controllable magnet. The microfluidic droplets may be manipulated with a combination of pressure, exerted by the stylus, in conjunction with a voltage provided by the electrode and/or a magnetic field provided by the magnet. FIG.1Ashows a portion of a microfluidic device100. Any of the devices described herein may be implemented in part or in whole as a system or any other feasible apparatus. The microfluidic device100may include a first sheet110and a second sheet120separated by a gap130. In some examples, the gap130may generally be filled with air. In some examples, the microfluidic device100may be a cartridge that may be selectively coupled to a control unit or base station. As shown, the first sheet110may be a “top” sheet and the second sheet120may be a “bottom” sheet. That is, the first sheet110may be higher or “above” the second sheet120. The second sheet120may be closer to the ground than the first sheet110. In other examples, the second sheet120may be above the first sheet110. The first sheet110and the second sheet120may form a planar structure that occupies any feasible area. The first sheet110and the second sheet120are shown in an initial position. In the initial position, the first sheet110and the second sheet120are relatively parallel to each other separated by a distance associated with and/or determined by the gap130. Each sheet may include two surfaces. For example, the first sheet110may include a first surface111and a second surface112and the second sheet120may include a first surface121and a second surface122. For ease of description, the first surfaces111and121may be disposed toward the gap130, while the second surfaces112and122may be disposed on opposite sides of the first sheet110and the second sheet120, respectively. In other words, the second surfaces121and122may be disposed away from the gap130. The first surfaces111and121may be hydrophobic (water repelling). In some examples, the first and second sheets110and120(and thus the first surfaces111and121) may be formed from a hydrophobic and oleophobic material. In some other examples, the first surfaces111and121may be a hydrophobic and oleophobic coating or layer applied upon the first and second sheets110and120, respectively. A droplet140may be introduced into the gap130. In some cases, the droplet140may be introduced in the gap130through a port or opening (not shown) on the first sheet110and/or the second sheet120. The droplet140may be mechanically manipulated by selectively reducing the gap near the droplet140. In some examples, one or more of the sheets110and120may be flexible. Flexible sheets may deflect in response to one or more forces. For example, the first sheet110may be flexible and the second sheet120may be rigid or semi-rigid. Rigid or semi-rigid sheets may resist deflection in response to one or more forces. In other examples, the second sheet120may be flexible and the first sheet110may be rigid or semi-rigid. In still other examples, both the first sheet110and the second sheet120may be flexible. As used herein, the term flexible may describe any material that may flex, deform, bend, move, or the like. The droplet140may have a predetermined volume. In some cases, the droplet140may be a microfluidic droplet having a volume of the droplet140may be between 10−6and 10−15liters, although in some examples the volume of the droplet140can have any other feasible volume. The gap130may be determined, at least in part, by the volume of the droplet140. In other words, the gap130may be chosen or selected such that the droplet140(e.g., the volume of the droplet140) can touch both the first and second sheets110and120. FIG.1Bshows another view of the microfluidic device100. In this view, the first sheet110may be deflected by a compression force near or adjacent to one side or end of the droplet140. The compression force creates a reduced gap132between the first sheet110and the second sheet120toward the end or side of the droplet140. As the reduced gap132is formed, the droplet140may deform asymmetrically and be drawn toward the reduced gap132. In some cases, the droplet movement may be caused by differential capillary action and/or a differential pressure gradient within the droplet140. The compression force may be provided by any feasible means. For example, an array of electro-mechanical, mechanical, and/or pneumatic actuators may be disposed next to the first sheet110and/or the second sheet120to selectively provide a compression force to form the reduced gap132. In another example, the compression force may be provided by a stylus that may contact the first sheet110and/or the second sheet120. In some examples, the microfluidic device100may include one or more optical sensors (not shown). The one or more optical sensors may detect the presence and/or position of the droplet140. In this manner, data from the optical sensors may be used to assist the application of a compression force near or adjacent to the droplet140. FIG.1Cshows another view of the microfluidic device100. In this view, the compression force on the first sheet110has been removed or reduced and the first sheet110and the second sheet120has returned to an initial position (as shown inFIG.1A). The gap130may be similar to the gap130ofFIG.1A. The droplet140is shown in a second position having moved in response to the compression force described with respect toFIG.1B. Thus, in the manner described withinFIGS.1A-1C, any droplet may be manipulated to any area within the microfluidic device100by reducing the gap near one end of the droplet. This method advantageously avoids the generation and control of high voltages as well as the need for a plurality of electrodes that are associated with conventional microfluidic devices. The compression force described herein may be provided by any feasible source. For example, mechanical levers, balls, rollers, or the like may apply the compression force to at least one of the first or second sheets110and120, respectively. In some examples, the compression force may be computer or processor controlled. Thus the manipulation of the droplet140may be computer and/or processor controlled. FIG.2is a flowchart showing an example operation200for manipulating a microfluidic droplet. Some examples may perform the operations described herein with additional operations, fewer operations, operations in a different order, operations in parallel, and some operations differently. The operation200is described below with respect to the microfluidic device100ofFIGS.1A-1C, however, the operation200may be performed by any other suitable system or device. The operation200begins in block202as a microfluidic droplet is introduced into a gap between two hydrophobic and oleophobic sheets. For example, the droplet140may be loaded into the gap130between the first sheet110and the second sheet120of the microfluidic device100. The gap130may be an initial separation distance between the first sheet110and the second sheet120. The first sheet110and the second sheet120may be hydrophobic and oleophobic or include surfaces covered with a hydrophobic and oleophobic layer. The droplet140may be placed in an initial position. The gap130may be filled with any feasible gas, such as air. In some examples, the gap130may be filled with an immiscible (with respect to the droplet140) fluid. The presence and/or location of the droplet140may be determined with an optical sensor (not shown). Example optical sensors may include one or more digital cameras, an array of visible and/or invisible light detectors, or the like. Thus, an optical sensor may determine when the droplet140is introduced into the gap130 Next, in block204the distance between the two hydrophobic and oleophobic sheets is selectively reduced, via mechanical actuation, near the microfluidic droplet. The reduced distance may result in a reduced gap132between the first sheet110and the second sheet120. In some examples, a compression force may be provided to the sheet110adjacent to (e.g., next to) one side of the droplet140. The compression force may reduce the gap130causing the droplet140to move toward the compression force. In some examples, the compression force may deform one end of the droplet140. Next, in block206the distance between the two hydrophobic and oleophobic sheets is restored. For example, the compression force applied in block204may be removed allowing the first sheet110and/or the second sheet120to return to its initial separation distance. In some examples, the distance between first sheet110and second sheet120is returned to a distance similar to the initial separation distance of block202. The microfluidic droplet may come to rest at a different position having moved from the initial position of block202. The steps of blocks202-206may be repeated any number of times to manipulate one or more droplets to any arbitrary location in the gap130of the microfluidic device100. In some examples, different compression forces (e.g., different force amplitudes) may be applied to the droplet to perform different manipulations. FIG.3Ashows a portion of another microfluidic device300. The microfluidic device300may include a first sheet310, a second sheet320, and a gap330that may be examples of the first sheet110, the second sheet120and the gap130ofFIG.1. A source droplet340(which may be similar to the droplet140) may be introduced into the gap330as described above with respect toFIGS.1A and2. A pinning compression force may be applied to the source droplet340. Although shown as being applied to the first sheet310, in other examples the pinning compression force may be applied to the second sheet320. As shown, the pinning compression force may be applied approximately toward the center or middle of the source droplet340. The pinning compression force may be provided by any technical feasible device or operation. The pinning compression force may begin to divide or separate the source droplet340into two droplets. FIG.3Bshows another view of the microfluidic device300. As shown, an actuation compression force may be applied to the source droplet340. The actuation compression force may be less than the pinning compression force applied inFIG.3A. The actuation compression force may be applied at the same time (coincident with) or after applying the pinning compression force. The actuation compression force may separate and guide a satellite droplet341away from the source droplet340. In some examples, the pinning compression force may cause the first sheet310to contact the second sheet320helping separate the satellite droplet341from the source droplet340. FIG.3Cshows another view of the microfluidic device300. As shown, the pinning and actuation forces have been removed or reduced allowing the first sheet310and/or the second sheet320to return to their initial positions, such as the initial positions shown inFIG.3A. The source droplet340is shown separated from the satellite droplet341. FIG.4is a flowchart showing an example operation400for separating a microfluidic droplet into two or more microfluidic droplets. The operation400is described below with respect to microfluidic device300ofFIGS.3A-3C, however, the operation400may be performed by any other suitable system or device. The operation400begins in block402as a pinning compression force is applied, via mechanical actuation, to a source microfluidic droplet. The source microfluidic droplet (which may be similar to the source microfluidic droplet340) may have previously been introduced into a gap between the first sheet310and the second sheet320, for example as described above with respect toFIGS.1A and2. In some examples, the pinning compression force may begin to divide or separate the source microfluidic droplet into two or more droplets. The pinning compression force may be a mechanical actuation force provided to the first sheet310and/or the second sheet320and may be provided by any feasible means. In some cases, the pinning compression force may be applied toward the middle or center of the source microfluidic droplet. In some examples, the pinning compression force may cause the first sheet310to contact the second sheet320. Next, in block404, an actuation compression force is applied, via mechanical actuation, to the source microfluidic droplet. The actuation force may be applied to separate, direct, and/or steer a satellite microfluidic droplet away from the source microfluidic droplet. The actuation compression force may be another mechanical actuation force that, in this instance, is less in force than the pinning compression force. The actuation compression force may be applied coincident with, or after the pinning compression force is applied. In block406, the pinning compression force and the actuation compression force is removed or reduced. In the absence of the compression forces, the first sheet310and the second sheet320may return to associated initial positions, such as depicted inFIG.3C. As the pinning and actuation compression forces are removed or reduced, the satellite droplet may remain separated from the source droplet. In some examples, two or more separate droplets may be merged together using a compression force. One such example is described in conjunction withFIGS.5A-5C and6. Droplets of different sizes or the same size may be merged. For example, 250 nL-80 μL volumes may be robustly actuated and merged with an equal volume, larger or smaller volume that already exists in the air gap. FIG.5Ashows a portion of another microfluidic device500. As shown inFIG.5A, the microfluidic device500may include a first sheet510, a second sheet520, and a gap530that may be other examples of the first sheet110, the second sheet120and the gap130ofFIG.1A. A first droplet540and a second droplet541(which may be similar to the droplet140ofFIG.1Aor the source droplet340and satellite droplet341ofFIG.3C) may be introduced into the gap530as described above with respect toFIGS.1A-1C,2,3A-3C, and4. A compression force may be applied to the first sheet510and/or the second sheet520. In some examples, the compression force may be applied between the first droplet540and the second droplet541causing the respective droplets to deform, move, and in some cases, combine. The compression force may be a mechanical actuation force as described herein. FIG.5B, shows another view of the microfluidic device500. The compression force is removed or reduced thereby allowing the first sheet510and/or the second sheet520to return to initial (uncompressed) positions. As shown, the first droplet540and the second droplet541may be combined into a merged droplet542. Although combined into a single droplet, the individual droplets, or components within the first droplet540and the second droplet541may not be well-mixed within the merged droplet542. FIG.5Cshows another view of the microfluidic device500. A compression force may be repeatedly applied and released to and from the first sheet510and/or the second sheet520to mix the contents of the merged droplet542. The repeated application of the compression force may repeatedly cause the merged droplet542to deform and recover thereby causing the contents of the merged droplet542to mix. In some examples, the compression/relaxation cycle, caused by the application and release of the compression force, may be repeated for a predetermined number of times to mix the contents of the merged droplet542. FIG.6is a flowchart showing an example operation600for mixing a microfluidic droplet. The operation600is described with respect to the microfluidic device500ofFIG.5A-5C, however the operation600may be performed by any other suitable system or device. The operation600begins in block602as a compression force is applied, via mechanical actuation, to the first sheet510and/or the second sheet520between first and second microfluidic droplets540and541. The compression force may be a mechanical actuation force provided by any feasible means. The compression force may cause the first and second microfluidic droplets540and541to move toward each other and, in some cases, combine into a single (merged) microfluidic droplet542. In block604, the compression force is reduced or removed from the first sheet510and/or the second sheet520. In some examples, reducing or removing the compression force may allow the first sheet510and/or the second sheet520to return to an initial position. In some cases, additional agitation of the merged microfluidic droplet542may be desired to provide additional mixing. To provide the additional agitation, a compression force may be repeatedly applied and removed (or reduced) for a predetermined number of cycles. Therefore, in block606, the number of completed compression cycles is determined. A completed compression cycle may include the application and removal or reduction of a compression force. If the number of compression cycles is less than a predetermined number, then the operation may return to block602. On the other hand, if the number of compression cycles is greater than or equal to the predetermined number, then the operation600may end. In some examples, ferrous particles may be suspended within a microfluidic droplet to assist with processing or assaying. After one or more processing steps have been completed, the ferrous particles may be removed from the droplet for further processing. FIG.7Ashows a portion of another microfluidic device700. The microfluidic device700may include a first sheet710, a second sheet720and a gap730which may be examples of the first sheet110, the second sheet120, and the gap130ofFIG.1. A droplet740may include one or more ferrous particles that741that may be suspended within the droplet740. The microfluidic device700may also include a magnet750(not shown). FIG.7Bshows another view of the microfluidic device700. The magnet750is activated or enabled. For example, the magnet750may be an electromagnet that may be enabled through an application of power. In another example, the magnet750may be a permanent magnet that may be moved toward the droplet740. In addition, a compression force may be applied to the first sheet710and/or the second sheet720toward one side of the droplet740. The compression force may be applied at or near the same time as the magnet750is enabled or moved. The magnet750may cause the ferrous particles741to collect into one or more ferrous beads742. Thus, the ferrous particles741may come out of suspension from the droplet740. In addition, the compression force may cause the droplet740to move away from the magnet750. The droplet movement may, in some cases, filter or remove the ferrous particles from the droplet740. FIG.7Cshows another view of the microfluidic device700. The compression force is removed or reduced and the first sheet710and the second sheet720return to initial positions. The compression force applied inFIG.7Band removed or reduced inFIG.7Cmay cause the droplet740to move away from the magnet750. Since the magnet750may attract and/or limit the movement of the ferrous bead742, droplet movement may filter the ferrous material from the droplet740. FIG.8is a flowchart showing an example operation800for removing suspended ferrous particles from a microfluidic droplet. The operation800is described with respect to the microfluidic device700ofFIGS.7A-7C, however the operation800may be performed by any other suitable system or device. The operation800begins in block802as a microfluidic droplet with suspended ferrous particles is moved via mechanical manipulation to a region proximate to a magnet. For example, a microfluidic droplet740may be moved near a magnet750. In some examples, the droplet740may be moved through the application of forces to one or more sheets as described herein. Next, in block804a magnet is enabled. In some cases this step may be optional as indicated with dashed lines inFIG.8. In some examples, the magnet750may be a permanent and stationary magnet. In some other examples, the magnet750may be enabled by moving the magnet750toward the microfluidic droplet740or the magnet750may be an electromagnet and may receive power. The magnet750may cause ferrous particles to fall out of suspension and collect toward the magnet750. In some examples, the ferrous particles741may be collected into one or more ferrous beads742. Next, in block806, the microfluidic droplet740may be moved away from the magnet750through mechanical actuation. For example, a compressive force may be applied to first or second sheets710or720to move the microfluidic droplet740away from the magnet750. Moving the microfluidic droplet740away from the magnet may filter the ferrous material from the microfluidic droplet740. In some examples, ferrous material may be placed back into suspension within a droplet through mechanical actuation. One such example is described below in conjunction withFIGS.9-10. FIG.9Ashows a portion of another microfluidic device900. The microfluidic device900may include a first sheet910, a second sheet920, and a gap930. The first sheet910, the second sheet920, and the gap930may be examples of the first sheet110, the second sheet120, and the gap130ofFIG.1A. A droplet940may include non-dispersed ferrous or non-ferrous particles. A compression force may be applied to the first sheet910and/or the second sheet920(not shown) that can compress or deform the droplet940. In some cases, a compression force may be applied to the center or middle of the droplet940. FIG.9Bshows another view of the microfluidic device900. The compression force may be removed or reduced from the first sheet910and/or the second sheet920. Removal or release of the compression force may allow the droplet940to return to a non-compressed or non-deformed state. Transitioning from a compressed to a non-compressed state (or vice-versa) may cause one or more ferrous or non-ferrous particles941within the droplet940to become suspended. In some cases, the compression force may be applied and/or removed quickly or abruptly. Sudden application and/or removal of compression forces may assist in dispersing ferrous and non-ferrous particles941throughout the droplet940. In some cases, the compression force may be repeatedly applied and removed to disperse particles more evenly. FIG.10is a flowchart showing an example operation1000for dispersing particles in a microfluidic droplet. The operation1000is described below with respect to the microfluidic device900ofFIGS.9A-9B, however the operation1000may be performed by any other suitable system or device. The operation1000begins in block1002where a compression force is applied via mechanical actuation, to a microfluidic droplet that includes ferrous and/or non-ferrous particles941that are to be suspended. The compression force may be provided by a mechanical actuation force that may be applied to the first sheet910and/or the second sheet920and also to the droplet940. The compression force may cause the droplet940to deform or spread. Next, in block1004the compression force may be released or reduced to suspend the ferrous and/or non-ferrous particles941in the droplet940. The removal or reduction of the compression force may cause the microfluidic droplet940to return to a spherical or quasi-spherical shape that causes ferrous or non-ferrous particles to become at least partially suspended within the droplet940. In some cases, additional agitation of the microfluidic droplet may be desired to enhance the distribution of the particles in the microfluidic droplet940. To provide the additional agitation, a compression force may be repeatedly applied and removed (or reduced) for a predetermined number of cycles. Therefore, in block1006, the number of completed compression cycles is determined. A completed compression cycle may include the application and removal or reduction of a compression force. If the number of compression cycles is less than a predetermined number, then the operation1000may return to block1002. On the other hand, if the number of compression cycles is greater than or equal to the predetermined number, then the operation1000may end. In some examples, heating of a droplet may be desired as part of droplet analysis or assay. However, a droplet may move during a heating operation and may not remain centered or positioned over a heating element. In some cases, pinning posts may be used to control the position of the droplet. FIG.11Ashows a portion of another microfluidic device1100. As shown inFIG.11A, the microfluidic device1100may include a first sheet1110, a second sheet1120, a gap1130, and a heater1140. The first sheet1110, the second sheet1120, and the gap1130may be examples of the first sheet110, the second sheet120, and the gap130ofFIG.1A. The first sheet1110may include one or more pinning posts1150attached to a first surface1111of the first sheet1110. In some examples, the pinning posts1150may be attached to the second sheet1120. The second sheet1120may include a first surface1121and a second surface1122. The first surface1121may be disposed toward (e.g., adjacent to) the gap1130. As shown, the heater1140may be disposed on the second surface1122of the second sheet1120opposite the pinning posts1150. The pinning posts1150may provide features on the first surface1111with which a droplet1160may temporarily bind with and thereby limit the movement of the droplet1160. The droplet1160may initially be disposed away from the heater1140and the pinning posts1150. FIG.11B, shows another view of the microfluidic device1100. InFIG.11B, a compression force may be provided to the first sheet1110and/or the second sheet1120to decrease the gap1130and move the droplet1160toward the heater1140and the pinning posts1150. FIG.11Cshows another view of the microfluidic device1100. InFIG.11C, the droplet1160is positioned in contact with the pinning posts1150and the compression force removed. Thus, the first sheet1110and the second sheet1120may return to an initial position and the droplet1160is positioned over the heater1140. As the pinning posts1150engage with the droplet1160, movement of the droplet1160may be reduced. Reduced motion may be particularly advantageous when the droplet1160is undergoing a procedure, such as heating by the heater1140. FIG.12is a flowchart showing an example operation1200for manipulating a microfluidic droplet in conjunction with pinning posts. The operation1200is described below with respect to microfluidic device1100ofFIGS.11A-11C, however, the operation1200may be performed by any other suitable system or device. The operation1200begins in block1202as a microfluidic droplet1160is moved via mechanical manipulation to a region of the microfluidic device1100that includes pinning posts1150. The mechanical manipulation may include the use of compression forces as described with respect toFIGS.1A-1C and2. Next, in block1204the microfluidic droplet1160in the region of the pinning posts1150is heated. In some examples, the heat may be provided by the heater1140. Next, in block1206the microfluidic droplet1160may be moved, via mechanical manipulation, away from the region of the microfluidic device that includes the pinning posts1150. In some examples, a well may be disposed within a microfluidic device to contain and process a microfluidic droplet. One example is described in conjunction withFIGS.13A-13E and14. FIG.13Ashows a portion of a microfluidic device1300. As shown inFIG.13A, the microfluidic device1300may include a first sheet1310, a second sheet1320, and a gap1330. The first sheet1310, the second sheet1320, and the gap1330may be examples of the first sheet110, the second sheet120, and the gap130ofFIG.1A. In addition, the second sheet1320may include an opening1325that couples the gap1330to a heater1350. The heater1350may be formed in the shape of a well1355. Thus, the well1355may be coupled to the gap1330through the opening1325. As shown, a droplet1340may be positioned away from the opening1325. For ease of use, the second sheet1320may be disposed below (e.g., closer to the ground) than the first sheet1310. Such a configuration may allow gravity to assist in receiving or moving the droplet1340in the well1355. In some other examples, an opening and well may be disposed on the first sheet1310. In such configurations, surface tension and/or capillary action may cause the droplet1340to remain in the well, despite the well1355being inverted. FIG.13Bshows another view of the microfluidic device1300. InFIG.13B, the droplet1340is moved, via mechanical manipulation, toward the opening1325in the second sheet1320. For example, a compression force may be applied to the first sheet1310and/or the second sheet1320to reduce the gap1330and cause the droplet1340to move. FIG.13Cshows another view of the microfluidic device1300. InFIG.13C, the droplet1340within the well1355of the heater1350. The compression force may be removed or reduced allowing the first sheet1310and the second sheet1320to return to an initial position. The well1355may advantageously restrict movement of the droplet1340, particularly while being heated by the heater1350. FIG.13Dshows another view of the microfluidic device1300. InFIG.13D, the droplet1340is being drawn out of well1355of the heater1350via mechanical manipulation. For example, a compression force may be applied to the first sheet1310and/or the second sheet1320to reduce the gap1330and contact the droplet1340. In some examples, the compression force may be applied to a region of the microfluidic device1300associated with a direction to receive the droplet1340. FIG.13Eshows the compression force removed or reduced from the microfluidic device1300. The first sheet1310and the second sheet1320may return to an initial position and the droplet1340may be positioned away from the well1355and the heater1350. FIG.14is a flowchart showing an example operation1400for manipulating a microfluidic droplet in conjunction with a well. The operation1400is described below with respect to the microfluidic device1300ofFIGS.13A-13E, however the operation1400may be performed by any other suitable system or device. The operation begins in block1402as a microfluidic droplet is moved, via mechanical actuation, into a well. For example, a compression force may be applied to the first sheet1310or the second sheet1320to cause the microfluidic droplet1340into the well1355. Next, in block1404the microfluidic droplet1340may be heated in the well. For example, the heater1350may heat the microfluidic droplet1340within the well1355. Next, in block1406, the microfluidic droplet1340may be moved, via mechanical manipulation, away from the well. For example, a compression force may be applied to the first sheet1310and/or the second sheet1320to reduce the gap1330and cause the microfluidic droplet1340to come out of the well1355. FIG.15Ashows a portion of a microfluidic device1500. As shown inFIG.15A, the microfluidic device1500may include a first sheet1510, a second sheet1520, a gap1530, and an electrode1550. The first sheet1510, the second sheet1520, and the gap1530may be examples of the first sheet110, the second sheet120, and the gap130ofFIG.1A. The electrode1550may be coupled to electrical circuits and the like (not shown) that provide high energy electric fields associated with causing electroporation (the creation of temporary pores or openings within cell membranes). As shown, a droplet1540may be positioned away from the electrode1550. FIG.15Bshows another view of the microfluidic device1500. InFIG.15B, a compression force may be applied to the first sheet1510and/or the second sheet1520. The compression force (e.g., mechanical actuation) may reduce the gap1530and cause the droplet1540to move toward the electrode1550. FIG.15Cshows another view of the microfluidic device1500. InFIG.15C, the compression force is removed or reduced thereby allowing the first sheet1510and/or the second sheet1520to return to an initial position. The mechanical actuation ofFIG.15Bhas positioned the droplet1540on the electrode1550. The droplet1540may undergo electroporation using the electrode1550. FIG.16is a flowchart showing an example operation1600for providing electroporation. The operation1600is described with respect to the microfluidic device1500ofFIGS.15A-15C, however the operation1600may be performed by any other suitable system or device. The operation1600begins in block1602where a microfluidic droplet is moved, via mechanical actuation, onto an electroporation electrode. For example, a compression force may be applied to the first sheet1510and/or the second sheet1520to move the microfluidic droplet1540onto the electrode1550. Next, in block1604, the electrode1550provides an electric field to the microfluidic droplet1540. The electric field may be a high-power electric field provided by one or more circuits and devices. The electric field may temporarily provide openings or “pores” in the cell walls of cellular material within the microfluidic droplet1540. Next, in block1606, the microfluidic droplet is moved, via mechanical manipulation, away from the electrode. For example, compressive forces may be used in conjunction with the first sheet1510and the second sheet1520to move the microfluidic droplet away from the electrode1550. FIG.17shows an example microfluidic system1700. The microfluidic system1700may include a cartridge1710, a pressure actuator1720, a magnet1760, a heater1770, and a controller1780. In some examples, the pressure actuator1720, the magnet1760, the heater1770, and the controller1780may be included with a housing or base station that may couple to the cartridge1710. The cartridge1710may be an example of the microfluidic devices100,300,500,700,900,1100,1300, and1500ofFIGS.1,3,5,7,9,11,13, and15, respectively. The cartridge1710may include an input port1711, a first sheet1712, a second sheet1714, an optical sensor1718, one or more pinning posts1730, one or more electrodes1740and a first heater1750. The first sheet1712and the second sheet1714may be hydrophobic and oleophobic sheets or may include a hydrophobic and oleophobic layer on one or more surfaces. The first heater1750may be coupled to a gap1716through an opening1715in and the second sheet1714. The first heater1750may form a well1755. One or more droplets may be inserted into the cartridge1710through the input port1711. Although only one input port1711is shown, in other examples the cartridge1710may include any feasible number of input ports. The pressure actuator1720may contact or otherwise be coupled to the cartridge1710. As shown, the pressure actuator1720may be coupled to the first sheet1712. In other examples, the pressure actuator1720may be coupled to the second sheet1714. The pressure actuator1720may also be coupled to the controller1780. The controller1780may cause the pressure actuator1720to selectively apply one or more compressive forces to the first sheet1712and/or the second sheet1714. The compressive forces may manipulate the position of any droplets within the gap1716. The optical sensor1718may detect the presence and/or location of a droplet (e.g., a microfluidic droplet) within the gap1716. The optical sensor1718may be coupled to the controller1780. In this manner, data from the optical sensor may be used to guide or direct the pressure actuator1720. The magnet1760may be disposed adjacent to or on the cartridge1710. Operation of the magnet1760may be controlled by the controller1780. Similarly, a second heater1770may be disposed adjacent to, or on the cartridge1710and may also be controlled by the controller1780. The controller1780may control operations of the microfluidic system1700. Thus, the controller1780may control operations of the pressure actuator1720, the magnet1760, the first and second heaters1750and1770and the one or more electrodes1740to perform one or more operations described herein. FIG.18Ashows a portion of another microfluidic device1800. The microfluidic device1800may include a first sheet1810, a second sheet1820, and a stylus1850. The first sheet1810may be separated from the second sheet1820by a gap1830. The first sheet1810, the second sheet1820and the gap1830may be other examples of the first sheet110, the second sheet120and the gap130ofFIG.1A. The stylus1850may selectively provide a compression force to either the first sheet1810or the second sheet1820(as shown, the stylus1850is selectively providing a compression force to the first sheet1810). The compression force from the stylus1850may selectively reduce the gap1830in some regions of the microfluidic device1800to move a droplet1840as described above in conjunction withFIGS.1-17. For example, a position and compression force of the stylus1850may be controlled by the controller1780ofFIG.17. In some examples, the stylus tip area may be selected to correspond to an anticipated size of a droplet1840. The droplet1840may be any feasible droplet, including any feasible microfluidic droplet. Thus, the droplet1840may be between 10−6and 10−15liters. Furthermore, in some examples, the tip of the stylus may be shaped or treated to avoid scratching and/or abrading the surface of the first sheet1810or the second sheet1820. For example, the tip of the stylus1850may include a roller to apply the compression force to the first sheet1810. In some other examples, the tip of the stylus1850may be coated with a lubricant. FIG.18Bshows the stylus1850and possible associated end profiles1860. The end profiles1860are not meant to be limiting (e.g., the end profiles1860are not an exhaustive listing of all possible end profiles) but are instead meant to be exemplary. Thus, other end profiles for the stylus1850are possible. Some end profiles1860may more effectively move or manipulate the droplet1840. For example, circular, rectangular, or oval profiles may more effectively move the droplet1840. FIG.19Ashows a portion of another microfluidic device1900. The microfluidic device1900may include a first sheet1910, a second sheet1920, a gap1930, and a stylus1950which may be examples of the first sheet1810, the second sheet1820, the gap1830, and the stylus1850ofFIG.18A. The stylus1950may include an insulated and/or exposed electrode1955. In some examples, the electrode1955may be disposed toward a tip of the stylus1950that may contact at least one of the first sheet1910or the second sheet1920. In some examples, the electrode1955may be provided a voltage (e.g., an electric potential) that attracts the droplet1940. When the stylus1950is placed in contract with at least one of the sheets of the microfluidic device1900(shown here as the first sheet1910), the associated sheet can perform as or be a hydrophobic and oleophobic dielectric separating the electrode1955from the droplet1940. The applied or provided voltage may be sufficient to affect or control surface tension of the droplet1940. In this manner, the stylus1950may attract and/or move the droplet1940in the gap1930without applying a compression force, but instead by providing a voltage to the electrode1955, and then moving the position of the stylus1950with respect to the first and second sheets1910and1920, respectively. FIG.19Bshows another view of the microfluidic device1900. As shown, the stylus1950may be moved planarly with respect to the first sheet1910and the second sheet1920. When the stylus1950is moved planarly while the electrode1955is energized with a sufficient voltage, the droplet1940may move to follow the stylus1950. Thus, any of the droplet manipulations described with respect toFIGS.1-17may be performed by energizing the electrode1955and moving the stylus1950instead of using a compressive force. FIG.20is a flowchart showing an example operation2000for manipulating a microfluidic droplet. The operation2000is described with respect to the microfluidic device1900ofFIGS.19A and19B, however the operation2000may be performed by any other suitable system or device. The operation2000begins in block2002as an electric potential is provided to an electrode disposed or coupled to a stylus. For example, a voltage may be provided to the electrode1955that is disposed on or near a tip of the stylus1950. In addition, the stylus1950may be in contact with at least one sheet (e.g., the first sheet1910or the second sheet1920) of the microfluidic device1900. The applied or provided voltage may be sufficient to affect or control surface tension of the droplet1940. Next, in block2004, the stylus is moved. For example, the stylus1950may be moved relative to the first sheet1910and the second sheet1920. Since a sufficient voltage is applied or provided to the electrode1955(in block2002), the droplet1940may move in response to motion of the stylus1950. Next, in block2006, the voltage or potential is removed from the electrode. For example, in block2004the stylus1950may be moved to position the droplet1940into a predetermined treatment zone. Since the movement is complete, the voltage or potential may be removed from the electrode1955. FIG.21Ashows a portion of another microfluidic device2100. The microfluidic device2100may include a first sheet2110, a second sheet2120, a gap2130, a stylus2150, and an electrode2155which may be examples of the first sheet1910, the second sheet1920, the gap1930, the stylus1950, and the electrode1955ofFIG.19A. In contrast to the microfluidic device1900, the microfluidic device2100may use a combination of a compression forces and applied voltages to manipulate a droplet2140. As shown, the stylus2150may be positioned to one side of the droplet2140. To move the droplet2140, the stylus2150may provide a compression force to reduce the gap2130while a voltage is provided to the electrode2155. In this manner, the droplet2140may be moved by a combination of compressive and electromotive (e.g., voltage) forces. For example, while the stylus2150is providing a compression force and a voltage is applied to the electrode2155, the stylus2150may be moved to change the position or location of the droplet2140within the gap2130. The compression force may be provided to either the first sheet2110or the second sheet2120.FIG.21Ashows one example as the stylus2150provides a compression force to the first sheet2110. FIG.21Bshows another view of the microfluidic device2100. In this view, the stylus2150has been moved to a new position with respect to the first sheet2110and the second sheet2120. The droplet2140has been moved in response to previously provided compression and voltage provided by and to the stylus2150. Thus, inFIG.21Bthe compression force is removed from the first sheet2110and the voltage is removed from the electrode2155. FIG.22is a flowchart showing an example operation2200for manipulating a microfluidic droplet. The operation2200is described with respect to the microfluidic device2100ofFIGS.21A and21B, however the operation2200may be performed by any other suitable system or device. The operation may begin in block2202as a compression force is applied, via mechanical actuation, to at least one of the sheets of a microfluidic device. For example, the stylus2150may provide a compression force to the first sheet2110and reduce the gap2130near a droplet2140. The reduced gap may manipulate, at least in part, the droplet2140between the first sheet2110and the second sheet2120. Next, in block2204an electric potential is provided to an electrode disposed or coupled to the stylus. For example, a voltage may be provided to the electrode2155that is disposed on or near the tip of the stylus2150. The stylus2150may be in contact with at least one sheet of the microfluidic device2100. The applied or provided voltage may be sufficient to affect or control surface tension of the droplet2140. Next, in block2206, the stylus is moved. For example, the stylus2150may be moved relative to the first sheet2110and the second sheet2120. In this manner, the droplet2140may be manipulated or moved using a combination of compression forces provided by the stylus2150and a voltage applied to the electrode2155. Next, in block2208the electric potential is removed from the electrode. For example, a voltage may be removed from the electrode2155. Then, in block2210the compression force is removed from at least one sheet of the microfluidic device. For example, the stylus2150may be moved away from the first sheet2110or the second sheet2120. Because the droplet2140has been moved into a predetermined (e.g., desired) position in block2206, the compression force and voltage may be removed from the stylus2150. In some examples, ferrous particles may be suspended within a microfluidic droplet to assist with processing or assaying. After one or more processing steps have been completed, the ferrous particles may be removed from the droplet for further processing. FIG.23Ashows a portion of another microfluidic device2300. The microfluidic device2300may include a first sheet2310, a second sheet2320, a gap2330, and a stylus2350which may be examples of the first sheet1910, the second sheet1920, the gap1930, and the stylus1950ofFIG.19A. In addition, the stylus2350may include a magnet2356. The magnet2356may be controllable. For example, the magnet2356may be an electromagnet that may be enabled and disabled through a control voltage. In another example, the magnet2356may be movable. Thus, the magnet2356may be moved toward a tip of the stylus2350(as shown) or away from the tip of the stylus2350(not shown). In this manner, magnetic field strength at or near the tip of the stylus2350may be controlled and/or variable. A plurality of ferrous particles2341may be distributed (suspended) throughout a droplet2340. FIG.23Bshows another view of the microfluidic device2300. In this view, the magnet2356is activated or enabled. For example, the magnet2356may be an electromagnet that may be enabled through the application of power. In another example, the magnet2356may be a permanent magnet that may be moved toward the droplet2340. The magnet2356may attract or cause the ferrous particles2341to collect into one or more ferrous beads2342. Thus, the ferrous particles2341may come out of suspension from the droplet2340. FIG.23Cshows another view of the microfluidic device2300. While the magnet2356is activated or enabled, the stylus2350is moved. The movement of the stylus2350may filter or remove the ferrous beads2342from the droplet2340. FIG.24is a flowchart showing an example operation2400for removing suspended ferrous particles from a microfluidic droplet. The operation2400is described with respect to the microfluidic device2300ofFIGS.23A-23C, however the operation2400may be performed by any other suitable system or device. The operation2400begins in block2402as a stylus with a magnet is moved to a region proximate to a droplet with suspended ferrous particles. For example, a stylus2350with a magnet2356may be moved near a droplet2340that includes suspended ferrous particles2341. Next, in block2404a magnet within or on the stylus is enabled. For example, the magnet2356may be an electromagnet that may be enabled through the application of power. In another example, the magnet2356may be moved toward the tip of the stylus2350. In this manner, the magnet2356may cause the ferrous particles2341to fall out of suspension and collect toward the magnet2356. In some cases, the collected ferrous particles2341may form a ferrous bead2342. Next, in block2406, the stylus may be moved away from the droplet. For example, moving the stylus2350may move the ferrous bead2342out of the droplet2340thereby filtering the ferrous particles2341out of the droplet2340. In some examples, ferrous material may be placed back into suspension within a droplet through mechanical actuation. Another such example is described below in conjunction withFIGS.25-26. FIG.25Ashows a portion of another microfluidic device2500. The microfluidic device2500may include a first sheet2510, a second sheet2520, a stylus2550, and a magnet2556. The first sheet2510, the second sheet2520, the stylus2550, and the magnet2556may be examples of the first sheet2310, the second sheet2320, the gap2330, the stylus2350and the magnet2356ofFIG.23A. In some examples, the magnet2556may be disengaged by either moving the magnet2556away from the tip of the stylus2550or by removing power if the magnet2556is an electromagnet. A droplet2540may include non-dispersed ferrous or non-ferrous particles. A compression force may be applied to the first sheet2510and/or the second sheet2520(not shown) that can compress or deform the droplet2540. In some cases, a compression force may be applied to a center or middle of the droplet2540by the stylus2550. FIG.25Bshows another view of the microfluidic device2500. The compression force may be removed or reduced from the first sheet2510and/or the second sheet2520. Removal or release of the compression force may allow the droplet2540to return to a non-compressed or non-deformed state. Transitioning from a compressed to a non-compressed state (or vice-versa) may cause one or more ferrous or non-ferrous particles2541within the droplet2540to become suspended. In some cases, the compression force may be applied and/or removed quickly or abruptly. Sudden application and/or removal of compression forces may assist in dispersing ferrous and non-ferrous particles2541throughout the droplet2540. In some cases, the compression force may be repeatedly applied and removed to disperse particles more evenly. FIG.26is a flowchart showing an example operation2600for dispersing particles in a microfluidic droplet. The operation2600is described below with respect to the microfluidic device2500ofFIGS.25A and25B, however the operation2600may be performed by any other suitable system or device. The operation2600begins in block2602where a magnet is disabled. For example, the magnet2556may be disabled either by moving the magnet2556away from the tip of the stylus2550or by removing power from an electromagnet comprising magnet2556. Next, in block2604a compression force is applied via mechanical actuation, to a microfluidic droplet that includes ferrous and/or non-ferrous particles that are to be suspended. For example, a compression force may be provided by a mechanical actuation force that may be applied by the stylus2550to the first sheet2510and/or the second sheet2520and also to the droplet2540. The compression force may cause the droplet2540to deform or spread. Next, in block2606the compression force may be released or reduced to suspend the ferrous and/or non-ferrous particles in the droplet. For example, the removal or reduction of the compression force may cause the microfluidic droplet2540to return to a spherical or quasi-spherical shape that causes ferrous or non-ferrous particles to become at least partially become suspended within the droplet2540. In some cases, additional agitation of the microfluidic droplet may be desired to enhance the distribution of the particles in the microfluidic droplet2540. To provide the additional agitation, a compression force may be repeatedly applied and removed (or reduced) for a predetermined number of cycles. Therefore, in block2608, the number of completed compression cycles is determined. A completed compression cycle may include the application and removal or reduction of a compression force. If the number of compression cycles is less than a predetermined number, then the operation2600may return to block2604. On the other hand, if the number of compression cycles is greater than or equal to the predetermined number, then the operation2600may end. Next, in block2604a compression force is applied via mechanical actuation, to a microfluidic droplet that includes ferrous and/or non-ferrous particles2541that are to be suspended. The compression force may be provided by a mechanical actuation force that may be applied to the first sheet2510and/or the second sheet2520through the stylus2550. The compression force may cause the droplet2540to deform or spread. Next, in block2604the compression force may be released or reduced to suspend the ferrous and/or non-ferrous particles2541in the droplet2540. The removal or reduction of the compression force may cause the droplet2540to return to a spherical or quasi-spherical shape that causes ferrous or non-ferrous particles to become at least partially become suspended within the droplet2540. In some examples, a stylus may include or be coupled to a reservoir or other liquid container that may be used to hold liquids aspirated from a gap of a microfluidic device. Example devices are described below in conjunction withFIGS.27-38. FIG.27Ashows a portion of another microfluidic device2700. The microfluidic device2700may include a first sheet2710, a second sheet2720, and a gap2730. The first sheet2710, the second sheet2720, and the gap2730may be examples of the first sheet1910, the second sheet1920, and the gap1930ofFIG.19A. The first sheet2710may include a pre-slit septa or other configurable opening (not shown) that may enable a droplet2740to be aspirated (removed) from the gap2730. FIG.27Bshows another view of the microfluidic device2700. A septa2711may be included on one of the sheets of the microfluidic device2700. As shown, the septa2711is located on (included with) the first sheet2710. In some examples, the septa2711may remain closed under most operating conditions. For example, a compressive force may be applied to the first sheet2710near the septa2711. However, the septa2711may remain substantially closed under the application of the compressive force. In other words, the septa2711may have a closing force to prevent liquid from “leaking” from the first sheet2710. The droplet2740may be moved under the septa2711. FIG.27Cshows another view of the microfluidic device2700. A stylus2750may be positioned substantially over the septa2711. The stylus2750may include a lumen2751that may be coupled to the septa2711and configured to receive the droplet2740. In some examples, a negative pressure may be provided to and/or through the stylus2750to aspirate the droplet2740through the septa2711and into the stylus2750. The stylus2750may now move the droplet2740to other locations within the microfluidic device2700. FIG.28is a flowchart showing an example operation2800for aspirating liquids in a microfluidic device. The operation2800is described below with respect to the microfluidic device2700ofFIGS.27A-27C, however the operation2800may be performed by any other suitable system or device. The operation2800begins in block2802where a droplet is disposed adjacent to a septa. For example, the droplet2740may be moved to be substantially under the septa2711though any feasible operation disposed herein. Next, in block2804a stylus is moved over the septa. For example, the stylus2750may be moved to be over the septa2711. The stylus2750may include a lumen2751that may couple to the septa2711. Next, in block2806, a droplet is aspirated into the stylus. For example, a negative pressure may be applied by or through the stylus2750. The negative pressure may draw the droplet2740into the lumen2751. In some examples, liquid may be provided or returned to a microfluidic device through a septa. Some examples are described below in conjunction withFIGS.29and30. FIG.29Ashows a portion of another microfluidic device2900. The microfluidic device2900may include a first sheet2910, a second sheet2920, a gap2930, and a stylus2950. The first sheet2910, the second sheet2920, the gap2930, and the stylus2950may be examples of the first sheet2710, the second sheet2720, the gap2730, and the stylus2750ofFIG.27A. Thus, first sheet2910may include a septa2911. In some examples, liquid that may be included within the stylus2950may be injected through the septa2911and into the gap2930. Prior to injecting the liquid, the stylus2950may be positioned over the septa2911. In some examples, a lumen2951of the stylus2950may be coupled to the septa2911. A positive pressure may be applied to the lumen2951to push the liquid out of the stylus2950and form a droplet2940within the gap2930. Thus, the applied pressure may overcome a closing force of the septa2911. FIG.29Bshows another view of the microfluidic device2900. The stylus2950may be moved away from the droplet2940. Furthermore, a compressive force may be provided by the stylus2950to the first sheet2910(and/or the second sheet2920) to reduce the gap2930. The reduced gap2930may cause the droplet2940to move relative to the first sheet2910and the second sheet2920. FIG.29Cshows another view of the microfluidic device2900. The stylus2950may move to move the droplet2940. After the motion of the droplet2940is complete, then the stylus2950may be positioned to remove the compression source to the first sheet2910and/or the second sheet2920. Thus, the stylus2950may operate as a pipette to move liquids (e.g., the droplet2940) within the microfluidic device2900. FIG.30is a flowchart showing an example operation3000for manipulating liquids in a microfluidic device. The operation3000is described below with respect to the microfluidic device2900ofFIGS.29A-29C, however the operation3000may be performed by any other suitable system or device. The operation3000begins in block3002where a droplet is dispensed from a stylus through a septa and into a gap of a microfluidic device. For example, the stylus2950may be positioned over the septa2911. A positive pressure may be applied to the stylus2950and/or lumen2951to inject a liquid through the septa2911into the gap2930. Next, in block3004the distance between the two sheets is selectively reduced, via mechanical actuation, near the microfluidic droplet. For example, the reduced distance may result in a reduced gap2930between the first sheet2910and the second sheet2920. In some examples, a compression force may be provided by the stylus2950adjacent to (e.g., next to) one side of the droplet2940. The compression force may reduce the gap2930causing the droplet2940to move toward the compression force. In some variations, the compression force may deform one end of the droplet2940. Next, in block3006the distance between the two sheets is restored. For example, the compression force applied in block3004may be removed allowing the first sheet2910and/or the second sheet2920to return to its initial separation distance. In some examples, the distance between first sheet2910and second sheet2920is returned to a distance similar to the initial separation distance associated with block3602. In some examples, a stylus may include additional devices or systems that may be used to process a droplet within the stylus. Some examples are described below in conjunction withFIGS.31-38. FIG.31Ashows a portion of another microfluidic device3100. The microfluidic device3100may include a first sheet3110, a second sheet3120, a gap3130, and a stylus3150. The first sheet3110, the second sheet3120, and the gap3130may be examples of the first sheet1810, the second sheet1820, and the gap1830ofFIG.18A. The stylus3150may include a temperature control element3155. Through the temperature control element3155, any liquid that is aspirated from the gap3130may be heated within the stylus3150as part of a chemical assay or other protocol or process. For example, a droplet3140may be disposed beneath a septa3111that is included in the first sheet3110. The stylus3150may be disposed over the septa3111. In some examples, the temperature control element3155may provide heating or cooling to surrounding area based on a control voltage, signal, or the like. FIG.31Bshows another view of the microfluidic device3100. The droplet3140may be aspirated from the gap3130, through the septa3111, and into the stylus3150. In this manner, while the droplet3140is within the stylus3150, the droplet3140may undergo temperature processing as provided by the temperature control element3155. In some examples, a temperature sensor (not shown) may be included with the stylus3150and/or the temperature control element3155. A controller (not shown) may monitor and control the temperature of the droplet3140as part of the temperature processing. For example, the controller may monitor the temperature of the droplet3140and control the temperature provided by the temperature control element3155. FIG.31Cshows another view of the microfluidic device3100. After temperature processing, the droplet3140may be injected into the gap3130through the septa3111in the first sheet3110. FIG.32is a flowchart showing an example operation3200for thermally treating liquids in a microfluidic device. The operation3200is described below with respect to the microfluidic device3100ofFIGS.31A-31C, however the operation3200may be performed by any other suitable system or device. The operation begins in block3202where a stylus is positioned over a septa and a droplet. For example, the stylus3150may be positioned over the septa3111which is over a droplet3140. Next, in block3204, the droplet is aspirated into the stylus through the septa. For example, a negative pressure may be provided to the stylus3150. In response, the droplet3140may be drawn through the septa3111and into the stylus3150. Next, in block3206, the temperature of the droplet is controlled. For example, a temperature control element3155may be used to monitor and control the temperature of the droplet3140which is contained within the stylus3150. Next, in block3208, the droplet is injected into the gap through the septa. For example, temperature processing may be complete. A positive pressure may be provided to the stylus3150causing the droplet3140to be injected though the septa3111and into the gap3130. In some examples, the stylus3150may be repositioned with respect to the first sheet3110and/or the second sheet3120prior to returning the droplet3140to the gap3130. FIG.33shows a portion of another microfluidic device3300. The microfluidic device3300may include a first sheet3310, a second sheet3320, a gap3330, and a stylus3350. The first sheet3310, the second sheet3320, and the gap3330may be examples of the first sheet1810, the second sheet1820, and the gap1830ofFIG.18A. The stylus3350may include a temperature control element3355. The temperature control element3355may be disposed toward a portion of the stylus3350that may contact the first sheet3310. The stylus3350and the temperature control element3355are positioned on the first sheet3310over a droplet3340. In this manner, the temperature control element3355, may provide heat for any temperature controlled processing to the droplet3340through the first sheet3310. In some examples, the temperature control element3355may include a temperature sensor (not shown). In this manner a controller (also not shown) may control the temperature of the droplet3340to be within a desired temperature. FIG.34Ashows a portion of another microfluidic device3400. The microfluidic device3400may include a first sheet3410, a second sheet3420, a gap3430, and a stylus3450. The first sheet3310, the second sheet3320, and the gap3330may be examples of the first sheet1810, the second sheet1820, and the gap1830ofFIG.18A. The stylus3450may include a light sensor3455and a light source3456. In some examples, a reaction that may have occurred or be occurring within a droplet3440may be monitored by sensing light that may be transmitted or reflected through the droplet3440. Thus, the droplet3440may be drawn into the stylus3450where transmitted and/or reflected light can be detected and/or measured. The amount of detected light may be associated with the progress or completion of a reaction. In some examples, to measure a reaction, the stylus3450may be positioned over a septa3411that is included in the first sheet3410. Additionally, the droplet3440may be located under the septa3411. FIG.34Bshows another view of the microfluidic device3400. As shown, the droplet3440may be aspirated through the septa3411and into the stylus3450. The light source3456may emit light into the droplet3440. The light source3456may be any feasible solid state and/or incandescent light source. The light may be reflected and/or transmitted through the droplet3440. This light may be detected by the light sensor3455. The light sensor3455may be any feasible light sensor or detector such as a photo diode or the like. The amount of detected light may be associated with the progress or completion of a reaction. In this manner, the detected light may indicate the progress or completion of a reaction. FIG.34Cshows another view of the microfluidic device3400. As shown, the droplet3440may be returned to the gap3430. In some examples, the stylus3450may inject the droplet3440through the septa3411in the first sheet3410. In this manner, after determining the light transmission or refraction of the droplet3440, the droplet3440may be returned to the gap3430for other processing. FIG.35is a flowchart showing an example operation3500for performing a reaction measurement. The operation3500is described below with respect to the microfluidic device3400ofFIGS.34A-34C, however the operation3500may be performed by any other suitable system or device. The operation begins in block3502where a stylus is positioned over a septa and a droplet. For example, the stylus3450may be positioned over the septa3411which is over a droplet3440. Next, in block3504, the droplet is aspirated into the stylus through the septa. For example, a negative pressure may be provided to the stylus3450. In response, the droplet3440may be drawn through the septa3411and into the stylus3450. Next, in block3506, the reaction of the droplet is monitored. For example, a light source3456may be used to emit light in the stylus3450and into the droplet3440. A light sensor3455may detect transmitted and/or reflected light from the droplet3440. In some cases, the transmitted and/or reflected light may be associated with an amount of progress of a reaction occurring within the droplet3440. Next, in block3508, the droplet is injected into the gap through the septa. For example, reaction monitoring may be complete. A positive pressure may be provided to the stylus3450causing the droplet3440to be injected though the septa3411and into the gap3430. In some examples, the stylus3450may be repositioned with respect to the first sheet3410and/or the second sheet3420prior to returning the droplet3440to the gap3430. FIG.36shows a portion of another microfluidic device3600. The microfluidic device3600may include a first sheet3610, a second sheet3620, a gap3630, and a stylus3650. The first sheet3610, the second sheet3620, and the gap3630may be examples of the first sheet1810, the second sheet1820, and the gap1830ofFIG.18A. The stylus3650may include a light source3655. The light source3655may be disposed toward a portion of the stylus3650that may contact the first sheet3610. Opposite the light source3655may be a light detector3621. As shown, the light detector3621may be disposed on the second sheet3620. When a droplet3640is disposed between the light source3655and the light detector3621, the light detector3621may detect transmitted and/or reflected light. Thus, the light source3655and the light detector3621may monitor progress of a reaction, similar to as described with respect toFIGS.34and35. In some examples the position of the light source3655and the light detector3621may be reversed. In other words, the light sensor3621may be included with the stylus3650and the light source3655may be disposed on the second sheet3620. FIG.37Ashows a portion of another microfluidic device3700. The microfluidic device3700may include a first sheet3710, a second sheet3720, a gap3730, and a stylus3750. The first sheet3710, the second sheet3720, and the gap3730may be examples of the first sheet1810, the second sheet1820, and the gap1830ofFIG.18A. The stylus3750may include a sonication probe3755. In some examples, the sonication probe3755may deliver sonic and/or ultrasonic stimulation to a droplet3740. The sonication probe3755may be any feasible piezo-electric device. In some examples, to deliver sonic or ultrasonic stimulation, the stylus3750may be positioned over a septa3711that is included in the first sheet3710. Additionally, the droplet3740may be located under the septa3711. FIG.37Bshows another view of the microfluidic device3700. As shown, the droplet3740may be aspirated through the septa3711and into the stylus3750. Once the droplet3740is in the stylus3750, the sonication probe3755may be activated or enabled allowing sonic and/or ultrasonic waves to be provided to the droplet3740. The delivery sonic stimulation may be controlled by a controller (not shown). FIG.37Cshows another view of the microfluidic device3700. As shown, the droplet3740may be returned to the gap3730. In some examples, the stylus3750may inject the droplet3740through the septa3711in the first sheet3710. In this manner, after delivering sonic stimulation to the droplet3740, the droplet3740may be returned to the gap3730for other processing. FIG.38is a flowchart showing an example operation3800for performing a sonic treatment. The operation3800is described below with respect to the microfluidic device3700ofFIGS.37A-37C, however the operation3800may be performed by any other suitable system or device. The operation begins in block3802where a stylus is positioned over a septa and a droplet. For example, the stylus3750may be positioned over the septa3711which is over a droplet3740. Next, in block3804, the droplet is aspirated into the stylus through the septa. For example, a negative pressure may be provided to the stylus3750. In response, the droplet3740may be drawn through the septa3711and into the stylus3750. Next, in block3806, the sonic treatment may be delivered to the droplet. For example, the sonication probe3755may deliver sonic and/or ultrasonic treatment to the droplet3740. Next, in block3808, the droplet is injected into the gap through the septa. For example, sonic treatment may be complete. A positive pressure may be provided to the stylus3750causing the droplet3740to be injected though the septa3711and into the gap3730. In some examples, the stylus3750may be repositioned with respect to the first sheet3710and/or the second sheet3720prior to returning the droplet3740to the gap3730. FIG.39shows a block diagram of a device3900that may be one example of the any microfluidic device or system described herein. The device3900may include a pressure actuator3920, one or more magnets3922, one or more heaters3924, one or more electrodes3926, an optical sensor3927, a light source and sensor3928, a sonic device3929, a processor3930, and a memory3940. In some examples, the pressure actuator3920, which is coupled to the processor3930, may be used to provide forces, including compression and actuation forces to one or more sheets of a microfluidic cartridge. In some examples, the pressure actuator3920may use mechanical, pneumatic, and/or electrical actuators to provide the compression and/or actuation forces. The compression and/or actuation forces may be provided through a controllable stylus. In some other examples, the pressure actuator3920may provide positive and/or negative pressure to a lumen of a stylus. In this manner a droplet may be aspirated from a gap of a microfluidic device and drawn into the stylus. The one or more magnets3922, which are also coupled to the processor3930, may be used to selectively provide magnetic fields that may be used for and during microfluidic droplet manipulation. In some examples the magnet may be disposed adjacent to a side of a hydrophobic and oleophobic sheet. In some other examples, the magnet may be disposed within a stylus. The one or more heaters3924, which are also coupled to the processor3930, may be used to provide heat to one or more microfluidic droplets. The heat may be used during analysis or assay of the microfluidic droplets. In some examples the heater (e.g., heating element) may be disposed adjacent to a side of a hydrophobic and oleophobic sheet. In some other examples, the heater may be disposed within a stylus. The one or more electrodes3926, which are also coupled to the processor3930, may be used to provide electric fields used for electroporation. In some examples, the processor3930may include one or more electrical circuits or devices to generate large magnitude electric fields for the one or more electrodes3926. The optical sensor3927, which is also coupled to the processor3930, may detect the presence and/or position of any droplet, such as any microfluidic droplet disposed between two or more hydrophobic and oleophobic sheets. The light source and sensor3928, which are also coupled to the processor3930, may provide light and detect a transmitted or reflected light associated with a microfluidic droplet. In some examples, the light source and sensor3928may be included with a stylus. In some other examples, the light source and sensor3928may be disposed on a side of a hydrophobic and oleophobic sheet and the stylus. The sonic device3929, which is also coupled to the processor3930, may provide sonic or ultrasonic treatment to a microfluidic droplet. In some examples, the sonic device3929may be included with the stylus. In some examples, the sone device3929may be a piezo electric device. The processor3930, which is also coupled to the memory3940, may be any one or more suitable processors capable of executing scripts or instructions of one or more software programs stored in the device3900(such as within the memory3940). The memory3940may include septa location data3941. In some examples, the septa location data3941may be a database of the locations of one or more septa openings that may be disposed on a hydrophobic and oleophobic sheet. Thus, the processor3930may use the septa location data3941to position the stylus over any particular septa. The memory3940may also include a non-transitory computer-readable storage medium (e.g., one or more nonvolatile memory elements, such as EPROM, EEPROM, Flash memory, a hard drive, etc.) that may store the following software modules: a pressure actuator control module3942to control the pressure actuator3920; a magnet control module3944to control the one or more magnets3922; a heater control module3946to control the one or heaters3924; an electrode control module3948to control the one or more electrodes3926; an optical sensor control module3949to control the optical sensor3927; a sonic control module3950to control sonic device3929; and a light source and sense control module3951. Each software module includes program instructions that, when executed by the processor3930, may cause the device3900to perform the corresponding function(s). Thus, the non-transitory computer-readable storage medium of memory3940may include instructions for performing all or a portion of the operations described herein. The processor3930may execute the pressure actuator control module3942to manipulate one or more microfluidic droplets disposed between at least two hydrophobic and oleophobic sheets by applying forces through the pressure actuator3920. For example, execution of the pressure actuator control module3942may cause compressive, pinning, and/or actuation forces to be applied to at least one of the hydrophobic and oleophobic sheets. The forces may be selectively applied to move, separate, combine, and/or mix one or more microfluidic droplets. In some examples, execution of the pressure control module3942may cause a stylus to move across at least one of the hydrophobic and oleophobic sheets, apply a compression force, and cause a droplet to move. The processor3930may execute the magnet control module3944to selectively control, enable, and/or disable one or more magnets3922. In some examples, execution of the magnet control module3944may cause power to be applied to electromagnets included in the magnets3922. In some examples, execution of the magnet control module3944may cause one or more magnets3922to be moved closer to, or away from, one or more microfluidic droplets. The processor3930may execute the electrode control module3948to selectively provide electric fields to the one or more electrodes. For example, execution of the electrode control module3948may provide one or more large magnitude electric fields to the electrodes3926and cause electroporation to occur on cell membranes within the microfluidic droplet. The processor3930may execute the optical sensor control module3949to control and processes data from the optical sensor3927. For example, execution of the optical sensor control module3949may cause the optical sensor3927to receive or capture image data as well as causing the processor3930to process the image data and determine the presence and/or location of any droplets. In some examples, the processor3930may use image data from the optical sensor3927to control actions of the pressure actuator3920. For example, the processor3930may process the image data with the pressure actuator control module3942and thereby guide the application of compressive forces on one or more hydrophobic and oleophobic sheets. The processor3930may execute the sonic control module3950to control the sonic device3929. For example, execution of the sonic control module3950may activate or enable the sonic device3929thereby allowing or enabling the sonic device3929to provide sonic and/or ultrasonic stimulation or treatment to a droplet. The processor3930may execute the light source and sense control module3951to control the light source and sensor3928. For example, execution of the light source and sense control module3951may cause light to be emitted by a light source and transmitted or reflected light to be sensed by a light detector. In this manner, a reaction or process may be detected in accordance with the detected light. Cartridges As mentioned above, the cartridges described herein may generally include a first (e.g., upper) sheet that is elastically deformable, a second (e.g., lower) sheet, and a frame separating the two to form an air gap. The first sheet may be an elastomeric material, such as a polyester (e.g., TPE) natural rubber, synthetic rubber, nitrile rubber, silicone rubber, urethane rubbers, chloroprene rubber, Ethylene Vinyl Acetate (EVA), etc. The second sheet may be the same of a different material. The sheets of the cartridge are generally planar structures and may be a membrane, a layer, etc. The first and second sheets may be held in tension over or against the frame. In some examples, multiple frames may be used. The frame may be formed of any appropriate material, such as a rigid semi-rigid polyester. FIGS.40A-40Dillustrate examples of a cartridge4006,4006′ as described herein. The cartridge includes a frame4017, a first sheet4007and a second sheet4009. In the example shown inFIGS.40A,40C and40D, the cartridge is divided into three lanes4005,4005′,4005″. In this example the frame is configured as a divider with the three separate lanes. The example cartridge shown inFIG.40Bhas eight lanes4015. Any appropriate number of lanes may be used (e.g., 1 lane, 2 lanes, 3 lanes, 4 lanes, 5 lanes, 6 lanes, 7 lanes, 8 lanes, 9 lanes, 10 lanes, 12 lanes, 15 lanes, 16 lanes, or more). The sectional view of a cartridge shown inFIGS.40C-40Dillustrates an example with three lanes formed by the frame/divider4017. The first sheet4007is held in tension to the top of the frame, e.g., by welding and/or an adhesive4013. The second sheet4009in this example is also held in tension on the frame and is welded and/or adhesively attached thereto. An air gap4011is formed between the first sheet and the second sheet. InFIGS.40C and40D, the portion of the cartridge is shown attached to a seating portion of a mechanical microfluidics actuator having a recessed region and a plurality of vacuum ports for sealing the second (bottom) sheet into the seating region to make a tight thermal connection between the second sheet and the seating region. Sealing the second sheet4009to the seat also expands the air gap4011to a larger height as compared to the unattached configuration of the cartridge, as shown inFIG.40D. In the example shown inFIGS.40A-40E, the initial height of the air gap may be between about 0.5 mm and about 5 mm. In general, the height may be between 0.1 mm and about 7 mm, and may be adjusted down or, as inFIGS.40C and40D, up. For example, compressing the first and/or second sheet to form a 0.5 mm air gap height from a neutral height of about 3 mm has been found to be very effective for mobility of droplets. In some examples the neutral height of the air gap may be about 3 mm in height (spacing between the first and second sheets) which has been found to be effective to move droplets without significant damage to the films tested, as compared to larger gap spacing. At a height of about 3 mm, a larger droplet (e.g., 140 uL aqueous+80 uL drop gloss) can touch the top film with a small amount of compression. However, the height of the gap may be adjusted based on the volume of the droplet, and the materials forming the first and second sheets. FIG.41shows an exploded view of one examples of cartridge4100. In this example, the cartridge includes a first (e.g., upper) frame4117onto which the first sheet4107is attached in tension, so that it is pulled flat. All four sides of the sheet may be held in tension. The sheet may be pinned, clamped, welded, adhesively attached, tacked, or otherwise secured to the frame. In this example, the first sheet4107also includes a pair of openings4133,4133′, configured as input/output windows (“windows”) into which a fluid material (droplet, drop gloss, etc.) can be applied by manual or automatic means (e.g., pipetting, etc.). Fluid material may be added to the air gap through the window adjacent to the sides of the window so that the mechanical microfluidics actuator may use the force applicator adjacent to the window to pull the droplet further into the air gap and manipulate the droplet (or droplets) within the cartridge. The window4133,4133′ may be any appropriate size. In some example the entire distal and/or proximal end of the cartridge may be open as a window (e.g., the first sheet may extend just between two opposite sides of the frame (e.g., the first frame). The edges of the window may be reinforced and/or smoothed. In some examples the edges may be thickened (e.g., doubled over itself). The window may be any size, or ratio of the size of the surface of the first sheet. For example, the window may be between 50% and 100% of the width of the surface of the first sheet, and between about 0.1% to 10% of the length of the surface of the first sheet. In some examples the window is between 1 mm and 10 cm long and between 1 mm and 5 cm wide. Larger windows may be used. As mentioned above, in some examples the cartridge may also or alternatively include one or more smaller openings for applying/removing fluid (e.g., by pipetting). The cartridge shown inFIG.41also includes a second frame4121to which a second sheet4109is attached. The second sheet may be under tension or, as it may be configured to be secured to the base of the mechanical microfluidics actuator, may be more loosely attached. The second sheet4109may be attached to the second frame4121in any appropriate manner. In this example, the first and second frames may be disposable and the first and second sheets may be, e.g., TPE film, FEP film, etc. The first sheet may be adhesively attached to the first frame by, e.g., an adhesive such as a double-sided adhesive film (e.g., 3M 300 L SE, 2 mil thick double adhesive). InFIG.41, the cartridge also includes a spacer frame4119that is sandwiched between the first and second frames and the first and second sheets. The first and second sheets may be attached or unattached to the spacer frame. The first frame and the second frame may be secured to the spacer frame. IN some examples the spacer frame is formed of a hydrophobic and oleophobic material, e.g., PTFE. Alternatively, in some examples only a single frame, which may or may not include spacers, may be used, and the first sheet may be attached to the first side of the frame while the second sheet is attached to the second side of the frame. The frame of the cartridge shown in this example may be rigid; in some examples the frame may be flexible and/or hinged. FIGS.42A-42Billustrate another example of a portion of a cartridge. In this example, the cartridge is shown having a first frame4217to which the first sheet4207is attached. The first sheet may be attached to the top or bottom of the first frame. InFIGS.41and42Athe sheet is shown attached to the bottom of the first frame. Frames may be formed in any appropriate matter, including laser cutting, injection molding, etc., and may be any appropriate material (e.g., polymeric material, such as polyester, ABS or POM (glass filled)).FIG.42Bshows an enlarged side sectional view of the first frame4217and first sheet4207. In this example, the first sheet is a TPE film and is adhesively held to the first frame under tension using an adhesive4210(e.g., 3 m 300LSE, 2 mil thick, double-sided adhesive). InFIGS.40and41A-41B, the first and second sheets are between about 20-60 μm thick (e.g., between 25-50 μm thick, etc.) and may be formed of an elastomeric material. Any of these cassettes may include a frame (backbone) that is hydrophobic, e.g., polypropylene, and may include one or more internal structures including, but not limited to spacer frames. For example, the apparatus may include posts (pinning posts), and/or an absorber (absorber material). The absorber may be used to remove waste (e.g., from rinsing/washing, drop gloss, etc.). In some cases an edge of the frame may include an absorber. The frames may include markings, including computer readable markings (e.g., QR codes, bar codes, etc.) that may uniquely identify the cassette. The cassettes may be oriented, e.g., to allow positioning in the mechanical microfluidics actuator seat in a preferred or exclusive orientation, or they may be non-oriented (allowing application in any orientation). In some cases the cartridge may include a specific “top” and “bottom” and may be marked or coded (including color coded) and or keyed to fit into the mechanical microfluidics actuator seat with the upper surface “up”. FIGS.43A-43Cillustrate the insertion of an example of a cartridge4302(seeFIG.43A) into a mechanical microfluidics actuator seat (as shown inFIGS.43B-43C). In this example the cartridge includes an elastically deformable upper sheet4307and an elastically deformable lower sheet4309,4309′ that are both attached to a frame4304(e.g., molded polymer frame) to form an air gap4312having an initial air gap height4319. The upper sheet and lower sheet in this example are attached to the same frame4304and are shown to be adhesively attached4314. InFIG.43Bthe cartridge is shown seated on the seat of the mechanical microfluidics actuator4322. The mechanical microfluidics actuator in this example includes a recessed seating region4320that include multiple vacuum ports coupled to a vacuum manifold4322coupled to a source of negative pressure and controlled by the controller of the mechanical microfluidics actuator. InFIG.43Bthe suction is shown applied, pulling the lower sheet4309of the cartridge into continuous contact with the seating region, and increasing the height of the air gap4312to a larger height4319′ (as compared to the neutral height4319). FIG.43Cillustrates the cartridge within the mechanical microfluidics actuator shown inFIG.43Bwith a droplet4331shown in the air gap4312. In this example, the upper and lower sheets4307,4309may be, e.g., an elastomeric polyester and the cartridge frame4304may be a molded polyester. FIGS.44A-44Bschematically show two alternative examples of cartridges seated and secured to mechanical microfluidics actuator seating regions. InFIG.44Athe cartridge includes a frame4406to which a first sheet4407and a second sheet4409are attached, separated from each other to form an air gap4421. InFIG.44A, similar toFIGS.43B-43C, the mechanical microfluidics actuator seating region4419includes vacuum ports securing the lower (second) sheet4409against the surface of the seating region so that there is no gap between the seating region and the second sheet, which is held immobilized against the seating region, as shown. InFIG.44Athe droplet4412may be heated/cooled or otherwise manipulated through the bottom (second) sheet by applying thermal energy through the particular sub-region of the seating region of the mechanical microfluidics actuator. In this example the entire seating region is shown as recessed; in other examples only a portion of the seating region is recessed, forming a well (described below) into which the droplet may be held. FIG.44Bshows another example of a cartridge held in a seating region of a mechanical microfluidics actuator. In this example the cartridge includes a frame4406and an upper sheet4407and a lower sheet4409; this cartridge is secured to the seating region by a securement such as a clamp4420applying a securing force against the frame to hold the cartridge immobile in place. In this example the mechanical microfluidics actuator does not need to include a vacuum (e.g., vacuum ports) to secure contact between the second sheet4409and the outer seating surface of the mechanical microfluidics actuator; inFIG.44Bthe outer seating surface may be raised along the length of the air gap4421. Thus, any of the mechanical microfluidics actuators described herein may not include a vacuum. Any of the mechanical microfluidics actuator described herein may include a securement (e.g., clamp, lock, etc.) holding the cartridge against the mechanical microfluidics actuator seating region. As described in greater detail below, any of these mechanical microfluidics actuators may include a controller, and one or more thermal regions that may locally heat/cool the seating region and therefore a droplet within the air gap of the cartridge over this portion of the seating region. In general, any of the seating regions of the mechanical microfluidics actuators may include a shape to which the lower sheet of the cartridge may conform, which may have numerous benefits, such as securing the droplet (e.g., pinning the droplet) to a particular region and/or enhancing the thermal energy transfer.FIGS.44C-44Eschematically illustrate examples in which the mechanical microfluidics actuator seating region include a projection. InFIG.44Cthe cartridge is shown seated on a mechanical microfluidics actuator4419″ seating region including a rail4411(e.g., rail region). The cartridge may be held down by a securement (not shown, such as a clamp, magnet, etc.). The droplet4412between the first sheet4407and the second sheet4409is therefore held (e.g., by capillary force) within the center of the air gap4421region, and may be moved within the channel (e.g., in/out of the plane of the section shown) by a force applicator applying force to reduce the height of the air gap.FIG.44Dshows an example in which the mechanical microfluidics actuator4419′″ includes a step-up raid4411′ that deforms the lower sheet4409′ slightly into the air gap4421but has a wider base than the rail ofFIG.44C. InFIG.44Ethe mechanical microfluidics actuator4419″″ is similar to that shown inFIG.44Dbut includes a dome-shaped rail4411″. Any of these examples may, but does not need to, including a vacuum manifold with vacuum ports to secure the second sheet4409,4409′,4409″ to the outer surface of the seating region. Alternatively or additionally these apparatuses may include a securement (such as a clamp, lock, magnetic securement, etc.) to hold the cartridge in position. In general, the methods and apparatuses described herein may include the use of a rail region within the air gap. The rail region may generally have a gap width that is less than the gap width of a region of the air gap surrounding the rail region, e.g., around the periphery of the air gap, on either side of the rail region. The rail region may form an elevated bed. As mentioned above, the rail region may be formed by deflecting the second (e.g., lower) sheet of the air gap; in some examples the second sheet is more rigid than the first sheet (e.g., is formed of a relatively stiff material) and the rail region may be formed of the more rigid second sheet. Surprisingly, the droplet may avoid the regions in the periphery (adjacent to the rail region) having a greater gap width, which may prevent loss of the droplet volume, particularly with smaller volume droplets (e.g., less than 15 μL, 10 μL or less, 5 μL or less, 1 μL or less, 1 μL or less, etc.). Mechanical Microfluidics Actuator As mentioned, any of these apparatuses may include a mechanical microfluidics actuator.FIGS.45A-45Eillustrate one example of a portion of a mechanical microfluidics actuator. InFIG.45Athe mechanical microfluidics actuator4500includes a seating region (seat)4531onto which a cartridge may be secured. In the example shown, the seating region includes a plurality of parallel lanes4532(eight are shown) running the length of the seating region. The seat in this example includes a plurality of vacuum ports coupled to a vacuum manifold4538to apply a suction to conformably secure the lower (second) sheet of a cartridge to the seating region. In addition, each of the lanes of the seating region includes a plurality of different zones for thermal control4533, magnetic field application4435, or both magnetic field and thermal control4542. The thermal control regions may be in thermal communication with a heater/cooler (e.g., Peltier device), and the magnetic control regions may each include a local electromagnet. This is illustrated inFIG.45B, in which the seating region4531has been made transparent to show the thermal control zones4533, electromagnet zones4539and combined thermal control/magnetic zones4542. In this example the base of the mechanical microfluidics actuator may be a heat sink4536to allow local application of heating/cooling.FIG.45Cshows an examples of a seating region of a mechanical microfluidics actuator with a cartridge4506attached to the seating region4531. Although this example includes three kinds of zones arranged in an alternating pattern along the length of each lane of the seating region (which may correspond to lanes in the cartridge4506, as shown inFIG.45C, other patterns of zones and/or other types of zones (e.g., heating/cooling, magnetic, electrical energy, sensing/imaging, UV applying, sonication application, etc.) may be included.FIGS.45D and45Eshow examples of the seating region topology in slightly greater detail. For example, inFIGS.45D and45Ethe seating regions may include a plurality of wells4541formed therein which may underlie a thermal control region. For example, inFIG.54Dthe mechanical microfluidics actuator seating region including a plurality of thermal control regions configured as wells4541having a shallow, bowl-shaped depression which is formed of a thermally conductive material4533. The bowl also includes a suction port4555in communication with a suction manifold4538to hold down the second sheet4509. The method of driving the droplet (e.g., with the force applicator) into the well may pin droplet in the well and may greatly reduce or limit evaporation, particularly when heating the droplet (e.g., for thermocycling the droplet). FIG.46schematically illustrates an example of a portion of an apparatus (such as the cartridge and mechanical microfluidics actuator) similar to that shown inFIG.45A-45E, including a vacuum port4638securing the second sheet4609of the cartridge to the seating region of the mechanical microfluidics actuator4631. InFIG.46a droplet4612is shown in the air gap region and is coated with a drop gloss4652material. The drop gloss coating may be formed of a material that limits evaporation and is immiscible with the droplet. In general, any appropriately sized droplet may be used, including microliter and sub-microliter droplets. However, in some cases it may be difficult for smaller (e.g., less than 2 μL) to be transferred reliably. It may also be beneficial to use fluid transfer of droplets of any size without requiring negative pressure (e.g., suction), e.g., without pipetting.FIG.47illustrates one example of a method for reliably transferring a very small droplet, including (but not limited to) transferring into a cartridge as described herein. In this example a solid transfer member4671having a concave end region4673(“droplet void”) may be included at the distal end of the device. This concave region/void may be configured to hold a specific droplet volume, e.g., less than a few microliters in volume (e.g., 0.1 μL, 0.2 μL, 0.3 μL, 0.4 μL, 0.5 μL, 0.6 μL, 0.7 μL, 0.8 μL, 0.9 μL, 1 μL, 1.1 μL, 1.2 μL, 1.3 μL, 1.4 μL, 1.5 μL, 1.6 μL, 1.7 μL, 1.8 μL, 1.9 μL, 2 μL, etc.). Larger volumes may be used as well (e.g., between 1-50 μL, between 0.1-50 μL, etc.). The droplet void region4673may be inserted into a solution of the fluid to be transferred4675and removed, leaving a droplet of the expected size and volume4677captured within the end of the solid transfer member4671, as shown. This droplet may be released, e.g., within the air gap, by immersing into a solution (e.g., another droplet) having a lower surface tension4679(e.g., drop gloss) causing displacement and release of the droplet4677, as shown. In general, these apparatuses may handle smaller volume droplets by increasing the volume/amount of the immiscible fluid (drop gloss), so that the final volume is sufficiently large for displacement within the air gap using the mechanical actuator as described herein. FIG.48shows another schematic illustration of a mechanical microfluidics actuator4800. In this example the mechanical microfluidics actuator includes a force applicator4878(e.g., stylus, bearing, roller, etc.), and a force applicator driver subassembly4874(e.g., a force applicator subassembly). The force applicator sub-assembly may include one or more drivers (e.g., an x and/or y motion driver, a z-motion driver4873, etc.), and/or a frame or gantry onto which the force applicator may be driven to change position and/or to apply force to the cartridge4877when one is seated in the cartridge seat4878of the device. The force applicator sub-assembly may include one or more stepper motors, motion rails (e.g., gantry/frame), and/or home switches. The mechanical microfluidics actuator ofFIG.48also includes a thermal sub-assembly4879for controlling the temperature of one or more regions of the air gap. In this example the thermal subassembly may include thermally conductive zones or regions of the seating region that may be in thermal communication with a heating and/or cooling element (e.g., Peltier device) multiple heating/cooling elements may be included. Any of these mechanical microfluidics actuator apparatuses4800may also include a magnetic control sub-assembly4885,4885′ for controllably applying a magnetic field within the air gap.FIG.49illustrates an example of a row of magnetic elements (electromagnets)4985within the base4819of a mechanical microfluidics actuator. In some examples, the mechanical microfluidics actuator apparatus may include a cartridge securement4876,4876′ (e.g., a holder, clamp, lock, etc.) for securing a cartridge to a cartridge seat or seating region4878of the mechanical microfluidics actuator. InFIG.48, the apparatus includes a vacuum/suction sub-assembly (not shown) for applying suction to secure the cartridge into the seating region. In some examples the mechanical microfluidics actuator apparatus may include a fluid handling (e.g., pipetting) sub-assembly4883for adding and/or removing fluid from the air gap. Other sub-assemblies forming a part of the mechanical microfluidics actuator apparatus may include imaging sub-assemblies (e.g., for imaging droplets within the air gap) and/or for sensing sub-assemblies (e.g., for sensing droplets or other inputs from the air gap and mechanical microfluidics actuator). The mechanical microfluidics actuator apparatuses described herein may also include one or more control inputs (e.g., keyboards, touchscreens, buttons, switches, etc.) and/or one or more outputs (e.g., displays, LEDs, wireless communications outputs/inputs, etc.) and hardware, software and/or firmware for controlling these. In some cases the same features may be used for control inputs and outputs. In general, the mechanical microfluidics actuators described herein may include one or more controllers4899for controlling and coordinating operation of the various sub-assemblies. Any of these apparatuses may include leveling. For example inFIG.48the apparatus includes adjustable leveling feet4881. In general, the mechanical microfluidics actuators described herein may be single cartridge use (e.g., for use with a single cartridge at a time) or may be configured to multiple-cartridge use.FIG.50illustrate an examples of a mechanical microfluidics actuator apparatus5001that is at least partially enclosed within a housing5095and is configured for use with a single cartridge5077. The apparatus includes a force applicator sub-system5097(e.g., 3 axis motor, encoders, home and limit sensors, solenoids, raise, shafts, couplings, bearings gears, belt, etc.) and an electrical subsystem5094for controlling the power requirements of the apparatus, e.g., controller, power distribution, user-interface boards, touchscreen, etc. (and in some examples, for applying power to one or more electrodes, e.g., for electroporation and/or electrochemical procedures on the cartridge). The apparatus also includes a thermal sub-system5092(e.g., Peltier, high-power TEC driver, heat spreader, heat sink, etc.), a controller5091and an input/output5093(e.g., display/touch screen).FIG.51illustrates an example of an apparatus that is multiplexed5101to allow parallel handling of multiple cartridges. Either the single-cartridge or a multi-configuration may also include or be configured for use with a fluid handling system (e.g., liquid handler5163) as shown inFIG.51. FIGS.52A-52Bschematically illustrates one example of a mechanical microfluidics actuator as described herein, showing one possible arrangement of the subassemblies described here. For example, inFIG.52Athe apparatus includes a liquid staging sub-assembly (e.g., temperature control, inputs, tip repository, tip waste, etc.) for adding/removing liquid from the cartridge, as well as a chassis sub-assembly (e.g., chassis, fans, leveling feet, switches/buttons, touchscreen, etc.) and a power distribution sub-assembly (mains power supply, power distribution circuitry, etc.). The controller (primary control PCBA) may also include sensors (e.g., ambient temperature sensor, ambient humidity sensors, level sensors) and Wi-Fi or other inputs/outputs. The controller may receive input from the chassis subassembly and may output/control all of these sub-assemblies. In particular, the controller may control the liquid handler sub-assembly, which includes motion controllers (drivers, position sensors, etc.), and may control the sub-module with the temperature sub-assembly (Peltier sub-assembly), magnetic sub-assembly, linear motion sub-assembly and cartridge receptacle (e.g., cartridge datum) each of which may provide input to the controller. Examples FIGS.5A-53Cillustrate one example of a method of moving an aqueous droplet as described herein. In this example one or more microfluidic droplets is manipulated so that it may be moved virtually anywhere in the air gap5321formed between the first elastic sheet5307and a second sheet5309. The second sheet may also be an elastic sheet as described above. Both the first5391and second5392surfaces of the first and second sheets (which may be referred to as the inner surfaces facing the air gap) may be hydrophobic and oleophobic. The sheets may be formed of a hydrophobic and oleophobic material, or they may be coated with a hydrophobic and oleophobic material. An aqueous fluidic droplet5312may be introduced into the air gap formed between the first sheet5307having a first surface that is hydrophobic and oleophobic and the second sheet5309having a second surface that is hydrophobic and oleophobic. As described above, the first sheet and the second sheet may be secured opposite and approximately parallel at a predetermined distance relative to each other with an air gap therebetween. The first sheet and/or the second sheet may be held in tension. At least the first sheet is formed of an elastomeric material so that it may deform when a force (e.g., a mechanical stylus, as shown inFIGS.53B and53C) is driven against it, will return to the approximately parallel configuration when the force is released. For example, inFIG.53Athe mechanical force applicator (stylus5375) is positioned above the top of the first (e.g., upper) elastomeric sheet5307. As described above, one or more movement drives (e.g., x, y stage/z-motion, robotic stage or control) may be used to drive the movement of the mechanical force applicator relative to the upper sheet. The first and second sheets may be part of a cartridge that may include one or more tensioners (e.g., tensioning frames, etc.) holding the first and/or second sheets in tension. As shown inFIG.53B, the mechanical force actuator5375may be driven down against the first sheet to a region that is adjacent to the droplet. Locally reducing the height of the air gap (in a continuous gradient, as shown) may cause the droplet to be driven by the resulting increased capillary force into the lower-height region. Thus, as the mechanical force actuator is driven across the top of the sheet (and against the top sheet), as shown byFIGS.53B and53Ccauses the droplet to move within the air gap. In any of these examples the height of the air gap may be reduced in a gradient and the distance between the upper and lower (first and second) sheets is reduced but do not contact each other. For example the height is reduced by between about 5% and 90% (e.g., between about 10% and 80%, between about 20% and 60%, between about 10% and 50%, etc.). In some cases it may be advantageous to reduce the height by between about 5% and 60%, but not more than 60% (e.g., not more than 55%, not more than 50%, not more than 45%, not more than 40%, not more than 35%, not more than 30%, not more than 25%, etc.). This may allow the gradient to drive movement but may limit the region to a region that is local to the droplet. This may allow the first (upper) elastic sheet to be restored to a parallel configuration (as shown inFIG.53C, in the regions where the stylet has moved away from the sheet). As shown inFIGS.53B-53C, applying force (by the mechanical force applicator/stylet) to elastically deform the first sheet reduces the distance of the air gap between the first sheet and the second sheet in a local region within the air gap that is adjacent to the fluidic droplet, and causes the droplet to move within the air gap, following the reduced height region formed by the stylet. In any of the methods and apparatuses described herein the sheets forming the air gap are made of a hydrophobic and oleophobic material; non-hydrophobic and oleophobic materials did not work in many of the examples shown. In addition, the materials forming the inner surface of the air gap may be substantially non-porous. As mentioned, any of the droplets may be coated with a layer of drop gloss, e.g., a gloss coat that may be a low surface-tension material (e.g., oil), and may be immiscible with the droplet, which may also prevent or limit evaporation. In general, the methods and apparatuses described herein may include the use of at least 0.01% of a surfactant in or surrounding the droplet being moved. Surprisingly, the inventors have found that the use of surfactant in the droplet (e.g., 0.01% or more, 0.02% or more 0.025% or more, between 0.01% and 1%, between 0.01% and 0.7%, between 0.01% and 0.5%, between 0.01% and 0.25%, between 0.01% and 0.1%, etc.) or in a gloss layer surrounding the droplet may allow the droplet to move more predictably within the air gap when pulled by the reduced gap width as described herein. Without being bound by theory, this may be due to the effective surface tension of the droplet; the use of a surfactant in either or both the drop gloss and/or the droplet may therefore allow the droplet to move predictably and robustly. Without the use of a surfactant, the droplet movement may be less predictable and may sometime fail to follow the mechanical actuator as it moved across the surface. Any appropriate surfactant may be used. For example, the drop gloss used may include a nonionic surfactant (e.g., Brij-35) or other hydrophobic polymer. In some examples the droplet may include a surfactant such as pluronics, Tween-20, Tetronic, etc.). Thus, in any of these methods an apparatuses, either or both the drop gloss and/or the droplet may include a surfactant (e.g., 0.01% or more surfactant). In some cases the surfactant may be added before beginning any of the step involving moving the droplet by locally reducing the gap width in the region adjacent to the droplet. In examples in which a mechanical force applicator (e.g., stylus) is used, the contact surface of the stylus may be sized proportional to the air gap and/or the droplet size/volume. In particular, the aspect ratio of the stylus, e.g., the size of the stylus tip relative to the size of the droplet, and/or the size of the stylus tip relative to the height of the air gap, may be selected to be between 1:0.5 and 1:20 (tip:droplet). DNA Sequencing and DNA Synthesis The methods and apparatuses described herein may be used specifically for performing enzymatic process on polynucleotides, including (but not limited to) sequencing and/or synthesis. For example, these methods and apparatuses may be used to perform DNA Sequencing-By-Synthesis (SBS). SBS provides many significant benefits to the scientific research community and has enabled many new diagnostic application, including an increase in the output by sequencing instrumentation, faster turnaround time for results and the reduction of costs by orders of magnitude versus the prior dominant sequencing methodology, Sanger Sequencing. Sanger Sequencing relies on electrophoretic separation of DNA fragments created by specially modified terminating nucleotides. SBS eliminates the requirement for the separation and allows the implementation of massively parallel sequencing approaches. Several important clinical applications have been developed as a result of these cost and throughput improvements including, Non-Invasive Pre-Natal Testing (NIPT) to detect aneuploidies such as Down's Syndrome in pregnant women's blood, genetic carrier testing to provide information to parents regarding potential genetic risks, oncology patient stratification, tumor profiling and early detection of cancer through the sequencing of nucleic acids in blood (known as cell-free sequencing). SBS is a flow-based sequencing technique in which a series of liquid formulations are introduced to a flow cell populated with DNA templates isolated, purified and processed to create a sequencing “library” and flowed into the sequencing flow cell. The flow cell is loaded with template DNA onto either random or structured arrays which create a distinct “cluster” for each DNA library fragment. Reagents are delivered in a sequential process which enzymatically adds a single fluorescently labeled nucleotide per cycle. After each fluorescent nucleotide addition, the flow cell is imaged, with each unique fluorescent labels representing a specific base (A, C, G, T) and processed through software which assigns the next base in the sequence. After imaging, the fluorescent dye and the nucleotide blocking group are chemically cleaved and washed away to prepare for the next cycle. Typically, this process is repeated for 75-600 cycles adding another base each cycle which is captured through the imaging process and software analysis. Many protocols have a process (mid-run in most cases) to create a complementary strand of DNA which is also sequenced to improve coverage and accuracy. The method for creating this complementary strand uses similar reagents to create newly synthesized DNA to be sequenced by SBS. Current systems typically use a delivery method to provide the continuous flow of each reagent sequentially. These are delivered by a pumping or pressure mechanism which floods the flow cell with each reagent completely filling the flow cell then flushed and replaced with the next reagents required to drive the cycle. While these volumes are fairly small, they do require excess volumes to ensure no carryover from step to step or cycle to cycle which could compromise the resulting sequencing.FIG.54schematically illustrates a sequencing cycle and overall process map for SBS. The microfluidic methods and apparatuses described herein may be used to flow the various components within the ‘flow cell’ configured as described herein, including the wash steps. Although traditional digital microfluidics (e.g., using electrowetting, etc.) has been proposed for use in sample preparation of nucleic acids as a front end to the sequencing process and as an alternative to manual benchtop library creation or conventional robotic pipetting systems, there are a number of drawbacks. Electro-wetting on Dielectric (EWOD) has been successfully applied to the front-end processes such as the isolation of DNA from patient samples and the creation of a sequencing libraries to be subsequently loaded on a sequencing instrument. While electrowetting has a reasonable fit for the automation of up-front processes, the complexities of the sequencing process itself present several technical and practical economic challenges. Of particular note are the requirements for imaging the flow cell after each nucleotide addition cycle. In an ideal implementation, a completely integrated sequencing processes would allow a sample to be introduced to a system and would provide DNA sequencing results as the output. EWOD is unlikely to be successful as a fluidic solution for such a fully integrated process. The methods and apparatuses described herein, which may be referred to as mechanical actuation on the surface, in which a mechanical force (e.g., compressive force) is applied to drive one or more droplets may provide significant advantages as compared to other microfluidic techniques, including electrowetting, and may allow for the possibility of using a single fluidic technology across the entire sequencing process, including SBS. As described above, the use of a mechanical compression to change the capillary force to move droplets in two dimensions may have many advantages, particularly in regards to sample preparation, and may be used for virtually all of the necessary steps, such as nucleic acid isolation, library generation, cluster generation, primer loading and hybridization, and multi-cycle sequencing reactions, including the steps illustrated inFIG.54. FIGS.55A-55Billustrate an example of the use of mechanical compression to change the capillary force in order to move droplets within a flow cell5501to introduce sequencing primers to clusters of DNA templates (e.g., part of the sequencing by synthesis process described above).FIG.55A, shows the loading and wash steps associated with primer introduction to the sequencing templates in the flow cell5501. As in any of the methods described herein, multiple mechanical force applicators (styluses5575) may be used concurrently on the same flow cell (e.g., cartridge). These mechanical force applicators may be independently or collectively controlled/actuated. InFIG.55A, the cartridge/flow cell includes a region in which primers to which clusters have been formed are arranged, either in an un-patterned or patterned (e.g., in nanowells) arrangement. The steps for generating the clusters may also be performed using the mechanical force applicator as described herein, or they may be performed by pipetting and washing. The first droplet5502is drawn onto the clusters first using the first stylet and may be allowed to incubate over the clusters (allowing hybridization), as shown inFIG.55B, and may then be drawn off, and in some cases out of the flow cell (e.g., to a waste depot). The second droplet5504(wash buffer) may then be drawn over the clusters to wash the clusters. FIGS.56A-56Eillustrate the steps associated with each cycle of SBS, as performed in a cartridge (e.g., flow cell)5501. As described above, either multiple mechanical force applicators (styluses5575), or the same stylus may be used sequentially. In this examples, the figures show one direction of movement of droplets, e.g., from left to right. However, the methods and apparatuses described herein may allow movement in two dimensions (e.g., in the entire plane of the air gap, and may allow movement in any arbitrary direction in this plane). Thus, in some examples the reagent droplets may be moved to the side and reintroduced and or reused (and even recharged with depleted components, e.g., nucleotides, enzymes, other chemicals). InFIG.56A, following primer hybridization and washing (seeFIGS.55A-55B), may be followed by the SBS cycles of applying nucleotide, polymerase, reaction mix, washing, and extension with imaging for multiplexed sequencing.FIG.56Ashows the start of the first cycle, in which nucleotides and polymerase are added to the clusters in the air gap of the cartridge/flow cell5501by pulling the droplet including the nucleotide and polymerase using a mechanical force actuator. After an appropriate time, the droplet may be pulled off of the clusters and one or more wash droplets may be moved onto the clusters (FIG.56B) while imaging (to identify the additional nucleotide). The wash droplet may again be moved off of the clusters and a droplet including dye/terminator cleavage components may be pulled onto the clusters (FIG.56C); this droplet may then be moved off using the mechanical force actuator and the same or a different mechanical force actuator may be used to move another droplet of nucleotides and polymerase for the start of the second cycle (FIG.56E). The microfluidic methods and apparatuses described herein may also be used for other applications, in addition to SBS Sequencing. For example, these methods and apparatuses may be used for enzymatic synthesis of DNA oligos (which is very similar to the SBS process), such as cyclical enzymatic addition of nucleotides with reversible terminators. Other non-limiting examples may include DNA oligo synthesis. For example, the methods and apparatuses described herein may be used for nucleic acid extraction (illustrated inFIGS.57and58A-58B) and library preparation (FIG.59,FIG.60, andFIG.61).FIG.57schematically illustrates an overall workflow from nucleic acid extraction to sequencing using a system for mechanical actuation on the surface (e.g., mechanical compression to change the capillary force). InFIG.57, a tope and side view of an 8-lane cartridge similar to those described above may be integrated to a system containing an array of cooling regions (e.g., Peltier) and magnetic and/or resistive heating zones that may allow the cartridge and system to perform DNA/RNA extraction, library preparation, and sequencing at specified regions. InFIG.57the cartridge includes an air gap with a plurality of different reaction wells (including thermal control/cooling). The cartridge is divided into lanes (8 lanes are shown) and includes regions for DNA/RNA sequencing, Library preparation and sequencing (e.g., SBS). Lane dividers may divide the lanes. FIG.58illustrates the operation of the cartridge and system shown inFIG.57for polynucleotide (e.g., DNA, RNA, etc.) extraction from a clinical sample.FIG.58Ashows a side-view schematic of DNA/RNA extraction from a clinical samples on the cartridge. In this example a droplet of a 250 μl clinical sample (e.g., blood, saliva and tissue homogenate, etc.) containing 45 μl of dropgloss and a 310 μL droplet of lysis buffer are merged and mixed by the methods described herein for 5 min in the PCR reaction well and incubate at 70° C. for 10 minutes. The reaction (Rxn) droplet is then actuated to the Magnet/Resistive Heater zone, merged with 400 μL HDQ Binding Buffer and 20 μL Mag-Bind® Particles HDQ, and mixed for 10 minutes; the magnet is then engaged until pellet formation, supernatant is discarded to waste, and the pellet is washed twice with 600 μL VHB wash Buffer. The pellet may be resuspended in 600 μL SPM wash Buffer and driven by mechanical actuation on the surface to clean the Magnet/Resistive Heater zone, the magnet may be engaged, and the wash buffer may be moved to waste. Finally, the elute nucleic acid is eluted in 30 μl of Eluent. InFIG.58, the droplet of clinical sample (e.g., blood, saliva and tissue homogenate) merges with the lysis buffer581and gets mixed by the techniques described herein (e.g., mechanical actuation on the surface) for 5 min in the reaction well and then incubates at 70° C. for 10 minutes. The lysate droplet is then actuated to the Magnet/Resistive Heater zone582, merged with Binding Buffer and Magnetic/Binding bead particles and may be mixed for 10 minutes. The magnet may then be engaged until pellet formation583, the supernatant discarded to waste, and the pellet may be washed twice with wash Buffer. The pellet is resuspended in wash Buffer and driven by mechanical actuation at the surface to clean the Magnet/Resistive Heater zone, the magnet may be engaged, and the wash buffer may be moved to waste. Finally, the elution buffer gets actuated to the pelleted beads to elute nucleic acid off beads. FIG.59illustrates an RNA sequencing workflow. InFIG.59, a side-view through the cartridge shows a schematic of RNAseq workflow on the cartridge. At step591, 2 ul droplet of fragmented RNA and first-stranded synthesis master mix with 45 μL of dropgloss droplet are actuated by mechanical actuation at the surface, as described herein (e.g., using a stylus) to the PCR Reaction Well and incubated (25° C. for 10 min, 42° C. for 15 min, 70° C. for 15 min). Thereafter, 6 μl droplet of second-strand synthesis master mix is added to the reaction (Rxn) droplet and incubated at 16° C. for 60 min. The Rxn droplet is actuated to the Magnet/Resistive Heater zone592, merged with 11.2 ul bead droplet, mixed and incubated for 5 min at RT, the magnet is engaged until pellet formation, the supernatant is discarded to waste, the pellet is washed twice with 25 ul with 80% EtOH (not shown in schematic), and the cDNA sample is eluted off beads into 6 μl elution buffer. Afterwards, 5 ul droplet of cDNA sample is then actuated as described herein to the PCR Reaction Well, merged with 1 μl of end prep master mix (with 10 μl dropgloss), and incubated at 20° C. for 30 min followed by 65° C. for 30 min. Then, 3.1 μl of adaptor ligation master mix and 0.25 μl of adaptors droplets are actuated as described herein, mixed with Rxn droplet and incubated at 20° C. for 15 min593. The adapter ligation Rxn droplet is actuated to the Magnet/Resistive Heater zone, merged with 7.28 μl of bead droplet, mixed and incubated for 5 min at RT, and the magnet is engaged until pellet formation, after which supernatant is discarded to waste, the pellet is washed twice with 25 ul with 80% EtOH (not shown in schematic), and the DNA library is eluted in 6 μl in nuclease-free water containing 5 uM TRUESEQ BARCODES594. 5 ul droplet of purified DNA library sample may then be actuated by mechanical actuation (e.g., using a stylus) to the PCR Reaction Well, merged with 10.9 μl of USER/PCR master mix (with 45 μl dropgloss), and incubated at 37° C. for 15 min, 98° C. for 30, and then cycled 19× at 98° C. for 10 sec, 65° C. for 75 sec595. The amplified DNA droplet is actuated to the Magnet/Resistive Heater zone, merged with 12.72 μl of bead droplet, mixed and incubated for 5 min at RT, a magnet is engaged until pellet formation, the supernatant is discarded to waste, the pellet is washed twice with 25 ul with 80% EtOH (not shown in schematic), and the DNA library is eluted in 25 μl of Eluent596. InFIG.59, the droplet of fragmented RNA and first-stranded synthesis master mix with dropgloss are actuated by mechanical actuation (e.g., stylus) to the Reaction Well and incubated (25° C. for 10 min, 42° C. for 15 min, 70° C. for 15 min)591. Then a droplet of second-strand synthesis master mix is added to the reaction (Rxn) droplet and incubated at 16° C. for 60 min. The Rxn droplet is actuated to the Magnet/Resistive Heater zone, merged with SPRI or Ampure beads droplet, mixed and incubated for 5 min at room temperature (RT), magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 80% EtOH (not shown in schematic), and cDNA sample eluted off beads into elution buffer592. The droplet of cDNA is then actuated (e.g., using a stylus) to the Reaction Well, merged with end prep master mix and incubated at 20° C. for 30 min followed by 65° C. for 30 min593. Then adaptor ligation master mix and adaptors droplets are actuated by mechanical actuation (e.g., stylus), mixed with Rxn droplet and incubated at 20° C. for 15 min. The adapter ligation Rxn droplet is actuated to the Magnet/Resistive Heater zone, merged with SPRI or Ampure bead droplet, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, the pellet washed twice with 80% EtOH (not shown in schematic), and DNA library eluted in nuclease-free water containing primers594. The purified DNA library plus primers mix is mechanically actuated as described herein (by stylus) to the PCR Reaction Well, merged with USER/PCR master mix with dropgloss and incubated at 37° C. for 15 min, 98° C. for 30, and then cycled up to 19× at 98° C. for 10 sec, 65° C. for 75 sec595. The amplified DNA droplet is actuated to the Magnet/Resistive Heater zone, merged with SPRI/Ampure bead droplet, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 80% EtOH (not shown in schematic), and RNA-seq library eluted in 25 μl of elution buffer596. FIG.61is a schematic side-view of a second part of a twist exome target enrichment methods using a cartridge as described herein. In this example, an 8.3 μl droplet of DNA and hybridization mix a with 45 μL of dropgloss droplet are actuated as described herein to the PCR Reaction Well and incubated at 95° C. for 5 min and 60 C for 2 hours 601. The Rxn droplet is actuated to the Magnet/Resistive Heater zone, merged with 33.3 μl Streptavidin beads, mixed for 30 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet is initially washed with a 70° C. pre-heated 50 μl buffer droplet followed by a 48° C. pre-heated 50 μl buffer droplet (not shown in schematic), and purified DNA library sample eluted off beads into 7.5 μl elution buffer602. Thereafter, 7.5 μl droplet of purified DNA library sample is then actuated as described herein to the PCR Reaction Well, merged with 0.83 μl Primer and 8.3 μl of master mix (with 10 μl dropgloss), and incubated at 97° C. for 45 sec followed by 8 cycles at 97° C. for 15 s, 60 for 30 s, 72 C for 30 s, and finally 72 C for 1 min603. The amplified DNA droplet is actuated to the Magnet/Resistive Heater zone, merged with 30 ul magnetic bead droplet, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 25 μl with 80% EtOH (not shown in schematic), and DNA library eluted in 30 μl of Eluent604. Thus, inFIG.60the method for twist exome target enrichment is performed on a cartridge as described herein, using mechanical actuation of the surface of the cartridge. InFIG.60the droplet of DNA and hybridization mix with dropgloss601and are actuated as described herein to the Reaction Well and incubated at 95° C. for 5 min and 60 C for up to 4 hours. The Rxn droplet is actuated to the Magnet/Resistive Heater zone, merged with Streptavidin beads, mixed for 30 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet is initially washed with a 70° C. pre-heated buffer droplet followed by a 48° C. pre-heated 50 μl buffer droplet (not shown in schematic), and purified DNA library sample eluted off beads into elution buffer602. The droplet of purified DNA library sample is then actuated by the mechanical actuation of the surface as described herein to the PCR Reaction Well, merged with Primers and dropgloss and incubated at 97° C. for 45 sec followed up to 18 cycles at 97° C. for 15 s, 60 for 30 s, 72 C for 30 s, and finally 72 C for 1 min603. The amplified DNA droplet is actuated to the Magnet/Resistive Heater zone, merged with SPRI/Ampure magnetic bead droplet, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 80% EtOH (not shown in schematic), and DNA library eluted in Elution buffer604. FIG.61illustrates a workflow showing Aplicon-seq. For example,FIG.61shows a side-view schematic of an Ampliseq (2 primer pools) workflow on a cartridge as described herein. First, three droplets of 13.5 μl DNA, 9 μl HiFi mix and 22.5 μl water are merged by mechanical actuation of the surface (e.g., using a stylus), mixed for 5 sec at RT, split into two equal droplets using a liquid handler (not shown in schematic)611. Second, each of the droplets were merged with a 5 μl unique primer droplets with 45 μL of dropgloss droplet, and Rxn droplets (1&2) actuated by mechanical actuation of the surface (e.g., using a stylus) to the PCR Reaction Well zones and incubated (99° C. for 2 min, and then 17 cycle: at 99 C for 15 s, 60 C for 4 min)611′. Next, Rxn droplets 1 &2 are merged by mechanical actuation of the surface (e.g., using a stylus), actuated to the Magnet/Resistive Heater zone, merged with 4 μl FuPa reagent droplet, mixed and incubated at 50° C. for 10 min, 55 C for 10 min and 60 C for 20 min. Second, 8 μl Switch solution, 4 μl Barcode adaptor mix and DNA Ligase droplets were added to the Rxn droplet by mechanical actuation of the surface (e.g., using a stylus) and incubated at 22° C. for 30 min, 68 C for 5 min, and 72 C for 5 min612. Afterwards, 90 μl droplet of beads were added to the Rxn droplet, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 150 ul of 80% EtOH droplets (not shown in schematic), and library eluted off beads into 50 μL of Platinum™ PCR SuperMix HiFi and 2 μL of Equalizer™ Primers droplets. In613, 50 μl droplet of purified library is actuated by mechanical actuation of the surface (e.g., using a stylus) to the PCR Reaction Well, and incubated at 98° C. for 2 min and cycled 9 times at 98 C for 15 s, 64 C for 1 min. Second, 10 μL of Equalizer Capture droplet is added to the Rxn droplet and mixed for 5 min at RT. In614, the Rxn droplet is actuated to the Magnet/Resistive Heater zone, merged with 6 μL of washed Equalizer™ Beads, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 150 μl with 80% EtOH (not shown in schematic), and DNA library eluted in 100 μl of Eluent droplet. Thus, as shown inFIG.61, the Ampliseq (2 primer pools) workflow, in611, three droplets of DNA, PCR mastermix and water are merged by mechanical actuation of the surface (e.g., using a stylus), mixed for 5 sec at RT, split into two equal droplets using a liquid handler (not shown in schematic). Second,611′ each of the droplets were merged with a unique primer droplet with dropgloss, and Rxn droplets (1&2) actuated by mechanical actuation of the surface (e.g., using a stylus) to the PCR Reaction Well zones and incubated (99° C. for 2 min, and then 17 cycle: at 99 C for 15 s, 60 C for 4 min). In step612, first, Rxn droplets 1 &2 are merged by mechanical actuation of the surface (e.g., using a stylus), actuated to the Magnet/Resistive Heater zone, merged with FuPa reagent droplet, mixed and incubated at 50° C. for 10 min, 55 C for 10 min and 60 C for 20 min. Second, Switch solution, Barcode adaptor mix and DNA Ligase droplets were added to the Rxn droplet by mechanical actuation of the surface (e.g., using a stylus) and incubated at 22° C. for 30 min, 68 C for 5 min, and 72 C for 5 min. Third, droplet of beads were added to the Rxn droplet, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 80% EtOH droplets (not shown in schematic), and library eluted off beads into Platinum™ PCR SuperMix HiFi and Equalizer™ Primers droplets. In613, first, 50 ul droplet of purified library is actuated by mechanical actuation of the surface (e.g., using a stylus) to the PCR Reaction Well, and incubated at 98° C. for 2 min and cycled 9 times at 98 C for 15 s, 64 C for 1 min. Second, Equalizer Capture droplet is added to the Rxn droplet and mixed for 5 min at RT. As614, The Rxn droplet is actuated to the Magnet/Resistive Heater zone, merged with washed Equalizer™ Beads, mixed and incubated for 5 min at RT, magnet engaged until pellet formation, supernatant discarded to waste, pellet washed twice with 80% EtOH (not shown in schematic), and DNA library eluted in Elution droplet. Introducing and Removing Liquid FIGS.62A-62Jillustrate one example of a method of applying liquid (droplets) into a cartridge such as the cartridges described herein. For example, inFIG.62A, a partial section through the cartridge shows an opening into which a pipette tip may be inserted. A standard pipette tip may be used. As an initial step, a droplet of drop gloss material (as described above) may be pipetted into the air gap of the cartridge. For example, between about 10-45 μL of drop gloss may be pipetted into the air gap, and the pipette tip removed (FIG.62B). A droplet of the aqueous reaction material may then be inserted into the air gap in the same way, as shown inFIG.62C. The droplet may be pipetted onto, into or adjacent to the drop gloss (which is added first). In some examples, the drop gloss may be combined with the droplet before they are pipetted together. Alternatively, the drop gloss may be added after the aqueous (reaction) droplet is added. In general, the liquid material may be introduced by pipette tip, using a unique (dedicated single tip/sample) application or universal (shared tip for multi-dispense) application of reagents across one or more lanes of the cartridge. InFIG.62Cany volume of aqueous reaction mixture may be used, such as between about 250 nL to 80 μL. InFIGS.62C-62D, pre-dispensed drop gloss encapsulates aqueous reagent and protects from surface fouling and evaporation during workflow steps. Ethanol and wash buffers do not need drop gloss. The volume of drop gloss may be more than, less than or the same as the volume of the aqueous droplet. In some example, as shown inFIGS.62A-62D, the volume of the drop gloss may exceed the volume of the reaction droplet (e.g., by more than 1.5×, 2×, 2.5×, 3×, 3.5×, 4×, 4.5×, 5×, between 1 and 10 times, between 1 and 8 times, between 1 and 7 times, between 1 and 6 times, between 1 and 5 times, between 1 and 4 times, etc. or more). Thus, very small volumes of reaction droplet (e.g., as small as 250 nL) can be manipulated; the reaction droplet may be combined with an excess of drop gloss which may encapsulate it and allow it to be manipulated as described herein (moved, combined, split, heated, mixed, etc.) even in channels having relatively large channel heights (e.g., 1.5 mm or more). Thus, in some examples the systems described herein can dispense as low as 250 nL and as high as 80 uL of reagents/mastermix/sample volumes. In some examples, for drop gloss the system can dispense 10-45 uL volumes. The lane width illustrated in some of these examples can accommodate up to 150 uL total volume (drop gloss+reagent) or up to 80 uL reagent volume. Larger or smaller lane widths and/or heights may be used. As shown above, during introduction of liquids into each lane's inlet, the dispensing tip is lowered (straight down) against the bottom film surface in a position to ensure that part of the droplet is inside the channel (due to the innate wetting properties of liquids) when dispensed. Capillary pressure may draw the droplet into the air gap and away from the opening (or to the edge of the opening) so that it can be manipulated, as shown inFIGS.62E-62G. Thus, for small volumes such as 250 nL, a pre-dispensed carrier dropgloss droplet (e.g., ˜5-10 ul) may be used into which the 250 nL droplet is dispensed, and then a compression force is applied to the one-side of the port pulling in the carrier drop gloss droplet containing the small volume. For example, as shown inFIG.62E-62F, the mechanical manipulator (stylus) may be lowered onto the elastically deformable upper sheet to reduce the height (either on or more preferably adjacent to the droplet) and the mechanical manipulator (stylus) may be drawn across the surface of the upper sheet as shown inFIG.62Gto move the droplet, which is surrounded by the drop gloss. As shown, the reagent is protected inside of the drop of drop gloss. InFIG.62F, the stylus compresses the film surface adjacent to the inlet hole (at a safe distance that will avoid contamination of the stylus). The droplet of drop gloss/reagent is then drawn into the narrower gap (by the capillary action, including the increase in capillary force) and the droplet is now fully inserted to the lane and sandwiched across its surface between a top and bottom film. The stylus will keep driving 2-phase mix (e.g., drop gloss and aqueous droplet) across the heating/cooling and/or magnet/isothermal heater zones to conduct different protocol steps. FIGS.62H to62Jillustrate removal of the droplet from the cartridge. The drop gloss material may be first removed from the droplet, e.g., by contacting an oleophilic material that may wick off the material, by mechanical separation, etc. Alternatively, the droplet may contain the drop gloss with the aqueous material. InFIG.62H, the stylus drives reaction droplet (e.g., containing a product library, or other reaction product, as illustrated and described above) adjacent to the opening through the upper sheet into the air gap (e.g., an inlet hole, etc.) at a safe distance that will avoid contamination of the stylus. This is illustrated inFIG.62I. The droplet to be removed is near but not in the opening into the air gap. However, because the upper sheet is formed of an elastic material, it may be deformed by the pipette top for access, as shown in FIG.62J. In this example, the pipette tip is inserted to the inlet hole (FIG>62I) and reaches a position over the bottom film. It then gets moved towards the droplet (FIG.62J), temporarily deforming the top sheet (film) until it reaches sample position (the droplet is now only partially sandwiched between a top and bottom sheets) and the droplet is aspirated up into the pipette until fully removed or until a specific volume is removed. The pipette tip may then move back to inlet hole opening and then elevates to travel to product destination (e.g., a tube/plate, etc.) so that the operator may collect the material at end of run. Evaporation Control In general, these methods and apparatuses may be configured to prevent or reduce evaporation. In general, drop gloss coatings of the aqueous material, alone or in combination with the application of force (e.g., mechanical force) against the droplet may both enhancing uniformity of heating and/or may prevent evaporation. For example in some variations of the methods and apparatuses described herein, the aqueous droplet may experience less than 10% evaporation (e.g., less than 9%, less than 8%, less than 7%, less than 6%, etc.) evaporation when heated to 95 degrees C. or higher for at least 30 minutes. In one example, a droplet of aqueous reaction mixture heated to 95° C. for 30 min (20 μL in 45 μL drop gloss) experienced approximately 5.8% evaporation in total. FIG.63illustrates an example in which the droplet (e.g., drop gloss plus aqueous droplet) were held in a reaction well formed in the bottom layer by applying suction to conform the bottom layer (which, like the top layer, is elastically deformable) to form a well in the air gap. The base of the drive system holding the cartridge, including the seating region, is therefore shaped to form the well as the bottom layer is attached via suction to the seating region. This well is also a thermal control region including a heater for controlling the temperature of the droplet in the air gap. InFIG.63the droplet was heated to 95° C. for 40 min (20 μL in 45 μL drop gloss). The stylet (shown in this example as a roller stylus) may be held over the top of the sheet, over the droplet. This applied mechanical force may hold or pin the droplet in position relative to the heating region. This may also help thermally insulate the droplet. In some examples the portion of the stylet over the droplet may be a thermal insulating material. In some examples the lower layer (sheet) may be more thermally permissive than the upper layer (sheet). Thus, even as compared to other microfluidic systems, the methods and apparatuses described herein may prevent evaporation in the air gap surprisingly well. It should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein and may be used to achieve the benefits described herein. The process parameters and sequence of steps described and/or illustrated herein are given by way of example only and can be varied as desired. For example, while the steps illustrated and/or described herein may be shown or discussed in a particular order, these steps do not necessarily need to be performed in the order illustrated or discussed. The various example methods described and/or illustrated herein may also omit one or more of the steps described or illustrated herein or include additional steps in addition to those disclosed. Any of the methods (including user interfaces) described herein may be implemented as software, hardware or firmware, and may be described as a non-transitory computer-readable storage medium storing a set of instructions capable of being executed by a processor (e.g., computer, tablet, smartphone, etc.), that when executed by the processor causes the processor to control perform any of the steps, including but not limited to: displaying, communicating with the user, analyzing, modifying parameters (including timing, frequency, intensity, etc.), determining, alerting, or the like. For example, any of the methods described herein may be performed, at least in part, by an apparatus including one or more processors having a memory storing a non-transitory computer-readable storage medium storing a set of instructions for the processes(s) of the method. While various embodiments have been described and/or illustrated herein in the context of fully functional computing systems, one or more of these example embodiments may be distributed as a program product in a variety of forms, regardless of the particular type of computer-readable media used to actually carry out the distribution. The embodiments disclosed herein may also be implemented using software modules that perform certain tasks. These software modules may include script, batch, or other executable files that may be stored on a computer-readable storage medium or in a computing system. In some embodiments, these software modules may configure a computing system to perform one or more of the example embodiments disclosed herein. As described herein, the computing devices and systems described and/or illustrated herein broadly represent any type or form of computing device or system capable of executing computer-readable instructions, such as those contained within the modules described herein. In their most basic configuration, these computing device(s) may each comprise at least one memory device and at least one physical processor. The term “memory” or “memory device,” as used herein, generally represents any type or form of volatile or non-volatile storage device or medium capable of storing data and/or computer-readable instructions. In one example, a memory device may store, load, and/or maintain one or more of the modules described herein. Examples of memory devices comprise, without limitation, Random Access Memory (RAM), Read Only Memory (ROM), flash memory, Hard Disk Drives (HDDs), Solid-State Drives (SSDs), optical disk drives, caches, variations or combinations of one or more of the same, or any other suitable storage memory. In addition, the term “processor” or “physical processor,” as used herein, generally refers to any type or form of hardware-implemented processing unit capable of interpreting and/or executing computer-readable instructions. In one example, a physical processor may access and/or modify one or more modules stored in the above-described memory device. Examples of physical processors comprise, without limitation, microprocessors, microcontrollers, Central Processing Units (CPUs), Field-Programmable Gate Arrays (FPGAs) that implement softcore processors, Application-Specific Integrated Circuits (ASICs), portions of one or more of the same, variations or combinations of one or more of the same, or any other suitable physical processor. Although illustrated as separate elements, the method steps described and/or illustrated herein may represent portions of a single application. In addition, in some embodiments one or more of these steps may represent or correspond to one or more software applications or programs that, when executed by a computing device, may cause the computing device to perform one or more tasks, such as the method step. In addition, one or more of the devices described herein may transform data, physical devices, and/or representations of physical devices from one form to another. Additionally or alternatively, one or more of the modules recited herein may transform a processor, volatile memory, non-volatile memory, and/or any other portion of a physical computing device from one form of computing device to another form of computing device by executing on the computing device, storing data on the computing device, and/or otherwise interacting with the computing device. The term “computer-readable medium,” as used herein, generally refers to any form of device, carrier, or medium capable of storing or carrying computer-readable instructions. Examples of computer-readable media comprise, without limitation, transmission-type media, such as carrier waves, and non-transitory-type media, such as magnetic-storage media (e.g., hard disk drives, tape drives, and floppy disks), optical-storage media (e.g., Compact Disks (CDs), Digital Video Disks (DVDs), and BLU-RAY disks), electronic-storage media (e.g., solid-state drives and flash media), and other distribution systems. A person of ordinary skill in the art will recognize that any process or method disclosed herein can be modified in many ways. The process parameters and sequence of the steps described and/or illustrated herein are given by way of example only and can be varied as desired. For example, while the steps illustrated and/or described herein may be shown or discussed in a particular order, these steps do not necessarily need to be performed in the order illustrated or discussed. The various exemplary methods described and/or illustrated herein may also omit one or more of the steps described or illustrated herein or comprise additional steps in addition to those disclosed. Further, a step of any method as disclosed herein can be combined with any one or more steps of any other method as disclosed herein. The processor as described herein can be configured to perform one or more steps of any method disclosed herein. Alternatively or in combination, the processor can be configured to combine one or more steps of one or more methods as disclosed herein. When a feature or element is herein referred to as being “on” another feature or element, it can be directly on the other feature or element or intervening features and/or elements may also be present. In contrast, when a feature or element is referred to as being “directly on” another feature or element, there are no intervening features or elements present. It will also be understood that, when a feature or element is referred to as being “connected”, “attached” or “coupled” to another feature or element, it can be directly connected, attached or coupled to the other feature or element or intervening features or elements may be present. In contrast, when a feature or element is referred to as being “directly connected”, “directly attached” or “directly coupled” to another feature or element, there are no intervening features or elements present. Although described or shown with respect to one embodiment, the features and elements so described or shown can apply to other embodiments. It will also be appreciated by those of skill in the art that references to a structure or feature that is disposed “adjacent” another feature may have portions that overlap or underlie the adjacent feature. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. For example, as used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items and may be abbreviated as “/”. Spatially relative terms, such as “under”, “below”, “lower”, “over”, “upper” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is inverted, elements described as “under” or “beneath” other elements or features would then be oriented “over” the other elements or features. Thus, the exemplary term “under” can encompass both an orientation of over and under. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. Similarly, the terms “upwardly”, “downwardly”, “vertical”, “horizontal” and the like are used herein for the purpose of explanation only unless specifically indicated otherwise. Although the terms “first” and “second” may be used herein to describe various features/elements (including steps), these features/elements should not be limited by these terms, unless the context indicates otherwise. These terms may be used to distinguish one feature/element from another feature/element. Thus, a first feature/element discussed below could be termed a second feature/element, and similarly, a second feature/element discussed below could be termed a first feature/element without departing from the teachings of the present invention. Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising” means various components can be co-jointly employed in the methods and articles (e.g., compositions and apparatuses including device and methods). For example, the term “comprising” will be understood to imply the inclusion of any stated elements or steps but not the exclusion of any other elements or steps. In general, any of the apparatuses and methods described herein should be understood to be inclusive, but all or a sub-set of the components and/or steps may alternatively be exclusive and may be expressed as “consisting of” or alternatively “consisting essentially of” the various components, steps, sub-components or sub-steps. As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers may be read as if prefaced by the word “about” or “approximately,” even if the term does not expressly appear. The phrase “about” or “approximately” may be used when describing magnitude and/or position to indicate that the value and/or position described is within a reasonable expected range of values and/or positions. For example, a numeric value may have a value that is +/−0.1% of the stated value (or range of values), +/−1% of the stated value (or range of values), +/−2% of the stated value (or range of values), +/−5% of the stated value (or range of values), +/−10% of the stated value (or range of values), etc. Any numerical values given herein should also be understood to include about or approximately that value, unless the context indicates otherwise. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. It is also understood that when a value is disclosed that “less than or equal to” the value, “greater than or equal to the value” and possible ranges between values are also disclosed, as appropriately understood by the skilled artisan. For example, if the value “X” is disclosed the “less than or equal to X” as well as “greater than or equal to X” (e.g., where X is a numerical value) is also disclosed. It is also understood that throughout the application, data is provided in a number of different formats, and that this data, represents endpoints and starting points, and ranges for any combination of the data points. For example, if a particular data point “10” and a particular data point “15” are disclosed, it is understood that greater than, greater than or equal to, less than, less than or equal to, and equal to 10 and 15 are considered disclosed as well as between 10 and 15. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed. Although various illustrative embodiments are described above, any of a number of changes may be made to various embodiments without departing from the scope of the invention as described by the claims. For example, the order in which various described method steps are performed may often be changed in alternative embodiments, and in other alternative embodiments one or more method steps may be skipped altogether. Optional features of various device and system embodiments may be included in some embodiments and not in others. Therefore, the foregoing description is provided primarily for exemplary purposes and should not be interpreted to limit the scope of the invention as it is set forth in the claims. The examples and illustrations included herein show, by way of illustration and not of limitation, specific embodiments in which the subject matter may be practiced. As mentioned, other embodiments may be utilized and derived there from, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. Such embodiments of the inventive subject matter may be referred to herein individually or collectively by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept, if more than one is, in fact, disclosed. Thus, although specific embodiments have been illustrated and described herein, any arrangement calculated to achieve the same purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description.
158,540
11857962
DETAILED DESCRIPTION While various embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed. The term “acrylic” product or material, as used herein, generally refers to a synthetic polymer, for example, a polymer of methyl methacrylate. For example, a kind of acrylic product may include at least 70 at most acrylic acid of 100 weight %. The term “acrylonitrile butadiene styrene”, as used herein, generally refers to a synthetic polymer, for example, a polymer of an acrylonitrile, a butadiene and/or a styrene. For example, the average repeating unit number may be more than 10 or 100. The term “adapter”, as used herein, generally refers to any device for connecting two parts, for example parts that are of different dimensions, structure and/or functions. For example, while one part is hard to connect to another part, a suitable adapter may be used to connect these two or more parts. The term “adhesive”, as used herein, generally refers to a substance applied to one or both surfaces of two separate items that may bind them together, for example, a glue or a tape. The term “area”, as used herein, generally refers to a quantity that expresses the extent of a two-dimensional region. The term “average diameter”, as used herein, generally refers to an average possible chord of any circle, for example, the longest chord. The term “average thickness”, as used herein, generally refers to an average distance between opposite sides of one subject. The term “biological sample”, as used herein, generally refers to a sample collected from Study subjects and any tangible material directly or indirectly derived there from. The term “blocking element”, as used herein, generally refers to an element that may be used to block something to prevent leaking. The term “bottom”, as used herein, generally refers to a lowest part, point, or level of some object. The term “cap”, as used herein, generally refers to an overlaying or covering structure. The term “conductive material”, as used herein, generally refers to a material having a property of conducting electricity. The term “container”, as used herein, generally refers to any receptacle for holding a product. The term “counter electrode”, as used herein, generally refers to an electrode used in a three-electrode electrochemical cell for voltametric analysis or other reactions. The term “DNA primer”, as used herein, generally refers to a short nucleic acid utilized in the initiation of DNA synthesis. The term “electrochemical signal”, as used herein, generally refers to signal of electrical energy from chemical reactions. The term “flow path”, as used herein, generally refers to a route that air or liquid takes when flowing. The term “fluid channel”, as used herein, generally refers to a deeper part of a route that fluid takes when flowing. The term “fluid fill electrodes”, as used herein, generally refers to an electrode that indicate whether or not an area or a section is at least partially filled and/or covered by a fluid. The term “fluid tight seal”, as used herein, generally refers to a tight seal that prevents a leakage of a fluid. The term “height”, as used herein, generally refers to a measure of vertical distance. The term “hydrophilic material”, as used herein, generally refers to a material that is attracted to water. The term “hydrophobic vent material”, as used herein, generally refers to a material that is seemingly repelled from a mass of water used for vent. The term “in fluidic communication with”, as used herein, generally refers to that a fluid may flow between two or more parts. The term “insulative area”, as used herein, generally refers to an area that is not conductive. The term “interior surface”, as used herein, generally refers to a surface of an inside part of something. The term “isothermal nucleic acid amplification”, as used herein, generally refers to a nucleic acid amplification in which the temperature of the system remains constant or basically constant. For example, an isothermal nucleic acid amplification may be a RT-LAMP reaction. The term “layer”, as used herein, generally refers to something lying over or under something else. The term “length”, as used herein, generally refers to a measure of distance. The term “living hinge”, as used herein, generally refers to a flexure bearing that connects two or more parts. The term “lyophilized reagent”, as used herein, generally refers to a reagent that is lyophilized. For example, lyophilized reagent may be a bead or may be of any shape or form. The term “mylar material”, as used herein, generally refers to a polyester film, for example, a stretched polyester film. The term “nucleic acid amplification enzyme”, as used herein, generally refers to enzyme or enzymes used for nucleic acid amplification. For example, nucleic acid amplification enzyme may be a DNA polymerase. The term “open end”, as used herein, generally refers to an end of an object that may permitting an air or a fluid to flow in. The term “opening”, as used herein, generally refers to an aperture or gap. For example, the opening may be allowing access. The term “outer base surface”, as used herein, generally refers to a surface that is of the outer base of an object. The term “outlet”, as used herein, generally refers to a place or opening through which something may be let out. The term “outwardly”, as used herein, generally refers to toward the outside. The term “PETE”, as used herein, generally refers to polyethylene terephthalate. For example, the average repeating unit number may be more than 10 or 100. The term “pierceable barrier”, as used herein, generally refers to a barrier that may be provided for preventing fluid communication between the chambers or the passageways, and the barrier may be capable of being pierced. The term “pierceable plastic film”, as used herein, generally refers to a plastic film that may be capable of being pierced. The term “piercing member”, as used herein, generally refers to a member or a feature that is capable of piercing something. For example, a piercing member may have a blunt or curved upper edge or a pointing. The term “polycarbonate”, as used herein, generally refers to a polymer containing carbonate groups in their chemical structures. For example, the average repeating unit number may be more than 10 or 100. The term “polyethylene”, as used herein, generally refers to a polymer made by polymerizing ethylene. For example, the average repeating unit number may be more than 10 or 100. The term “polyethylene terephthalate”, as used herein, generally refers to a polymer synthesized from ethylene glycol and terephthalic acid. For example, the average repeating unit number may be more than 10 or 100. The term “polypropylene”, as used herein, generally refers to a polymer built up by the polymerization of propylene. For example, the average repeating unit number may be more than 10 or 100. The term “polystyrene”, as used herein, generally refers to a polymer produced by the polymerization of styrene. For example, the average repeating unit number may be more than 10 or 100. The term “polysulfone”, as used herein, generally refers to a polymer containing a sulfone group and alkyl- or aryl-groups. For example, the average repeating unit number may be more than 10 or 100. The term “polytetrafluoroethylene”, as used herein, generally refers to a polymer of tetrafluoroethylene. For example, the average repeating unit number may be more than 10 or 100. The term “polyvinyl chloride”, as used herein, generally refers to a polymer made from the polymerization of vinyl chloride. For example, the average repeating unit number may be more than 10 or 100. The term “protruding element”, as used herein, generally refers to an element extended beyond or above a surface. The term “qualitative signal”, as used herein, generally refers to a signal relating to, measuring, or measured by the quality. The term “quantitative signal”, as used herein, generally refers to a signal relating to, measuring, or measured by the quantity. The term “reader”, as used herein, generally refers to a device or a machine that may be capable of reading a signal. The term “recess element”, as used herein, generally refers to an element recessed below or under a surface. The term “reference electrode”, as used herein, generally refers to an electrode that may provide a standard for the electrochemical measurements. The term “reservoir”, as used herein, generally refers to a place where something may be kept in store. The term “saliva”, as used herein, generally refers to a watery liquid secreted into the mouth by glands. For example, saliva may be used as a sample. The term “sample”, as used herein, generally refers to a part of a subject. For example, a sample may be a saliva or a blood. The term “sample receiving inlet”, as used herein, generally refers to sample inlet for receiving a solid, a fluid or an air sample. The term “sample receptacle”, as used herein, generally refers to a receptacle that may receive and contain a sample. The term “self-sealing”, as used herein, generally refers to an element or an object, for example a vent, that may be capable of sealing itself. For example, sealed by a pressure or a moisture. The term “side”, as used herein, generally refers to a surface or a line that may be forming a border or face of an object. The term “signal detection module”, as used herein, generally refers to a device or a module that may be capable of a detection of a signal. The term “silicone material”, as used herein, generally refers to a polymer consist of chains made of alternating silicon and oxygen atom. For example, a silicone material may be used as an adhesive. The term “snap feature”, as used herein, generally refers to a feature that used to join two components. For example, a snap feature may be a protruding part or a recess part that connecting two components during a joining operation. The term “subject”, as used herein, generally refers to a person, an animal or a thing that is being discussed, described, or studied with. The term “substrate”, as used herein, generally refers to an underlying substance or layer. The term “target”, as used herein, generally refers to a thing that may be selected as an object of attention or detected. For example, a target may be a virus or a DNA or RNA of a virus. The term “thermo control module”, as used herein, generally refers to a module that may be used for regulating temperature. For example, a thermo control module may be an automatic thermo control module. The term “top inner surface”, as used herein, generally refers to a surface that is of the top inner of an object. The term “twisting action”, as used herein, generally refers to an action of turning, rotating, bending or curling. The term “vent”, as used herein, generally refers to an opening that may be used for the escape of a gas or liquid or for the relief of pressure. The term “vertical plane”, as used herein, generally refers to a plane that may pass through a vertical line. The term “wall”, as used herein, generally refers to a layer enclosing space. For example, a wall may be a wall of a container. The term “width”, as used herein, generally refers to a measurement or extent of something from side to side. The term “working area”, as used herein, generally refers to an area where the action of work is performing. For example, a working area may be an area for the detection of a target. The term “working electrode”, as used herein, generally refers to an electrode that may be used for directing the course of the electrochemical reaction. For example, a working electrode may be a gold. Container In one aspect, the present disclosure provides a container. The container may comprise a sample receptacle and a cap. As illustrated inFIG.1, the present disclosure provides a container100, comprising a sample receptacle110and a cap120. The cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120. The present disclosure provides a container100, wherein said first piercing member1202may extend downwardly toward said first open end1101of the sample receptacle110when said first open end1101is closed by said cap120. For example, some of said first piercing member1202may extend downwardly toward said first open end1101of the sample receptacle110. The present disclosure provides a container100, wherein said cap120may comprise a top inner surface1204, and said first piercing member1202may extend from the top inner surface1204of said cap120. For example, said first piercing member1202may extend from the side inner surface1204of said cap120. The present disclosure provides a container100, wherein said first piercing member1202may extend approximately perpendicularly from said top inner surface1204. For example, some of said first piercing member1202may extend approximately perpendicularly from said top inner surface1204. The present disclosure provides a container100, wherein said first piercing member1202may comprise a blunt or curved upper edge. For example, wherein said first piercing member1202may comprise a feature other than a blunt or curved upper edge, for example, a pointed end. Wherein said first piercing member1202may be configured to maintain a suitable tension in the first pierceable barrier1203and pierce the first pierceable barrier1203, when said first open end1101is closed by said cap120. The present disclosure provides a container100, wherein said sample receptacle110may comprise an inner base surface1103, and the width of said first open end1101may be greater than or equal to the width of said inner base surface1103. For example, the width of said first open end1101may be 1% greater, 2% greater, 5% greater, 10% greater, 20% greater, 50% greater, 1 time greater, 2 times greater, or 3 times greater than or equal to the width of said inner base surface1103. The present disclosure provides a container100, wherein said one or more second piercing members1102may extend upwardly toward said first open end1101of the sample receptacle110. The present disclosure provides a container100, wherein said one or more second piercing members1102may extend from the inner base surface1103of said sample receptacle110. The present disclosure provides a container100, wherein said one or more second piercing members1102may extend approximately perpendicularly from said inner base surface1103of said sample receptacle110. The present disclosure provides a container100, wherein said sample receptacle110may comprise two of said second piercing members1102arranged opposite one another on either side of a vertical plane extending through the length of said sample receptacle110. The present disclosure provides a container100, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120. For example, the distance of two of said second piercing members1102may be larger or equal to the thickness of said first piercing member1202. For example, the sum of the length of said second piercing members1102and said first piercing member1202may be larger than the depth of the reservoir1201.For example, two of said second piercing members1102and said first piercing member1202may be configured to maintain a suitable tension in the first pierceable barrier1203and pierce the first pierceable barrier1203, when said first open end1101may be closed by said cap120. The present disclosure provides a container100, wherein each of said one or more second piercing members1102may comprise a blunt or curved upper edge. For example, wherein said one or more second piercing members1102may comprise a feature other than a blunt or curved upper edge, for example, a pointed end. The present disclosure provides a container100, wherein said first and second piercing members may be configured to disestablish said first pierceable barrier1203without a twisting action during closure of said cap120. The present disclosure provides a container100, wherein said first pierceable barrier1203may comprise a pierceable plastic film or a foil film. The present disclosure provides a container100, wherein said first pierceable barrier1203comprises a pierceable film made from a material selected from the group consisting of polyethylene terephthalate (PETE), polycarbonate, polyethylene, and polyvinyl chloride (PVC). The present disclosure provides a container100, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120, wherein said first and second piercing members may be configured to disestablish said first pierceable barrier1203without a twisting action during closure of said cap120, wherein said first pierceable barrier1203comprises a pierceable film made from a material selected from the group consisting of polyethylene terephthalate (PETE), polycarbonate, polyethylene, and polyvinyl chloride (PVC). The present disclosure provides a container100, wherein said sample receptacle110may comprise an outlet1104, and said outlet1104may be in fluidic communication with said sample receptacle110. The present disclosure provides a container100, wherein said outlet1104may be on said inner base surface1103of said sample receptacle110. The present disclosure provides a container100, wherein said outlet1104may be sealed by a second pierceable barrier1105. The present disclosure provides a container100, wherein said second pierceable barrier1105may comprise a pierceable plastic film or a foil film. The present disclosure provides a container100, wherein said second pierceable barrier1105may comprises a pierceable film made from a material selected from the group consisting of polyethylene terephthalate (PETE), polycarbonate, polyethylene, and polyvinyl chloride (PVC). The present disclosure provides a container100, wherein said cap120may be attached to said sample receptacle110via a living hinge, or said cap120may be not attached to said sample receptacle110. The present disclosure provides a container100, wherein said cap120may comprise a wall1205defining the outer perimeter of said reservoir1201. The present disclosure provides a container100, wherein said wall1205may have an outer edge and said first pierceable barrier1203may be sealingly attached to said outer edge so as to cover said reservoir1201. Wherein, first pierceable barrier1203may be sealingly attached to other part of said reservoir1201, for example the inner surface or outer surface of said reservoir1201, so as to cover said reservoir1201. The present disclosure provides a container100, wherein said wall1205may nest within the first open end1101of said sample receptacle110to form a fluid tight seal when said first open end1101may be closed by said cap120. The present disclosure provides a container100, wherein an outer surface of said wall1205may be made from or may be coated with an elastomeric material for sealingly engagement against an inner surface of said sample receptacle110when said first open end1101may be closed by said cap120. The present disclosure provides a container100, wherein at least a portion of an interior surface1106of the sample receptacle110, configured to be in contact with said wall1205of the cap120when the cap120is closed, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of the wall1205, for sealing the first open end1101against flow when the atmospheric pressure may be equal to or greater than the pressure in the container100. For example, at least a portion of an interior surface1106of the sample receptacle110may be configured to be in contact with said wall1205of the cap120for sealing the first open end1101against flow of a gas or a fluid. For example, each portion of an interior surface1106of the sample receptacle110may be configured to be in contact with said wall1205of the cap120for sealing the first open end1101against flow of a gas or a fluid. The present disclosure provides a container100, wherein said elastomeric material may be independently selected from the group consisting of polytetrafluoroethylene (PTFE), polycarbonate (PCTE), polyethylene (PE) and polypropylene (PP). The present disclosure provides a container100, wherein the reservoir1201may be sized to accommodate no less than about 500 μL fluid. Wherein the reservoir may be sized to accommodate about 500 μL to about 3000 μL of said composition, for example, about 500 μL to about 3000 μL, about 700 μL to about 3000 μL, about 900 μL to about 3000 μL, about 1000 μL to about 3000 μL, about 1100 μL to about 3000 μL, about 1300 μL to about 3000 μL, about 1500 μL to about 3000 μL, about 1700 μL to about 3000 μL, about 1900 μL to about 3000 μL, about 2000 μL to about 3000 μL, about 2100 μL to about 3000 μL, about 2300 μL to about 3000 μL, about 2500 μL to about 3000 μL, about 2700 μL to about 3000 μL, about 2900 μL to about 3000 μL, about 500 μL to about 2500 μL, about 1000 μL to about 2500 μL, about 1500 μL to about 2500 μL, about 500 μL to about 2000 μL, about 1000 μL to about 2000 μL, about 1500 μL to about 2000 μL, about 500 μL to about 1500 μL, about 1000 μL to about 1500 μL or about 500 μL to about 1000 μL of said composition. The present disclosure provides a container100, wherein said sample receptacle110may be configured to receive about 0.5 ml to about 1.5 ml of said sample. Wherein said sample receptacle110may be configured to receive about 0.5 ml to about 1.5 ml, 0.7 ml to about 1.5 ml, 0.9 ml to about 1.5 ml, 1.0 ml to about 1.5 ml, 1.1 ml to about 1.5 ml, 1.3 ml to about 1.5 ml, 0.5 ml to about 1.0 ml, 0.7 ml to about 1.0 ml, or 0.9 ml to about 1.0 ml of said sample. The present disclosure provides a container100, wherein said sample may be a biological sample. Wherein said biological sample may be saliva. Wherein said biological sample may be blood. The present disclosure provides a container100, wherein said sample receptacle110may include an interior surface1106that may be sloped downward from said first open end1101toward said inner base surface1103, wherein said interior surface1106may define a flow path for said composition following release of said composition from said reservoir1201when said first pierceable barrier1203may be disestablished by said first and second piercing members. The present disclosure provides a container100, wherein said cap120may further comprise said composition sealed within said reservoir1201. The present disclosure provides a container100, wherein said composition may comprises a sample treatment buffer. The present disclosure provides a container100, wherein said composition may comprises the reagent selected from the group consisting of: redox reagent, .For example, a redox reagent may be a dithiothreitol (DTT); a nucleic acid may be RNA, or tRNA (transfer ribonucleic acid); a nonionic detergent may be a Tween, or Tween 20; a DNA intercalating redox reporter may be a methylene blue; a ribonuclease inhibitor may be a Murine RNase Inhibitor (NEB M0314), Protector RNase Inhibitor (Roche, RNAINH-RO) or a RNAsecure (Thermo Fisher Scientific, AM7005). The present disclosure provides a container100, wherein said composition may comprises the reagent selected from the group consisting of: dithiothreitol (DTT), tRNA, Tween 20, methylene blue, RNase Inhibitor—Murine (NEB M0314), Protector RNase Inhibitor (Roche, RNAINH-RO), and RNAsecure (Thermo Fisher Scientific, AM7005). As an alternative sample receptacle110illustrated inFIG.2, the present disclosure provides a container100, wherein said sample receptacle110may comprise one or more third piercing members1107located on an outer base surface of said sample receptacle110, said one or more third piercing members1107may extend outwardly from said outer base surface. Wherein said sample receptacle110may comprise 1 to 50, 1 to 20, 1 to 10, 1 to 5, 1 to 4, 1 to 3 or 1 to 2 third piercing members1107. Wherein said sample receptacle110may comprise 1, 2, 3, 4, or 5 third piercing members1107. Wherein said one or more third piercing member1107may be arranged in a generally circular fashion on said outer surface of said extension. Wherein the distance of said one or more third piercing member1107may be basically the same. Said one or more third piercing members1107may extend outwardly from said first open1101. Said one or more third piercing members1107may extend to a basically different direction of said second piercing members1102. Said one or more third piercing members1107may extend outwardly from said first open1101, and said second piercing members1102extend towards said first open1101. The present disclosure provides a container100, wherein sample receptacle110may comprise an extension1108, said extension1108may extend outwardly from said outer base surface of said sample receptacle110and an inner of said extension may be in fluidic communication with said first open1101. The present disclosure provides a container100, wherein the diameter of an outer surface of said extension1108may be smaller or equal to the diameter of an inner surface of a sample receiving inlet2101of an adapter210, as an alternative adapter210illustrated inFIG.3. For example, the diameter of an inner surface of a sample receiving inlet2101of an adapter210may be 1% greater, 2% greater, 5% greater, 10% greater, 20% greater, 50% greater, 1 time greater, 2 times greater, or 3 times greater than the diameter of an outer surface of said extension1108. The present disclosure provides a container100, wherein said outer surface of said extension1108may be made from or may be coated with an elastomeric material for sealingly engagement against said inner surface of said sample receiving inlet2101when said container100may be mounted on said adapter210. The present disclosure provides a container100, wherein at least a portion of said inner surface of said sample receiving inlet2101, configured to be in contact with said extension1108of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said extension1108, to form a fluid tight seal when said container100may be mounted on said adapter210. Each portion of said inner surface of said sample receiving inlet2101may be configured to be in contact with said extension1108of said container100when said container100may be mounted on said adapter210, to form a fluid tight seal when said container100may be mounted on said adapter210. The present disclosure provides a container100, wherein said one or more third piercing members1107may extend outwardly from an outer base surface of said extension1108. Wherein said one or more third piercing members1107may extend outwardly from any surface, such as outer peripheral surface, of said extension1108. The present disclosure provides a container100, wherein said one or more third piercing members1107may extend approximately perpendicularly from said outer base surface. The present disclosure provides a container100, wherein said one or more third piercing members1107may extend in a direction substantially oppositely to said one or more second piercing members1102. Said one or more third piercing members1107may extend outwardly from said first open1101, and said second piercing members1102may extend towards said first open1101. The present disclosure provides a container100, wherein said one or more third piercing member1107may be arranged in a generally circular fashion on said outer surface of said extension. The present disclosure provides a container100, wherein said one or more third piercing members1107may be arranged surrounding said outlet1104of the sample receptable110. Wherein said one or more third piercing member1107may be arranged in a generally circular fashion on said outer surface of said extension. Wherein said one or more third piercing member1107may be arranged in a generally polygon fashion on said outer surface of said extension. Wherein said one or more third piercing member1107may be arranged in a generally regular polygon fashion on said outer surface of said extension. Wherein said one or more third piercing member1107may be arranged in a generally regular triangle fashion on said outer surface of said extension. Wherein said one or more third piercing member1107may be arranged in a generally regular rectangle fashion on said outer surface of said extension. The present disclosure provides a container100, wherein said one or more third piercing members1107may be configured to disestablish a pierceable barrier of an adapter210when said container100is mounted on said adapter210. The present disclosure provides a container100, wherein said one or more third piercing members1107may comprise a blunt or curved lower edge. Wherein said one or more third piercing members1107may comprises a feature other than a blunt or curved upper edge, for example, a pointed end. The present disclosure provides a container100, wherein said one or more third piercing members1107may have a height of no less than about 0.5 mm. For example, the height of said one or more third piercing members1107may be of 0.1 to 0.5 mm, 0.2 to 0.5 mm, 0.3 to 0.5 mm, or 0.4 to 0.5 mm. The present disclosure provides a container100, wherein said one or more third piercing member1107may extend downwardly toward a sample receiving inlet2101of an adapter210when said container100may be mounted on said adapter210. The present disclosure provides a container100, wherein said one or more third piercing member1107may extend approximately perpendicularly downwardly toward said sample receiving inlet2101of an adapter210. The present disclosure provides a container100, wherein said sample receptacle110may comprise one or more outer rings1109, said one or more outer ring may extend outwardly from said outer base surface. The present disclosure provides a container100, wherein an outer surface of said one or more outer rings1109may be made from or may be coated with an elastomeric material for sealingly engagement against an inner surface of an adapter when said container100may be mounted on said adapter210. The present disclosure provides a container100, wherein at least a portion of said inner surface of said adapter210, configured to be in contact with said one or more outer rings1109of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said one or more outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210. Each portion of said inner surface of said adapter210may be configured to be in contact with said one or more outer rings1109of said container100when said container100may be mounted on said adapter210, to form a fluid tight seal when said container100may be mounted on said adapter210. The present disclosure provides a container100, wherein said cap may comprise a first snap feature1206and said sample receptacle110may comprise a second snap feature1110, said first snap feature1206and said second snap feature1110may be configured for said first open1101to be irreversibly closed by said cap120. The join of said first open1101and said cap120may be separable or inseparable depending on the shape of snap feature; the force required to separate the components varies greatly according to the design. FIGS.17A-17Eillustrate each view of another cap120. The cap120may comprise a first snap feature1206and first snap feature1206has a shape of hook. Wherein, said first snap feature1206and said second snap feature of a sample receptacle may be configured to be irreversibly closed by said cap120. Wherein, an audible CLICK may be made for positive user feedback when said sample receptacle is capping. When said sample receptacle is capping, a top-sealing1207may be positioned between the top surface of said sample receptacle and inner surface of said cap120. Wherein said top-sealing1207may provide a leak-proof seal when said sample receptacle is capping. Said top-sealing1207may be made from or may be coated with an elastomeric material. Wherein, said top-sealing1207may be pressed when said sample receptacle is capping, which may generate positive pressure inside container100. FIGS.18A-18Eillustrate each view of another cap120. The volume of said reservoir1201of a cap120may be about 1.5 mL or about 3 mL. FIGS.19A-19Eillustrate each view of another sample receptacle110. The sample receptacle110may comprise a second snap feature1110. Wherein, said first snap feature1206and said second snap feature of a sample receptacle may be configured to be irreversibly closed by said cap120. Wherein, an audible CLICK may be made for positive user feedback when said sample receptacle is capping. The second snap feature1110may be printed, such as to be black, for user checking the completion of capping. Wherein said sample receptacle110may comprise four of second piercing members1102configured to allow first piercing member1202to be positioned between two of second piercing members1102when said first open end1101may be closed by said cap120. A fill line1112may be printed on the inner surface or outer surface of the sample receptacle110, which may be used for guiding user depositing the requisite amount of sample in sample receptacle110. Wherein said sample receptacle110may comprise a filter1113, which may filter out debris that might otherwise interfere with the test. The filter1113may be made of a porous sintered HDPE material. The diameter of the filter1113may be 6 mm, and the thickness may be 3-5 mm. Wherein said sample receptacle110may comprise one or more guide ribs. The guide ribs of the sample receptacle110may be positioned on the inner surface of the sample receptacle110. wherein ribs may guide the insertion of the cap120onto the sample receptacle110. When said sample receptacle is capping, the top surface of said sample receptacle may be non-R-angle, which keeps the air pressure in the sample receptacle110. FIG.20illustrates longitudinal section view of another extension1108. Wherein, said extension1108may extend outwardly from said outer base surface of said sample receptacle110. Wherein about six filter stoppers1108amay be positioned on the inner side of said extension1108, which may be used to prevent filter1113being inside the sample receptacle110. The extension1108may comprise two or more sections, the first section1108bis the part near the bottom of the sample receptacle110, and the second section1108cis the part away from the bottom of the sample receptacle110. The outer surface of the first section1108bmay be almost vertical with 0.5-degree draft angle. The diameter of outer surface of the second section1108cmay be smaller than the first section1108b,and the outer surface of the second section1108cmay be with about 2-degree to 10-degree draft angle, wherein the diameter of the outer surface of the second section1108cmay be smaller when the part is away from the bottom of the sample receptacle110. The inner surface of the first section1108bmay be almost vertical with 0.5-degree draft angle. The diameter of inner surface of the second section1108cmay be larger than the first section1108b,which may guide the filter insertion. FIGS.21A-21Gillustrate each view of another sample receptacle110. The sample receptacle110may be used as a swab collector. The sample receptacle110may comprise one or more swab holder1114. The number of the swab holder1114may be 1, 2, 3, 4, 5, 6 or 7. FIGS.22A-22Gillustrate each view of a protector130. The protector130may be used to snap reversibly onto a container100and protect the container100from contaminated. The protector130may comprise a snap feature1301. Wherein the snap feature1301has a protrusion, which is easy to be clicked into the indent of the sample receptacle110. Wherein, the protector130may be easy to be taken out from the sample receptacle110. he protector130may comprise one or more extension, configured to be in contact with one or more outer rings1109of an outer base surface of a container100when said container100may be mounted on said protector130. The present disclosure provides a container100, wherein said first snap feature1206comprises at least one protruding element and said second snap feature1110may comprise at least one recess element configured to irreversibly catch said at least one protruding element. Wherein said first snap feature1206may comprise at least one recess element and said second snap feature1110comprises at least one protruding element configured to irreversibly catch said at least one protruding element. For example, a protruding element may be a hook, a stud or a bead, which may be deflected briefly during a joining operation and catch in a depression in the mating component. The join of the catch may be separable or inseparable depending on the shape of snap feature; the force required to separate the components varies greatly according to the design. The present disclosure provides a container100, wherein said sample receptacle110may comprise one or more third snap features1111, said one or more third snap features1111may be on bottom of said sample receptable110. The present disclosure provides a container100, wherein said one or more third snap features1111and one or more snap features2102of an adapter210, as an alternative adapter210illustrated inFIG.3, may be configured for said container100to be irreversibly mounted on said adapter210. The join of said container100and said adapter210may be separable or inseparable depending on the shape of snap feature; the force required to separate the components varies greatly according to the design. The present disclosure provides a container100, wherein said one or more third snap features1111may comprise at least one protruding element, and said one or more snap features2102of said adapter210may comprise at least one recess element configured to irreversibly catch said at least one protruding element. Wherein said one or more third snap features1111may comprise at least one recess element, and said one or more snap features2102of said adapter210comprise at least one protruding element configured to irreversibly catch said at least one protruding element. The join of said third snap features1111and said snap features2102may be separable or inseparable depending on the shape of snap feature; the force required to separate the components varies greatly according to the design. The present disclosure provides a container100, wherein said container100and said adapter210may form a tight seal when said container100may be mounted on said adapter210. The present disclosure provides a container100, wherein said one or more third snap features1111may be arranged opposite one another on either side of said outer base surface of said sample receptable110. The present disclosure provides a container100, said one or more third snap features1111may have a height of about 2 mm to 5 mm. For example, said one or more third snap features1111may have a height of about 2 mm to 5 mm, 3 mm to 5 mm, 4 mm to 5 mm, 2 mm to 4 mm, 3 mm to 4 mm or 2 mm to 3 mm. The present disclosure provides a container100, wherein said one or more third snap features1111may comprise at least one protruding element or at least one recess element. The present disclosure provides a container100, wherein said sample receptacle110may have a height of no less than about 10 mm. The present disclosure provides a container100, wherein said sample receptacle may have a height of about 10 mm to about 500 mm. For example, said sample receptacle110may have a height of no less than about 10 mm, no less than about 50 mm, no less than about 100 mm, no less than about 150 mm, no less than about 200 mm, no less than about 230 mm, no less than about 240 mm, no less than about 250 mm, no less than about 260 mm, no less than about 300 mm, no less than about 350 mm, no less than about 400 mm, no less than about 450 mm, or no less than about 500 mm. For example, the height of said sample receptacle110may be measured from the bottom of said sample receptable110to the top of the cap120. For example, the height of said sample receptacle110may be measured from the bottom of said sample receptable110to the top of said sample receptable110. For example, the height of said sample receptacle110may be measured from the bottom of said sample receptable110to the top of the cap120, when said sample receptable110may be fully closed by the cap120. The present disclosure provides a container100, wherein said sample receptacle110may have a height of about 250 mm. For example, said sample receptacle110may have a height of about 10 mm, about 30 mm, about 50 mm, about 100 mm, about 150 mm, about 200 mm, about 500 mm, about 750 mm, or about 1000 mm. The present disclosure provides a container100, wherein said inner base surface of said sample receptacle110may have an area of about 200 mm2to about 600 mm2. For example, said inner base surface of said sample receptacle110may have an area of about 200 mm2to about 600 mm2, about 300 mm2to about 600 mm2, about 400 mm2to about 600 mm2, about 500 mm2to about 600 mm2, about 200 mm2to about 500 mm2, about 300 mm2to about 500 mm2, about 400 mm2to about 500 mm2, about 200 mm2to about 400 mm2, about 300 mm2to about 400 mm2, or about 200 mm2to about 300 mm2. The present disclosure provides a container100, comprising a sample receptacle110and a cap120, wherein said cap120may further comprise said composition sealed within said reservoir1201, said cap may comprise a first snap feature1206and said sample receptacle110may comprise a second snap feature1110, said first snap feature1206and said second snap feature1110may be configured for said first open1101to be irreversibly closed by said cap120, said sample receptacle110may have a height of about 250 mm and said inner base surface of said sample receptacle110may have an area of about 200 mm2to about 600 mm2. The present disclosure provides a container100, comprising a sample receptacle110and a cap120, wherein said sample receptacle110may comprise two of second piercing members1102configured to allow first piercing member1202to be positioned between two of second piercing members1102when said first open end1101may be closed by said cap120, said first pierceable barrier1203may comprise a pierceable plastic film or a foil film, said outlet1104may be sealed by a second pierceable barrier1105, said cap120may further comprise said composition sealed within said reservoir1201, one or more third piercing members1107may be configured to disestablish a pierceable barrier of an adapter210when said container100is mounted on said adapter210, said sample receptacle110may have a height of about 250 mm and said inner base surface of said sample receptacle110may have an area of about 200 mm2to about 600 mm2. The present disclosure provides a container100, comprising a sample receptacle110and a cap120, wherein said sample receptacle110may comprise two of second piercing members1102configured to allow first piercing member1202to be positioned between two of second piercing members1102when said first open end1101may be closed by said cap120, said first pierceable barrier1203may comprise a pierceable plastic film or a foil film, said outlet1104may be sealed by a second pierceable barrier1105, said cap120may further comprise said composition sealed within said reservoir1201, sample receptacle110may comprise an extension1108, said one or more third piercing members1107may extend outwardly from an outer base surface of said extension1108, said one or more third piercing members1107may be configured to disestablish a pierceable barrier of an adapter210when said container100is mounted on said adapter210, said cap may comprise a first snap feature1206and said sample receptacle110may comprise a second snap feature1110, said first snap feature1206and said second snap feature1110may be configured for said first open1101to be irreversibly closed by said cap120, said sample receptacle110may have a height of about 250 mm and said inner base surface of said sample receptacle110may have an area of about 200 mm2to about 600 mm2. The present disclosure provides a container100, comprising a sample receptacle110and a cap120, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120, said first pierceable barrier1203may comprise a pierceable plastic film or a foil film, said outlet1104may be sealed by a second pierceable barrier1105, at least a portion of an interior surface1106of the sample receptacle110, configured to be in contact with said wall1205of the cap120when the cap120is closed, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of the wall1205, for sealing the first open end1101against flow when the atmospheric pressure may be equal to or greater than the pressure in the container100, said cap120may further comprise said composition sealed within said reservoir1201, at least a portion of said inner surface of said sample receiving inlet, configured to be in contact with said extension of said container when said container is mounted on said adapter, is made from or is coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said extension, to form a fluid tight seal when said container is mounted on said adapter, sample receptacle110may comprise an extension1108, said one or more third piercing members1107may extend outwardly from an outer base surface of said extension1108, said one or more third piercing members1107may be configured to disestablish a pierceable barrier of an adapter210when said container100is mounted on said adapter210, at least a portion of said inner surface of said adapter210, configured to be in contact with said one or more outer rings1109of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said one or more outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210, said cap may comprise a first snap feature1206and said sample receptacle110may comprise a second snap feature1110, said first snap feature1206and said second snap feature1110may be configured for said first open1101to be irreversibly closed by said cap120, said sample receptacle110may have a height of about 250 mm and said inner base surface of said sample receptacle110may have an area of about 200 mm2to about 600 mm2. An alternative sample receptacle110may be illustrated inFIG.6andFIG.7, an alternative adapter210may be illustrated inFIG.8, an alternative cap120may be illustrated inFIG.9andFIG.10, and an alternative container100and an alternative adapter210may be illustrated inFIG.11andFIG.12. Device As illustrated inFIG.4, the present disclosure provides a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said first layer310may have an average thickness of about 0.1 mm to about 0.3 mm. For example, said first layer310may have an average thickness of about 0.1 mm to about 0.3 mm, about 0.1 mm to about 0.2 mm, or about 0.2 mm to about 0.3 mm. Wherein said at least one fluid channel3102may be configured to be completely filled with about 20 μL to about 150 μL fluid. For example, said at least one fluid channel3102may be configured to be completely filled with about 20 μL to about 150 μL fluid, about 30 μL to about 150 μL fluid, about 50 μL to about 150 μL fluid, about 70 μL to about 150 μL fluid, about 100 μL to about 150 μL fluid, about 120 μL to about 150 μL fluid, about 140 μL to about 150 μL fluid, about 20 μL to about 140 μL fluid, about 30 μL to about 140 μL fluid, about 50 μL to about 140 μL fluid, about 70 μL to about 140 μL fluid, about 100 μL to about 140 μL fluid, about 120 μL to about 140 μL fluid, about 20 μL to about 100 μL fluid, about 30 μL to about 100 μL fluid, about 50 μL to about 100 μL fluid, about 70 μL to about 100 μL fluid, about 20 μL to about 50 μL fluid, about 30 μL to about 50 μL fluid, or about 20 μL to about 30 μL fluid. For example, that said at least one fluid channel3102may be configured to be completely filled with certain fluid may mean that said fluid channel3102may be configured to be filled from the sample receiving inlet3101to said vent3103. For example, that said at least one fluid channel3102may be configured to be completely filled with certain fluid may mean that said fluid channel3102may be configured to be filled from the sample receiving inlet3101to halfway of said fluid channel3102, for example the opening3301of a third layer330. The present disclosure provides a device300, wherein said at least one fluid channel3102may comprise two or more fluid channels3102substantially equidistant from said sample receiving inlet3101. The present disclosure provides a device300, wherein said at least one fluid channel3102may comprise two or more fluid channels3102with substantially equal channel width. The present disclosure provides a device300, wherein pore size of said vent3103may have an average diameter of about 0.1 μm to about 10 μm. For example, pore size of said vent3103may have an average diameter of about 0.1 μm to about 10 μm, about 0.2 μm to about 10 μm, about 0.5 μm to about 10 μm, about 1 μm to about 10 μm, about 5 μm to about 10 μm, or about 7 μm to about 10 μm. For example, pore size of said vent3103may have an average diameter of about 0.1 μm, about 0.3 μm, about 0.5 μm, about 1 μm, about 2 μm, about 5 μm, about 7 μm, or about 10 μm. The present disclosure provides a device300, wherein said vent3103may be a self-sealing vent. For example, the material for sealing the vent3103may be self-sealing. The present disclosure provides a device300, wherein said hydrophobic vent material may be selected from the group consisting of: polytetrafluoroethylene (PTFE), polycarbonate (PCTE), polyethylene (PE) and polypropylene (PP). The present disclosure provides a device300, wherein side walls of the at least one fluid channel3102may be not coated with a hydrophilic material. The present disclosure provides a device300, wherein said sample receiving inlet3101may comprise a lyophilized reagent2105, as illustrated inFIG.5. The present disclosure provides a device300, wherein said lyophilized reagent2105may comprise an assay reagent. The present disclosure provides a device300, wherein said assay reagent may comprise a nucleic acid amplification enzyme and a DNA primer. The present disclosure provides a device300, wherein a height of each fluid channel3102may be about 0.1 mm to about 1.5 mm. For example, height of each fluid channel3102may be about 0.1 mm to about 1.5 mm, about 0.5 mm to about 1.5 mm, about 1.0 mm to about 1.5 mm, about 0.1 mm to about 1.0 mm, about 0.5 mm to about 1.0 mm, or about 0.1 mm to about 0.5 mm. The present disclosure provides a device300, wherein a width of each fluid channel3102may be about 0.3 mm to about 1 mm. For example, width of each fluid channel3102may be about 0.3 mm to about 1 mm, about 0.5 mm to about 1 mm, about 0.7 mm to about 1 mm, about 0.3 mm to about 0.7 mm, about 0.5 mm to about 0.7 mm, or about 0.3 mm to about 0.5 m. The present disclosure provides a device300, wherein a length of each fluid channel3102may be about 50 mm to about 150 mm. For example, length of each fluid channel3102may be about 50 mm to about 150 mm, about 100 mm to about 150 mm, or about 50 mm to about 100 mm. The present disclosure provides a device300, wherein a height of each fluid channel3102may be about 0.1 mm to about 1.5 mm, a width of each fluid channel3102may be about 0.3 mm to about 1 mm and a length of each fluid channel3102may be about 50 mm to about 150 mm. The present disclosure provides a device300, wherein said first layer310may be made of a polycarbonate material, an acrylic material or a mylar material. The present disclosure provides a device300, said device300further may comprise a second layer320with at least one side coated with a hydrophilic material, and when said second layer320is operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310. For example, the side of said second layer320coated with a hydrophilic material may indicate the side that may be contact with the first layer310. The present disclosure provides a device300, said side may be coated with said hydrophilic material via an acrylic material or a silicone material. The present disclosure provides a device300, wherein said second layer320may comprise a sample receiving inlet3201, and when said second layer320may be operably coupled with said first layer310, said sample receiving inlet3201in the second layer320may be vertically aligned to said sample receiving inlet3101in the first layer310. For example, when said second layer320may be operably coupled with said first layer310, at least a portion of said sample receiving inlet3201in the second layer320may be vertically aligned to said sample receiving inlet3101in the first layer310, so that said sample receiving inlet3201in the second layer320may be in fluidic communication with said sample receiving inlet3101in the first layer310. The present disclosure provides a device300, wherein said second layer320may be made of a polycarbonate material, an acrylic material or a mylar material. The present disclosure provides a device300, wherein said second layer320may have an average thickness of about 1 mm to about 4 mm. For example, said second layer320may have an average thickness of about 1 mm to about 4 mm, about 2 mm to about 4 mm, about 3 mm to about 4 mm, about 1 mm to about 3 mm, 2 mm to about 3 mm, or about 1 mm to about 2 mm. The present disclosure provides a device300, wherein said second layer320may be bound to said first layer310with an adhesive. The present disclosure provides a device300, wherein said adhesive may comprise an acrylic material or a silicone material. The present disclosure provides a device300, wherein said device300may further comprise a third layer330with at least one side coated with a hydrophilic material, and when said third layer330is operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310. For example, the side of said third layer330coated with a hydrophilic material may indicate the side that may be contact with the first layer310. The present disclosure provides a device300, wherein said third layer330may have an average thickness of about 0.1 mm to about 0.3 mm. For example, said third layer330may have an average thickness of about 1 mm to about 4 mm, about 2 mm to about 4 mm, about 3 mm to about 4 mm, about 1 mm to about 3 mm, 2 mm to about 3 mm, or about 1 mm to about 2 mm. The present disclosure provides a device300, wherein said third layer330may be bound to said first layer310with an adhesive. The present disclosure provides a device300, wherein said adhesive may comprise an acrylic material or a silicone material. For example, said adhesive may be an adhesive of a tape, the adhesive of the tape may comprise an acrylic material or a silicone material, and the carrier material of the tape may be selected from various materials, e.g., a polyester film. Examples may be 3M 1513, 3M 1524A, 3M 9965, 3M 1522, 3M 1522 H, Vancive MED 1832, Vancive MED 6361U, Adhesives Research 90445 or Adhesives Research 92712. Examples may be Adhesive Research 90880, or Adhesive Research 8026. The present disclosure provides a device300, wherein said third layer330may comprise at least one opening3301, when said third layer330may be operably coupled with said first layer310, each of said at least one opening3301may be aligned to and in fluid communication with a fluid channel in the first layer310. For example, one of said at least one opening3301may be aligned to and in fluid communication with a fluid channel in the first layer310. For example, 2, 3, 4 or 5 of said at least one opening3301may be aligned to and in fluid communication with a fluid channel in the first layer310. The present disclosure provides a device300, wherein said third layer330may comprise two or more said openings3301, and when said third layer330may be operably coupled with said first layer310, none of the openings3301may be aligned to the same fluid channel3102with another opening3301. The present disclosure provides a device300, wherein said third layer330may be made of a hydrophilic material. The present disclosure provides a device300, wherein said hydrophilic material may be polyester. A polyester may be selected from the group consisting of 3M 9984, 3M 9971, 3M 9962, 3M 9960, Kemafoil HNVV, and Kemafoil HNW-W. A polyester film may have a thickness of 23 mm to 350 mm; a polyester film may have a color of white, clear or translucent. The present disclosure provides a device300, wherein said device300may further comprise a fourth layer340, and the fourth layer340may comprise at least one vent3401sealed by a hydrophobic vent material, when said device300may be assembled, said terminus of each fluid channel3102in said first layer310may be in fluid communication with said at least one vent3401of the fourth layer340. The present disclosure provides a device300, wherein said fourth layer340may have a thickness of about 0.1 mm to about 0.3 mm. For example, said fourth layer340may have an average thickness of about 0.1 mm to about 0.4 mm, about 0.2 mm to about 0.4 mm, about 0.3 mm to about 0.4 mm, about 0.1 mm to about 0.3 mm, 0.2 mm to about 0.3 mm, or about 0.1 mm to about 0.2 mm. The present disclosure provides a device300, wherein said fourth layer340may be bound to said second layer320with an adhesive, or said fourth layer340may be an adhesive. The present disclosure provides a device300, wherein said adhesive may comprise an acrylic material or a silicone material. The present disclosure provides a device300, wherein said fourth layer340may be made of an acrylic material or a silicone material. The present disclosure provides a device300, wherein said fourth layer340may comprise a sample receiving inlet3402, and when said fourth layer340may be operably coupled with said second layer320, said sample receiving inlet3402in the fourth layer340may be vertically aligned to said sample receiving inlet in the second layer320. For example, when said second layer320may be operably coupled with said fourth layer340, at least a portion of said sample receiving inlet3201in the second layer320may be vertically aligned to said sample receiving inlet3401in the fourth layer340, so that said sample receiving inlet3201in the second layer320may be in fluidic communication with said sample receiving inlet3401in the fourth layer340. The present disclosure provides a device300, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350. The present disclosure provides a device300, wherein said conductive material may be gold. For example, said conductive material may be a bare gold, or a gold coated with certain material. The present disclosure provides a device300, wherein said substrate may be made from a material selected from the group consisting of polyethylene terephthalate (PETE), acrylonitrile butadiene styrene (ABS), polystyrene, polycarbonate, an acrylic, polyethylene terephthalate (PETG), polysulfone, and polyvinyl chloride (PVC). The present disclosure provides a device300, wherein said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300is assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350. For example, said insertion monitoring electrodes3501may be an electrode embraced by an insulative area. For example, said insertion monitoring electrodes3501may be a conductive area embraced by an insulative area. The present disclosure provides a device300, wherein said two insertion monitoring electrodes3501may be substantially identical, for example of shape or of area. The present disclosure provides a device300, wherein the length of said insertion monitoring electrode3501may be about 2 mm to about 4 mm. For example, the length of said insertion monitoring electrode3501may be about 1 mm to about 4 mm, about 2 mm to about 4 mm, about 3 mm to about 4 mm, about 1 mm to about 3 mm, 2 mm to about 3 mm, or about 1 mm to about 2 mm. The present disclosure provides a device300, wherein the width of said insertion monitoring electrode may be about 1 mm to about 3 mm. For example, the width of said insertion monitoring electrode3501may be about 1 mm to about 4 mm, about 2 mm to about 4 mm, about 3 mm to about 4 mm, about 1 mm to about 3 mm, 2 mm to about 3 mm, or about 1 mm to about 2 mm. The present disclosure provides a device300, wherein said insertion monitoring electrode3501may be located in a corner of said fifth layer350, for example, each corner of the fifth layer350. The present disclosure provides a device300, wherein said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes. For example, said fifth layer350may comprise at least one, at least 2, at least 3, at least 4 or at least 5 working areas3502. For example, said fifth layer350may comprise 1, 2, 3, 4 or 5 working areas3502. The present disclosure provides a device300, wherein said counter electrode may embrace said working electrode. The present disclosure provides a device300, wherein at least one of said fluid fill electrodes may be positioned prior to said working electrode and at least one of said fluid fill electrodes may be positioned after said working electrode along the direction of the current flow. The present disclosure provides a device300, wherein said fifth layer350may have an average thickness of about 0.1 mm to about 0.3 mm. For example, said fifth layer350may have an average thickness of about 0.1 mm to about 0.4 mm, about 0.2 mm to about 0.4 mm, about 0.3 mm to about 0.4 mm, about 0.1 mm to about 0.3 mm, 0.2 mm to about 0.3 mm, or about 0.1 mm to about 0.2 mm. The present disclosure provides a device300, wherein said fifth layer350may be bound to said third layer with an adhesive. The present disclosure provides a device300, wherein said adhesive may comprise an acrylic material or a silicone material. The present disclosure provides a device300, wherein when said third layer330is operably coupled with said fifth layer350, said opening3301in said third layer330may be aligned to and in fluid communication with said working area3502in the fifth layer350. The present disclosure provides a device300, wherein when said third layer330may be operably coupled with said fifth layer350, said working area3502may be not covered by said third layer330. The present disclosure provides a device300, wherein when said device300may be assembled, said working area3502of said fifth layer350may be in fluid communication with said fluid channel3102of said first layer310. The present disclosure provides a device300, wherein said device300further may comprise an adapter210for operably coupling to a container100. The present disclosure provides a device300, wherein said container100may comprise the container100according to any one of the present disclosures. The present disclosure provides a device300, wherein said adapter210may comprise a sample receiving inlet2101configured to be in fluid communication with said sample receiving inlet3101of said first layer310of an assembled device300. The present disclosure provides a device300, wherein said sample receiving inlet2101of said adapter210may be sealed by a pierceable barrier. The present disclosure provides a device300, wherein said pierceable barrier may comprise a pierceable plastic films or a foil film. The present disclosure provides a device300, wherein said first pierceable barrier may comprise a pierceable film made from a material selected from the group consisting of polyethylene terephthalate (PETE), polycarbonate, polyethylene, and polyvinyl chloride (PVC). The present disclosure provides a device300, wherein said sample receiving inlet2101of said adapter210may comprise a blocking element2104having a bottom configured to prevent said lyophilized reagent2105from leaving said device300, as illustrated inFIG.5. The present disclosure provides a device300, wherein the bottom of said blocking element2104may have a width greater than that of the lyophilized reagent2105. The present disclosure provides a device300, wherein said blocking element2104may comprise at least one piercing member2103extending upwardly toward said pierceable barrier. The present disclosure provides a device300, wherein said piercing member2103may be configured to disestablish a pierceable barrier of a container100and a sample receptacle110of said container100may be in fluidic communication with said sample receiving inlet2101of said device300, when said container may be mounted on said device300. The present disclosure provides a device300, wherein said container100may comprise one or more piercing member1107, and said piercing member2103of said device300may be allowed to be positioned between said piercing member1107of said container100when said container100may be mounted on said device300. The present disclosure provides a device300, wherein said one or more piercing member2103may have a height of less than 5 mm. For example, said one or more piercing member2103may have a height of less than 5 mm, less than 4 mm, less than 3 mm, less than 2 mm, less than 1 mm, or less than 0.5 mm. The present disclosure provides a device300, wherein said piercing member1107of said container100may be configured to disestablish said pierceable barrier of said device300, said piercing member2103of said device300may be configured to disestablish a pierceable barrier of said container100and a sample receptacle110of said container100may be in fluidic communication with said sample receiving inlet2101of said adapter210, when said container100may be mounted on said device300. The present disclosure provides a device300, wherein said piercing member2103may comprise a blunt or curved upper edge. Wherein said piercing member2103may comprise a pointed ending. The present disclosure provides a device300, wherein said adapter210may comprise one or more snap features2102. The present disclosure provides a device300, wherein said one or more snap features2102of said adapter210may comprise at least one protruding element or at least one recess element. The present disclosure provides a device300, wherein said one or more snap features2102of said adapter210and one or more snap features1111of a container100may be configured for said container100to be irreversibly mounted on said device300. The join of said snap features1111of a container100and said snap features2102of said adapter210may be separable or inseparable depending on the shape of snap feature; the force required to separate the components may vary greatly according to the design. The present disclosure provides a device300, wherein said one or more snap features1111of said container100may comprise at least one protruding element, and said one or more snap features2102of said device300may comprise at least one recess element configured to irreversibly catch said at least one protruding element. The present disclosure provides a device300, wherein at least a portion of the inner surface of the adapter210, configured to be in contact with one or more outer rings1109of an outer base surface of a container100when said container100is mounted on said device300, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of said outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210. The present disclosure provides a device300, wherein a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, said at least one fluid channel3102may be configured to be completely filled with about 20 μL to about 150 μL fluid, the material for sealing the vent3103may be self-sealing, said sample receiving inlet3101may comprise a lyophilized reagent2105, a height of each fluid channel3102may be about 0.1 mm to about 1.5 mm, a width of each fluid channel3102may be about 0.3 mm to about 1 mm, a length of each fluid channel3102may be about 50 mm to about 150 mm, said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300is assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, at least one of said fluid fill electrodes may be positioned prior to said working electrode and at least one of said fluid fill electrodes may be positioned after said working electrode along the direction of the current flow. The present disclosure provides a device300, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300is assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, at least one of said fluid fill electrodes may be positioned prior to said working electrode and at least one of said fluid fill electrodes may be positioned after said working electrode along the direction of the current flow. The present disclosure provides a device300, wherein a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, said at least one fluid channel3102may be configured to be completely filled with about 20 μL to about 150 μL fluid, the material for sealing the vent3103may be self-sealing, said sample receiving inlet3101may comprise a lyophilized reagent2105, a height of each fluid channel3102may be about 0.1 mm to about 1.5 mm, a width of each fluid channel3102may be about 0.3 mm to about 1 mm, a length of each fluid channel3102may be about 50 mm to about 150 mm. The present disclosure provides a device300, wherein a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, said at least one fluid channel3102may be configured to be completely filled with about 20 μL to about 150 μL fluid, the material for sealing the vent3103may be self-sealing, said sample receiving inlet3101may comprise a lyophilized reagent2105, a height of each fluid channel3102may be about 0.1 mm to about 1.5 mm, a width of each fluid channel3102may be about 0.3 mm to about 1 mm, a length of each fluid channel3102may be about 50 mm to about 150 mm, said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300is assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, at least one of said fluid fill electrodes may be positioned prior to said working electrode and at least one of said fluid fill electrodes may be positioned after said working electrode along the direction of the current flow, when a third layer330is operably coupled with said fifth layer350, an opening3301in a third layer330may be aligned to and in fluid communication with said working area3502in the fifth layer350, said device300further may comprise an adapter210for operably coupling to a container100, said adapter210may comprise a sample receiving inlet2101configured to be in fluid communication with said sample receiving inlet3101of said first layer310of an assembled device300, said sample receiving inlet2101of said adapter210may be sealed by a pierceable barrier, said container100may comprise one or more piercing member1107, and said piercing member2103of said device300may be allowed to be positioned between said piercing member1107of said container100when said container100may be mounted on said device300. The present disclosure provides a device300, wherein a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, said at least one fluid channel3102may be configured to be completely filled with about 20 μL to about 150 μL fluid, the material for sealing the vent3103may be self-sealing, said sample receiving inlet3101may comprise a lyophilized reagent2105, a height of each fluid channel3102may be about 0.1 mm to about 1.5 mm, a width of each fluid channel3102may be about 0.3 mm to about 1 mm, a length of each fluid channel3102may be about 50 mm to about 150 mm, said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300is assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, at least one of said fluid fill electrodes may be positioned prior to said working electrode and at least one of said fluid fill electrodes may be positioned after said working electrode along the direction of the current flow, when a third layer330is operably coupled with said fifth layer350, an opening3301in a third layer330may be aligned to and in fluid communication with said working area3502in the fifth layer350, said device300further may comprise an adapter210for operably coupling to a container100, said adapter210may comprise a sample receiving inlet2101configured to be in fluid communication with said sample receiving inlet3101of said first layer310of an assembled device300, said sample receiving inlet2101of said adapter210may be sealed by a pierceable barrier, said sample receiving inlet2101of said adapter210may comprise a blocking element2104having a bottom configured to prevent said lyophilized reagent2105from leaving said device300, said container100may comprise one or more piercing member1107, and said piercing member2103of said device300may be allowed to be positioned between said piercing member1107of said container100when said container100may be mounted on said device300, said adapter210may comprise one or more snap features2102, one or more snap features2102of said adapter210and one or more snap features1111of a container100may be configured for said container100to be irreversibly mounted on said device300, at least a portion of the inner surface of the adapter210, configured to be in contact with one or more outer rings1109of an outer base surface of a container100when said container100is mounted on said device300, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of said outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210. The present disclosure provides a device300, wherein a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, said at least one fluid channel3102may be configured to be completely filled with about 20 μL to about 150 μL fluid, the material for sealing the vent3103may be self-sealing, said sample receiving inlet3101may comprise a lyophilized reagent2105, a height of each fluid channel3102may be about 0.1 mm to about 1.5 mm, a width of each fluid channel3102may be about 0.3 mm to about 1 mm, a length of each fluid channel3102may be about 50 mm to about 150 mm, said device300further may comprise a second layer320with at least one side coated with a hydrophilic material, when said second layer320is operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, said second layer320may comprise a sample receiving inlet3201, and when said second layer320may be operably coupled with said first layer310, said sample receiving inlet3201in the second layer320may be vertically aligned to said sample receiving inlet3101in the first layer310, said device300may further comprise a third layer330with at least one side coated with a hydrophilic material, and when said third layer330is operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, said third layer330may comprise at least one opening3301, when said third layer330is operably coupled with said first layer310, each of said at least one opening3301may be aligned to and in fluid communication with a fluid channel in the first layer310, said device300may further comprise a fourth layer340, and the fourth layer340may comprise at least one vent3401sealed by a hydrophobic vent material, when said device300may be assembled, said terminus of each fluid channel3102in said first layer310may be in fluid communication with said at least one vent3401of the fourth layer340, said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300is assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, at least one of said fluid fill electrodes may be positioned prior to said working electrode and at least one of said fluid fill electrodes may be positioned after said working electrode along the direction of the current flow, when said third layer330is operably coupled with said fifth layer350, said opening3301in said third layer330may be aligned to and in fluid communication with said working area3502in the fifth layer350, said device300further may comprise an adapter210for operably coupling to a container100, said adapter210may comprise a sample receiving inlet2101configured to be in fluid communication with said sample receiving inlet3101of said first layer310of an assembled device300, said sample receiving inlet2101of said adapter210may be sealed by a pierceable barrier, said sample receiving inlet2101of said adapter210may comprise a blocking element2104having a bottom configured to prevent said lyophilized reagent2105from leaving said device300, said container100may comprise one or more piercing member1107, and said piercing member2103of said device300may be allowed to be positioned between said piercing member1107of said container100when said container100may be mounted on said device300, said adapter210may comprise one or more snap features2102, one or more snap features2102of said adapter210and one or more snap features1111of a container100may be configured for said container100to be irreversibly mounted on said device300, at least a portion of the inner surface of the adapter210, configured to be in contact with one or more outer rings1109of an outer base surface of a container100when said container100is mounted on said device300, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of said outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210. FIGS.14A-14Billustrate top visible view and top see-through view of another present device. The device300may comprise at least one reaction chamber3104. Wherein the reaction chamber3104may be the shape of a doom. Wherein lyophilized reagent may be present in the chamber3104. Said lyophilized reagent may comprise a nucleic acid amplification enzyme and a DNA primer for LAMP reaction. Wherein, each of the reaction chamber3104may be independent. Wherein, the lyophilized reagent in one reaction chamber3104may be different from the lyophilized reagent in another reaction chamber3104. The device300may comprise at least one fluid channel3102in fluidic communication with said reaction chamber3104. Wherein the diameter of the outlet fluid channel3102from the chamber3104is smaller than the diameter of the lyophilized reagent. Wherein the lyophilized reagent may not be washed out of the reaction chamber3104. FIGS.15A-15Dillustrate each layer of another present device. The device300may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350. Wherein said fifth layer350may comprise at least one insertion monitoring electrodes3501. Electrical short of insertion monitoring electrodes3501triggers sensor insertion detection which may automatically initiate test protocol. The combination of the outer pins of the fifth layer350may be used to identify sensor type and may automatically initiate one or more test-specific protocol. The device300may comprise a third layer330with at least one side coated with a hydrophilic material, and said third layer330is operably coupled with said fifth layer350. The device300may comprise a first layer310, said first layer310may comprise at least one fluid channel3102. The device300may further comprise a fourth layer340, and the fourth layer340may comprise at least one vent3401sealed by a hydrophobic vent material. FIGS.16A-16Hillustrate each view of another present device. The device300may comprise an adapter210. An exterior ring may be positioned between an adapter210and a container100. Wherein, when said container is mounted on said device300, the exterior ring may seal the fluidic system. The adapter210may comprise one or more ribs2106, wherein the ribs2106may guide the insertion of the container100into the adapter210. The ribs2106may be on the inner face of the adapter210. The ribs2106may be configured to adapt to the ribs on the container100. For example, the distance of the ribs2106may be the same as or slightly larger than the thickness of ribs on the container100. System The present disclosure provides a system. The system may comprise the container according to any one of the present disclosures. Wherein said container100may comprise a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120. Wherein said cap120further may comprise said composition sealed within said reservoir1201. The present disclosure provides a system, comprising a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material. The present disclosure provides a system, said system may comprise a container100, comprising a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120, and said system may comprise a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said device300further may comprise a fifth layer350, wherein said fifth layer350may comprise at least one working area3502, wherein said device300further may comprise an adapter210for operably coupling to a container100. The present disclosure provides a system, said system may comprise a container100, comprising a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120, wherein said sample receptacle110may comprise an outlet1104, and said outlet1104may be in fluidic communication with said sample receptacle110, wherein the reservoir1201may be sized to accommodate no less than about 500 μL fluid, and said system may comprise a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, wherein said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, wherein said device300further may comprise an adapter210for operably coupling to a container100. The present disclosure provides a system, said system may comprise a container100, comprising a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120, wherein said cap120may comprise a top inner surface1204, and said first piercing member1202may extend from the top inner surface1204of said cap120, wherein said one or more second piercing members1102extend from the inner base surface1103of said sample receptacle110, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120, wherein said sample receptacle110may comprise an outlet1104, and said outlet1104may be in fluidic communication with said sample receptacle110, wherein said outlet1104may be sealed by a second pierceable barrier1105, wherein at least a portion of an interior surface1106of the sample receptacle110, configured to be in contact with said wall1205of the cap120when the cap120may be closed, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of the wall1205, for sealing the first open end1101against flow when the atmospheric pressure may be equal to or greater than the pressure in the container100, wherein the reservoir1201may be sized to accommodate no less than about 500 μL fluid, and said system may comprise a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said first layer310may have an average thickness of about 0.1 mm to about 0.3 mm, wherein said at least one fluid channel3102may comprise two or more fluid channels3102substantially equidistant from said sample receiving inlet3101, wherein pore size of said vent3103may have an average diameter of about 0.1 μm to about 10 μm, wherein said sample receiving inlet3101may comprise a lyophilized reagent2105, wherein a width of each fluid channel3102may be about 0.3 mm to about 1 mm, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, wherein said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300may be assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, wherein said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, wherein said device300further may comprise an adapter210for operably coupling to a container100. The present disclosure provides a system, said system may comprise a container100, comprising a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120, wherein said cap120may comprise a top inner surface1204, and said first piercing member1202may extend from the top inner surface1204of said cap120, wherein said one or more second piercing members1102extend from the inner base surface1103of said sample receptacle110, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120, wherein said sample receptacle110may comprise an outlet1104, and said outlet1104may be in fluidic communication with said sample receptacle110, wherein said outlet1104may be sealed by a second pierceable barrier1105, wherein at least a portion of an interior surface1106of the sample receptacle110, configured to be in contact with said wall1205of the cap120when the cap120may be closed, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of the wall1205, for sealing the first open end1101against flow when the atmospheric pressure may be equal to or greater than the pressure in the container100, wherein the reservoir1201may be sized to accommodate no less than about 500 μL fluid, wherein said sample receptacle110may comprise one or more outer rings1109, said one or more outer ring may extend outwardly from said outer base surface, wherein at least a portion of said inner surface of said adapter210, configured to be in contact with said one or more outer rings1109of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said one or more outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210, and said system may comprise a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said first layer310may have an average thickness of about 0.1 mm to about 0.3 mm, wherein said at least one fluid channel3102may comprise two or more fluid channels3102substantially equidistant from said sample receiving inlet3101, wherein pore size of said vent3103may have an average diameter of about 0.1 μm to about 10 μm, wherein said sample receiving inlet3101may comprise a lyophilized reagent2105, wherein a width of each fluid channel3102may be about 0.3 mm to about 1 mm, wherein said device300further may comprise a second layer320with at least one side coated with a hydrophilic material, and when said second layer320may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a third layer330with at least one side coated with a hydrophilic material, and when said third layer330may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a fourth layer340, and the fourth layer340may comprise at least one vent3401sealed by a hydrophobic vent material, when said device300may be assembled, said terminus of each fluid channel3102in said first layer310may be in fluid communication with said at least one vent3401of the fourth layer340, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, wherein said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300may be assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, wherein said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, wherein said device300further may comprise an adapter210for operably coupling to a container100. The present disclosure provides a system, said system may comprise a container100, comprising a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120, wherein said cap120may comprise a top inner surface1204, and said first piercing member1202may extend from the top inner surface1204of said cap120, wherein said one or more second piercing members1102extend from the inner base surface1103of said sample receptacle110, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120, wherein said sample receptacle110may comprise an outlet1104, and said outlet1104may be in fluidic communication with said sample receptacle110, wherein said outlet1104may be sealed by a second pierceable barrier1105, wherein at least a portion of an interior surface1106of the sample receptacle110, configured to be in contact with said wall1205of the cap120when the cap120may be closed, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of the wall1205, for sealing the first open end1101against flow when the atmospheric pressure may be equal to or greater than the pressure in the container100, wherein the reservoir1201may be sized to accommodate no less than about 500 μL fluid, wherein sample receptacle110may comprise an extension1108, said extension1108may extend outwardly from said outer base surface of said sample receptacle110and an inner of said extension may be in fluidic communication with said first open1101, wherein at least a portion of said inner surface of said sample receiving inlet2101, configured to be in contact with said extension1108of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said extension1108, to form a fluid tight seal when said container100may be mounted on said adapter210, wherein said sample receptacle110may comprise one or more outer rings1109, said one or more outer ring may extend outwardly from said outer base surface, wherein at least a portion of said inner surface of said adapter210, configured to be in contact with said one or more outer rings1109of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said one or more outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210, and said system may comprise a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said first layer310may have an average thickness of about 0.1 mm to about 0.3 mm, wherein said at least one fluid channel3102may comprise two or more fluid channels3102substantially equidistant from said sample receiving inlet3101, wherein pore size of said vent3103may have an average diameter of about 0.1 μm to about 10 μm, wherein said sample receiving inlet3101may comprise a lyophilized reagent2105, wherein a width of each fluid channel3102may be about 0.3 mm to about 1 mm, wherein said device300further may comprise a second layer320with at least one side coated with a hydrophilic material, and when said second layer320may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a third layer330with at least one side coated with a hydrophilic material, and when said third layer330may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a fourth layer340, and the fourth layer340may comprise at least one vent3401sealed by a hydrophobic vent material, when said device300may be assembled, said terminus of each fluid channel3102in said first layer310may be in fluid communication with said at least one vent3401of the fourth layer340, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, wherein said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300may be assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, wherein said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, wherein said device300further may comprise an adapter210for operably coupling to a container100, wherein said sample receiving inlet2101of said adapter210may comprise a blocking element2104having a bottom configured to prevent said lyophilized reagent2105from leaving said device300. The present disclosure provides a system, said system may comprise a container100, comprising a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120, wherein said cap120may comprise a top inner surface1204, and said first piercing member1202may extend from the top inner surface1204of said cap120, wherein said one or more second piercing members1102extend from the inner base surface1103of said sample receptacle110, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120, wherein said sample receptacle110may comprise an outlet1104, and said outlet1104may be in fluidic communication with said sample receptacle110, wherein said outlet1104may be sealed by a second pierceable barrier1105, wherein at least a portion of an interior surface1106of the sample receptacle110, configured to be in contact with said wall1205of the cap120when the cap120may be closed, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of the wall1205, for sealing the first open end1101against flow when the atmospheric pressure may be equal to or greater than the pressure in the container100, wherein the reservoir1201may be sized to accommodate no less than about 500 μL fluid, wherein said sample receptacle110may comprise one or more third piercing members1107located on an outer base surface of said sample receptacle110, said one or more third piercing members1107extend outwardly from said outer base surface, wherein sample receptacle110may comprise an extension1108, said extension1108may extend outwardly from said outer base surface of said sample receptacle110and an inner of said extension may be in fluidic communication with said first open1101, wherein at least a portion of said inner surface of said sample receiving inlet2101, configured to be in contact with said extension1108of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said extension1108, to form a fluid tight seal when said container100may be mounted on said adapter210, wherein said sample receptacle110may comprise one or more outer rings1109, said one or more outer ring may extend outwardly from said outer base surface, wherein at least a portion of said inner surface of said adapter210, configured to be in contact with said one or more outer rings1109of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said one or more outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210, and said system may comprise a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said first layer310may have an average thickness of about 0.1 mm to about 0.3 mm, wherein said at least one fluid channel3102may comprise two or more fluid channels3102substantially equidistant from said sample receiving inlet3101, wherein pore size of said vent3103may have an average diameter of about 0.1 μm to about 10 μm, wherein said sample receiving inlet3101may comprise a lyophilized reagent2105, wherein a width of each fluid channel3102may be about 0.3 mm to about 1 mm, wherein said device300further may comprise a second layer320with at least one side coated with a hydrophilic material, and when said second layer320may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a third layer330with at least one side coated with a hydrophilic material, and when said third layer330may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a fourth layer340, and the fourth layer340may comprise at least one vent3401sealed by a hydrophobic vent material, when said device300may be assembled, said terminus of each fluid channel3102in said first layer310may be in fluid communication with said at least one vent3401of the fourth layer340, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, wherein said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300may be assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, wherein said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, wherein said device300further may comprise an adapter210for operably coupling to a container100, wherein said sample receiving inlet2101of said adapter210may comprise a blocking element2104having a bottom configured to prevent said lyophilized reagent2105from leaving said device300, wherein said blocking element2104may comprise at least one piercing member2103extending upwardly toward said pierceable barrier, wherein said container100may comprise one or more piercing member1107, and said piercing member2103of said device300may be allowed to be positioned between said piercing member1107of said container100when said container100may be mounted on said device300. The present disclosure provides a system, said system may comprise a container100, comprising a sample receptacle110and a cap120, wherein: the cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; the sample receptacle110may comprise a first open end1101for receiving a sample, and one or more second piercing members1102, said first open end1101may be configured for closure by said cap120and for receiving said composition; said first piercing member1202and said one or more second piercing members1102may be configured to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203when said first open end1101may be closed by said cap120, wherein said cap120may comprise a top inner surface1204, and said first piercing member1202may extend from the top inner surface1204of said cap120, wherein said one or more second piercing members1102extend from the inner base surface1103of said sample receptacle110, wherein said sample receptacle110may comprise two of said second piercing members1102configured to allow said first piercing member1202to be positioned between two of said second piercing members1102when said first open end1101may be closed by said cap120, wherein said sample receptacle110may comprise an outlet1104, and said outlet1104may be in fluidic communication with said sample receptacle110, wherein said outlet1104may be sealed by a second pierceable barrier1105, wherein at least a portion of an interior surface1106of the sample receptacle110, configured to be in contact with said wall1205of the cap120when the cap120may be closed, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of the wall1205, for sealing the first open end1101against flow when the atmospheric pressure may be equal to or greater than the pressure in the container100, wherein the reservoir1201may be sized to accommodate no less than about 500 μL fluid, wherein said sample receptacle110may comprise one or more third piercing members1107located on an outer base surface of said sample receptacle110, said one or more third piercing members1107extend outwardly from said outer base surface, wherein sample receptacle110may comprise an extension1108, said extension1108may extend outwardly from said outer base surface of said sample receptacle110and an inner of said extension may be in fluidic communication with said first open1101, wherein at least a portion of said inner surface of said sample receiving inlet2101, configured to be in contact with said extension1108of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said extension1108, to form a fluid tight seal when said container100may be mounted on said adapter210, wherein said sample receptacle110may comprise one or more outer rings1109, said one or more outer ring may extend outwardly from said outer base surface, wherein at least a portion of said inner surface of said adapter210, configured to be in contact with said one or more outer rings1109of said container100when said container100may be mounted on said adapter210, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of said outer surface of said one or more outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210, wherein said cap may comprise a first snap feature1206and said sample receptacle110may comprise a second snap feature1110, said first snap feature1206and said second snap feature1110may be configured for said first open1101to be irreversibly closed by said cap120, wherein said sample receptacle may have a height of about 10 mm to about 500 mm; and said system may comprise a device300comprising a first layer310, said first layer310may comprise a sample receiving inlet3101, and at least one fluid channel3102extending from and in fluidic communication with said sample receiving inlet3101, the terminus of each fluid channel may be in fluid communication with a vent3103sealed by a hydrophobic vent material, wherein said first layer310may have an average thickness of about 0.1 mm to about 0.3 mm, wherein said at least one fluid channel3102may comprise two or more fluid channels3102substantially equidistant from said sample receiving inlet3101, wherein pore size of said vent3103may have an average diameter of about 0.1 μm to about 10 μm, wherein said sample receiving inlet3101may comprise a lyophilized reagent2105, wherein a width of each fluid channel3102may be about 0.3 mm to about 1 mm, wherein said device300further may comprise a second layer320with at least one side coated with a hydrophilic material, and when said second layer320may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a third layer330with at least one side coated with a hydrophilic material, and when said third layer330may be operably coupled with said first layer310, said side coated with the hydrophilic material faces and/or may be in contact with the first layer310, wherein said device300further may comprise a fourth layer340, and the fourth layer340may comprise at least one vent3401sealed by a hydrophobic vent material, when said device300may be assembled, said terminus of each fluid channel3102in said first layer310may be in fluid communication with said at least one vent3401of the fourth layer340, wherein said device300further may comprise a fifth layer350, said fifth layer350may comprise a substrate coated with a layer of conductive material, and said conductive material may be ablated to form insulative areas on said fifth layer350, wherein said fifth layer350may comprise two symmetrically positioned insertion monitoring electrodes3501, and when said device300may be assembled, said insertion monitoring electrodes3501may be exposed and not covered by any other layer of said device350, wherein said fifth layer350may comprise at least one working area3502, said working area3502may comprise a working electrode, a counter electrode, a reference electrode and at least two fluid fill electrodes, wherein said device300further may comprise an adapter210for operably coupling to a container100, wherein said sample receiving inlet2101of said adapter210may comprise a blocking element2104having a bottom configured to prevent said lyophilized reagent2105from leaving said device300, wherein said blocking element2104may comprise at least one piercing member2103extending upwardly toward said pierceable barrier, wherein said container100may comprise one or more piercing member1107, and said piercing member2103of said device300may be allowed to be positioned between said piercing member1107of said container100when said container100may be mounted on said device300, wherein said one or more snap features2102of said adapter210and one or more snap features1111of a container100may be configured for said container100to be irreversibly mounted on said device300, wherein at least a portion of the inner surface of the adapter210, configured to be in contact with one or more outer rings1109of an outer base surface of a container100when said container100may be mounted on said device300, may be made from or may be coated with an elastomeric material substantially coextensive with said elastomeric material of the outer surface of said outer rings1109, to form a fluid tight seal when said container100may be mounted on said adapter210. FIG.13illustrates an overview of the present system. The system may comprise the container100and a device300. Wherein said container100may comprise a sample receptacle110and a cap120. Wherein said device300may further comprise an adapter210for operably coupling to a container100. FIGS.23A-23Gillustrate each view of a reader. The reader may comprise a thermo control module, a signal detection module, one or more lights, and one or more enclosures. FIGS.24A-24Nillustrate each view of one or more enclosures. The reader may comprise one or more lights, which may be used to indicate the test status and/or test results. The reader may comprise electronics that enable: electrochemical monitoring of the reaction, temperature control for optimal reaction conditions, and/or data interpretation for calling positive/negative. The reader may be powered by cable and be wirelessly connecting to other devices and remote database. Reader may have an opening that guides the sensor into the proper position for simple, reliable electrical contact. Reader may be constructed from chemically resistant material for easy cleaning. The two enclosures may be snapped for assembly. The enclosures may comprise rib and/or lock to hold the PCB. The enclosures may comprise notches to hold the PCB. FIGS.25A-25Billustrate the present main PCB400of the reader. The main PCB400may comprise an Aluminum heating block (AHB)4001for local heating. The main PCB400may comprise an Aluminum heating block (AHB)4001for uniform local heating. The main PCB400may comprise the top layer copper wire as the resistive heating element. The main PCB400may comprise temperature sensor4002embedded under AHB4001for temperature sensing. When the device300is inserted into the reader, the reaction chamber3104may be covered by the Aluminum heating block4001. The reaction chamber3104may be positioned under the Aluminum heating block4001for uniform local heating. The present disclosure provides a system, said system further may comprise a thermo control module. The present disclosure provides a system, wherein said thermo control module may be configured to perform isothermal nucleic acid amplification. The present disclosure provides a system, wherein said thermo control module may be configured to maintain a temperature of about 55° C. to about 75° C. For example, said thermo control module may be configured to maintain a temperature of about 55° C. to about 75° C., about 55° C. to about 70° C., about 55° C. to about 65° C., about 55° C. to about 60° C., about 60° C. to about 75° C., about 60° C. to about 70° C., about 60° C. to about 65° C., about 65° C. to about 75° C., about 65° C. to about 70° C., or about 70° C. to about 75° C. For example, said thermo control module may be configured to maintain a temperature of about 55° C., about 60° C., about 65° C., about 70° C., or about 75° C. The present disclosure provides a system, the system further may comprise a signal detection module. The present disclosure provides a system, wherein said signal may be an electrochemical signal. The present disclosure provides a system, wherein said signal may be a qualitative signal and/or a quantitative signal. For example, the signal of a current. A container of the present disclosure may be used for processing and/or modifying a biological sample (e.g., diluting, mixing or reacting). A container in the present disclosure may be for performing biological assays by modifying properties of biological samples and detecting these modified properties. As used herein, a “biological sample” may be a sample containing a quantity of organic material, e.g., one or more organic molecules, such as one or more nucleic acids e.g., DNA and/or RNA or portions thereof, which may be taken from a subject. As such, a “biological sample assay” may be test on a biological sample which may be performed to evaluate one or more characteristics of the sample. In some aspects a biological sample may be a nucleic acid amplification sample, which may be a sample including or suspected of including one or more nucleic acids or portions thereof which can be amplified. A biological sample may be provided by a subject and include one or more cells, such as tissue cells of the subject. As used herein, the term “tissue” generally refers to one or more aggregates of cells in a subject (e.g., a living organism, such as a mammal, such as a human) that may have a similar function and structure or to a plurality of different types of such aggregates. Tissue may include, for example, organ tissue, muscle tissue (e.g., cardiac muscle; smooth muscle; and/or skeletal muscle), connective tissue, nervous tissue and/or epithelial tissue. Tissue may, in some versions, include cells from the inside of a subject's cheek and/or cells in a subject's saliva. As noted above, a biological sample may be provided by a subject. A subject may be a “mammal” or a “mammalian” subject, where these terms may be used broadly to describe organisms which may be within the class mammalia, including the orders carnivore (e.g., dogs and cats), rodentia (e.g., mice, guinea pigs, and rats), and primates (e.g., humans, chimpanzees, and monkeys). The subject may be a human. The term “humans” may include human subjects of both genders and at any stage of development (e.g., fetal, neonates, infant, juvenile, adolescent, and adult), where the human subject may be a juvenile, adolescent or adult. While the devices and methods described herein may be applied in association with a human subject, it may be to be understood that the subject devices and methods may also be applied in association with other subjects, that is, on “non-human subjects”. A biological sample, as referred to herein, may in some versions be a prepared biological sample. A prepared biological assay sample may be a biological assay sample which may have been processed for example by exposing the sample to a preparation solution, such as a solution including a lysing agent, such as a detergent. Accordingly, a biological sample may be a lysate. Such preparation may enable the prepared biological sample to react, for example, with assay reagents and/or a property modifying reagent upon exposure thereto. The exposure may include lysing cells of the sample with a lysing agent of the preparation solution and/or extracting nucleic acids therefrom. Such extracted nucleic acids may be released into a resulting prepared sample solution. A step of extracting genomic deoxyribonucleic acid (DNA) from a biological sample may be included. Where desired, the preparation solution may be a nucleic acid amplification preparation solution and exposure to the solution prepares nucleic acids of the sample for amplification, e.g., isothermal amplification. Methods The present disclosure provides a method for collecting and/or storing a sample, comprising using the container of the present disclosure. The present disclosure provides a method for determining the presence and/or amount of a target in a sample, comprising using the container of the present disclosure, the device of the present disclosure, and/or the system of the present disclosure. The present disclosure provides a method for preparing a sample derived from a subject, comprising: I) introducing the sample into a sample receptacle110through a first open end1101of said sample receptable110; II) closing said first open end1101irreversibly by attaching a cap120to said sample receptable110; III) said cap120may comprise a reservoir1201for retaining a composition, a first piercing member1202and a first pierceable barrier1203for sealing said composition within said reservoir1201; IV) said sample receptacle110may comprise one or more second piercing members1102; and V) when the first open end1101of the sample receptacle110may be closed by said cap120, said first piercing member1202and said one or more second piercing members1102effect a force to disestablish the first pierceable barrier1203from opposite side of said first pierceable barrier1203. The method may further comprise mixing the composition released from the cap120and the sample within said irreversibly closed sample receptable110. Wherein said first piercing member1202may extend downwardly toward said first open end1101of the sample receptacle110when said first open end1101may be closed by said cap120. The method may further comprise using the container of the present disclosure. The present disclosure provides a method for determining the presence and/or amount of a target in a sample, the method may comprise: I) preparing the sample using the container of any one of the present disclosures, II) mounting the container comprising the prepared sample on the device of any one of the present disclosures; and III) inserting said device into a reader comprising a thermo control module and a signal detection module. Wherein said first piercing member1202may extend downwardly toward said first open end1101of the sample receptacle110when said first open end1101may be closed by said cap120. EXAMPLES The following examples are set forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the present invention, and are not intended to limit the scope of what the inventors regard as their invention nor are they intended to represent that the experiments below are all or the only experiments performed. Efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, molecular weight is weight average molecular weight, temperature is in degrees Celsius, and pressure is at or near atmospheric. Standard abbreviations may be used, e.g., s or sec, second(s); min or minute(s); h or hr., hour(s); and the like. Example 1 A user deposits saliva directly into the opening of the sample receptacle110device up to the fill line (approximately 750 μL). The user then inserts the provided cap120, which contains the dilution buffer (1.5 mL), into the sample receptacle110which brings the buffer seal into contact with the piercing features. The user continues to apply pressure to/insert the cap which pierces the seal and triggers the buffer to automatically flow into the sample receptacle110and dilute the sample. When fully inserted, the cap snaps onto sample receptacle110(irreversibly) and a seal is formed to prevent sample leakage. The user may then shake or invert the container100to mix the sample. Example 2 The user mates the container100with the adapter210on top of the device300. As the user inserts the container100into the adapter210, the first contact between the piercing features1107on the bottom of the sample receptacle110and the foil seal on the adapter inlet is made. Continued insertion/applied pressure breaks this seal and then allows the contact between the piercing feature2103inside the sample receiving inlet2101of an adapter210and the foil seal of the outlet1104of the sample receptable110. Continued insertion/applied pressure pierces this foil and triggers the fluid inside of the sample receptable110to automatically flow into the sample receiving inlet2101of an adapter210. This fluid flow is driven by gravity and the fluid height within the sample receptable110. Noted that successful fluid flow requires that 0.75 mL of liquid is provided. When fully inserted, the container100snaps irreversibly onto the adapter210and forms a liquid seal at the joining interfaces. As fluid flows out of the sample receptable110and into the sample receiving inlet2101of an adapter210, fluid comes into contact with the lyophilized reagent2105which immediately dissolves. The lyophilized reagent2105contains all necessary reagents to perform the RT-LAMP reaction as well as an electrochemical reporter. The fluid continues to flow into the device300and carries an equal amount of dissolved master mix into each reaction chamber where each chamber's dried primer is resuspended. The fluid continues to flow towards the vent3103of first layer310of the device300; and when the fluid contacts the self-sealing membranes placed at the terminus of each fluid channel3102, all liquid flow is halted and the device300is ready to be inserted into a reader for measurement. Example 3 While powered on and ready to accept a new device300for measurement, the reader continuously scans the insertion monitoring electrodes3501to detect an electrical short which is provided once the device300is fully inserted. Once insertion is detected, the reader will then scan the fluid fill electrodes at the entrance and exit of each working area3502to ensure that each working area3502is completely filled with fluid. The scan method for this process is square wave voltammetry and a positive fluid fill trigger is denoted by an increase in baseline current above a defined threshold. Once a positive fluid fill trigger is observed by the reader, the measurement will start automatically. This process begins by heating the device300platform, and thus the device300, to 65° C. which initiates the RT-LAMP reaction. When the test target is present in the reaction chamber, the RT-LAMP reaction produces a significant amount of double-stranded DNA which sequesters the electrochemical reporter via intercalation. When intercalated with dsDNA, the electrochemical reporter is hindered in producing signal current which is monitored via square wave voltammetry. In a sample with the target present, the result observed is a decrease in peak current relative to a negative control. If the target is not present in the sample, then peak current remains unchanged and matches that of the negative control. Once the test protocol is complete, the reader will notify the user via LED lights on the reader itself as well as through a mobile application and/or web-based application. The user can remove the device300and dispose of it. The reader is then ready to accept a new device300. While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. It is not intended that the invention be limited by the specific examples provided within the specification. While the invention has been described with reference to the aforementioned specification, the descriptions and illustrations of the embodiments herein are not meant to be construed in a limiting sense. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. Furthermore, it shall be understood that all aspects of the invention are not limited to the specific depictions, configurations or relative proportions set forth herein which depend upon a variety of conditions and variables. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is therefore contemplated that the invention shall also cover any such alternatives, modifications, variations or equivalents. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.
137,963
11857963
DETAILED DESCRIPTION Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. FIG.1is a perspective view schematically illustrating a microfluidic device according to an exemplary embodiment, and a structure of a test system including the same. Referring toFIG.1, the microfluidic device10according to the illustrated embodiment includes a platform100on which one or more microfluidic structures are formed, and a microfluidic structure formed thereon. The microfluidic structure includes a plurality of chambers to accommodate a fluid and a channel to connect the chambers. Here, the microfluidic structure is not limited to a structure with a specific shape, but comprehensively refers to structures including channels connecting the chambers to each other and formed on or within the microfluidic device, especially on the platform of the microfluidic device to allow the flow of a fluid. The microfluidic structure may perform different functions depending on the arrangements of the chambers and the channels, and the kind of the fluid accommodated in the chambers or flowing along the channels. The platform100may be made of various materials including plastics such as polymethylmethacrylate (PMMA), polydimethylsiloxane (PDMS), polycarbonate (PC), polypropylene, polyvinyl alcohol and polyethylene, glass, mica, silica and silicon (in the form of a wafer), which are easy to work with and whose surfaces are biologically inactive. The above materials are simply examples of materials usable for the platform100, and the exemplary embodiments disclosed herein are not limited thereto. Thus, any material having proper chemical and biological stability, optical transparency and mechanical workability may be used as a material of the platform100. The platform100may be formed in multiple layers of plates. A space to accommodate a fluid within the platform100and a channel allowing the fluid to flow therethrough may be provided by forming intaglio structures corresponding to the microfluidic structures, such as the chambers and the channels, on the contact surfaces of two plates, and thereafter, joining the plates. The joining of two plates may be accomplished using any of various techniques such as bonding with an adhesive agent or a double-sided adhesive tape, ultrasonic welding, and laser welding. The illustrated exemplary embodiment ofFIG.1employs a circular plate-shaped disc type platform100, but the platform100used in the illustrated embodiment may have the shape of a whole circular plate which is rotatable, may be a circular sector that is rotatable in a rotatable frame when seated thereon, or it may have any polygonal shape provided that it is rotatable by power supplied from a drive unit310. The microfluidic device10may be mounted to a test device300including a drive unit310and a controller320, and may be rotated by the drive unit310as shown inFIG.1. The controller320may control actuation of the drive unit310. More specifically, the drive unit310includes a motor to provide rotational force to the platform100, thereby enabling fluids accommodated in chambers disposed in the platform100to move to other chambers according to centrifugal force. Rotation of the platform100through the drive unit310, as well as overall operations of the test device300including positioning a magnet and detecting by a detection unit, which will be described later, may be controlled by the controller320. A platform100may be provided with one test unit. However, for faster throughput at lower cost, the platform100may be divided into a plurality of sections, and each section may be provided with independently operable microfluidic structures. The microfluidic structures may perform different tests and/or may perform several tests at the same time. Alternatively, a plurality of test units that perform the same test may be provided. For convenience of description of the illustrated exemplary embodiment, a description will be given of a case in which a chamber to receive a sample from a sample supply chamber and a channel connected to the chamber form a single unit, and different units may receive the sample from different sample supply chambers. Since the microfluidic device10according to the illustrated embodiment causes a fluid to move using centrifugal force, the chamber130to receive the fluid is disposed at a position more distant from the center C of the platform100than the position of the chamber120to supply the fluid, as shown inFIG.1. The two chambers are connected by a channel125, and in the microfluidic device10of the illustrated embodiment, a siphon channel may be used as the channel125to control the fluid flowing therethrough. FIG.2is a graph illustrating a basic principle of a siphon channel. As used herein, the term “siphon” refers to a channel that causes a fluid to move using a pressure difference. In the microfluidic device10, the flow of the fluid through the siphon channel is controlled using capillary pressure that forces the fluid to move up through a tube having a very small cross-sectional area and centrifugal force generated by rotation of the platform100. The graph ofFIG.2corresponds to the platform100as viewed from the top. The inlet of the siphon channel, which has a very small cross-sectional area is connected to a chamber in which the fluid is accommodated, and the outlet of the siphon channel is connected to another chamber to which the fluid is transferred. As shown, a point at which the siphon channel is bent, i.e., the highest point (rcrest) of the siphon channel should be higher than the level of the fluid accommodated in the chamber. In addition, since the fluid positioned closer to the outer edge of the platform100than the inlet of the siphon channel is not transferred, the positioning of the inlet of the siphon channel will depend on the amount of the fluid to be transferred. When the siphon channel is filled with the fluid by capillary pressure of the siphon channel, the fluid filling the siphon channel is transferred to the next chamber by centrifugal force. FIG.3is a plan view schematically illustrating a microfluidic structure to which siphon channels are applied and a basic structure of a microfluidic device having the same, according to the exemplary embodiment. Hereinafter, the embodiment will be described assuming that the upper and lower plates of the microfluidic device are not coupled to each other in order to expose the microfluidic structure. Referring toFIG.3, the sample supply chamber110is formed at a position close to the center of rotation C, and a plurality of chambers is arranged in parallel on a circumference of a circle the center of which coincides with the center of rotation C of the platform100. In the illustrated embodiment as described below, the chambers to receive a fluid sample from the sample supply chamber110are referred to as first chambers120, and the chambers to which the fluid sample is transferred from the first chambers are referred to as second chambers130. In addition, according to the sample supply sequence, the first chambers120are respectively referred to as a “1-1”-th120-1to a “1-n”-th chamber120-n. The second chambers130are respectively referred to as a “2-1”-th chamber130-1to a “2-n”-th chamber130-naccording to the first chambers connected thereto. The other chambers subsequently connected are defined in the same manner. Also, for convenience of description, when the term “first chambers120” is used throughout, it means at least one of the first chambers120-1to120-n. This is also applied to the other structures ranging from the second chambers130to the fifth chambers170(seeFIG.7). The “1-1”-th chamber120-1to the “1-n”-th chamber120-n, which are the first chambers120, are connected to the sample supply chamber110through the distribution channel115, and are respectively connected to the “2-1”-th chamber130-1to the “2-n”-th chamber130-n, which are the second chambers120, through the siphon channel125. As shown inFIG.3, the first chambers120-1to120-nare arranged about a circumference of the platform100, but they are not arranged at the same circumference. That is, each of the first chambers has a different distance from the center of rotation C of the platform100. Specifically, the “1-1”-th chamber120-1that first receives the sample from the sample supply chamber110is disposed on a circumference closest to the center of the platform100, i.e., the circumference having the shortest radial distance from the center of rotation C of the platform100, and the “1-2”-th chamber120-2is disposed on a circumference more distant from the center of rotation C of the platform100than the “1-1”-th chamber120-1, i.e., on a circumference having a larger radial distance from the center of rotation. As described above, the platform100may be formed in various shapes including circles, circular sectors and polygons, and in the illustrated embodiment, the platform100has a circular shape. In addition, as shown inFIGS.5A to5C, at least one first chamber may be connected to a distribution channel. For convenience of description, in the illustrated embodiment it will be assumed that three first chambers120, namely, chambers120-1,120-2and120-3are connected in parallel to the distribution channel115and three second chambers130-1,130-2and130-3are connected to the respective first chambers120, as shown inFIG.5C. As the ordinal number increases from the “1-3”-th chamber120-3to the “1-4”-th chamber120-4and to the “1-n”-th chamber120-n, the distance of the corresponding chamber from the center of rotation C of the platform100increases. When the platform100rotates, the fluid sample accommodated in the sample supply chamber110flows through the distribution channel115. When the “1-1”-th chamber120-1is filled with the sample, the sample flowing through the distribution channel115is introduced, by centrifugal force, into the “1-2”-th chamber120-2arranged more distant from the center of the platform100. In the same manner, the “1-2”-th to “1-n”-th chambers are filled with the sample. After the first chambers120-1to120-nare all filled with the sample, the remaining sample flows into an excess chamber180to accommodate excess fluid. After filling the first chambers120, the sample flows into the second chambers130through the siphon channels125, and thus, to transfer the sample through the siphon channel125, the crest point of the siphon channel125should be higher than the highest level of the fluid accommodated in the sample supply chamber110, as shown inFIG.2. As shown inFIG.3, in the microfluidic structure of the illustrated embodiment, the difference between the crest point of a siphon channel125and the corresponding one of the first chambers120may be kept uniform when the distance of the first chambers120from the center of the platform100increases in the order of the ordinal numbers from the “1-1”-th chamber120-1to the “1-n”-th chamber120-n. The capillary force of the siphon channel125may be established by narrowing the cross-sectional area of the siphon channel125or by hydrophilic treatment of the inner surfaces of the siphon channel125. In the illustrated embodiment, the cross-sectional area of the siphon channel125is not limited, but the width and depth thereof may be adjusted to have a value between 0.01 mm and 3 mm, between 0.05 mm and 1 mm, or between 0.01 mm and 0.5 mm to establish a high capillary pressure. The capillary force may also be established by plasma treatment or hydrophilic polymer treatment of the inner surfaces of the siphon channel125. In the microfluidic device10according to the illustrated embodiment, the fluid sample may be a biosample of a bodily fluid such as blood, lymph and tissue fluid or urine, or an environmental sample for water quality control or soil management. However, the embodiment is not limited so long as the fluid is movable by centrifugal force. A microfluidic structure may be formed as one unit as in the illustrated embodiment ofFIG.3, or as a plurality of units. FIGS.4A and4Bare plan views schematically illustrating a microfluidic device having a microfluidic structure that includes a plurality of units. Referring toFIG.4A, the platform100of the microfluidic device10according to the illustrated exemplary embodiment may be divided into two sections, with one unit having been formed in each section. As shown, each unit includes one sample supply chamber110, a plurality of first chambers120and a plurality of second chambers130. Referring toFIG.4B, the platform100of the microfluidic device10according to the illustrated exemplary embodiment may be divided into four sections, with one unit having been formed in each section. Thus, when the platform100rotates, the sample accommodated in the sample supply chamber110of each unit is independently distributed to the respective first chambers120and thereafter, introduced into the respective second chambers130through the respective siphon channels125. As shown inFIGS.4A and4B, when a platform100is provided with two or more test units disposed thereon, several kinds of tests may be performed at the same time. For example, a bodily fluid sample may be used to conduct an immunoserologic test in the first test unit and a biochemical test in the second test unit. Alternatively, immuno-serological tests of different kinds or biochemical tests of different kinds may be independently conducted using different samples in each of the first test unit and the second test unit. As shown inFIG.4B, a first immuno-serological test to detect, for example, troponin I, which is a cardiac marker, may be performed in a first test unit, a second immuno-serological test to detect, for example, β-hCG indicating pregnancy may be performed in a second test unit, a first biochemical test to detect, for example, alanine aminotransferase (ALT) and aspartate aminotransferase (AST) to evaluate liver function may be performed in a third test unit, and a second biochemical test to detect, for example, amylase and lipase indicating abnormalities of the digestive system may be performed in a fourth test unit. Thus, when a platform100is provided with a plurality of test units to simultaneously perform several tests as shown inFIGS.4A and4B, test results may be obtained rapidly using a small sample size. It should be understood thatFIGS.4A and4Bare shown for illustration purposes only, and the number of units that may be formed on a single platform100and/or the kind of tests to be performed in the respective units are not limited thereto. FIGS.5A to5Dare plan views schematically illustrating the flow of a fluid in the microfluidic device according to an exemplary embodiment. The structure of the microfluidic device shown inFIGS.5A to5Dis identical to that of the microfluidic device ofFIG.3. First, as shown inFIG.5A, a sample is introduced into the sample supply chamber110while the platform100is at rest. Any of various types of fluid may be introduced, depending on the function of the first chambers120and/or the second chambers130or the test to be performed. Then, the platform100is rotated such that the sample accommodated in the sample supply chamber110is distributed to all of the first chambers120through the distribution channel115, as shown inFIG.5B.FIG.5Bshows the microfluidic structure having all of the first chambers120, from the “1-1”-th chamber120-1to the “1-n”-th chamber120-n, filled with the sample. However, in real-world implementation, the chambers120from the “1-1”-th chamber120-1to the “1-n”-th chamber120-nare sequentially filled with the sample. FIG.6is a plan view illustrating a sequence of fluid distribution to the first chambers in the microfluidic device according to the exemplary embodiment. Referring toFIG.6, when the platform100rotates, the sample accommodated in the sample supply chamber110flows into the distribution channel115through the outlet of the sample supply chamber110, and then flows into the “1-1” chamber120-1via the distribution channel115. Here, the platform100may rotate clockwise or counterclockwise. The direction of rotation of the platform100is not limited. When the “1-1” chamber120-1is filled with sample, the fluid flowing through the distribution channel115does not flow into the “1-1” chamber120-1anymore and instead moves up to the inlet of the “1-2” chamber120-2and flows into the “1-2” chamber120-2. Similarly, when the “1-2” chamber120-2is filled with sample, the fluid flowing through the distribution channel115does not flow into the “1-2” chamber120-2anymore and instead moves up to the inlet of the next chamber, i.e., the “1-2” chamber120-2and flows into the “1-2” chamber120-2. In a similar manner, all the chambers from the “1-1”-th chamber120-1to the “1-n”-th chamber120-nare filled with the sample. The portion of the sample remaining after filling the “1-n”-th chamber120-nis accommodated in the excess chamber180. Referring toFIG.5B, when the first chamber120is filled with the sample by centrifugal force, part of the siphon channel125may also be filled with the sample. However, the sample does not fill the siphon channel125up to the crest point thereof, but rather, to a point between the crest point of the siphon channel125and the highest level of fluid in the first chamber120. The portion of the sample remaining after filling the first chambers120-1to120-nis accommodated in the excess chamber180. Once distribution of the sample to the first chambers120-1to120-nis completed, rotation of the platform is stopped. When the platform100is stopped, the sample contained in the first chambers120-1to120-nflows into the siphon channels125-1to125-nby capillary pressure, thereby filling all of the siphon channels125-1to125-n, as shown inFIG.5C. When the siphon channels125-1to125-nare filled with the sample, the platform100is rotated again causing the sample to flow into the second chambers130-1to130-nby centrifugal force, as shown inFIG.5D. Thus, the sample accommodated in the sample supply chamber110is distributed to the second chambers130in a fixed amount via the first chambers120and the siphon channels125according to the operations ofFIGS.5A to5D. The amount of the sample distributed to each of the second chambers130may be adjusted by altering the size of the first chamber and the position of the outlet of the first chamber120connected to the inlet of the siphon channel125. When the outlets of the first chambers120connected to the inlets of the siphon channels125are located at the lowest portions of the first chambers120(i.e., the portions distal to the center of rotation), as shown inFIGS.5A to5D, all the sample filling the first chambers120flows into the second chambers130, and thus the first chambers120are formed to have a size corresponding to the amount of sample to be distributed to the second chambers130. In the illustrated exemplary embodiment ofFIGS.5A to5D, the first chambers120are equally sized. However, each of the first chambers120may be sized differently so as to contain different volumes of sample, and the size thereof may be varied depending on the amount of sample required by the chamber connected thereto. Hereinafter, the structure and operation of the microfluidic device according to the illustrated exemplary embodiment will be described in detail with reference toFIGS.7to14. FIG.7is a plan view illustrating the structure of the microfluidic device according to an exemplary embodiment in detail. Hereinafter, the structure of the microfluidic device10according to the illustrated embodiment will be described in detail with reference toFIG.7. As described above, the platform100may be formed in various shapes including circles, circular sectors and polygons. Also, for convenience of description, in the illustrated exemplary embodiment, it will be assumed that three first chambers120, namely, chambers120-1,120-2and120-3are connected in parallel to the distribution channel115and three second chambers130-1,130-2and130-3are connected to the respective first chambers120. Each of the first chambers120, each of the corresponding second chambers130connected thereto, and any microfluidic structures connected to the corresponding second chambers130form a single test part, and in the illustrated embodiment, three test parts are provided. Each test part may be provided with a different configuration and a different material to be accommodated therein such that a different test may be independently conducted. The sample supply chamber110is arranged closest to the center of rotation C to accommodate a sample supplied from the outside. The sample supply chamber110accommodates a fluid sample, and for illustration purposes only, blood is supplied as the fluid sample. A sample introduction inlet111is provided at one side of the sample supply chamber110, through which an instrument such as a pipette may be used to introduce blood into the sample supply chamber110. Blood may be spilled near the sample introduction inlet111during the introduction of blood, or the blood may flow backward through the sample introduction inlet111during rotation of the platform100. To prevent the microfluidic device10from being contaminated in this manner, a backflow receiving chamber112may be formed at a position adjacent to the sample introduction inlet111to accommodate any spilled sample during introduction thereof or any sample that flows backward. In another exemplary embodiment, to prevent backflow of the blood introduced into the sample supply chamber110, a structure that functions as a capillary valve may be formed in the sample supply chamber110. Such a capillary valve allows passage of the sample only when a pressure greater than or equal to a predetermined level is applied. In another exemplary embodiment, to prevent backflow of the blood introduced into the sample supply chamber110, a rib-shaped backflow prevention device may be formed in the sample supply chamber110. Such a rib-shaped back flow prevention device may include one or more protrusions formed on a surface of the sample supply chamber110. Arranging the backflow prevention device in a direction crossing the direction of flow of the sample from the sample introduction inlet111to the sample discharge outlet may produce resistance to flow of the sample, thereby preventing the sample from flowing toward the sample introduction inlet111. The sample supply chamber110may be formed to have a width that gradually increases from the sample introduction inlet111to the sample discharge outlet113in order to facilitate discharge of the sample accommodated therein through the sample discharge outlet113. In other words, the radius of curvature of at least one side wall of the sample supply chamber110may gradually increase from the sample introduction inlet111to the sample discharge outlet113. The sample discharge outlet113of the sample supply chamber110is connected to a distribution channel115formed on the platform100in the circumferential direction of the platform100. Thus, the distribution channel115is sequentially connected to the “1-1”-th chamber120-1, the “1-2”-th chamber120-2and the “1-3”-th chamber120-3proceeding counterclockwise. A Quality Control (QC) chamber128to indicate completion of supply of the sample and an excess chamber180to accommodate any excess sample remaining after supply of the sample may be connected to the end of the distribution channel115. The first chambers120(i.e.,120-1,120-2, and120-3) may accommodate the sample supplied from the sample supply chamber110and cause the sample to separate into a supernatant and sediment through centrifugal force. Since the exemplary sample used in the illustrated embodiment is blood, the blood may separate into a supernatant including serum and plasma and sediment including corpuscles in the first chambers120. Each of the first chambers120-1,120-2and120-3is connected to a corresponding siphon channel125-1,125-2and125-3. As described above, the crest points (i.e., bend) of the siphon channels125-1,125-2and125-3should be higher than the highest level of the fluid accommodated in the first chambers120-1,120-2and120-3. To secure a difference in height, the “1-2”-th chamber120-2is positioned on a circumference that is further from the center of rotation C, or a circumference of a larger radius, than the circumference on which the “1-1”-th chamber120-1is positioned, and the “1-3”-th chamber120-3is positioned on a circumference that is further from the center of rotation C, or a circumference of a larger radius, than the circumference on which the “1-2”-th chamber120-2is positioned. In this arrangement, a chamber120positioned farther away from the sample discharge outlet113along the direction of flow of the distribution channel115, will have a shorter length in a radial direction. Accordingly, if the first chambers120are set to have the same volume, the first chamber120positioned farther away from the sample discharge outlet113has a larger width in a circumferential direction, as shown inFIG.7. As described above, the positions at which the inlets of the siphon channels125-1,125-2and125-3meet the outlets of the first chambers120-1,120-2and120-3may vary depending on the amount of fluid to be transferred. Thus, if the sample is blood, as in the illustrated exemplary embodiment, a test is often performed only on the supernatant, and therefore the outlets of the first chambers120may be arranged at upper portions (i.e., above the middle portion) thereof, at which the supernatant is positioned. This is simply an embodiment provided for illustration, and if the sample is not blood or the test is performed on the sediment in addition to the supernatant, outlets may be provided at lower portions of the first chambers120. The outlets of the siphon channels125-1,125-2and125-3are connected to the respective second chambers130-1,130-2and130-3. The second chambers130may accommodate only a sample (e.g., blood), or may have a reagent or reactant pre-stored therein. The reagent or reactant may be used, for example, to perform pretreatment or first order reaction for blood, or to perform a simple test prior to the main test. In the illustrated exemplary embodiment, binding between an analyte and a first marker conjugate occurs in the second chambers130. Specifically, the first marker conjugate may remain in the second chamber130in a liquid phase or solid phase. When the marker conjugate is solid phase, the inner wall of the second chamber130may be coated with the marker conjugate or the marker conjugate may be temporarily immobilized on a porous pad disposed therein. The first marker conjugate is a complex formed by combining a marker and a capture material which specifically reacts with an analyte in the sample. For example, if the analyte is antigen Q, the first marker conjugate may be a conjugate of the marker and antibody Q which specifically reacts with antigen Q. Exemplary markers include, but are not limited to, latex beads, metal colloids including gold colloids and silver colloids, enzymes including peroxidase, fluorescent materials, luminescent materials, superparamagnetic materials, materials containing lanthanum (III) chelates, and radioactive isotopes. Also, If test paper on which a chromatographic reaction occurs is inserted into the reaction chamber150, as described below, a second marker conjugate which binds with a second capture material may be immobilized on the control line of the test paper to confirm reliability of the reaction. In various exemplary embodiments, the second marker conjugate may also be in a liquid phase or solid phase and, when in solid phase, the inner wall of the second chamber130may be coated with the second marker conjugate or the second marker conjugate may be temporarily immobilized on a porous pad disposed therein. The second marker conjugate is a conjugate of the marker and a material specifically reacting with the second capture material immobilized on the control line. The marker may be one of the aforementioned exemplary materials. If the second capture material immobilized on the control line is biotin, a conjugate of streptavidin and the marker may be temporarily immobilized in the second chamber130. Accordingly, when blood flows into the second chamber130, antigen Q present in the blood binds with the first marker conjugated with antibody Q and is discharged to the third chamber140. At this time, the second marker conjugated with streptavidin is also discharged. The second chambers130-1,130-2and130-3are connected to the third chambers140-1,140-2and140-3, and in the illustrated embodiment, the third chambers140-1,140-2and140-3are used as metering chambers. The metering chambers140function to meter a fixed amount of sample (e.g., blood) accommodated in the second chamber130and supply the fixed amount of blood to the respective fourth chambers150(150-1,150-2, and150-3). The metering operation of the metering chambers will be described below with reference toFIG.14andFIGS.15to17. The residue in the metering chambers140which has not been supplied to the fourth chambers150may be transferred to the respective waste chambers170(170-1,170-2, and170-3). In the illustrated exemplary embodiment, the connection between the metering chambers140and the waste chambers170is not limited toFIG.14. The metering chambers140may not be directly connected to the waste chambers170(seeFIGS.15and16), or the metering chambers140and the waste chambers170may be connected in different arrangements (see FIG.18). The third chambers140-1,140-2and140-3are connected to the reaction chambers150-1,150-2and150-3which are the fourth chambers. Although not shown in detail, the third chambers may be connected to the fourth chambers via channels, or by a specific structure to transfer the fluid. The latter case will be described in detail with reference toFIGS.15to17. A reaction may occur in the reaction chambers150in various ways. For example, in the illustrated embodiment, chromatography based on capillary pressure is used in the reaction chambers150. To this end, the reaction chamber150includes a detection region20to detect the presence of an analyte through chromatography. FIG.8is a view illustrating a structure of a detection region included in a reaction chamber, andFIGS.9A to9Care views illustrating detection of an analyte using chromatography. The detection region20is formed from a material selected from a micropore, micro pillar, and thin porous membrane such as cellulose, upon which capillary pressure acts. Referring toFIG.8, a sample pad22on which the sample is applied is formed at one end of the detection region20, and a test line24is formed at an opposite end, on which a first capture material24ato detect an analyte, is permanently immobilized. Here, permanent immobilization means that the first capture material24aimmobilized on the test line24does not move along with flow of the sample. Referring toFIGS.9A and9B, when a biosample such as blood or urine is dropped on the sample pad22, the biosample flows to the opposite side due to capillary pressure. For example, if the analyte is antigen Q and binding between the analyte and the first marker conjugate occurs in the second chamber130, the biosample will contain a conjugate of antigen Q and the first marker conjugate. When the analyte is antigen Q, the capture material24apermanently immobilized on the test line24may be antibody Q. In this case, when the biosample flowing according to the capillary pressure reaches the test line24, the conjugate22aof antigen Q and the first marker conjugate binds with antibody Q24ato form a sandwich conjugate24b. Therefore, if the analyte is contained in the biosample, it may be detected by the marker on the test line24. A normal test may fail for various reasons such as small sample amount and/or sample contamination. Accordingly, to determine whether the test has been properly performed, the detection region20may be provided with a control line25on which is permanently immobilized a second capture material25athat specifically reacts with a material contained in the sample regardless of presence of the analyte. As the second capture material25aimmobilized on the control line25, biotin may be used, and thus the second marker conjugate23acontained in the sample in the second chamber130may be a streptavidin-marker conjugate, which has a high affinity to biotin. Referring toFIGS.9A to9C, the second marker conjugate23ahaving a material that specifically reacts with the second capture material25ais contained in the sample. When the sample is transferred to the opposite side by capillary pressure, the second marker conjugate23ais also moved along with the sample. Accordingly, regardless of presence of the analyte in the sample, a conjugate25bis formed by conjugation between the second marker conjugate23aand the second capture material25a, and is marked on the control line25by the marker. In other words, if a mark by the marker appears on both the control line25and the test line24, the sample will be deemed positive, which indicates that the analyte is present in the sample. If the mark appears only on the control line25, the sample will be deemed negative, which indicates that the analyte is not present in the sample. However, if the mark does not appear on the control line25, test malfunction may be determined. As shown inFIGS.8and9, the maker conjugate may be provided in the second chamber130. However, such embodiments are not limited thereto. It may be possible that the maker conjugate is temporarily immobilized on a conjugate pad23provided in the detection region20in the reaction chamber150. Here, temporary immobilization means the marker conjugate immobilized on the conjugate pad23is moved away by flow of the sample. FIGS.10and11are views illustrating the structure of a detection region including a conjugate pad and the detection operation therein. Referring toFIG.10, the detection region20may be provided with a conjugate pad23in addition to the sample pad22, the test line24, and the control line25. A first marker conjugate22a′ which is a conjugate of a marker and the first capture material specifically reacting with the analyte may be temporarily immobilized on the conjugate pad23. The second marker conjugate23a, which is a conjugate between the marker and a material specifically reacting with the second capture material25aimmobilized on the control line25, may also be temporarily immobilized on the conjugate pad23. Referring toFIG.11A, when a biosample such as blood is dropped on the sample pad22, the biosample flows toward the control line25due to capillary pressure. If the analyte of interest is contained in the sample, it binds with the first marker conjugate22a′on the conjugate pad23to form the conjugate22aof the analyte and the marker conjugate, as shown inFIG.11B. The biosample further flows due to capillary force, thereby causing the conjugate22aand the second marker conjugate23ato flow therewith. As the flowing biosample reaches the test line24and the control line25, the capture material24abinds with the conjugate22ato form a sandwich conjugate24bon the test line24, as shown inFIG.11C. On the control line25, the second marker conjugate23abinds with the second capture material25ato form a conjugate25b. If the reaction chamber150of the microfluidic device is provided with the detection region20ofFIGS.10and11, the marker conjugates22a′ and23aare temporarily immobilized on the detection region20, and thus the second chamber130may be used as the metering chamber. When the second chamber130is used as the metering chamber, the third chamber140is used as the reaction chamber. In another exemplary embodiment, rather than using chromatography, a capture antigen or capture antibody may be provided in the reaction chamber150to react with a certain antigen or antibody in the sample such that a binding reaction with the capture antigen or capture antibody occurs in the reaction chamber150. Referring toFIG.7, the reaction chambers150-1,150-2and150-3are connected to the respective fifth chambers, i.e., the waste chambers170-1,170-2and170-3. The waste chambers170-1,170-2and170-3accommodate impurities discharged from the reaction chambers150-1,150-2and150-3and/or residue remaining after the reaction is completed. Meanwhile, the platform100may be provided with one or more magnetic bodies for position identification. For example, in addition to chambers in which a sample or residue is accommodated or a reaction occurs, the platform100may be provided with magnetic body accommodating chambers160-1,160-2,160-3and160-4. The magnetic body accommodating chambers160-1,160-2,160-3and160-4accommodate a magnetic body, which may be formed of a ferromagnetic material such as iron, cobalt and nickel which have a high intensity of magnetization and form a strong magnet like a permanent magnet, a paramagnetic material such as chromium, platinum, manganese and aluminum which have a low intensity of magnetization and thus do not form a magnet alone, but may become magnetized when a magnet approaches to increase the intensity of magnetization, or a diamagnetic material such as bismuth, antimony, gold and mercury which are repelled by magnetic fields. FIG.12is a view illustrating a function of a magnetic body accommodating chamber provided in the microfluidic device according to an exemplary embodiment. Referring toFIG.12, the test device300using the microfluidic device10is provided with a magnetic module330to attract a magnetic body under the platform100, and a detection unit350arranged over the platform100to detect various kinds of information on the platform100. The detection unit350may be arranged adjacent to the position facing the magnetic module330. Operations of the magnetic module330and the detection unit350may be controlled by a controller320. The magnetic module330may be positioned so as not to influence the rotation of the platform100, and may be transported to a position under the platform100when the operation of position identification is required. When the magnetic module330is positioned under the platform100, it may attract the magnetic body accommodated in the magnetic body accommodating chamber160, thereby causing the platform100to rotate according to magnetic attractive force such that the magnetic body accommodating chamber160is aligned with the magnetic module330. To allow the magnetic body accommodating chamber160to be easily attracted by the magnet module330, the magnetic body accommodating chamber160may be formed to protrude downward from the platform100. Since the detection unit350is located adjacent to a position facing the magnetic module330, information contained in a detection area may be detected by the detection unit350by forming the magnetic body accommodating chamber160at a position adjacent to the detection object region within the platform100. The detection area may be a QC chamber128or a reaction chamber140. Any area which has detectable information may be used as the detection area. The detection unit350may be provided with a light emitting unit and a light receiving unit. The light emitting unit and the light receiving unit may be integrally formed and arranged facing in the same direction, as shown inFIG.12, or formed separately and arranged to face each other. If the light emitting unit is a planar luminous body having a large light emitting area, the detection unit350may detect information related to a chamber to be detected even when the distance between the magnetic body accommodating chamber160and the chamber is long. The detection operation of the detection unit350will be described below in detail with reference toFIG.14. In the illustrated exemplary embodiment, the magnetic module330is adapted to move on the lower side of the platform. Alternatively, it may be adapted to move on the upper side of the platform. Allowing the magnetic body accommodating chambers160-1,160-2and160-3to perform the operation of position identification as in the illustrated embodiment is simply one example. In another example, instead of providing the magnetic body accommodating chamber160in the microfluidic device, a motor may be used to control an angular position of the platform100such that a certain position on the platform100faces the detection unit350. FIG.13is a graph schematically illustrating the rotational speed of a platform during respective fluid transfer operations in the microfluidic device according to an exemplary embodiment, andFIGS.14A to14Eare plan views illustrating flow of a fluid within the microfluidic device according to the exemplary embodiment. The structure of the microfluidic device ofFIGS.14A to14Eis the same as that of the microfluidic device ofFIG.7. Referring toFIG.13, the operation of transferring the fluid within the microfluidic device10may be broadly divided into: introducing a sample (A), distributing the sample (B), wetting a siphon channel (C), and transferring the sample (D). Here, wotting refers to an operation of filling the siphon channel125with the fluid. Hereinafter, operations of the microfluidic device will be described with reference to the graph ofFIG.13and the plan views ofFIG.14A to14Eshowing the respective operations. FIG.14Ais a plan view of the microfluidic device10during the operation of introducing a sample (A). A sample is introduced into the sample supply chamber110through the sample introduction inlet111while the platform100is at rest (rpm=0). In the present exemplary embodiment, a blood sample is introduced. Since a backflow receiving chamber112is arranged at a portion adjacent to the sample introduction inlet111, contamination of the microfluidic device10due to blood dropped at a place other than the sample introduction inlet111may be prevented during the operation of introducing the sample. FIG.14Bis a plan view of the microfluidic device10which is in the operation of distributing the sample (B). When introduction of the sample is completed, distribution of the sample to the first chambers120is initiated. At this lime, the platform100begins to rotate and the rate of rotation (rpm) thereof increases. If a test is performed on a blood sample as in the illustrated exemplary embodiment, centrifugation may be performed along with distribution of the sample. Through such centrifugation, the blood may separate into the supernatant and the sediment. The supernatant includes serum and plasma, and the sediment includes corpuscles. The portion of the sample used in the test described herein is substantially the supernatant. As illustrated inFIG.13, the rotational speed is increased to v1 to distribute the blood accommodated in the sample supply chamber110to the “1-1”-th chamber120-1, the “1-2”-th chamber120-2and the “1-3”-th chamber120-3using centrifugal force. Thereafter, the rotational speed is increased to v2 to allow centrifugation to occur within each chamber. When the blood accommodated in each chamber is centrifuged, the supernatant gathers at a position proximal to the center of rotation, while the sediment gathers at a position distal to the center of rotation. In the exemplary embodiment shown inFIGS.14A to14E, the first chambers120are formed to contain the same volume of sample. However, the first chambers120may be formed with different sizes, depending on the amounts of fluid to be distributed thereto. In addition, as describe above with reference toFIG.5B, the siphon channels125may be partially filled with blood by capillary force during distribution of the blood. When supply of blood to the “1-1”-th chamber120-1, the “1-2”-th chamber120-2and the “1-3”-th chamber120-3is completed, any excess blood not supplied to the first chambers120remains in the sample supply chamber110and flows into the QC chamber128through the distribution channel115. Further, any excess blood which does not flow into the QC chamber128flows into the excess chamber180. As shown inFIG.14B, a magnetic body accommodating chamber160-4is formed at a position adjacent to the QC chamber128. As such, the magnetic module330described above may cause the QC chamber128to face the detection unit350. Accordingly, when the detection unit350faces the QC chamber128, it may measure transmittance of the QC chamber128and determine whether the supply of blood to the first chambers120has been completed. FIG.14Cis a plan view of the microfluidic device which is in the operation of wetting siphon channels (C). Once distribution and centrifugation of the blood are completed, the platform100is stopped (rpm=0), thereby permitting the blood accommodated in the first chambers120-1,120-2and120-3fills the siphon channels125-1,125-2and125-3by capillary pressure. FIG.14Dis a plan view of the microfluidic device which is in the operation of transferring the sample to the second chamber130(D). When wetting of the siphon channels125is completed, the platform100is rotated again to allow the blood filling the siphon channels125-1,125-2and125-3to flow into the second chambers130-1,130-2and130-3. As shown inFIG.14D, the inlets of the siphon channels125-1,125-2and125-3are connected to the upper portions of the first chambers120-1,120-2and120-3(the portions proximal to the center of rotation), and thus the supernatant of the blood sample flows into the second chambers130-1,130-2and130-3via the siphon channels125-1,125-2and125-3. The second chambers130may simply serve to temporarily accommodate the blood flowing thereinto, or allow, as described above, binding between a specific antigen in the blood and a marker conjugate pre-provided in the second chambers130. FIG.14Eis a plan view of the microfluidic device which is in the operation of transferring the sample to the motoring chambers140(D). The blood flowing into the second chambers130-1,130-2and130-3is then introduced into the third chambers, i.e., the metering chambers140-1,140-2and140-3by centrifugal force. By centrifugal force, the metering chambers140-1,140-2and140-3are filled with blood from the lower portion of the second chambers130, i.e., from the portion distal to the center of rotation. After the metering chambers140-1,140-2and140-3are filled with blood up to the outlets thereof, blood subsequently introduced into the metering chambers140-1,140-2and140-3flows into the reaction chambers150-1,150-2and150-3through the outlets of the metering chambers140-1,140-2and140-3. Therefore, the positions of the outlets of the metering chambers140may be adjusted to supply a fixed amount of blood to the reaction chambers150. This is simply an example of metering. Metering the fluid sample may be performed in the manner illustrated inFIGS.15to17. The reaction occurring in the reaction chambers150may be immunochromatography or a binding reaction with a capture antigen or capture antibody, as described above. As shown inFIG.14E, if the magnetic body accommodating chambers160-1,160-2and160-3are formed at positions adjacent to the corresponding reaction chambers150-1,150-2and150-3, the positions of the reaction chambers150-1,150-2and150-3may be identified by a magnet. Accordingly, when the reaction is completed, the magnet is moved to a position under the platform100, thereby causing the detection unit350and the reaction chamber150to be positioned facing each other due to attractive force between the magnet330and the magnetic body. The detection unit350may therefore detect the result of the reaction in the reaction chamber150by capturing an image of the reaction chamber. Hereinafter, another example of metering a fluid in the microfluidic device will be described in detail. FIG.15is a plan view illustrating the structure of the microfluidic device which further includes a fluid transfer assist unit. Referring toFIG.15, the microfluidic device10described with reference toFIG.7may further include a fluid transfer assist unit155arranged between the metering chamber140and the reaction chamber150to support the transfer of the fluid. In the illustrated embodiment, the three pairs of the metering chambers140-1,140-2and140-3and the reaction chambers150-1,150-2and150-3respectively include fluid transfer assist units155-1,155-2and155-3. The fluid transfer assist unit155includes a fluid guide155bto guide movement of the fluid from the metering chamber140to the reaction chamber150, and a fluid passage155aallowing the fluid to flow from the metering chamber140to the reaction chamber150therethrough. The fluid guide155bis shaped to protrude from the reaction chamber150toward the metering chamber140, and the fluid passage is formed to have a greater width than other channels so as to facilitate passage of the fluid. However, the fluid transfer assist unit155does not necessarily require inclusion of the fluid guide155b. Alternatively, only the fluid passage155amay be provided. In addition, in the illustrated embodiment, the reaction occurs in the reaction chamber using chromatography, and to this end, the reaction chamber150is provided with the detection region20described above with reference toFIGS.8to11. Each of the three test units may perform testing independently, and in the illustrated embodiment, the three test units are respectively provided with detection regions20-1,20-2and20-3. The fluid transfer assist unit155not only serves to control the rotational speed of the platform100, but also causes the fluid accommodated in the metering chamber to be transferred to the reaction chamber150by the amount desired by a user. Hereinafter, the function of the fluid transfer assist unit155will be described with reference toFIG.16. FIGS.15A to16Eare plan views illustrating the flow of a fluid within the microfluidic device ofFIG.15, andFIG.17is a graph schematically illustrating the rotational speed of the platform during respective fluid transfer operations ofFIGS.16A to16E. The rotational speed of the platform100may be controlled by the controller320of the test device300on which the platform100is mounted. FIGS.16A to16Eshow respective fluid transfer operations performed after the fluid sample is transferred to the second chamber130. The process from the operation of introducing the sample to the operation of transferring the sample to the second chamber130is the same as the process described above with reference toFIG.14. FIG.16Ais a plan view of the microfluidic device in the operation of transferring the sample from the second chamber130to the third chamber140. The third chamber140is a metering chamber, and the previously described marker conjugate is assumed to be contained in the second chamber130. Here, the marker conjugate may include only the first marker conjugate, or may include both the first marker conjugate and the second marker conjugate. When the marker conjugate includes only the first marker conjugate, the second marker conjugate is provided on the detection region20within the reaction chamber150. When the marker conjugate includes both the first marker conjugate and the second conjugate, the detection region20may not be provided with the second marker conjugate. When the platform100is rotated, the sample and the marker conjugate in the second chamber130move to the metering chamber140. As shown in the interval (a) inFIG.17, when sufficient centrifugal force is provided by increasing the rotational speed from v1 to v3, most of the marker conjugate remaining in the second chamber130moves to the metering chamber140. The binding reaction between the first marker conjugate and the analyte in the sample may occur in the second chamber130(seeFIG.7) or in the metering chamber140. In the illustrated embodiment, the binding reaction occurs in the metering chamber140. In the metering chamber140, a first order reaction occurs between the sample and the first marker conjugate, i.e., between the analyte and the first marker conjugate. In addition, rotation of the platform100is stopped as shown in the interval (b) inFIG.17. Thereby, the difference in concentration among positions of the reactant that has been created in the metering chamber140by the centrifugal force disappears. FIG.16Bis a plan view of the microfluidic device in the operation of transferring the sample from the metering chamber140to the reaction chamber150. When the first order reaction in the metering chamber140is completed within the time desired by the user, the reacted sample is supplied to the reaction chamber150. Referring to the interval (c) ofFIG.17, the rotational speed of the platform100may be controlled in a aw-shaped pattern to transfer the sample to the reaction chamber150. The saw-shaped pattern of the rotational speed represents repeated intervals of increasing the rotational speed of the platform100and stopping. The saw-shaped control pattern of the rotational speed may be implemented by allowing the controller320of the test device300to directly control the rotational speed of the platform100as in the interval (c) ofFIG.17, or by using the magnetic module330and the magnetic body accommodating chamber160. When the magnetic module330and the magnetic body accommodating chamber160are used to control the rotational speed of the platform100, the saw-shaped control pattern of the rotational speed may be implemented by placing the magnetic module330at a position at which the magnetic module330does not influence the magnetic body accommodating chamber160at the early stage of rotation and thereafter, positioning the magnetic module330at a position under or over the magnetic body accommodating chamber160at a certain point of time while the rotational speed of the platform100is increasing. In this case, the combination of the magnetic force of the magnetic body and inertial force resulting from rotation of the sample act simultaneously to rotate the platform100, thereby driving the fluid sample toward the reaction chamber150as shown inFIG.16B. The fluid guide155bguides the driven fluid sample such that the fluid sample flows into the reaction chamber150. The fluid passage155aallows the fluid sample guided by the fluid guide155bto enter the reaction chamber therethrough. The platform100is rotated in the direction heading from the metering chamber140to the reaction chamber150, i.e., counterclockwise in the illustrated embodiment. Therefore, the fluid sample positioned outside the point at which the metering chamber140and the reaction chamber150are connected to each other may be transferred to the reaction chamber150by control of the rotational speed as previously described. Thus, the occurrence of the second order reaction within the reaction chamber150at a desired time may be accomplished by adjustment of the control timing by the user, thereby supplying a desired amount of the fluid sample to the reaction chamber150with a small amount of torque applied to the platform100. Here, the second order reaction is the chromatography reaction by the detection region20. FIG.16Cis a plan view of the microfluidic device which is in the initial state of the second order reaction in the reaction chamber150. When the fluid sample passes through the fluid passage155aand reaches the sample pad22of the detection region20, the second order reaction begins as the fluid sample is moved by the capillary force. At the same time, the fluid sample remaining in the metering chamber140is also absorbed by the detection region20. As shown in interval (d) ofFIG.17, the sample is moved by capillary force as the second order reaction begins, and therefore the rotation of the platform100may be stopped. FIG.16Dis a plan view of the microfluidic device in which the second order reaction is completed in the reaction chamber. When the sample supplied to the reaction chamber150flows from the sample pad22of the detection region20and passes both the test line24and the control line25, the second order reaction is completed. Although not shown inFIGS.8to11, an absorption pad may be provided on the side opposite to the test line and the control line, so as to absorb the sample when the reactions are completed. FIG.16Dis a plan view of the microfluidic device in the operation of drying the reaction chamber in which the second order reaction is completed. When the second order reaction is completed in the reaction chamber150, the platform is rotated at a high speed to dry the detection region20and remove the remaining fluid sample. If there is any fluid sample remaining in the first chamber120, the siphon channels may be filled with the fluid sample by capillary force, and when the platform100is rotated at a high speed, the fluid sample filling the siphon channels125may pass through the second chambers130, thereby flowing into the metering chambers140. However, if the fluid sample in the metering chambers140flows into the reaction chamber150, the detection region20indicating the result of the second order reaction may be contaminated. Accordingly, the microfluidic device10may further include a second siphon channel to transfer additional inflow of the fluid sample to the waste chamber170. FIG.18is a plan view illustrating the microfluidic device further including a second siphon channel. Referring toFIG.18, the microfluidic device10described above with reference toFIG.15may further include an additional siphon channel145connecting the metering chamber140to the waste chamber170. The added siphon channel145serves as the second siphon channel, and the siphon channel125connecting the first chamber120to the second chamber130serves as the first siphon channel. When the fluid sample remaining in the first chamber120flows into the metering chamber140during rotation of the platform100at high speed, it may in turn flow into the second siphon channel145connected to the lower portion of the metering chamber140. The fluid sample is driven by capillary force to fill the second siphon channel145, and the fluid sample filling the second siphon channel145is deposited into the waste chamber170by centrifugal force during the rotation of the platform100. Therefore, additional inflow of the fluid sample into the reaction chamber in which the reaction has been completed may be prevented even when there is remaining fluid sample in the first chamber. As is apparent from the above description, a microfluidic structure and a microfluidic device having the same according to an exemplary embodiment allows for the efficient distribution of a fixed amount of a fluid to a plurality of chambers. Adjustment of the distribution speed and supply speed of the fluid, without a separate driving source, may thus be accomplished by arranging the chambers at different positions on the platform100and connecting them in parallel using a siphon channel. Also, a multi-step reaction is allowed by connection of a first chamber (an accommodation chamber), a second chamber (a first order reaction chamber), a third chamber (a metering chamber) and a fourth chamber (a second order reaction chamber), and therefore reaction sensitivity is enhanced. Further, contamination of a reaction result may be prevented by arranging a second siphon channel between the metering chamber and the waste chamber, and directing a fluid sample flowing to the reaction chamber to the waste chamber after completion of reaction. Although a few exemplary embodiments have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the inventive concept, the scope of which is defined in the claims and their equivalents.
59,867
11857964
DETAILED DESCRIPTION OF THE INVENTION A flow cell for carrying out analysis comprises an essentially plate-shaped substrate1which is produced by the injection molding method from a plastic, preferably from PP, PE, PMMA, PC, COC or COP. The substrate1is connected to a housing component2, which is configured in its basic shape as a plate and covers, in the example shown partially, the substrate1on a plate side. The housing component2is produced as a composite part from a hard constituent and a soft constituent by the two-constituent injection molding method. The hard constituent consists for example of PP, and the soft constituent of an elastomer, in particular a thermoplastic elastomer, or silicone. The soft constituent could be at least partially transparent. On its side facing away from the housing component2, the substrate1is connected to a film3, which closes cavities formed in the substrate1and is adhesively bonded or welded to the substrate1. Preferably, the film3consists of the same material as the substrate1. The substrate1comprises a sample chamber4, which is configured as an outward curvature of the substrate plate, is covered by the film3and has a sample introduction opening5. The sample introduction opening5can be closed by a tab6, which is articulatedly connected by means of a film hinge to the housing component2and can be latched in an opening7of a profiled grip part8of the substrate1. The substrate1furthermore comprises a recess9which, together with a bulge10, oriented towards the recess9, in the hard constituent of the housing component2, forms a storage chamber11for a liquid reagent. As may be seen particularly inFIG.3, a channel12having a predetermined breaking barrier22is formed between the recess9, which forms the storage chamber11, and a channel structure13, and by means of the channel structure13a connection may be established both to the sample chamber4and to an analysis section14, which is essentially formed by the substrate1and film3. In the example shown, the analysis section14comprises four insertion openings for plug-shaped carriers15of a dry reagent. By means of a further channel16having a predetermined breaking barrier26, the storage chamber11can be connected to a pump volume18which is formed by a curved section17of the soft constituent of the housing component2. A further pump volume20, formed by a curved section19of the soft constituent, is connected via a channel21to the sample chamber4. In order to use the flow cell described above, a sample to be analyzed is introduced through the sample introduction opening5into the sample chamber4, and the sample chamber4is subsequently closed by pressing down the closure tab6. It is to be understood that, on its side facing toward the sample introduction opening5, the closure tab6comprises a sealing element that closes the opening, as is described in more detail below with the aid ofFIG.13. Optionally, a pressing force of the closure tab6against the sample introduction opening5, achieved by latching with the opening7, is reinforced with the aid of an operating instrument (not shown here or below) that receives the flow cell, for example by mechanical plunger pressure. The hermetically closed flow cell is arranged in a predetermined position in an operating instrument so that sample material accumulates at the exit of the sample chamber4because of the force of gravity, and air bubbles that may occur rise in the desired direction upward inside the hermetically closed flow cell. By mechanical actuation of the curved section17forming a pump element and a consequent reduction in the pump volume18, after opening of the predetermined breaking barriers22and26and of a valve23by the operating instrument, liquid reagent is conveyed from the storage chamber11into the sample chamber4while building up an internal pressure in the flow cell which is higher than atmospheric pressure. Actuation of the section19forming a further pump while reducing the pump volume20allows transport of the liquid reagent mixed with the sample back into the storage chamber11, this reagent coming in contact with a dry reagent of a plug-shaped dry reagent carrier24both during the forward transport and during the backward transport. By alternate actuation of the sections or pump elements17,19, full washing of the dry reagent from the dry reagent carrier24and mixing of the liquid reagent with the sample take place. The mixture of sample material and reagents, which is again located in the sample chamber11after completed washing out, is transferred from the storage chamber11into the analysis section14after the valve23is closed and a valve25is opened, and the fluid material is divided into four aliquots. In the hermetically closed flow cell, the movement of the liquid inside the analysis section takes place against the pressure of an air cushion27, as is described inFIG.18. By actuation of the pump element17, the fluid material inside the analysis section can be moved to and fro as required. During the transport of the fluid material against the air cushion27, a pressure buildup takes place, which typically lies in the range of from 0.1 to 5 bar above atmospheric pressure. An internal pressure of 1-2 bar is advantageous for carrying out the heat treatment steps in the analysis section14, as are conventional for example in PCR or lysis processes, liquids being heated up to 100° C. The internal pressure built up by the liquid transport can prevent or reduce degassing of the heat-treated liquids. The analysis section comprises detection sections for recording the analysis result. After the end of the analysis, all the actuation elements of an operating instrument are brought into the initial position at the instant of inserting the flow cell into the operating instrument. The pump elements17and19therefore return to their initial shape and the internal pressure advantageously increased in the flow cell during the analysis is reduced back to atmospheric pressure. In conjunction with hermetic closure of the flow cell, this reduction advantageously prevents undesired egress of the analyzed sample mixture when disposing of the flow cell. Exemplary embodiments of functional sections, which fulfil various functions, of flow cells, are described below, such as may for example be used in the above-described flow cell comprising a housing component having a hard and a soft constituent. A first variant of the connection of the housing component2to the substrate1, in particular for fluid-tight and/or hermetically connection of the soft constituent of the housing component2to the substrate1, relates to thermal riveting according toFIG.4. Rivet pins95connected in one piece to the substrate1and protruding from the substrate1extend through corresponding openings28in the hard constituent of the housing component2, as may be seen fromFIG.4a. According toFIG.4b, the rivet pins95are thermally deformed to form mushroom heads29engaging behind the openings28, so that the housing component2is clamped between the substrate1and the mushroom heads29. FIG.5indicates the possibility of ultrasound welding of the housing component2to the substrate1, the hard constituent of the housing component2being provided with prismatic direction guides30optionally extending around a soft constituent section. When ultrasound is applied, the direction guides90melt and weld to the surface of the substrate1. In the exemplary embodiments shown inFIGS.4and5, fluid-tight or hermetic connection takes place between the soft constituent of the housing component2and the substrate1by pressure and clamping. FIG.6shows an exemplary embodiment in which the housing component2and the substrate1are adhesively bonded to one another, in the example shown by a double-adhesive adhesive tape31. FIG.7shows connection of a housing part2to a substrate1, in the case of which a soft constituent section of the housing component2is adhesively bonded or welded at32locally to the substrate1. The connection could also be configured continuously circumferentially. FIG.8shows three different possibilities of the formation of a storage chamber for a liquid. In the case of the exemplary embodiment ofFIG.8a, a storage chamber33is formed only by a bulge of the hard constituent of the housing component2. In the case of the exemplary embodiment of8b, the formation of a storage chamber33′ takes place only using a recess in the substrate1. FIG.8cshows a storage chamber33″, corresponding to the storage chamber11described above, which is formed both by a bulge of the housing component2and by a recess in the substrate1. In all variants8ato8c, the storage chamber33,33′ or33″ is respectively closed on the entry and exit sides by breakable predetermined breaking barriers34,34′. A prismatic barrier member closes the channel and is adhesively bonded or welded at the apex to the film3. In order to break the predetermined breaking barriers34,34′, an arrangement provided inFIG.9by way of example for the predetermined breaking position34′ is respectively envisioned. A membrane35, made of an elastomer material, welded fluid-tightly circumferentially to the substrate1is a part of the soft constituent of the housing component2and can be stretched by an actuation element36of an operating instrument into a through-opening37in the substrate1until it deflects the film3adhesively bonded or welded to the substrate1according to the dashed line38so that the predetermined breaking barrier34′ breaks. By the deflection of the film3, the film3tears off from the apex of the prismatic barrier member closing the channel. A predetermined breaking barrier shown inFIG.10is formed by a barrier film39which covers a through-opening40in the substrate1that is in fluid connection with the storage chamber33′ and, in particular, bears against an annular projection enclosing the through-opening40and is welded tightly thereto, in order to ensure hermetic closure of the storage chamber at least partially filled with the liquid for the period of time between production and use of the flow cell. An actuation element36of an operating instrument stretches an elastomer membrane35, which is a part of the soft constituent of the housing component2, in such a way that the barrier film39breaks while opening the predetermined breaking barrier. Advantageously, the elastomer membrane35does not come in contact with the liquid stored in the storage chamber33′ so long as the predetermined breaking barrier is not removed. A material that is compatible in the long term with the liquid in the flow cell is therefore not needed for the membrane35. A functional section, shown inFIG.11and fulfilling a pump function, as already similarly described above with the aid ofFIGS.1to3, of a flow cell comprises a curved pump element41, made of elastomer material, forming a pump volume42. The pump element41is a part of the soft constituent of the housing component2connected to the substrate1in this case by riveting. The pump element41is intended for actuation by an actuation element43of an operating instrument. The delivery flow may be controlled by adjusting the rate of advance of the actuation element43and furthermore depends on the geometry of the actuation element43. The pump element41is resilient and has a restoring moment such that a delivery flow in the opposite direction can be produced by the pump element when being restored. A functional section, represented inFIG.12, of a flow cell comprises a membrane45made of elastomer material, which is formed by the soft constituent of the housing component2connected to the substrate1. The membrane45made of elastomer material forms a septum, which can be pierced with a cannula44and through which material can be introduced into the flow cell before or after an analysis. FIG.13shows a closure tab47, connected in one piece to the housing component2by means of a film hinge46, for covering a sample introduction opening48of the flow cell. The tab comprises an elastomer membrane49, which is a part of the soft constituent of the housing component2and seals the sample introduction opening48. An actuation element50of an operating instrument ensures hermetic closure of the sample introduction opening. FIGS.14and15show exemplary embodiments of a functional section, fulfilling a valve function, of a flow cell. An elastomer membrane52, which is a part of the housing component2connected to the substrate1, may in the closed state of the valve be pressed by an actuation element51of an operating instrument against a raised valve seat53. The valve opens when the pressure due to the actuation element51is released. The functional section ofFIG.15differs from the functional section ofFIG.14in that the elastomer membrane52is covered on its side facing toward the valve seat53by a plastic film54that prevents direct contact of the elastomer membrane52with liquid inside the flow cell. FIG.16shows a pump (or a valve) which can be actuated by applying a pressure p and has a housing component2, comprising an elastomer membrane55, and a substrate1. The housing component2is connected to the substrate1by means of an extensible film56, which can be stretched over a pressure application channel57according to the dashed line58, the elastomer membrane55being stretched and a volume59being generated between the elastomer membrane55and the film56. Respectively, the film56is connected to the substrate1by an annular weld seam60and the elastomer membrane55is connected to the film56by an annular weld seam61. A pump shown inFIG.17, operating according to the peristaltic principle comprises three pump chambers62,62′,62″ connected in series, which are formed between the substrate1and outwardly curved pump elements63,63′,63″. The pump elements, consisting of elastomer material, are a part of the soft constituent of the housing component2. In order to convey fluid, actuation elements64,64′,63″ of an actuation instrument act successively on the outwardly curved pump elements63,63′,63″. In order to form the pump chambers62,62′,62″, in the example shown the substrate1is respectively indented. In an alternative variant, the soft constituent, forming the pump elements63,63′,65″, of the housing component2is covered by a barrier film so that the soft constituent does not come in contact with the fluid in the flow cell and materials incompatible with the fluid may be used for the soft constituent. FIG.18shows a flow cell having a substrate1and a housing component2, the soft constituent of which comprises an elastomer membrane65that bounds a gas cushion. Air pressure increasing in a channel66makes the elastomer membrane65bulge out according to the dashed line67. An actuation element68of an operating instrument can control the deflection of the elastomer membrane and therefore the volume of the gas cushion. It is to be understood that a gas cushion volume may be formed not just by deflection but in advance by shaping of the elastomer membrane and/or by indentation of the substrate1. FIG.19shows a functional section of a flow cell, by which section a hermetically tight connection to a line, leading for example to a pump, of an operating instrument may be established. An elastomer membrane69, which is a part of the soft constituent of the housing component2, comprises an opening70to which, for example, a connecting line71of an operating instrument may be connected while exerting an application pressure. A channel72in the substrate1, which is connected to the opening, is covered by a film73which is adhesively bonded or welded to the substrate and is permeable for air but impermeable for liquids and vapors. The flow cell may therefore have pressure applied to it through the line71and, for example in conjunction with a pneumatic valve of an operating instrument, form a switchable vent opening or switchable gas cushion for controlling the liquid transport in the flow cell. FIG.20shows a functional section of a flow cell, which is used for clamp connection of the flow cell to a sensor element74or other component made of a material which cannot be connected directly either to the substrate1or to the housing component2. An annular sealing element75made of elastomer, which seals the sensor element74against the substrate1, is a part of the soft constituent of the housing component2. For the clamp connection between the sensor element74and the substrate1, rivet pins76protruding from the substrate1are used which are deformed to form a mushroom head77pressing the sensor element74against the sealing ring75. FIG.21shows a functional section of a flow cell having a substrate1and a housing component2, the soft constituent of which comprises an elastomer membrane78. The elastomer membrane78closes a sample introduction opening79of the flow cell. A slit80in the elastomer membrane ensures that a pipette81introducing the sample is firmly enclosed and spraying of sample material or reagent liquid cannot occur. After the sample introduction, the sample introduction opening79is hermetically sealed by a closure element (not shown). The elastomer membrane78, which closes the introduction opening and comprises the slit80, may also advantageously be used when the flow cell comprises devices for generating reduced pressure in the sample introduction channel, in which case the reduced pressure may, for example, be generated by outwardly curved pump elements described above. For example, a capillary tube, which has a blood sample and is inserted through the slit, may then be drained by the reduced pressure, the elastomer membrane78closing and sealing the tube. FIG.22shows a functional section of a flow cell having a substrate1and a housing component2, the functional section being used to remove air bubbles from a liquid flowing in a channel82. The channel82is connected to a pump volume84by means of a membrane83which is air-permeable but impermeable for liquids. By means of an outwardly curved pump element85, which is a part of the soft constituent of the housing component2, a reduced pressure may be generated as described above, so that air can pass from the liquid into the pump volume. FIG.23shows a functional section of a flow cell comprising a substrate1and a housing component2, which section makes it possible to meter a sample quantity to be processed in the flow cell. A flow chamber56, which is formed by an indentation in the substrate1and has a defined volume, is covered by an elastomer membrane87which is a part of the soft constituent of the housing component2. An entry channel88of the flow chamber86is connected to the sample introduction opening of the flow cell, and one exit channel89connects the flow chamber86to a vent opening (not shown). A further exit channel90of the flow chamber86connects the flow chamber to the channel system, required for the processing and analysis, of the flow cell and is closed outward. A sample is pressed by the user into the sample introduction opening of the flow cell, the flow chamber86being filled and excess material escaping through the channel89. The channel90(perpendicular to the channels88,89) is not vented. After the sample introduction, the sample introduction opening at the entry of the flow cell, i.e. of the channel88, as well as a vent opening at the exit of the channel89are tightly closed by means of a cap, a stopper or a tape (with or without assistance by the operating instrument). The lowering of a plunger91in an operating instrument leads to a volume displacement of the sample volume metered in the flow chamber86into the channel90and the subsequent channel system, required for the processing and analysis, of the flow cell. In the same way, an aliquot of a sample mixture or of another liquid quantity may also be metered during the analysis or sample processing. FIG.24shows a functional section of a flow cell having a component2and a flow chamber92. An elastomer membrane93, which is transparent and is a part of the soft constituent of the housing component2, forms an inspection window for monitoring the filling of the flow cell with liquid sample or for monitoring the liquid transport during the analysis.
20,208
11857965
DETAILED DESCRIPTION The present disclosure describes microfluidic valves that utilize a flexible blister that can be pressed to actuate the microfluidic valves. The microfluidic valves include normally-open valves and normally-closed valves. According to the present disclosure, a microfluidic valve includes a substrate having a microfluidic channel formed in the substrate. A sealing layer is over the microfluidic channel. A flexible blister layer is over the sealing layer, wherein the flexible blister layer includes a blister formed as a distended portion with a blister volume between the flexible blister layer and the sealing layer. The microfluidic valve is actuatable by puncturing the sealing layer by pressing on the blister. Actuating the microfluidic valve either allows fluid to flow through the microfluidic channel or blocks fluid from flowing through the microfluidic channel. The microfluidic valve can be a normally-open valve; in which a non-newtonian plugging fluid is in the blister volume. The blister can be positioned to inject the non-newtonian plugging fluid into the microfluidic channel when the blister is pressed and the sealing layer is punctured. The non-newtonian plugging fluid can have a sufficient viscosity to block fluid from flowing through the microfluidic channel. In some examples, the substrate can include a puncturing point beneath the blister oriented toward the sealing layer to puncture the sealing layer when the blister is pressed. In other examples, the flexible blister layer can include a puncturing point at the blister, where the puncturing point is oriented toward the sealing layer to puncture the sealing layer when the blister is pressed. In certain examples, the non-newtonian plugging fluid can be in the blister volume at the puncturing point such that a single press of the blister punctures the sealing layer and injects the non-newtonian plugging fluid into the microfluidic channel. The non-newtonian plugging fluid can be a Bingham plastic, a viscoplastic, a shear thinning fluid, or a curable fluid. The microfluidic valve can also be a normally-closed valve. In such examples, the microfluidic channel can be a first microfluidic channel and the substrate can also include a second microfluidic channel formed in the substrate. The second microfluidic channel can be in fluid communication with the blister, and the sealing layer can separate the blister from fluid communication with the first microfluidic channel. Puncturing the sealing layer can place the blister into fluid communication with the first microfluidic channel to allow fluid to flow between the first microfluidic channel and the second microfluidic channel through the blister volume. The blister volume can be initially filled with air in some cases. The microfluidic valves can also include an opening well formed in the substrate under the blister. The opening well can be in fluid communication with the microfluidic channel, and the opening well can have a greater depth, width, or both compared to the microfluidic channel. The present disclosure also describes microfluidic devices. A microfluidic device includes a substrate having a fluid flow microfluidic channel formed in the substrate. A microfluidic valve is positioned in fluid communication with the fluid flow microfluidic channel such that the microfluidic valve initially allows or blocks fluid flow through the fluid flow microfluidic channel. The microfluidic valve includes a sealing layer over the fluid flow microfluidic channel and a flexible blister layer over the sealing layer. The flexible blister layer includes a blister formed as a distended portion with a blister volume between the flexible blister layer and the sealing layer. The microfluidic valve is actuatable by puncturing the sealing layer by pressing on the blister, wherein actuating the microfluidic valve switches the microfluidic valve from allowing fluid flow to blocking fluid flow or from blocking fluid flow to allowing fluid flow. In some examples, the microfluidic valve can be a normally-open valve that initially allows fluid flow through the fluid flow microfluidic channel. A non-newtonian plugging fluid can be in the blister volume. The blister can be positioned to inject the non-newtonian plugging fluid into the fluid flow microfluidic channel when the blister is pressed and the sealing layer is punctured. The non-newtonian plugging fluid can have a sufficient viscosity to block fluid from flowing through the fluid flow microfluidic channel. The microfluidic device can also include a second microfluidic valve that is a normally-closed microfluidic valve. The second microfluidic valve can include a second blister formed in the flexible blister layer, and the substrate can also include a second microfluidic channel formed in the substrate, where the second microfluidic channel is in fluid communication with the second blister. The sealing layer can separate the second blister from fluid communication with the fluid flow microfluidic channel. Puncturing the sealing layer can place the second blister into fluid communication with the fluid flow microfluidic channel to allow fluid to flow between the fluid flow microfluidic channel and the second microfluidic channel through the second blister volume. The present disclosure also describes methods of directing fluids. A method of directing fluids includes flowing a fluid through a fluid flow microfluidic channel formed in a substrate, wherein a microfluidic valve is positioned in fluid communication with the fluid flow microfluidic channel such that the microfluidic valve initially allows or blocks fluid flow through the fluid flow microfluidic channel. The microfluidic valve includes a sealing layer over the fluid flow microfluidic channel and a flexible blister layer over the sealing layer. The flexible blister layer includes a blister formed as a distended portion with a blister volume between the flexible blister layer and the sealing layer. The method also includes actuating the microfluidic valve by puncturing the sealing layer by pressing on the blister. Actuating the microfluidic valve switches the microfluidic valve from allowing fluid flow to blocking fluid flow or from blocking fluid flow to allowing fluid flow. In some examples, the microfluidic valve can be a normally-open valve, and flowing fluid through the fluid flow microfluidic channel is performed before actuating the microfluidic valve. Actuating the microfluidic valve can stop the fluid flow. The normally-open valve can include a non-newtonian plugging fluid in the blister volume, wherein pressing the blister punctures the sealing layer and injects the non-newtonian plugging fluid into the fluid flow microfluidic channel. The non-newtonian plugging fluid can have a sufficient viscosity to block fluid from flowing through the fluid flow microfluidic channel. In further examples, flowing the fluid through the fluid flow microfluidic channel can include flowing the fluid in a first direction, and the method can also include actuating a second microfluidic valve, which is a normally-closed valve, to allow the fluid to flow in a second direction. The second microfluidic valve can include a second blister formed in the flexible blister layer, and the substrate can include a second microfluidic channel formed in the substrate, wherein the second microfluidic channel is in fluid communication with the second blister. The sealing layer can separate the second blister from fluid communication with the fluid flow microfluidic channel. Puncturing the sealing layer can place the second blister into fluid communication with the fluid flow microfluidic channel to allow fluid to flow between the fluid flow microfluidic channel and the second microfluidic channel through the second blister volume. It is noted that when discussing examples of microfluidic valves, microfluidic devices, and methods of directing fluids described herein, such discussions can be considered applicable to one another whether or not they are explicitly discussed in the context of that example. Thus, for example, when discussing a non-newtonian plugging fluid in a microfluidic valve, such disclosure is also relevant to and directly supported in the context of a microfluidic device or a method of directing fluids, and vice versa. Terms used herein will have the ordinary meaning in the relevant technical field unless specified otherwise. In some instances, there are terms defined more specifically throughout the specification or included at the end of the present specification, and thus, these terms can have a meaning as described herein. Microfluidic Valves A variety of microfluidic devices and microfluidic processes can benefit from valves to control the flow of fluid through microfluidic channels. However, it can be difficult to design and manufacture valves for the small scale of microfluidic channels, which can have small sizes such as less than 1 mm down to 1 μm in diameter or width. Mechanical valves are often used in larger systems such as pipes and tubing, but these types of valves can be complex and expensive to miniaturize. Some microfluidic applications call for disposable and consumable microfluidic devices, such as one-time-use devices that are used to process biological samples. Using expensive miniaturized mechanical valves can add greatly to the cost of such disposable devices. Additionally, valves in microfluidic devices can encounter different forces than in larger devices. For example, forces due to surface tension can have a much larger effect on fluid flow in small-scale devices. Some types of non-mechanical valves have been used, such as capillary breaks and bubble valves. These can provide separation between fluids in different parts of a microfluidic channel, but these types of valves do not provide a hermetic seal and the separation can be broken quite easily if any pressure is applied to the fluids to move the bubble or break the capillary barrier. The microfluidic valves described herein can be more robust, simpler, and cheaper compared to the other types of valves previously used. The microfluidic valves utilize a flexible blister that can be pressed to actuate the valve. Pressing the blister can either open or close the valve, depending on whether the valve is designed as a “normally-closed” or “normally-open” valve, respectively. Some microfluidic systems can already be designed to make use of a blister pack with blisters that contain various fluids, such as reactants for use in the microfluidic system. These systems often already include a mechanism for pressing blisters, such as a robotically-controlled piston. It can be relatively simple to add a microfluidic valve as described herein, because actuating the valve can be performed by pressing a blister similar to the other blisters already present in the system. A microfluidic valve as described herein includes a substrate with a microfluidic channel formed in the substrate. A sealing layer is positioned over the microfluidic channel, A flexible blister layer is positioned over the sealing layer. The flexible blister layer includes a blister that has the form of a distended, bulging portion of the flexible blister layer. This leaves a space between the bulging flexible blister layer and the sealing layer, which space is referred to as a “blister volume,” The microfluidic valve can be actuated by pressing the blister, which can puncture the sealing layer beneath the blister. Depending on whether the microfluidic valve is a normally-open valve or a normally-closed valve, pressing the blister can cause the valve to either block fluid flow through the microfluidic channel, or to allow fluid flow through the microfluidic channel, respectively. In a normally-open microfluidic valve, the blister can be filled with a non-newtonian plugging fluid. In some examples, the non-newtonian plugging fluid can be a viscous fluid, such as a grease. When the blister is pressed, the sealing layer can be punctured and the non-newtonian plugging fluid can be injected into the microfluidic channel. This can form a plug of the non-newtonian plugging fluid, which blocks the microfluidic channel so that no other fluids (i.e., liquids, air, or other gases) can flow through the microfluidic channel. This type of microfluidic valve is referred to as “normally-open” because the microfluidic channel is open and unobstructed before the blister is pressed, and then after the blister is pressed the microfluidic channel is closed off by the plug of non-newtonian plugging fluid. The non-newtonian plugging fluid can be any fluid that has a sufficiently high viscosity, after being injected into the microfluidic channel, to block fluid flow through the microfluidic channel. This fluid is referred to as “non-newtonian” because the fluid may have a non-constant viscosity. For example, the fluid can be shear-thinning fluid, Bingham plastic fluid, viscoplastic fluid, or curable fluid. In some examples, the non-newtonian plugging fluid can have a relatively lower viscosity when pressure is applied to the blister and the non-newtonian plugging fluid is injected into the microfluidic channel. Then, after the non-newtonian plugging fluid has been injected and has come to rest, the viscosity can be higher so that the non-newtonian plugging fluid can block fluid flow through the microfluidic channel. When the blister is pressed to inject the non-newtonian plugging fluid into the microfluidic channel, the force applied to the blister can be from 10 Newtons (kg·m·s−2) to 40 Newtons (kg·m·s−2), or from 10 Newtons (kg·m·s−2) to 20 Newtons (kg·m·s−2), or from 20 Newtons (kg·m·s−2) to 40 Newtons (kg·m·s−2). FIG.1Ashows a side cross-sectional view of one example of a normally-open microfluidic valve100. This microfluidic valve includes a substrate110with a microfluidic channel120formed in the substrate. This example also includes an injection channel122and an opening well124formed in the substrate.FIG.1Bshows a top-down view of the substrate alone to illustrate the layout of the microfluidic channel, injection channel, and opening well. In this example, the opening well has a greater depth and width compared to the injection channel and the microfluidic channel. Returning toFIG.1A, a sealing layer130is positioned over the substrate. The sealing layer in this example covers the opening well, injection channel, and microfluidic channel. Thus, the sealing layer forms the ceiling of the microfluidic channel. A flexible blister layer140is positioned over the sealing layer. The flexible blister layer includes a blister150that is a distended portion of the flexible blister layer that bulges upward. In this particular example, the blister includes both an opening blister152and an injection blister154. The opening blister includes a puncturing point156that points downward toward the sealing layer. When the opening blister is pressed, the puncturing point can puncture the sealing layer. A non-newtonian plugging fluid160is contained inside the blister. Most of the non-newtonian plugging fluid is inside the injection blister portion of the blister.FIG.10shows a top-down view of the blister layer to illustrate the shape of the opening blister and the injection blister. The opening blister has a shape similar to a donut or a volcano, with the puncturing point forming a depression in the center of the opening blister. The injection blister is formed as a simple hemispherical shape. FIGS.2A-20illustrate a process of actuating an example microfluidic valve100. This example microfluidic valve has the same design as shown inFIGS.1A-1C. InFIG.2A, the opening blister152is pressed to puncture the sealing layer130. After the opening blister has been pressed and the sealing layer has been punctured, the injection blister154can be pressed to squeeze the non-newtonian plugging fluid160out of the blister into the opening well124. The non-newtonian plugging can then proceed through the injection channel122and into the microfluidic channel120to block of the microfluidic channel.FIG.2Bshows the injection blister after being pressed. The injection blister is deformed and collapsed, and the non-newtonian plugging fluid has been injected into the microfluidic channel.FIG.2Cshows a top-down view of the substrate110to show how the non-newtonian plugging fluid flows into the microfluidic channel and forms a plug in the microfluidic channel. This plug prevents fluid from flowing through the microfluidic channel. The non-newtonian plugging fluid can be a fluid having sufficient viscosity to block fluid flow through a microfluidic channel. In various examples, the viscosity level that is sufficient can vary depending on the conditions of fluids in a particular microfluidic device. In certain examples, fluid in a microfluidic device may be under pressure do the force of gravity on a pressure head of fluid upstream of the plug of non-newtonian plugging fluid. The non-newtonian plugging fluid can have a sufficient viscosity to hold the plug in place, against the pressure head. In other examples, the fluid in the microfluidic channel may be under pressure exerted in some other way. Additionally, the diameter of the microfluidic channel can affect the level of viscosity that is sufficient. A smaller microfluidic channel can allow a less-viscous plugging fluid to support a given pressure. In some examples, the microfluidic channel can have a diameter or width from 50 μm to 3 mm, or from 100 μm to 1 mm, or from 200 μm to 1 mm. The fluid upstream of the non-newtonian fluid plug can exert a pressure of up to 8 inches of water, or up to 12 inches of water, or up to 16 inches of water. The non-newtonian plugging fluid can have a holding pressure from 1,000 Pa to 5,000 Pa when the non-newtonian plugging fluid is injected into the microfluidic channel. The level of viscosity that is sufficient to block the microfluidic channel can be 5,000 centipoise or greater in some examples. In other examples, the sufficient viscosity can be 10,000 centipoise or greater, or 15,000 centipoise or greater, or 20,000 centipoise or greater. Viscosity is often referred to more specifically as dynamic viscosity, and can be measured using a viscometer such as viscometers available from AMETEK, Inc. (USA), Anton Paar GmbH (Austria), or IKA (Germany). Some non-newtonian fluids can act as if they have an infinite viscosity when the amount of shear stress applied to the fluid is below a certain threshold, Thus, in some examples the non-newtonian fluid plug can effectively have an infinite viscosity when the non-newtonian fluid is at rest in the microfluidic channel. In certain examples, the non-newtonian plugging fluid can be a Bingham plastic, a viscoplastic, a shear thinning fluid, or a curable fluid. Bingham plastics can include materials that behave as rigid bodies at low stress but which flow as a viscous fluid at high stress. The transition between the rigid body behavior and the viscous fluid behavior can occur at various different stress levels, depending on the particular Bingham plastic material. Bingham plastics can include greases, slurries, suspensions of pigments, and others. Viscoplastics are a broader category of materials that can include Bingham plastics. Viscoplastic materials can experience irreversible plastic deformation when stress over a certain level is applied. When stress under this level is applied, the viscoplastic material can behave as a rigid body, as is the case with Bingham plastics, or the viscoplastic material can undergo reversible elastic deformation. Shear thinning fluids are materials that behave as a fluid with a high viscosity when low stress is applied, but the viscosity of the fluid decreases when the stress is increased. Examples of shear thinning fluids can include polymer solutions, molten polymers, suspensions, colloids, and others. In certain examples, the non-newtonian plugging fluid can include a mineral oil-based grease, a vegetable oil-based grease, a petroleum oil-based grease, a synthetic oil-based grease, a semi-synthetic oil-based grease, a silicone oil-based grease, or a combination thereof. Regarding the viscosity of greases, because of the strong shear thinning behavior of many greases, an additional measurement of the consistency can be useful besides normal dynamic viscosity. Consistency of grease can be expressed as an NLGI (National Lubricating Grease Institute) consistency number. This number can be measured using the standard classification and specification of lubricating grease, which is reproduced in ASTM D4950. The NLGI consistency number can be one of nine grades, included grade 000, grade 00, grade 0, grade 1, grade 2, grade 3, grade 4, grade 5, and grade 6. The grades progress from softer consistency to harder consistency. In some examples, the non-newtonian plugging fluids described herein can have an NLGI consistency number from 0 to 6. In further examples, the NLGI consistency number can be from 1 to 5, from 2 to 5, from 1 to 4, or from 2 to 4. In certain examples, the non-newtonian plugging fluid can be grease-based. As used herein, “grease” can refer to a dispersion of a thickening agent in a liquid lubricant. Some greases can include a soap emulsified with a base oil, such as a mineral oil, vegetable oil, or petroleum oil. Greases often have a high initial viscosity when at rest, and the viscosity can drop upon application of shear stress. Thus, greases are often used on bearings to give the effect of an oil-lubricated bearing when the bearing is in motion, where the grease has approximately the viscosity of the base oil when the bearing is in motion. Accordingly, greases can often act as a solid when not under stress or when low stress is applied. However, greases can flow as a viscous fluid when higher stresses are applied. This can allow the grease to be injected into the microfluidic channel to form a plug, and then the plug can act as a solid when under low stress. Examples of greases that can be used can include greases available under the trade names ANTI-SEIZE TECHNOLOGY™ (A.S.T. Industries, Inc., USA), CITGO® (Citgo Petroleum Corporation, USA), JET-LUBE® (Whitmore Manufacturing LLC, USA), KRYTOX™ (Chemours Company, USA), MOBIL® (Exxon Mobil Corporation, USA), MYSTIK® (Mystik Lubricants, USA), SPRAYON® (Sprayon, USA), and SUPER LUBE® (Super Lube, USA). Grease-based plugging fluids can also include additives such as PTFE particles, polyurea, calcium stearate, sodium stearate, lithium stearate, clay, graphite, silica, molybdenum disulfide, aluminum, copper, zinc, and others. Curable fluids can also be used as the non-newtonian plugging fluid. Curable fluids can include fluids that can undergo a curing process to increase the viscosity of the fluid and/or cause a phase change from liquid to solid. Although solids are often not considered to have a viscosity, the non-newtonian plugging fluids described herein can include curable fluids that change from a liquid to a solid when cured, as the solid form will be capable of preventing fluid flow through a microfluidic channel. The curing process can include thermal curing, chemical curing, ultraviolet radiation curing, or other curing methods. In some examples, curable fluids can include monomers that can polymerize to form polymers and/or polymers that can become crosslinked during the curing process. Examples of curable fluids can include two-part epoxy resins, two-part polyurethane resins, ultraviolet curing epoxies, ultraviolet curing acrylates, ultraviolet curing urethanes, ultraviolet curing thiols, and others, Curable fluids can also include gels, cross-linkable polymers, and other materials. In some examples, a curable adhesive such as ultraviolet curable adhesives can be used. Some example ultraviolet curable adhesives can include MASTER BOND® UV adhesives from Master Bond Inc. (USA). In other examples, a two-part curable resin such as a two-part epoxy resin can be used. In these examples, two blisters can hold the two parts of the resin and the two parts can be mixed together when the two parts are injected into the microfluidic channel. In further examples, the non-newtonian plugging fluid can be insoluble in the fluids that will contact the non-newtonian plugging fluid after being injected into the microfluidic channel. For example, an aqueous fluid may be flowing through the microfluidic channel before the non-newtonian plugging fluid is injected. The non-newtonian plugging fluid can be a non-aqueous fluid such as a grease that will not dissolve in the aqueous fluid. In other examples, the fluids in the microfluidic channel can be non-aqueous fluids and the non-newtonian plugging fluid can be an aqueous fluid such as a hydrogel. Microfluidic valves can also include additional components and different designs.FIG.3shows an example microfluidic valve100that includes multiple additional layers of material. As in the previous examples, this microfluidic valve includes a substrate110. A pressure-sensitive adhesive layer170is adhered to the top surface of the substrate. A label layer172is then adhered to the top of the pressure sensitive adhesive layer. Another pressure-sensitive adhesive layer is placed over the label layer, and then the sealing layer130and flexible blister layer140are added as in the previous examples. The pressure-sensitive adhesive layers can be included to adhere neighboring layers together. The label layer can be a layer of material that is mechanically strong enough to not be punctured when the blister150is pressed. The label layer can be made from a thin material such as a plastic film, foil, paper, or similar material. In this example, the label layer has an opening directly over the opening well124to allow the sealing layer to be punctured and open over the opening well to inject non-newtonian plugging fluid160into the opening well. However, the label layer covers the top of the injection channel122and the microfluidic channel120. Thus, the label layer provides a ceiling for these channels and ensures that the sealing layer does not rupture over these channels or deform downward into the channels, which could cause partial or total blockage of the channels if part of the sealing layer were to clog the channels. Accordingly, the label layer can be designed to have openings at locations where the sealing layer is designed to by punctured, and the label layer can cover other features such as microfluidic channels. A label layer and/or pressure-sensitive adhesive layers can be added to any of the other example microfluidic valves and microfluidic devices described herein. In some examples, the pressure-sensitive adhesive layers can include double-sided tape, glue, or other pressure-sensitive adhesives. As used herein “pressure-sensitive” refers to adhesives that can adhere to a surface when pressure is applied to stick the adhesive to the surface, without solvents, water, heat, activators, or other components to activate the adhesive. In some examples, pressure-sensitive adhesives can include an elastomer, such as acrylic, acrylate, rubber, silicone rubber, ethylene-vinyl acetate, or other elastomers. Pressure-sensitive adhesives can also include a tackifier, such as a rosin ester. In various examples, the pressure-sensitive adhesive layers can have a thickness from about 0,005 mm to about 1 mm, or from about 0,005 mm to about 0.5 mm, or from about 0,005 mm to about 0.1 mm. FIG.4shows another example microfluidic valve100. This example does not include an opening blister with a puncturing point as in the previous examples. Instead, this example includes a single blister150filled with non-newtonian plugging fluid160. The substrate110includes a puncturing point112formed as a sharp pointed protrusion from the opening well124. When the blister is pressed, the sealing layer130flexes downward until the sealing layer is punctured by this puncturing point. The non-newtonian plugging fluid can then flow out of the blister and into the opening well. This example also includes a microfluidic channel120, injection channel122, sealing layer130, and flexible blister layer140as in the previous examples. FIG.5shows an example microfluidic valve100having a different design. This example does not include an opening well or an injection channel. Instead, an opening blister152is positioned directly over the microfluidic channel120. A cross-section of the microfluidic channel is shown in this figure. The opening blister includes a puncturing point156that can puncture the sealing layer130when the opening blister is pressed. Additionally, this microfluidic valve includes an opening blister without an additional injection blister as in the previous examples. The opening blister is made with a sufficient blister volume to hold enough non-newtonian plugging fluid160to plug the microfluidic channel. The opening blister is formed in the flexible blister layer140. This microfluidic valve can be actuated with a single press of the opening blister, which both punctures the sealing layer and injects the non-newtonian plugging fluid into the microfluidic channel. A variety of additional designs can be used for normally-open microfluidic valves. For example, a normally-open microfluidic valve can be positioned on a microfluidic channel that leads to a vent opening. The vent opening can be sealed by actuating the microfluidic valve. In other examples, the microfluidic channel can include multiple branching channel segments. The microfluidic valve can inject non-newtonian plugging fluid into one of the segments to prevent fluid from flowing through that particular segment. Alternatively, the microfluidic valve can be designed to inject the non-newtonian plugging fluid into multiple channel segments or all of the channel segments. The normally open microfluidic valve can also be used to close off a reservoir in order to stop fluid flow out of the reservoir. Some microfluidic processes can include hazardous materials in fluids flowing through microfluidic channels. In such cases, microfluidic valves can be used to block exits from the microfluidic device to contain hazardous materials within the device before the device is disposed of. In some cases, the microfluidic valve may be used to intentionally foul a microfluidic device by injecting non-newtonian fluid into microfluidic channels to prevent the device from being re-used. The examples described above are examples of normally-open valves that can be closed by pressing a blister. As mentioned above, the microfluidic devices described herein can also include normally-closed valves that can be opened by pressing a blister. In normally-closed valves, the sealing layer of the microfluidic valve can initially provide a hermetic seal prevent fluid from flowing through the valve. The sealing layer can then be punctured and the puncture hole can allow fluid to flow through the valve. In more detail, a normally-closed valve can include two microfluidic channel segments. These can be referred to as a first microfluidic channel and a second microfluidic channel. The first and second microfluidic channels are formed in the substrate, but are not in fluid communication one with another, A blister is formed overlapping a portion of both of the microfluidic channels. As explained above, the blister includes a blister volume inside the blister, between the flexible blister layer and the sealing layer. The first microfluidic channel is separated from the blister volume by an intact sealing layer. However, an opening is pre-formed in the sealing layer connecting the second microfluidic channel to the blister volume. Thus, the second microfluidic channel is initially in fluid communication with the blister volume. However, because the sealing layer is intact over the first microfluidic channel, no fluid can flow between the first and second microfluidic channels through the blister. When the blister is pressed, the sealing layer is punctured over the first microfluidic channel, placing the first microfluidic channel into fluid communication with the blister volume and the second microfluidic channel. FIG.6Ashows a side cross-sectional view of an example normally-close microfluidic valve100. This microfluidic valve includes a substrate110, a sealing layer130over the substrate, and a flexible blister layer140over the sealing layer. The substrate includes a first microfluidic channel120, a second microfluidic channel128, and an opening well124connected to the first microfluidic channel. A blister150is formed in the flexible blister layer. This blister includes an opening blister152and a connecting blister segment158. The opening blister includes a puncturing point156oriented downward toward the sealing layer. The connecting blister segment extends to a pre-formed opening132in the sealing layer. The pre-formed opening connects to the second microfluidic channel, so that the second microfluidic channel is in fluid communication with the blister volume inside the blister. FIG.6Bshows the normally-closed microfluidic valve100as the opening blister152is being pressed. The puncturing point156punctures the sealing layer above the opening well124. This places the opening well and the first microfluidic channel120into fluid communication with the blister150and the second microfluidic channel128. When the pressing force is removed from the opening blister, the opening blister can rebound somewhat and leave a clear passageway through the punctured hole in the sealing layer. Fluid can then flow freely from the second microfluidic channel to the first microfluidic channel or vice versa.FIG.6Cshows the microfluidic valve after liquid180has flowed through the second microfluidic channel, into the blister volume, and then into the first microfluidic channel120. FIG.6Dshows a top-down view of the substrate110of the microfluidic valve to illustrate the layout of the first microfluidic channel120, opening well124, and second microfluidic channel128.FIG.6Eshows the sealing layer130positioned over the substrate. The sealing layer has a pre-formed opening132over the second microfluidic channel.FIG.6Fshows the flexible blister layer140positioned over the sealing layer. This figure shows the shape of the blister150, which includes an opening blister152positioned over the opening well and a connecting blister segment158that extends to the pre-formed opening in the sealing layer. The blister may have a variety of other shapes, so long as the blister volume is able to connect the first microfluidic channel to the second microfluidic channel when the blister is actuated. Normally-closed microfluidic valves can also include a variety of additional components and different designs. The normally-closed microfluidic valves can include additional layers of material, such as pressure sensitive adhesive layers and label layers as described above. In some examples, normally-closed microfluidic valves can include an opening blister with a puncturing point that breaks the sealing layer from above. In other examples, a puncturing point can be formed on the substrate as a sharp protrusion that can break the sealing layer from below when the blister is pressed. The microfluidic valves can also be designed with or without opening wells, as described above. Regarding the substrate of the microfluidic valves described herein, the substrate can be a solid material having a microfluidic channel or microfluidic channels formed therein. The solid material can include various polymers (e.g. Polypropylene, TYGON, PTFE, COO, SU-8 photoresist, PDMS, or others), glass (e.g. borosilicate), metal (e.g. stainless steel), or a combination of materials. The microfluidic channels and other features can be formed in the substrate by a variety of processes, including molding, machining, etching, 3-D printing, photolithography, laser cutting, and so on. In some examples, the microfluidic channels can be formed as trenches that are open on a top surface of the substrate. The ceiling of these microfluidic channels can be formed by a label layer or by sealing layer or some other material layer that can be positioned over the top surface of the substrate. In other examples, the microfluidic channels can be formed beneath the surface of the substrate, so that the microfluidic channels have a ceiling made of the substrate material. The substrate can be monolithic or may be a combination of multiple components fitted together. Thus, the substrate can be modular in some examples. Microfluidic Devices The present disclosure also describes microfluidic devices that can include the microfluidic valves described above. A microfluidic device can include a substrate with a fluid flow microfluidic channel formed in the substrate. A microfluidic valve can be positioned in fluid communication with the fluid flow microfluidic channel. Initially, the microfluidic valve can either allow fluid flow or block fluid flow through the fluid flow microfluidic channel. The microfluidic valve includes a sealing layer over the fluid flow microfluidic channel and a flexible blister layer over the sealing layer. The flexible blister layer includes a blister that is formed as a distended portion with a blister volume between the flexible blister layer and the sealing layer. The microfluidic valve is actuatable by puncturing the sealing layer by pressing on the blister. As explained above, microfluidic valves can be designed as normally-open valves or normally-closed valves. When a normally-open valve is actuated, the valve switches to closed so that the fluid flow is blocked. When a normally-closed valve is actuated, the valve switches to open so that the fluid flow is allowed. A wide variety of applications can be found for normally-open valves and normally-closed valves in microfluidic devices. The microfluidic devices described herein can include such valves used in any way. In some examples, a normally-closed valve can retain a fluid inside a reservoir and then the valve can be opened to allow fluid to flow out of the reservoir. In other examples, a normally-closed valve can block an air vent. Air pressure within the system may prevent a fluid from flowing through a microfluidic channel until the air vent is opened. Thus, opening the valve can allow air to escape and this can allow fluid to flow through the microfluidic channel. Normally-open valves can also be used in a variety of ways. A normally-open valve can be actuated to shut off a reservoir, or to block an air vent at a desired time. Many other microfluidic device designs can also utilize these microfluidic valves. In certain examples, a microfluidic device can include a combination of a normally-open valve and a normally-closed valve. In particular examples, these valves can be used to change the direction of fluid flow through a microfluidic channel. A normally open valve can initially allow fluid to flow in a first direction. The normally-open valve can then be actuated to block the fluid flow and stop the flow of the fluid. The normally-closed valve can then be actuated to open up a new pathway for the fluid, and the fluid can flow through the new pathway. Microfluidic devices can often include additional blisters besides the blisters that are a part of a microfluidic valve. Additionally blisters can contain fluids such as air, other gases, liquids, solvents, reactants, and so on. For example, a blister can contain a liquid that is to be used in the microfluidic device. The blister can be pressed at an appropriate time to inject the liquid into the microfluidic device, such as by injecting the liquid into a particular microfluidic channel. The flow of this liquid can be controlled using the microfluidic valves described herein. In further examples, a blister filled with air can be included. Air pressure can be used to move liquids through microfluidic channels. Thus, an air blister can be pressed to inject air into a microfluidic channel and to push liquid through the microfluidic channel. A microfluidic device can be designed to precisely meter a specific volume of fluid. This can be useful in processes where it is desired to use a known volume of fluid, such as chemical reactions that may depend on the volume of fluid. As mentioned above, fluids for use in the microfluidic device can be contained in blisters and the fluid can be introduced into the microfluidic device by pressing the blister. However, bursting a blister to inject fluid into the microfluidic device can be a somewhat imprecise process, and the volume of fluid that is injected may vary depending on the way the blister deforms when pressed. Accordingly, it can be useful to design the microfluidic device to meter a more precise volume of fluid. In certain examples, the microfluidic device can include a fluid flow microfluidic channel into which the fluid is introduced from a reservoir blister. As the fluid is introduced into the fluid flow microfluidic channel, the fluid can flow towards a branch point in the channel. The microfluidic device can also include a fluid outlet valve at an opposite end of the fluid flow microfluidic channel from the branch: however, the fluid outlet valve can be close initially so that the fluid flows to the branch point. The branches at the branch point can include an overflow branch and a bypass branch. The bypass branch can lead to a normally-closed microfluidic valve, while the overflow branch can lead to a normally-open valve that is connected to an air vent. The air vent can allow the fluid to flow into the overflow branch, while the static air pressure present in the bypass branch prevents the fluid from flowing into the bypass branch. After the reservoir blister has been pressed, an unknown amount of the fluid has flowed down the overflow branch. At this point, the normally-open valve can be actuated to close the valve, which closes off the air vent. The fluid outlet valve is then opened. The normally-closed valve on the bypass branch can then be actuated to open the valve. This valve can connect to an air blister. The air blister can be pressed to force air through the bypass column. The air can push fluid in the fluid flow microfluidic channel backward towards the fluid outlet. The air pushes the fluid out the fluid outlet while bypassing the fluid that is in the overflow branch. Thus, the volume of fluid that is dispensed from the device is the fluid that was in the portion of the fluid flow microfluidic channel leading up to the branch point. The volume of this portion of the fluid microfluidic channel can be known, so that a known, precise volume of fluid is dispensed from the device. FIGS.7A-7Dillustrate such a microfluidic device200.FIG.7Ashows a top-down view of the substrate210of the device. Multiple microfluidic channels and chambers are formed in the substrate. This particular example also includes a dried reactant pellet290held inside a pellet chamber292. The dried reactant pellet in this example includes dried FOR master mix reactants. The dried FOR master mix reactants can be reconstituted by dissolving the pellet in a reconstitution buffer, and the reconstituted master mix can then be used in a process such as a FOR assay. FOR assays are processes that can rapidly copy millions to billions of copies of a very small DNA or RNA sample. FOR can be used for many different applications, including sequencing genes, diagnosing viruses, identifying cancers, and others. In the FOR process, a small sample of DNA or RNA is combined with master mix reactants that can form copies of the DNA or RNA. The particular example microfluidic device shown in this figure is designed to reconstitute the master mix reactants and then dispense a precisely metered volume of reconstituted master mix fluid for use in a FOR process. The substrate210includes a buffer opening well212connected to the pellet chamber292. A blister filled with reconstitution buffer will be positioned over this buffer opening well, so that when the blister is pressed the reconstitution buffer liquid will flow into the buffer opening well and then into the pellet chamber to dissolve the pellet. The substrate also includes a fluid outlet214. This outlet is where the metered volume of reconstituted master mix liquid is ultimately dispensed. Although not shown in this figure, the fluid outlet can initially be closed using a valve such as a stopcock or other mechanical valve. Alternatively, a microfluidic valve as described herein can be used to close the fluid outlet. As shown in the figure, the fluid outlet is connected to the buffer opening well by an outlet channel216. The outlet channel leads deeper beneath the surface of the substrate to pass under the other microfluidic channels on the surface of the substrate. This is shown by the section of the outlet channel that is in dashed lines. Because the fluid outlet is initially closed, when the reconstitution buffer is injected from the reconstitution buffer blister, the buffer does not flow out the outlet channel but instead flows into the pellet chamber. As more of the buffer flows into the devices, excess buffer continues to flow up a fluid flow microfluidic channel220to a branch point222. At the branch point, the buffer flows into an overflow branch224that leads to an overflow chamber218. The overflow branch leads further to a normally-open microfluidic valve. The normally-open microfluidic valve includes a blister filled with a non-newtonian plugging fluid, which is not shown in this figure. The non-newtonian plugging fluid blister is positioned over a non-newtonian plugging fluid opening well226. This opening well is also connected to an air vent228. Because this valve is initially open, the air vent allows air to pass out of the device while the reconstitution buffer flows into the overflow branch. The branch point222is also connected to a bypass branch202. The bypass branch leads to a normally-closed microfluidic valve that includes an opening well204under a blister with an intact sealing film (not shown in this figure) to prevent air flow through the valve. The normally-closed microfluidic valve also includes a pre-formed opening in the sealing layer that connects the blister to an air channel206that leads to an air blister opening well208, Because the normally-closed valve is initially closed when the reconstitution buffer is injected into the device, the static air pressure in the bypass branch prevents the reconstitution buffer from flowing into the bypass branch. However, the reconstitution buffer has been injected, the normally-closed valve can be opened, the normally-open valve can be closed and the fluid outlet214can be opened. Then, the air blister can be pressed to inject air that forces the reconstitution buffer with dissolved master mix reactants out through the fluid outlet. This process is described in more detail below. Thus, the various channels and chambers in the substrate are designed to reconstitute the dried FOR master mix reactants and then to dispense a metered volume of the reconstituted master mix reactants. FIG.7Bshows the substrate210with a label layer272positioned over the substrate. The label layer includes openings where fluids flow from blisters to the substrate and vice versa. Specifically, the label layer includes openings over the reconstitution buffer opening well212, the non-newtonian fluid opening well126, the normally-close valve opening well204, and the air blister opening well208. An opening is also included in the location of the pre-formed opening in the sealing layer in the normally-closed valve. The label layer forms a ceiling for the various microfluidic channels formed in the surface of the substrate. Although not shown in the figure, a pressure-sensitive adhesive layer may be included to adhere the label layer to the substrate. FIG.7Cshows the substrate210after the label layer has been applied and then a sealing layer230has been applied over the label layer. The sealing layer includes a single opening, which is the pre-formed opening232made as a part of the normally-closed valve. FIG.7Dshows the complete microfluidic device200after the flexible blister layer240has been applied. The flexible blister layer includes several blisters. First, a reconstitution buffer blister242is positioned over the reconstitution buffer opening well. The reconstitution buffer blister includes an opening blister portion with a puncturing point that punctures the sealing layer when pressed. The reconstitution buffer blister also includes a reservoir portion that holds most of the reconstitution buffer. In operation, the opening blister can be pressed first and then the reservoir blister can be pressed second to inject the reconstitution buffer into the reconstitution buffer opening well. A non-newtonian plugging fluid blister250is positioned over the non-newtonian plugging fluid opening well. As explained above, this blister can be pressed to inject the non-newtonian plugging fluid and the non-newtonian plugging fluid can block off the air vent228. The flexible blister layer also includes a normally-closed valve blister252. This blister includes an opening blister portion that can be pressed to puncture the sealing film. The remainder of the normally-closed valve blister extends to cover the pre-formed opening in the sealing layer that leads to the air channel, Finally, the flexible blister layer also includes an air blister254that is filled with air. This blister can be pressed after opening the normally-closed valve to inject air into the bypass branch channel. The air can force the reconstituted FOR master mix reactants out through the fluid outlet214. Methods of Directing Fluids The present disclosure also describes methods of directing fluids. The microfluidic valves described above can be used to direct fluids by blocking the flow of fluid or allowing the flow of fluid. In some examples, methods of directing fluids can utilize a microfluidic device that includes a microfluidic valve or multiple microfluidic valves. FIG.8is a flowchart illustrating an example method300of directing fluids. This method includes flowing310afluid through a fluid flow microfluidic channel having a microfluidic valve positioned in fluid communication with the fluid flow microfluidic channel. The method also includes actuating320the microfluidic valve to switch the microfluidic valve from allowing fluid flow to blocking fluid flow or from blocking fluid flow to allowing fluid flow, Flowing the fluid through the fluid flow microfluidic channel may occur before, after, or during the actuating of the microfluidic valve. Thus, the order shown inFIG.8is not limiting. For example, if the microfluidic valve is a normally closed valve, then the method can begin without any fluid flow because the microfluidic valve is blocking the fluid flow. The valve can be actuated to switch the valve from blocking fluid flow to allowing fluid flow (i.e., switching from closed to open) and then the fluid can flow after the valve has been opened. In another example, the valve can be a normally-open valve and the method can begin with the fluid flowing through the fluid flow microfluidic channel. The valve can then be closed to stop the flow of the fluid. The microfluidic valves used in the methods of directing fluid flow can include any of the components and features of microfluidic valves described above. Multiple microfluidic valves can also be used in combination to direct fluid flow in different ways. As described above, in some examples a combination of a normally-closed valve and a normally-open valve can be used to cause fluid to flow in a first direction through the microfluidic channel, and then the direction of flow can be reversed and the fluid can flow the opposite direction. A more specific example of this was described above in connection with the microfluidic device shown inFIGS.7A-7D. An example method of directing fluid flow in such a microfluidic devices is shown in more detail inFIGS.9A-9D.FIG.9Ashows the substrate210of the microfluidic device from the earlier example. As explained above, the substrate includes a pellet chamber292holding a dried reactant pellet290. Although not shown in the figure, the fluid outlet214is initially closed using an external valve such as a stopcock. The flexible blister layer is not shown in this figure, but the microfluidic device can include several blisters as described above. The blisters can include a reconstitution buffer blister, a non-newtonian fluid blister, an air blister, and a blister for the normally-closed valve. FIG.9Bshows the substrate210after the reconstitution buffer blister has been pressed. This injects reconstitution buffer into the reconstitution buffer opening well212and the buffer flows up into the pellet chamber292to dissolve the dried reactant pellet, making reconstituted reactant fluid360. The reconstituted reactant fluid continues to flow up into the overflow branch224that leads to an overflow chamber218. Since the volume fluid that is injected by the blister can be imprecise, the overflow chamber may fill completely or may be partially filled. FIG.9Cshows the substrate210after the non-newtonian plugging fluid blister has been pressed. This injects non-newtonian plugging fluid160into the non-newtonian plugging fluid opening well226. The non-newtonian plugging fluid forms a plug that blocks the air vent228, which prevents the reconstituted reactant fluid360from flowing any farther along the overflow branch224. After the non-newtonian plugging fluid has closed off the air vent in this way, the fluid outlet214is opened. The normally-closed valve blister is pressed, which breaks the sealing layer and opens a flow path from the air blister to the bypass branch202. The air blister is then pressed to force air through the bypass branch. This air pushes the reconstituted reactant fluid out through the fluid outlet. The air bypasses the overflow branch, so any reconstituted reactant fluid that is in the overflow branch and the overflow chamber218is not dispensed from the fluid outlet. FIG.9Dshows the substrate after the air has forced the reconstituted reactant fluid from the microfluidic channel220, pellet chamber292, and opening well212out through the fluid outlet. As shown in the figure, some fluid remains behind in the overflow chamber and the overflow branch. The internal volume of the opening well, pellet chamber, and the microfluidic channel up to the branch point is constant. Therefore, the volume of fluid that is dispensed from this internal volume can also be constant. If the volume of fluid that is injected into the device from the blister has any variability, then the amount of fluid that flows into the overflow chamber and the overflow branch can vary while the volume of fluid that is ultimately dispensed from the fluid outlet can remain constant. Thus, the method illustrated in this example can remove the variability and dispense a metered volume of fluid. In various examples, the methods of directing fluid flow can include any processes described above. In a specific example, a method of processing fluids can include the process depicted inFIGS.9A-9D. Any of the devices, materials, and components described above can be used in the methods of directing fluid flow. Definitions It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. As used herein, the term “about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be “a little above” or “a little below” the endpoint. The degree of flexibility of this term can be dictated by the particular variable and determined based on experience and the associated description herein. As used herein, “Bingham plastic” refers to a class of materials that behave as rigid bodies at low stress but which flow as a viscous fluid at high stress. The transition between the rigid body behavior and the viscous fluid behavior can occur at various different stress levels, depending on the particular Bingham plastic material. Bingham plastics can include greases, slurries, suspensions of pigments, and others. As used herein, “viscoplastic” refers to a broader category of materials that can include Bingham plastics. Viscoplastic materials can experience irreversible plastic deformation when stress over a certain level is applied. When stress under this level is applied, the viscoplastic material can behave as a rigid body, as is the case with Bingham plastics, or the viscoplastic material can undergo reversible elastic deformation. As used herein, “shear thinning fluid” refers to materials that behave as a fluid with a high viscosity when low stress is applied, but the viscosity of the fluid decreases when the stress is increased. Examples of shear thinning fluids can include polymer solutions, molten polymers, suspensions, colloids, and others. As used herein, “curable fluids” refers to fluids that can undergo a curing process to increase the viscosity of the fluid and/or cause phase change from liquid to solid. The curing process can include thermal curing, chemical curing, ultraviolet radiation curing, or other curing methods. In some examples, curable fluids can include monomers that can polymerize to form polymers and/or polymers that can become crosslinked during the curing process. Examples of curable fluids can include two-part epoxy resins, two-part polyurethane resins, ultraviolet curing epoxies, ultraviolet curing acrylates, ultraviolet curing urethanes, ultraviolet curing thiols, and others. As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though individual members of the list are individually identified as separate and unique members. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on presentation in a common group without indications to the contrary. Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. A range format is used merely for convenience and brevity and thus should be interpreted flexibly to include the numerical values explicitly recited as the limits of the range, and also to include individual numerical values or sub-ranges encompassed within that range as if numerical values and sub-ranges are explicitly recited. As an illustration, a numerical range of “about 1 wt % to about 5 wt %” should be interpreted to include the explicitly recited values of about 1 wt % to about 5 wt %, and also to include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3.5, and 4 and sub-ranges such as from 1-3, from 2-4, and from 3-5, etc. This same principle applies to ranges reciting one numerical value. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described. Example—Microfluidic Device A microfluidic device was constructed according to the design shown inFIGS.7A-7D and9A-9D. A dried FOR master mix reactant pellet was placed in the pellet chamber before adhering the blister pack to the substrate surface. A red dye was also added to the pellet so that the liquid in the device would be colored red to allow for visual observation of the process. The substrate was made of transparent plastic, which allowed the red liquid to be visible through the substrate. The microfluidic device included the substrate with a label layer, sealing layer, and flexible blister layer as shown inFIGS.7A-7D. This device was placed in a system with a robotically-controlled piston for pressing the blisters. The system was used to press the blisters in a specific sequence. First, the opening blister portion of the reconstitution buffer blister was pressed. This punctured the sealing layer above the reconstitution buffer opening well, and a small amount of reconstitution buffer flowed into the well. Next, the main reservoir portion of the reconstitution buffer blister was pressed. This injected a larger volume of reconstitution buffer into the well. The amount of buffer was sufficient to flow up and fill the pellet chamber, and then flow into the overflow branch of the microfluidic channel and partially fill the over flow chamber. The pellet dissolved in the buffer to form reconstituted reactant fluid. Next, the normally-closed valve was opened by pressing the opening blister of the normally-closed valve. The stopcock on the fluid outlet was also opened at this time. The non-newtonian plugging fluid blister was pressed next, which injected non-newtonian plugging fluid into the non-newtonian plugging fluid opening well and blocked off the air vent. Finally, the air blister was pressed and the air from the air blister forced the reconstituted reactant fluid (except for the fluid that was in the overflow branch and the overflow chamber) out through the fluid outlet. The volume of fluid that was dispensed from the fluid outlet was then carefully measured. This process was repeated 9 times and the volume of fluid dispensed was measured. It was found that average volume of fluid dispensed was 63 μL with a standard deviation of 2.6 μL The greatest volume dispensed out of the 9 runs was 67 μL and the smallest volume was 60 μL. This shows that the device can consistently dispense a precise amount of fluid. While the present technology has been described with reference to certain examples, various modifications, changes, omissions, and substitutions can be made without departing from the spirit of the disclosure. The disclosure is not limited other than by the scope of the following claims.
62,314
11857966
DESCRIPTION OF THE SPECIFIC EMBODIMENTS It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. It may be noted that, as used in the specification and the appended claims, the singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a material” may include mixtures of materials, reference to “a compound” may include multiple compounds, and the like. References cited herein are hereby incorporated by reference in their entirety, except to the extent that they conflict with teachings explicitly set forth in this specification. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings: “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, if a device optionally contains a feature for a sample collection unit, this means that the sample collection unit may or may not be present, and, thus, the description includes both structures wherein a device possesses the sample collection unit and structures wherein sample collection unit is not present. As used herein, the terms “substantial” means more than a minimal or insignificant amount; and “substantially” means more than a minimally or insignificantly. Thus, for example, the phrase “substantially different”, as used herein, denotes a sufficiently high degree of difference between two numeric values such that one of skill in the art would consider the difference between the two values to be of statistical significance within the context of the characteristic measured by said values. Thus, the difference between two values that are substantially different from each other is typically greater than about 10%, and may be greater than about 20%, preferably greater than about 30%, preferably greater than about 40%, preferably greater than about 50% as a function of the reference value or comparator value. As used herein, a “sample” may be but is not limited to a blood sample, or a portion of a blood sample, may be of any suitable size or volume, and is preferably of small size or volume. In some embodiments of the assays and methods disclosed herein, measurements may be made using a small volume blood sample, or no more than a small volume portion of a blood sample, where a small volume comprises no more than about 5 mL; or comprises no more than about 3 mL; or comprises no more than about 2 mL; or comprises no more than about 1 mL; or comprises no more than about 500 μL; or comprises no more than about 250 μL; or comprises no more than about 100 μL; or comprises no more than about 75 μL; or comprises no more than about 50 μL; or comprises no more than about 35 μL; or comprises no more than about 25 μL; or comprises no more than about 20 μL; or comprises no more than about 15 μL; or comprises no more than about 10 μL; or comprises no more than about 8 μL; or comprises no more than about 6 μL; or comprises no more than about 5 μL; or comprises no more than about 4 μL; or comprises no more than about 3 μL; or comprises no more than about 2 μL; or comprises no more than about 1 μL; or comprises no more than about 0.8 μL; or comprises no more than about 0.5 μL; or comprises no more than about 0.3 μL; or comprises no more than about 0.2 μL; or comprises no more than about 0.1 μL; or comprises no more than about 0.05 μL; or comprises no more than about 0.01 μL. As used herein, the term “point of service location” may include locations where a subject may receive a service (e.g. testing, monitoring, treatment, diagnosis, guidance, sample collection, ID verification, medical services, non-medical services, etc.), and may include, without limitation, a subject's home, a subject's business, the location of a healthcare provider (e.g., doctor), hospitals, emergency rooms, operating rooms, clinics, health care professionals' offices, laboratories, retailers [e.g. pharmacies (e.g., retail pharmacy, clinical pharmacy, hospital pharmacy), drugstores, supermarkets, grocers, etc.], transportation vehicles (e.g. car, boat, truck, bus, airplane, motorcycle, ambulance, mobile unit, fire engine/truck, emergency vehicle, law enforcement vehicle, police car, or other vehicle configured to transport a subject from one point to another, etc.), traveling medical care units, mobile units, schools, day-care centers, security screening locations, combat locations, health assisted living residences, government offices, office buildings, tents, bodily fluid sample acquisition sites (e.g. blood collection centers), sites at or near an entrance to a location that a subject may wish to access, sites on or near a device that a subject may wish to access (e.g., the location of a computer if the subject wishes to access the computer), a location where a sample processing device receives a sample, or any other point of service location described elsewhere herein. As used herein, the term “separator” may include a mesh, a filter, a membrane, a porous membrane, an asymmetric porous membrane, a semipermeable hollow fiber membrane, a percolating network structure, a material that can be used for size-exclusion of objects greater than a certain dimension, or other filtering material. Materials useful for the preparation of the separating material may be selected from the group comprising polyethylene (coated by ethylene vinyl alcohol copolymer), polyacrylates, polystyrene, polyethylene oxide, cellulose, cellulose derivatives, polyethersulfone (PES), polypropylene (PP), polysulfone (PSU), polymethylmethacylate (PMMA), polycarbonate (PC), polyacrylonitrile (PAN), polyamide (PA), polytetrafluorethylene (PTFE), cellulose acetate (CA), regenerated cellulose, and blends or copolymers of the foregoing, or blends or copolymers with hydrophilizing polymers, including with polyvinylpyrollidone (PVP) or polyethyleneoxide (PEO). Suppliers of such materials and/or membranes include but are not limited to BASF, Advanced Microdevices P. Ltd., International Point of Care Inc., Gambro Lundia AB, Asahi Kasei Kuraray Medical Co., Ltd., GE Healthcare (Whatman division), or the like. As used herein, the terms “sample” and “biological sample” refer to a blood, urine, sputum, tears, material(s) from a nasal swab, throat swab, cheek swab, or other bodily fluid, excretion, secretion, or tissue obtained from a subject. These terms are inclusive of an entire sample and of a portion of a sample. As used herein, reference to a fluid sample includes reference to a sample and a biological sample. Such samples may include fluids into which material has been deposited, where such material may be obtained from a nasal swab, throat swab, cheek swab, or other sample which may include solid or semi-solid material, whether along with or without natural fluids. Such fluids and samples comprise fluid samples and sample solutions. As used herein, the term “formed component” may include solid, semi-solid, or cellular structures such as but not limited to red blood cells, white blood cells, platelet, or other components that may be found in a sample, a biological sample, bodily fluid, or natural fluid. As used herein, the terms “fill” and “filled” and their grammatical equivalents, e.g., as used in phrases such as “a vessel may be filled with a sample solution” refer to the transfer of any amount, including partial filling and complete filling. These terms as used herein do not require that such filling completely fill a container, but include any lesser amount of filling as well. It should be understood that the devices herein can be configured for use with sample applied to the device, sample drawn into the device by capillary force, sample delivered into the device by way of venipuncture, sample delivered into the device by way of arterial puncture, nasal swab, tear collection, collection from any open wound, biopsy, or other sample delivery or acquisition technique and is not limited to any specific example described herein. Referring now toFIG.1, one embodiment of a formed component separation device will now be described.FIG.1shows a side cross-sectional view of a device10having a formed component separator20positioned along a pathway as indicated by arrow30. In this non-limiting example, the device10has at least one sample inlet40for receiving a liquid sample that has the formed components there and at least a first outlet50for outputting only a liquid portion of the formed component liquid sample. As seen inFIG.1, the pathway30fluidically couples the sample inlet with the first outlet.FIG.1also shows that sample such as but not limited to blood flows from the inlet40and into and/or over the formed component separator20. In this non-limiting example, blood enters the formed component separator20, where blood cells are trapped based on the principle of size exclusion. The formed component separator20, in one embodiment, may have a plurality of pores wherein those on one surface are significantly smaller than those on another surface of the separator20. In this manner, the cells in the blood can enter the separator20through the larger pores but cannot pass completely through the separator due to the much smaller pores on the output side of the separator20. As the sample flows across the separator20, the liquid portion of the sample such as but not limited to plasma is pulled away from the back of the separator20via a combination of capillary action and/or applied pressure differential. Plasma flows away from the separator20as indicated by arrow30. In one embodiment, the walls within the device10may be coated with material such as but not limited to anti-coagulant for mixing with the sample during filling. Referring now toFIG.2, another embodiment of a formed component separation device will now be described. In this non-limiting example, the device100has an inlet102that is open towards a top surface of the device100. The inlet102is connected by a channel104to a distributor110that preferentially spreads the sample over the separator20. The liquid portion of the sample is outputted to the collector120which may be directed to an external channel130such as a needle or adapter channel. It should be understood that the distributor110is not restricted to any particular structure or material and may be a plurality of capillary channels or tubes that distribute the sample over the membrane. In some embodiments, it may be a hydrophilic coating that may be a continuous coating or a patterned coating to draw sample to flow over the membrane. Referring now toFIGS.3and4, a cross-sectional view of one portion of the device100(as shown inFIG.3, indicated by arrows3-3inFIG.2) shows some of the details regarding this embodiment of the distributor110that preferentially spreads the sample over the separator20, and the collector120which draws liquid away from the separator20. Sample will flow across the separator20as indicated by arrow122. In this non-limiting example, the lead-in channel130wicks blood in from the inlet102and transports it into the distribution channel network of distributor110via capillary action. The distribution channel network comprises a network of capillaries on the blood side of the separator20. This distributor110pulls sample away from the lead-in channel and distributes it evenly over the membrane. In one embodiment, the separator20separates plasma from whole blood via a two-step process. One process uses a passive mechanism: gravity and capillary force gradient. A second process uses an active mechanism: application of a pressure differential. These processes can act in a sequential manner or in a simultaneous manner. Capillaries of collector120also route the liquid portion of the sample into the extraction port when the pressure differential is applied. Sample flow through the device100is indicated by arrow140. Referring now toFIGS.5A and5B, various embodiments of collection devices will now be described.FIG.5Ashows a sample separation device150that has an aspect ratio that provides for fewer numbers of channels but increases the length of each of the channels. The length of the membrane along a longitudinal axis of the device, relative to the width may be in a range of about 3:1 to about 5:1.FIG.5Bshows another embodiment of a separation device160that has a different aspect ratio which an increased number of capillary channels, but reduced length for each. The length of the membrane along a longitudinal axis of the device, relative to the width may be in a range of about 1:1 to about 1:3. It should also be understood that the cross-sectional size of channels over separator20and those beneath the separator20can also be different. In one embodiment, the channels in the collector120that are beneath the separator20are at least 2× smaller in cross-sectional area than those over the channel. In one embodiment, the channels in the collector120that are beneath the separator20are at least 5× smaller in cross-sectional area than those over the channel. In one embodiment, the channels in the collector120that are beneath the separator20are at least 10× smaller in cross-sectional area than those over the channel. The decreased size of the channels will increase the capillary pressure and thus preferentially direct liquid portions of the sample towards the output of the device. Referring now toFIGS.6and7, yet another embodiment of a sample separation device170is shown.FIG.6shows a top-down view of a bottom portion of the separation device170is shown with a vent172, a vent inlet channel173, and a collector176is shown with a plurality of channels to draw sample from an underside of the separator20(more clearly shown inFIG.7). An outlet tube178such as but not limited to a needle can be used to engage a container such as but not limited to a sealed container with piercable septum or cap, wherein the interior or the container is under vacuum pressure therein to pull liquid sample into the container when it is fluidically engaged by the needle of the outlet tube178. Optionally, the container may take the form of a test tube-like device in the nature of those marketed under the trademark “Vacutainer” by Becton-Dickinson Company of East Rutherford, NJ. FIG.7shows, in one embodiment, a side cross-sectional view of the device170. As can be seen, the separator20is “sandwiched” between the distributor174and the collector176. The separation material along the first pathway configured to remove formed components from the sample prior to outputting at the first outlet. Processed sample will be outputted through the outlet tube178into a container or other receptacle. Some embodiments as seen here may have a funneled portion in the collector176to direct sample that has been processed towards the outlet tube178. By way of example and not limitation, the sample can be applied directly to the distributor174or directly to the separator20. Referring now toFIGS.8and9, a still further embodiment will now be described.FIG.8is a perspective view of a sample separation device190. This embodiment of the sample separation device190is configured to allow for direct application of the sample onto the separator by way of opening192over the separator. Processed liquid will be drawn by the collector194to be output through the outlet196. Referring now toFIG.10, a sample collection device200according to one embodiment herein will now be described. In this non-limiting example, the sample collection device200includes a first pathway202that is configured to direct sample to a separator204. The sample collection device200also includes a second pathway206that collects sample but does not direct it through a formed component separator204. Both pathways202and206have openings that are co-located, adjacent, coaxial, or otherwise closely positioned at a distal end208of the device200that will be in contact with the subject. Optionally, some embodiments may share a common pathway that has a single opening at the distal end208. The collected sample may exit from one or more adapter channels210to one or more sample containers (not shown for ease of illustration).FIG.10shows that the distributor212may have features that extend beyond the area of the separator204. These off-membrane features are helpful in drawing the sample towards and over the membrane, particularly as the channel widens to accommodate the membrane. FIG.11is a cross-sectional view of one embodiment of the distributor212over the separator204as indicated by arrows11-11inFIG.10. As seen inFIG.11, at least a portion of the separator204may have reduced thickness area214where the material may be thinner or optionally where the material is compressed from its normal thickness to hold the material in place. In one non-limiting example, one purpose of this compressed region is to compress the pores in the membrane and thereby create a seal that is impassable by the formed components. In one non-limiting example, normal separator thickness may be in range of about 100 to about 1000 microns. Optionally, normal separator thickness may be in range of about 200 to about 900 microns. Optionally, normal separator thickness may be in range of about 200 to about 500 microns. Optionally, normal separator thickness may be in range of about 300 to about 500 microns. Optionally, normal separator thickness may be in range of about 300 to about 800 microns. Optionally, normal separator thickness may be in range of about 400 to about 700 microns. Optionally, normal separator thickness may be in range of about 500 to about 600 microns.FIG.11also shows that the collector216may be a plurality of capillary channels that have a v-shaped cross-section. These are used to draw the liquid only sample to the outputs of the device at adapter channel210. Referring now toFIGS.12and13, a still further embodiment of a sample collection and separator device220will now be described.FIG.12shows the device220as having an inlet222for receiving sample as indicated by arrow224. The sample received at inlet222enters a channel226that is aligned along an axis configured to intersect the plane in which the separator228is positioned. In this manner, the sample when it contacts the separator228is placed onto primarily a planar surface of the separator228. In one embodiment, the peripheral portion230of separator228is compressed to hold the separator in place and to prevent sample from exiting along the edge of the membrane, instead of through the back and into the collector232. At the point of sample contact with the separator228and the end of channel226, the sample contact both the separator228and channels234of the distributor236. In this manner as will be discussed in more detail elsewhere herein, the sample is drawn by both the separator and the distributor236to be distributed over and/or through the separator. Optionally, this can be beneficial to prevent clogging of sample at any one location or junction point on the separator. Optionally, the distributor may be used to facilitate longitudinal uniformity of the sample with respect to concentration of formed components in the liquid portion of the sample. Optionally, use of the distributor236can also speed the filling process. The channels234may be coupled to one or more vents238that allow for gas or air to be displaced when sample enters the distributor236.FIG.12shows that each channel234may have its own individual vent238. Optionally, some embodiment may have two or more channels234couple to share a vent by way of common manifold configuration or the like. As seen, the vents are positioned at the ends of the channels234to allow for the channels to fully fill. FIG.13shows a lateral cross-sectional view of one embodiment the device220wherein the channels234of the distributor236are shown over the capillary collection channels240of the collector242.FIG.13also shows that not ever channel in the collector242has the same cross-sectional shape. By way of non-limiting example, the channels244along a perimeter of the collector242may have a different shape such as but not limited to a rectangular cross-section that is different from other channels in the collector242. Referring now toFIG.14, a cross-sectional view of one embodiment of a sample inlet channel will now be described. As seen inFIG.14, the inlet channel226directs sample from inlet222towards the separator232. The angled orientation of channel226relative to the plane of the separator232allows for sample to be placed onto the planar surface of the separator and not relying purely on lateral pulling. The angled cross-sectional shape also increases the area of sample contact to be greater than merely the lateral cross-section of the channel. FIGS.15and16also show other embodiments wherein sample inlet channels250and252that have sample channel transition features254and256that minimize detrimental effects due to change in channel dimension. These transitions features may be configured to reduce dimension in one axis (feature254) or minimize a sudden change in dimension (feature256) by gradually transitioning the change in dimension over a longer and/or wider area. It should be understood that some embodiments may combine the use of features254and256. Other embodiments herein may also have these features or others that use embody the concepts described herein to minimize detrimental impact of certain channel features. Inlet channel desirably leads to direct contact with the membrane, which in one non-limiting example, is without an intermediary reduction in capillary forces, which can stop the blood flow and prevent distribution. Referring now toFIGS.17to19, other configurations for sample inlet channels according to embodiments herein will now be described.FIG.17shows an angled sample inlet channel260that has a “splitter” configuration wherein at least one opening of channel262couples with the inlet channel260to direct a portion of the sample to channel262. This can be particularly useful in configurations such as but not limited to that shown inFIG.10wherein one portion of the sample will be treated to separate formed components from the liquid portion of the sample while other portions of the sample are not treated in the same manner and thus progress down one or more other pathways. In this non-limiting example, the opening for channel260is at least as large as if not larger than the cross-sectional shape of the inlet channel260. The sample continues in a second portion264of the inlet channel260to reach the separator232. The openings266of a distributor for the separator232can be located at the end portion of the channel260. As seen in this non-limiting example, the second portion264of channel260is smaller in cross-sectional area than an initial portion of the channel260.FIG.17also shows that the channel260is directing sample at an upper portion of the channel profile to the second portion264while the opening for channel262collect at least sample in the lower portion of the channel profile. A higher entry point can help with lengthwise blood distribution along the length of the separator by delaying and reducing initial penetration of the separator by the sample as it flows into the distribution volume. FIG.18shows yet another embodiment of the sample inlet channel wherein the opening for channel263is now configured to interface only a smaller portion of the channel260. As seen inFIG.18, the opening263of the channel intersects only a lower portion of the channel profile for channel260. This can useful to customize the volume of sample that is directed towards each channel. FIG.19shows yet another embodiment wherein the inlet channel270connects to the second channel272and has a significantly larger cross-sectional profile relative to the second portion274of the inlet channel. The second portion274is configured to draw sample from an upper portion of the cross-sectional profile of the inlet channel. The openings276for the sample distributor draw from the lower portion of the portion274to distribute sample over the separator232. A collector278will draw liquid sample from the separator232. At least one vent280can be coupled to the separator232to provide a controlled inlet of external atmosphere to facilitate the pull of liquid device. In one non-limiting example, vent280may allow at least some venting to occur during the dynamic stage of extraction, in which a pressure differential or other motive force is applied to draw the liquid portion of the sample into at least one collection container. Optionally, the vent280may be separated from the collector278by the separator232to provide a controlled inlet. The vent280may couple to compressed portion of the separator232. The vent280may couple to normal portion of the separator232. Referring now toFIGS.20and21, various shapes can be configured for use to engage a subject for sample collection according to embodiments herein.FIGS.20and21both show protrusions for use on collection devices as described herein.FIG.20shows a protrusion290that is shaped in a scoop or spoon configuration having both vertical and horizontal portions of the opening292in the protrusion accessible to the user to collect sample. The opening292may lead to a single or multiple pathways in the device. FIG.21shows one embodiment of a protrusion294that extends away from the body of the device so that the user is provided a visual cue as to where the contact the device to the subject to collect sample. The opening may be funnel shaped to assist in sample collection and in engagement with the skin of the patient. The protrusion294has an opening that may lead to a single or multiple pathways in the device. It should be understood that some embodiments may have protrusions that are shaped to be convex or concave to facilitate engagement of the device protrusion with bead or droplet of bodily fluid sample on the subject. The protrusion may be coated with hydrophilic and/or hydrophobic material to push or pull the sample in a desired direction. Referring now toFIGS.22to24, it should also be understood that sample can be delivered to one or more different locations on the sample separator according to at least one embodiment herein. As seen inFIGS.19to21, some embodiments may deliver sample to one end of the separator, away from a central portion of the separator. Optionally, some embodiments as seen inFIGS.22to23, deliver sample from an inlet at one end to one or more openings closer to the center of the separator. The sample may be delivered both at the one end and at locations closer to the center. For example,FIG.22shows embodiments of inlet tubes310,312, and314for use in delivering sample from an inlet on a periphery of the device to one or more locations along a central area of the separator316. The locations320,322, and324may be openings or other structures that allow the inlet tubes310,312, and314to deliver sample to the desired location on the separator316.FIG.22shows that these locations may be distributed over various locations on the separator316.FIG.23shows an embodiment wherein the locations330,332, and334are located in a line near the central area of the separator. Optionally, some embodiments may use single or multiple combinations of one or more of the structures inFIGS.19to24to provide a desired sample distribution pattern over the separator. It should be understood that the embodiments herein can deliver the sample directly onto the separator, onto network of distributor channels over the separator, or a combination of the foregoing. FIG.24shows a still further embodiment wherein the inlet is not located at either end of the collection device, but instead has an inlet that is substantially centrally located as seen inFIG.24. This embodiment shows that the inlet340leads to a channel342that feeds to a central portion of the separator344.FIG.24is a simplified drawing showing primarily only the separator344and an outlet port346that draws liquid portion of the sample away from the separator after processing. Referring now to the embodiments ofFIGS.25and26, it should be understood that the distribution of the channels of the distributor is not limited to the patterns, sizes, or shapes disclosed in the previous figures. As seen inFIG.25, one embodiment may align all of the channels350orthogonal to the longitudinal axis of the device and/or separator. In the embodiment ofFIG.25, this results in a greater number of channels350, but each has a shorter length. Optionally, the orientation of the channels is not limited to orthogonal to the longitudinal axis of the device. Other angles relative to the longitudinal axis of the device and/or the separator are not excluded. Optionally, some embodiments may use different patterns over different portions of the separator. Optionally, some embodiments can use a combination of patterns over the same area. It should also be understood that this same or similar pattern of channels can also be implemented on the collector that is used on the opposite side of separator. Optionally, the distributor can use one channel pattern and the collector can use a different channel pattern. Optionally, some of the sideways capillaries350on the collector uses a non-vented configuration. Some of these sideways capillaries350demonstrated a different extraction behavior as blood separates. Lengthwise capillaries tend to extract from back of device first, then towards the front. Sideways capillaries350extract first towards the middle of the separator and outwards towards front and back of device, which can be used to create a more even extraction process across the separator. As seen inFIG.26, some embodiments may also use a configuration having a manifold360having a plurality of outlets362that can distribute sample over the separator and/or into the distributor. Some embodiments can have shorter or longer outlets362, depending on the pattern that one desires to deliver sample to the separator and/or distributor. It should also be understood that some embodiments may more than one manifold360that delivers sample to the separator and/or distributor. For example, one embodiment may have another manifold360deliver sample along the other longitudinal edge of the separator. FIG.26also shows in phantom a potential pattern for a collection manifold364for use on the opposite side of the separator for sample collection. This manifold364would typically not be used on the same side as the distribution manifold360but would instead be on an opposite side of the separator. Referring now toFIG.27A, a still further embodiment is shown with a patterned manifold370with channels that distribute sample along various locations over the separator372.FIG.27Ashows that there may be a plurality of vents374that allow for gas or air in the separator372or other part of the manifold to escape as sample fills the area. It should also be understood that although the manifold370is shown with a distribution pattern of substantially similar length channels376, such channels can be pattern to have same, different, repeating, or other patterns of size, length, contact area with the separator, or other dimension to provide a desired performance. It should also be understood that the manifold370can be used to directly distribute sample onto the separator or it may opt to deliver sample in a pattern to a distributor which then further distributes the sample over the separator. Some embodiments of the manifold370uses tubes with openings at select locations to allow sample to exit. Some embodiments can use channels with at least one open side to distribute sample along a certain length of the separator and/or distributor. Referring now toFIG.27B, a still further embodiment is shown with a patterned manifold371with channels that distribute sample along various locations over the separator372. It should also be understood that although the manifold371is shown with a distribution pattern of substantially channels377, such channels can be pattern to have same, different, repeating, or other patterns of size, length, contact area with the separator, or other dimension to provide a desired performance. Relative the embodiment ofFIG.27A, this embodiment with manifold371uses shorter length channels377as compared to channels376of manifold370.FIG.27Balso shows that embodiments of the manifold371may include multiple longer length channels378to distribute sample to the intersection channels377.FIG.27Bshows there are three channels378, but it should be understood that other embodiments may have a different number of channels. It should also be understood that the manifold371can be used to directly distribute sample onto the separator or it may opt to deliver sample in a pattern to a distributor which then further distributes the sample over the separator. Some embodiments of the manifold371uses tubes with openings at select locations to allow sample to exit. Some embodiments can use channels with at least one open side to distribute sample along a certain length of the separator and/or distributor. FIGS.27C and27Dshow a still further embodiment with a manifold designed to have an aspect ratio where the distribution pattern of the channels is configured to pass along a short dimension of the separator versus another longer dimension. It should be understood that this type of distribution pattern may be modified for use in any of the embodiments described herein, such as but not limited to those ofFIG.77A-77B. Referring now toFIG.28, yet another embodiment of a manifold380is shown. This can be as a distributor that has twelve channels that distribute sample over the separator. As seen, the channel pattern of manifold380initially has six channels leading away from a single inlet channel, and those six channels are each split once to achieve twelve channels. Referring now toFIGS.29to34, still other embodiments showing different combinations of inlet channels and distributors are shown.FIGS.29and30show a single inlet390having a circular cross-sectional shape leading to a multi-channel distributor392with channels394, with each of the channels coupled to its own vent396, similar to that shown forFIG.12. It should be understood, however, that embodiments where vents are shared are not excluded.FIG.30shows the cross-sectional shape of the channels394and their size relative to the capillary channels398of the liquid sample collector. FIGS.31and32show at least one embodiment of an inlet channel400having a low aspect ratio in terms of channel height to width. The narrow height, wide inlet channel400leads to a multi-channel distributor402, wherein the channels404also have low height to width aspect ratios and also have intersecting connectors406that provide connector pathways between the channels to form a grid or other pattern. In this particular embodiment, the connectors406are pathways with narrower cross-sectional areas that of the channels404. Each of the channels404is coupled to its own vent408, but it should be understood that embodiments where vents are shared are not excluded. The low aspect ratio of the channels404are more clearly shown inFIG.32along with their cross-sectional area relative to the cross-sectional area of the channels409of the collector. FIGS.33and34show an embodiment having an inlet420comprising a plurality of individual channels422that are co-located as the inlet420. Once sample is collected, each of inlet channels422directs its portion of the sample to the distributor424, which in this case is a multi-channel distributor, wherein the channels426have intersecting connectors428that provide connector pathways between the channels to form a grid or other pattern. In this particular embodiment, the connectors428are pathways with at least the same or greater cross-sectional area than that of the channels426. Each of the channels426is coupled to its own vent429, but it should be understood that embodiments where vents are shared are not excluded. The low aspect ratio of the channels426are more clearly shown inFIG.34along with their cross-sectional area relative to the cross-sectional area of the channels430of the collector. As seen inFIGS.29-34, the separators are shown with its upper surface in contact at location427with a wall surface of the device so that there is no gap. Some embodiments may have the separator under compression to maintain this contact and to account for any variation due manufacturing tolerances. This contact may also be true for the surfaces below the separator. By way of non-limiting example, this vertical compression of the separator to overcome any manufacturing tolerances can be applied to any of the embodiments discussed or suggested herein. Referring now toFIG.35, it should be understood that the separator shown in the embodiments up to this point have been rectangular, race track, oval, or some combination of the foregoing.FIG.35shows that other shapes are not excluded and that the separator may be material shaped such as but not limited to elliptical, triangular, quadrilateral (e.g., square, rectangular, trapezoidal, parallelogram), pentagonal, hexagonal, heptagonal, octagonal, square, circular, star, other two dimensional patterns, or single or multiple combinations of the foregoing. It should also be understood that the separator may be configured to be in certain three dimensional configurations such as but not limited to tubular, cylindrical, disc, pyramid, mesa, or the like can also be adapted for use herein. By way of non-limiting example, some inlet locations440for sample distribution are shown for some embodiments. These are merely exemplary and other positioning of the number and location of inlets440are not excluded. Sample Flow over Separator Referring now to the non-limiting examples ofFIGS.36to38, it should be understood that configuration wherein the channels234are open on one side to separator232allows for a multi-mode sample propagation pattern wherein at least a first portion is propagating laterally within the separator and a second portion is propagating through the channels234of the distributor over the separator232. In this non-limiting example, the multi-mode sample propagation shows a leading edge450that is ahead of the sample in the channels at filled surface452, which can exhibit a meniscus type shape as seen inFIG.36. The sample continues to fill the separator232with the multi-mode sample propagation pattern as seen inFIG.37until the fill is completed as seen inFIG.38, when sample is filled in the channels to reach the vents238. In some embodiments, the volume of sample in the channels is greater than that in the separator232and this may account for part of the reason that the leading edge in the separator232may be moving ahead of that in the channels234. Sample Collection from Separator Referring now to the non-limiting examples ofFIGS.39to42, at least one non-limiting example of sample flow during separation will now be described. Although not shown in the illustrations, at the point when the device is in the minimum fill condition as seen inFIG.39, the sample is ready to be engaged by a force to draw sample more completely through the separator232. In non-limiting example, there has already been some liquid sample that has traversed though the thickness of the separator232and has been pulled by capillary pressure from the capillary channels240of collector242to fill at least some of those channels and “prime” the channels with liquid that can then be used as part of the system to complete processing of the remaining sample held in the channels of the distributor above the separator232. As indicated by arrow460, a pulling force such as but not limited to full or partial vacuum in a sealed container like a vacutainer can be used to start moving liquid only sample into the container. As long as there is no “meniscus” break or if such breaks are recoverable, the sample still in the separator232or above it will begin to be drawn though the device. As seen inFIG.40, the pull of liquid in the direction of arrow460on the underside of the separator232will also create a pull that draws sample laterally toward and/or downward into the separator232. It is often desirable that this flow be without destructive trauma to formed components trapped in the separator232, as the release of material from inside these formed components into the sample is generally undesirable.FIG.40shows that some sample that was in the inlet222has been drawn into the channels234. Sample has begun to drain into the separator232in the channels234closest to the edge near the pulling force indicated by arrow460.FIG.41also shows that the sample continues to be drawn downward and in the direction of arrow460, there is also movement of sample further away from the inlet222.FIG.42shows that upon completion of the separation process, form components such as but not limited to red blood cells that have been size-excluded from the sample remain and leave a light red color on the separator232. Referring now toFIGS.43and44, a side cross-sectional view is shown of various embodiments of a sample collection and sample separation device.FIG.43shows that maximum trans separator pressure occurs closest to the end of the device where the outflow460is occurring. The further away from the area of outflow460, the lesser the trans pressure across the separator. This gradient can explain in part the flow pattern seen inFIGS.39-42. As the separator beings to become clogged with formed components near the extraction end at arrow460, flow has an increasing lengthwise component. Lengthwise intra separator flow increases shear stress on RBCs, and this trauma leads to greater hemolysis, even at lower pressures. Shorter, wider separator exhibit this effect in a manner that is less pronounced, while the effect is more pronounced in separators of greater lengths. Referring now toFIG.44, one embodiment herein comprises at least one or more vents470on the back side/collector side of the collector that decouples filtration from extraction. By providing a controlled inlet, the excessive force conditions that may cause excess shear stress it relieved by the controlled inlet from a pathway different from those occupied by the formed components, thus shifting pressure away from those components and still allowing for lateral liquid flow during extraction. In one non-limiting example, the controlled venting is balanced by having the pathway to reach the vent470pass through a portion of the separator232. In one embodiment, this is a portion of the separator232is not filled with sample. Optionally, this is a compressed portion of the separator232not filled with sample. In this manner, there will be some level of venting that creates a pathway for air to enter by way of the vent to relieve the pressure put on formed components in the sample if there is no separate inlet. In one embodiment, the resistance is substantially equal to the resistance associated with venting through the separator232filled with sample. In one embodiment, the resistance is less than the resistance associated with venting through the separator232filled with sample. With the vent structure, one can extract plasma with reduced risk of hemolysis when dealing with blood samples. Referring now to non-limiting examples ofFIGS.45and46, top down views of vent structures in the lower half of the device is shown.FIG.45shows that in this embodiment, the vent480is coupled to a shaped pathway482that is configured to be in communication with the capillary channels240of the collector242. Some embodiment may include a valve, porous material, mesh material, reduced diameter pathway, or other flow reducing material to control the flow of air from the vent to the interior of the collector242. Some embodiments may also have the shaped pathway482be compressed with material from the separator (not shown) to slow the flow to the collector242. Referring now toFIG.46, the vent484of this embodiment is coupled to a shaped pathway486that is configured to be in the area where the separator material (shown in phantom by line487) will cover it. The coverage may be in a compressed manner. Optionally, the coverage may be without substantial compression. The communication with the capillary channels350of the collector are separated by a pre-selected distance488from the shaped pathway486of the vent. In this manner, the pathway travels through at least that distance488of separator material (which may be gas porous) before air from the vent is able to be in fluid communication with the channels350. This can be useful in some embodiments to regulate the rate in when venting occurs. It should be understood that although the shaped pathways482and486are shown as continuous pathways, they may optionally be a plurality of discontinuous, discrete openings linked to a common vent or having their own individual vents. In some embodiments, it is desirable to locate the vent near the end of the device distant from the end where liquid sample is being pulled from the device. Some embodiments may combine one or more components ofFIGS.45and46together regarding venting and regulation of air through any such vent. Referring now to non-limiting examples ofFIGS.47and48, these figures show cross-sectional views of the separator showing different percentages of saturation by the sample. As seen inFIG.48A, the spacing of the channels of the distributor over the separator can be selected to increase separator saturation.FIG.47Ashows large channels spaced farther apart yields lower saturation that a combination of smaller channels spaced closer together to achieve a more uniform saturation pattern in the material. As seen in the top down view inFIG.47B, directed wetted area490as compared to indirectly wetted area492can be configured to increase overall saturation of the separator. The directly wetted surface area inFIG.47Brelative to total surface area is about 30%. Channel SAN=DWAN=5.0 forFIG.47B. FIG.48Bshows directed wetted area492as compared to indirectly wetted area496can be configured to increase overall saturation of the separator. The directly wetted surface area inFIG.48Brelative to total surface area is about 60%. Channels in the new configuration have a larger ratio of directly wetted surface area (DWA) to volume V, and nearly twice the directly wetted area as a fraction of total surface area (SA), wherein V is the volume of the separator. This results in a more effective wetting of the membrane; takes in more liquid per surface area. Channel SAN=DWAN=6.3 forFIG.48B. In one embodiment, the desired range of channel surface area relative to the surface area of the separator on that side of the separator is in the range of about 35% to 70%. Optionally, the desired range of channel surface area relative to the surface area of the separator on that side of the separator is in the range of about 40% to 70%. Optionally, the desired range of channel surface area relative to the surface area of the separator on that side of the separator is in the range of about 50% to 60%. In one embodiment, the ratio of Channel SAN which is also DWAN is in the range of about 5 to about 10. In one embodiment, the ratio of Channel SAN which is also DWAN is in the range of about 4.5 to about 9. In one embodiment, the ratio of Channel SAN which is also DWAN is in the range of about 5 to 8. Optionally, the ratio of Channel SAN which is also DWAN is in the range of about 6 to 8. Optionally, the ratio of Channel SAN which is also DWA/V is in the range of about 5.5 to 7. Optionally, the ratio of Channel SAN which is also DWAN is in the range of about 6 to 7. Referring now to non-limiting examples ofFIGS.49to51, various patterns of channels for distribution over the separator are shown.FIG.49shows an embodiment wherein there are no channels over the separator20.FIG.50shows an embodiment with ten channels. Although distributed symmetrically about a longitudinal axis of the separator, it should be understood that other embodiments where channel size, distribution, or length are not symmetrical about the longitudinal axis may be used.FIG.51shows an embodiment with twenty two distribution channels. FIG.52shows a plurality of cross-sections of the device showing the distributor, separator, and collector. As seen, the channels500of the distributor can be of various cross-sectional shapes such as but not limited to elliptical, triangular, quadrilateral (e.g., square, rectangular, trapezoidal, parallelogram), pentagonal, hexagonal, heptagonal, octagonal, square, circular, star, other two dimensional patterns, oval, half-oval, half-circular, polygonal, or single or multiple combinations of the foregoing. The lengthwise pathway shape can also be configured such as to distribute sample in a desired manner over the separator. The channels510of the collector can be of various cross-sectional shapes such as but not limited to elliptical, triangular, quadrilateral (e.g., square, rectangular, trapezoidal, parallelogram), pentagonal, hexagonal, heptagonal, octagonal, square, circular, star, other two dimensional patterns, oval, half-oval, half-circular, polygonal, or single or multiple combinations of the foregoing. In one embodiment, the channels shapes of the distributor and the collector may be the same or different. Some embodiment of the distributor may have different shaped and/or sized channels in the distributor to provide a certain desired sample distribution pattern. Some embodiment of the collector may have different shaped and/or sized channels in the collector to provide a certain desired sample collection pattern. FIGS.53to55show various non-limiting examples of different aspect ratios for the separators for use with the device.FIGS.53and55also show different aspect ratios for the distributor used with such a device. In one embodiment, the separator has a configuration where the aspect ratios, defined as the length of the separator520(lengthwise along the direction of flow, toward the extraction port as indicated by arrow521) divided by its width along arrow523are in the range of about 1:1 to 3:1. Optionally, the aspect ratio may be in the range of 1:1 to 5:1. Optionally, some embodiments may have aspect ratios in the range of 5:1 to 1:1. It should be understood that in these figures, the channels500are shown over the separator520. A common vent530which is shown inFIGS.53and54can be also adapted for use with other embodiments described herein.FIG.55shows a plurality of different aspect ratios for the separator520and the distributor having channels500. FIG.56shows one example of an exit conduit540below the collector550that shows a round inner surface542in the 90 degree elbow that transitions directions of sample flow out of the device from a vertical to a lateral flow. FIGS.57to59show that in addition to the pathway600for separation of formed components from the sample, some embodiments of the device are also configured to allow for other pathways610,620, or630that collect sample for treatment in a different manner. As seen in the figures, these pathways can be shaped and sized so that they can contain a desired amount of sample therein. Some embodiment may be configured so that the pathlength is such that the fill times for both the formed component separated sample and the un-separated sample are substantially the same. In this manner, a single indicator can be used to alert the user that sufficient fill has been achieved in both pathways. FIGS.57to59also show that the output of the devices may be into containers660. In one non-limiting example, the container may be but is not limited to a sealed container with piercable septum or cap, wherein the interior or the container is under full, partial, or some level of vacuum pressure therein to pull at least a certain volume of liquid sample into the container when it is fluidically engaged by the needle of the outlet tube or needle of the devices described herein. Optionally, the container may take the form of a test tube-like device in the nature of those marketed under the trademark “Vacutainer” by Becton-Dickinson Company of East Rutherford, NJ. The output of one device may be both blood (B) and plasma (P). Optionally, the output can be viewed as a) separated liquid-only sample and b) other sample output. Optionally, the output can be viewed as a) separated liquid-only sample (and any formed components smaller than the size exclusion limit) and b) other sample output. One or more of the pathways may be treated, coated, or otherwise prepared to deliver a material into the sample such as but not limited to an anti-coagulant, ethylenediaminetetraacetic acid (EDTA), citrate, heparin, or the like as currently known or will be developed in the future. Some may have two or more the pathways treated with the same or different material. FIG.59shows a still further embodiment showing a Y-split to separate sample to go in to both pathways. It should be understood that although this indication of fill level in one or more of the pathways may be by way of a visual indication. It should also be understood that other indication methods such as but not limited to audio, vibratory, or other indication methods may be used in place of or in combination with the indication method. The indicator may be on at least one of the collection pathways. Optionally, indicators are on all of the collection pathways. It should be understood that the devices herein can be configured to have three or more pathways and are not limited to only two pathways. For any of the embodiments herein, there can be container(s) such as but not limited to container660for use in drawing liquid sample that has gone through or will be drawn through the separator. In some embodiments, this is a two phase process, where there is an initial filling phase of sample into the separator using a first motive force and then a second phase using a second motive force to complete the sample separation process. The at least two different motive forces can be sensitive to timing in that it may be undesirable to activate the second motive force until a sufficient volume of sample has been metered into one or more of the pathways or until a sufficient fill allows for drawing of sample into the container without a meniscus break during the draw process under the second motive force. Suitable methods, devices, features, indicators, or the like can be found in U.S. Patent Application Ser. No. 61/786,351 filed Mar. 15, 2013, fully incorporated herein by reference for all purposes. Unified holders for multiple containers660, shipping units, additional pieces for attaching/sliding/integrating the containers660and/or their holders to the sample collection/separation device, frits, and other adapter channels structures can also be found in U.S. Patent Application Ser. No. 61/786,351 filed Mar. 15, 2013. FIG.60shows a still further embodiment wherein the output tube, needle, channel, or other structure670can be oriented to exit from a bottom part of the device. It can be orthogonal to the plane or at other angles. Some embodiments may have both bottom and side exiting output structures670. Some embodiments may have multiple output structures670in side and/or bottom surfaces. In one embodiment, the collection and/or separation pathways such as but not limited to channels may also have a selected cross-sectional shape. Some embodiments of the pathways may have the same cross-sectional shape along the entire length of the pathway. Optionally, the cross-sectional shape may remain the same or may vary along the length. For example, some embodiments may have one shape at one location and a different shape at one or more different locations along the length of the pathways. Some embodiments may have one pathways with one cross-sectional shape and at least one other pathway of a different cross-sectional shape. By way of non-limiting example, some may have a circular, elliptical, triangular, quadrilateral (e.g., square, rectangular, trapezoidal), pentagonal, hexagonal, octagonal, or any other cross-sectional shape. The cross-sectional shape may be the same for the body, support, and base, or may vary. Some embodiments may select a shape to maximize volume of liquid that can be held in the pathways for a specific pathway width and/or height. Some may have one of the pathways with one cross-sectional shape while another pathway has a different cross-sectional shape. In one embodiment, the cross-sectional shape of the pathway can help maximize volume therein, but optionally, it can also optimize the capillary pulling forces on the blood. This will allow for maximized rate of filling. It should be understood that in some embodiments, the cross-sectional shape of the pathway can directly affect the capillary forces. By way of non-limiting example, a volume of sample can be contained in a shallow but wide pathway, or a rounded pathway, both containing the same volume, but one might be desirable over the other for filling speed, less possibility of air entrapment, or factors related the performance of the pathway. Although the pathways may have any shape or size, some embodiments are configured such that the pathway exhibits a capillary action when in contact with sample fluid. In some instances, the pathway may have a cross-sectional area of less than or equal to about 10 mm2, 7 mm2, 5 mm2, 4 mm2, 3 mm2, 2.5 mm2, 2 mm2, 1.5 mm2, 1 mm2, 0.8 mm2, 0.5 mm2, 0.3 mm2, or 0.1 mm2. The cross-sectional size may remain the same or may vary along the length. Some embodiments may tailor for greater force along a certain length and then less in a different length. The cross-sectional shape may remain the same or may vary along the length. Some pathways are straight in configuration. Some embodiments may have curved or other shaped path shapes alone or in combination with straight portions. Some may have different orientations within the device body. For example, when the device is held substantially horizontally, one or more pathways may slope downward, slope upward, or not slope at all as it carries fluid away from the initial collection point on the device. In some embodiments the inner surface of the pathway and/or other surfaces along the fluid pathway such as but not limited to the sample inlet to the interior of a sample collection vessel may be coated with a surfactant and/or an anti-coagulant solution. The surfactant provides a wettable surface to the hydrophobic layers of the fluidic device and facilitate filling of the metering pathway with the liquid sample, e.g., blood. The anti-coagulant solution helps prevent the sample, e.g., blood, from clotting when provided to the fluidic device. Exemplary surfactants that can be used include without limitation, Tween, TWEEN®20, Thesit®, sodium deoxycholate, Triton, Triton®X-100, Pluronic and/or other non-hemolytic detergents that provide the proper wetting characteristics of a surfactant. EDTA and heparin are non-limiting anti-coagulants that can be used. In one non-limiting example, the embodiment the solution comprises 2% Tween, 25 mg/mL EDTA in 50% Methanol/50% H20, which is then air dried. A methanol/water mixture provides a means of dissolving the EDTA and Tween, and also dries quickly from the surface of the plastic. The solution can be applied to the pathway or other surfaces along the fluid flow pathway by any technique that will ensure an even film over the surfaces to be coated, such as, e.g., pipetting, spraying, printing, or wicking. It should also be understood for any of the embodiments herein that a coating in the pathway may extend along the entire path of the pathway. Optionally, the coating may cover a majority but not all of the pathway. Optionally, some embodiments may not cover the pathway in the areas nearest the entry opening to minimize the risk of cross-contamination, wherein coating material from one pathway migrates into nearby pathways by way of the pathways all being in contact with the target sample fluid at the same time and thus having a connecting fluid pathway. Although embodiments herein are shown with two separate pathways in the sample collection device, it should be understood that some embodiments may use more than two separate pathways. Optionally, some embodiments may use less than two fully separate pathways. Some embodiments may only use one separate pathway. Optionally, some embodiments may use an inverted Y-pathway that starts initially as one pathway and then splits into two or more pathways. Any of these concepts may be adapted for use with other embodiments described herein. Optionally, one or more of the pathways may be coated with a material to be incorporated into the sample. Optionally, it is desirable to fill the separator as quickly as possible relative to the other pathway in order to allow for maximum pre-filtration via the passive mechanisms described above. Thus, in one embodiment, one of the pathways fills first before the unfiltered/separated pathway fills. In one embodiment, the sample volume in one pathway is greater than the sample volume in the other pathway. In one embodiment, the sample volume in one pathway is greater by 1× than the sample volume in the other pathway. Optionally, a cap (not shown for ease of illustration) may attach to the collection device using any technique known or later developed in the art. For instance, the cap may be snap fit, twist on, friction-fit, clamp on, have magnetic portions, tie in, utilize elastic portions, and/or may removably connect to the collection device body. The cap may form a fluid-tight seal with the collection device body. The cap may be formed from an opaque, transparent, or translucent material. Optionally, the collection device body of the sample collection and separation device may be formed in whole or in part from an optically transmissive material. By way of non-limiting example, the collection device body may be formed from a transparent or translucent material such as but not limited to Poly(methyl methacrylate) (PMMA), Polyethylene terephthalate (PET), Polyethylene Terephtalate Glycol-modified (PETG or PET-G), or the like. Optionally, only select portions of the body are transparent or translucent to visualize the fluid collection channel(s). Optionally, the body comprises an opaque material but an opening and/or a window can be formed in the body to show fill levels therein. The collection device body may enable a user to view the channels within and/or passing through the device body. The channels may be formed of a transparent or translucent material that may permit a user to see whether sample has traveled through the channels. The channels may have substantially the same length. In some instances a support may be formed of an opaque material, a transparent material, or a translucent material. The support may or may not have the same optical characteristics of the collection device body. The support may be formed from a different material as the collection device body, or from the same material as the collection device body. The collection device body may have any shape or size. In some examples, the collection device body may have a circular, elliptical, triangular, quadrilateral (e.g., square, rectangular, trapezoidal), pentagonal, hexagonal, octagonal, or any other cross-sectional shape. The cross-sectional shape may remain the same or may vary along the length of the collection device body. In some instances, the collection device body may have a cross-sectional area of less than or equal to about 10 cm2, 7 cm2, 5 cm2, 4 cm2, 3 cm2, 2.5 cm2, 2 cm2, 1.5 cm2, 1 cm2, 0.8 cm2, 0.5 cm2, 0.3 cm2, or 0.1 cm2. The cross-sectional area may vary or may remain the same along the length of the collection device body120. The collection device body may have a length of less than or equal to about 20 cm, 15 cm, 12 cm, 10 cm, 9 cm, 8 cm, 7 cm, 6 cm, 5 cm, 4 cm, 3 cm, 2 cm, 1 cm, 0.5 cm, or 0.1 cm. The collection device body may have a greater or lesser length than the cap, support or base, or an equal length to the cap, support, or base. There may be variations and alternatives to the embodiments described herein. Referring now toFIG.61, a still further embodiment of a sample collection and sample separation device will now be described. This embodiment shows a cartridge1400with a sample collection and sample separation device1402integrated therein having one or two pathways700and702. It should be understood that the device1402may be integrally formed with the cartridge. Optionally, it may be a separate unit that this is removable from the cartridge. Optionally, it may be a separate unit that this is added to the cartridge after sample has been collected from the subject. Optionally, it may be a separate unit that this is added and/or attached to the cartridge and sample is collected from the subject after the unit it added and/or attached to the cartridge. In this non-limiting example, there is a collection location1322and one or more sample openings1325and1329where sample collection at location1322can then be accessed such as but not limited to handling by a pipette tip (not shown). The sample from droplet D will travel along pathway1326as indicated by arrow towards the openings1325and1329, where the sample in the opening and any in the pathways1324and/or1326leading towards their respective openings1325and1329are drawn into a sample handling system such as but not limited to a pipette P. In some embodiments, particularly for the pathway702with separation member and the distributor channel500, a vacuum or suction by the sample handling device can be used to fully draw sample though the separator720and complete the separation process. As indicated by arrows near the pipette P, the pipette P is movable in at least one axis to enable transport of sample fluid to the desired location(s). Although only a single pipette P is shown inFIG.61for ease of illustration, it should be understood that other embodiments may use a plurality of pipettes to engage one or more items associated with the cartridge. In this embodiment, the cartridge1400can have a plurality of holding containers1410for reagents, wash fluids, mixing area, incubation areas, or the like. Optionally, some embodiments of the cartridge1400may not include any holding containers or optionally, only one or two types of holding containers. Optionally, in some embodiments, the holding containers may be pipette tips. Optionally, in some embodiments, the holding containers are pipette tips that are treated to contain reagent(s) on the tip surface (typically the interior tip surface although other surfaces are not excluded). Optionally, some embodiments of the cartridge1400may include only the sample collection device1402without the tissue penetrating member or vice versa. A suitable device for use with cartridge can be found in U.S. patent application Ser. No. 13/769,798, filed Feb. 18, 2013. It should be understood that some embodiments may be configured to have only one of the above pathways in the sample collection and/or sample separation device. Some may have more than two of the pathways. Some may have more than one separator per pathway. Some may have multiple pathways each with one or more separators. Some embodiments may use the sample handling device such as but not limited to the pipette P to draw sample towards or onto the separator and then use the pipette to draw sample out of the underside or other side of the processor after the sample has been or has begun to be separated. It should be understood that other cartridge configuration are not excluded. Some embodiments may directly incorporate the separator and/or distributor and/or collector into and integrated as part of the cartridge body. Referring now toFIG.62, a perspective view is shown of a still further embodiment showing a device such as a fluid circuit portion800with extraction ports802and804. The embodiment ofFIG.62uses a single inlet806to direct portions of the sample to two different pathways, wherein at least one portion passes through a formed component separation member. Referring now toFIG.63, a perspective view is shown of a still further embodiment showing a device with fluidic circuit portion800, a housing portion822, and a sample container unit824. As seen inFIG.63, this non-limiting sample shows housing portion822coupling the fluidic circuit portion800with the sample container unit824. The housing portion822allows for the sample container unit824to be coupled to the same fluidic circuit portion800but still have the sample container unit824movable between a first position (as shown inFIG.63) and a second position. In one embodiment, an inlet port centered along a mid-line of the fluidic circuit with an entry point on to the formed component separation member that is off-center relative to the midline of the formed component separation member. In one embodiment, a vent channel of a curved configuration is coupled to a vent channel with a curved portion and an intersection linear (bent or straight) portion. The vents, in this non-limiting example are collection features that are on the side of the separation member were fluid, but not formed components, can exit the membrane. In on embodiment, a vent channel has a linear (bent or straight) portion coupled to a distribution portion, wherein the linear portion is closer to an external vent and distribution portion is closer to the separator. Referring now toFIGS.64to67, various embodiments of the cross-sectional shapes of the capillary structure.FIG.64shows structures with sharp corners890whileFIG.65shows an embodiment with radii or rounded corners892. As more clearly seen in the non-limiting example ofFIG.67A, tangency and curvature of the rounded corners892may provide continuous liquid contact to assist with fluid flow out of a separation member such as but not limited to a membrane and into an opposing portion of the fluid circuit such as but not limited to the capillary flow structure. It should be understood that the round corners892creates at least one transition region894which can assist drawing or leaching of fluid from one region towards the fluid collection structures in the device. In some embodiments, this drawing or leaching of fluid out of the separation member can be desirable. By contrast, the embodiments with a sharp corner890which opens directly the capillary structure with a transition region diminishes the assistance that may come from have the closely spaced area associated with the tangency and curvature provided by rounded corners892. Optionally as seen inFIG.67B, some embodiments may have a sharp corner896but further include at least one transition region that may provide continuous liquid contact to assist with fluid flow out of the separation member. Optionally, some embodiments may have at least one increased width region between the capillary structure898and the transition region894. Optionally in one non-limiting example, the capillary structure may be formed of or have a surface treated to create a hydrophilic fluidic structure. In one non-limiting example, the structure can be made of a hydrophilic material such as but not limited Polyethylene terephthalate glycol-modified (PET-G) which has a small wetting angle and is a hydrophilic material which can draw fluid toward the back side of the membrane. Optionally, some embodiments may use cellulose acetate, cellulose acetate butyrate, or other suitable material. Plasma collection vent: more plasma without hemolysis; distributors also are; capillary structures on the back side membrane. The other vent (blood side/distributor vents) is shown on the top side of the separation device that coupled to vent915. Alternate plasma extraction methods are provided wherein different motive force, other than vacuum in a container, are used to draw fluid away from the separation membrane. In one embodiment, inlet flow control features may be used in the sample container to control the rate and/or amount of motive force applied to filtered sample and/or sample about to be filtered. It should be understood that hemolysis will corrupt the sample for many assays and is thus generally undesirable. Optionally, some embodiments may go without a dual channel inlet and use a single channel. Some embodiments may have an opening over the membrane, instead of at one end. Optionally, this embodiment can have a passive, always open vent instead of a valve. Optionally, some alternate extraction methods may include: providing a much higher extraction vacuum (crimp opening to meter pull forces, wherein the crimp results in a 5 to 10 micron wide opening in the tube, almost a cold weld when cutting so as to form a flow regulator). It should be understood that high vacuum in the container or from was another source was high enough to collect a desired liquid volume, but the initial spike from the high vacuum will cause excess pull on the form components that creates hemolysis when the sample is a blood sample. In one embodiment, there is at least 70% of theoretical fluid recovery. In one embodiment, there is at least 80% of theoretical fluid recovery. In one embodiment, there is at least 90% of theoretical fluid recovery. For the final steps, the amount of friction can provide sufficient mechanical resistance from rapidly pushing sample vessel rapidly into the holder. The friction can be from the plunger, an external guide, and/or other component to provide a controlled movement between a first position and a second position. Other mechanical mechanism can be used to regulate speed that the user pushes it on. On the non-separator side, in one non-limiting example, there is no plunger. One embodiment may use deflected point needle that is anti-coring and also provides a side opening needle tip. In one-nonlimiting example, the anti-coring is desirable to prevent coring of the frit, which may introduce undesirable frit parts into the sample. The needle pierces through the frit. It should be understood that the frit is sized to cover or at least substantially cover the opening of the needle pointed tip opening. In this non-limiting example, the plunger may have a harder portion in the center while a circumferential portion is softer for liquid seal performance. Optionally, the capillary channels with fluid therein can also settle a bit before being engaged to be extracted. This delayed fill of the non-separator side ensures that the separator side has filled and had some settling time before being engaged to the sample collection unit for fluid transfer into the sample collection unit. In one embodiment, 80 microliters of whole blood results in 16 to 20 microliters of plasma. Referring now toFIG.68, a cross-sectional view is shown of one non-limiting example wherein an inlet channel808is shown penetrating one non-limiting example of a sample container unit824. As seen inFIG.68, the movement of the plunger828of the sample container unit824can be used to create a motive force such as but not limited to at least a partial vacuum to draw liquid from the channel808into the sample container unit824. In this non-limiting example, as the plunger is displaced as shown by arrow831inFIG.68, this increases the interior volume829of the sample container unit824between the cap portion832. It should be understood that, in one non-limiting example, there may be no sample in the sample container unit824until the motive force is provided to overcome any inherent capillary force of the channel808which brings the sample fluid into but not out a needle end834of the channel808, In one non-limiting example, extracting fluid from the channel808may involve using one or more additional motive forces. It should be understood that this configured described herein may be similar to a reverse plunger. Optionally, some embodiments may use a conventional plunger, in place of or in combination with the structures herein, to provide motive force to draw sample into the sample container. FIG.68also shows that, in at least one embodiment, the channel808may have a pointed distal end834. Still further embodiments may have the channel808be of a non-coring design so as not to introduce any cored portion or debris of the cap832into the collected fluid. Regardless of whether a non-coring, conventional, or other shaped channel808, it should be understood that some embodiments of plunger828may have a hardened core portion838that can withstand force input from the channel808. As seen inFIG.68, at least some embodiments will have a compliant material between the hardened core portion838and the side walls of the sample container so as to provide at least a sufficient fluid seal as the plunger828is moved from at least a first position to at least a second position. Referring now to the non-limiting examples ofFIGS.69and70, inlet design of inlet806may include flow guide structures910and912such as one or more small capillary channels in the sides of the inlet806encourage flow to enter pathway leading to the separation member, rather than the pathway without the separation member. As seen inFIG.73, the flow guide structures910and912are located as positions along the inlet806that have surfaces that extend toward the separation component920. In one non-limiting example, the fluid guide structures910and912are not along the bottom surface of the inlet, which may be where the other channel connects to the inlet. In one non-limiting example, the fluid guide structures910and912are not positioned along a surface of the inlet where the other channel connects to the inlet. AlthoughFIG.69shows that the inlet806has at least two flow guide structures910and912, it should be understood that some embodiments may only have a single flow guide structure. Optionally, some embodiments may have more than two flow guide structures. Optionally, some embodiments may have a single structure at the inlet806but forks into two or more structures as the fluid flows deeper into the inlet. Optionally, some embodiments may have a plurality of fluid guide structures wherein at least two of the structures merge together so that there are fewer guide structures as the fluid flow deeper into the structure. It should be understood that some embodiments may take a plurality of guide structures and merge them all into one guide structure. FIG.71shows a still further embodiment wherein at least one stop structure930such as but not limited to a frit is included on at least one of the extraction channels808. In the non-limiting example ofFIG.71, the stop structure930is included on the channel808coupled to the non-separation member pathway, which may flow more freely and thus have a different flow resistance than the other pathway which passes through the separation member. Venting of the non-separation member pathway channel allows filling via capillary flow. In this embodiment, the channel808is vented through a pointed end of a needle, wherein an air porous frit such as but not limited to one of Porex or similar porous material, is coupled to a tip of needle, still allowing air through, but with more resistance. In this manner, filling on the non-separation member pathway side is slowed down so that separation member pathway can fill first. Other techniques for slowing flow along one pathway are not excluded and may be used alone or in combination with the stop structure930discussed herein.FIG.71also shows that in this embodiment, a combined vent915can be used to provide a vent path for the various vents associated with the sample distributor over the fluid entry surface of the separation member. Furthermore, fill metering can be done using an indicator950(seeFIG.73) on the non-separation member pathway, because due to its lagging indicator quality due to a slower fill, if a fill level is reached on the non-separation member pathway, due to the slower, fill a user can safely conclude that the other pathway has already completed its fill process due to the slower fill in the non-separation member pathway.FIG.73also shows that there are at least two fluid flow paths within the device as indicated by arrows951and953.FIG.73also shows that there may be guide955, such as but not limited a guide member in a slot, that may act as a visual indicator that the movement of the sample collection unit824is complete and may optionally provide sufficient resistance to encourage a controlled rate of movement of the collection unit824so that the flow will be sufficient to minimize hemolysis of formed components in the sample. Referring now toFIG.72A, it should also be understood that structures without a penetration tip, such a pipette tip, can also be adapted for use with certain embodiments of the sample container.FIG.72Aalso shows that in at least some embodiments, the plunger828is only in one vessel and not in all of the vessels defined by the sample container unit.FIG.72Amay also be shown with the top plug832removed to allow for sample extraction using a pipette tip that is shaped to reach a bottom interior portion of the vessel being emptied. Referring now to the non-limiting example ofFIG.72B, the various initial positions are shown for a stop structure930on the channel808and that non-coring tip of the channel808has engaged a plug832of the container unit824. Referring now toFIG.74, this non-limiting example shows a sample container unit824with one sample container sized larger to accommodate a pressure drop volume, that is the volume to which air on the plasma side of the formed member separation membrane (including inside the sample container unit) expands due to the pressure drop across the membrane. FIG.75shows a side view of the device wherein the sample flow pathway indicated by arrow1010shows that sample enters at an angle, flows along one plane, downward to a different plane and is drawn laterally out at the lower plane. Movement of the sample collection unit824is indicated by arrow1020, wherein in this embodiment, movement of the sample collection unit824provides motive force to draw sample substantially free of formed components into the sample collection unit. Although many of the embodiments shown herein use linear movement of the sample collection unit824, it should be understood that embodiments using rotary motion to provide the motive force or rotary motion translated into linear motion to provide the desired movement to draw sample into the sample container. Some embodiments of the collection unit may have a cross-sectional shape with an asymmetry, a protrusion, or other feature that serves as a keying feature for orienting the SCU in any receiving device or structure. While the invention has been described and illustrated with reference to certain particular embodiments thereof, those skilled in the art will appreciate that various adaptations, changes, modifications, substitutions, deletions, or additions of procedures and protocols may be made without departing from the spirit and scope of the invention. For example, with any of the above embodiments, it should be understood that some embodiments may handle other types of samples and necessarily biological samples. Although many illustrations are shown with only a single inlet port, it should be understood that some embodiments may have at least two inlet ports. In some embodiments, both inlet ports are on the same end of the device. Optionally, some embodiments may have inlet ports on the same surface of the device. Optionally, at least the two inlets are adjacent to each other. Optionally, there are at least three inlet ports. Optionally, at least two inlet ports are each defined by at least one capillary tube. In this embodiment where each inlet has its own capillary tube, at least one tube directs fluid to a non-separation pathway while a second tube directs fluid to a separation pathway. Optionally, some embodiments may combine inlets formed by capillary tubes with inlet(s) associated with a non-capillary pathway. Some embodiments may have the inlet along a centerline axis of the device. Optionally, some embodiments may have the inlet aligned off the centerline. Optionally, some embodiments may orient the inlet to be along or parallel to the axis of the centerline of the device. Optionally, some embodiments may orient the inlet along an axis that is at an angle to the plane of the device. Optionally, instead of having the inlet at one end of the separation device, it should be understood that some embodiments may have the inlet directly over at least one portion of the separation device. In this manner, the opening may direct fluid onto the membrane with a minimal amount of travel in a lateral tube or pathway. Optionally, some embodiments may be configured with a co-axial design such as shown inFIG.76. One embodiment may have sample enter along an inner lumen for an inside-out type filtration as indicated by arrow1010. Optionally, some embodiments may use an outside-in type filtration if the separation membrane is located in the inner lumen and sample fluid enters from a surface opening (shown in phantom) as indicated by arrow1012or from an inlet on one end of the device. Optionally as seen inFIG.77A, some embodiments may have a portion800such as the fluid circuit portion that includes the separation member fluidly coupled to a second portion1040. Optionally, it may be configured not to include the non-separation pathway. Optionally, it may be configured to include the non-separation pathway. Some embodiments may have this combination of portion800with portion1040in a test strip configuration. Some embodiments may have this combination of portion800with portion1040in a lateral flow device configuration. Some embodiments may have a unibody structure or other merged structure that is formed to provide support to both portions800and1040. Motive force can be provided to move the sample as indicated by arrow1030which flow out or the fluid circuit of portion800and that the fluid portion of the sample, substantially free of the formed components, can enter a second region1040which may be but is not limited to an analytical region. In some embodiments, the second region1040also provides a motive force such as but not limited to wicking force associated with such material in at least a portion of the second region1040. FIG.77Bshows a still further embodiment wherein the sample collection device has a plurality of tissue penetrating member or members1292mounted to an actuation mechanism1293. In one embodiment, the tissue penetrating members1292are microneedles. In one embodiment, the tissue penetrating member1292comprises a lancet. In one embodiment, the actuation mechanism1293can be a spring-like device in a dome, curved, or other shape. In some embodiments, the dome shape can also provide a certain suction force to draw sample upward from the collection site. Although a mechanical actuation method is shown, it should be understood that other types of actuation techniques such as but not limited to electromechanical, pneumatic, mechanical cam, or other technique known or developed in the future may be used for actuation. It should also be understood that some embodiments may use a tissue interface (shown in phantom) to facilitate interaction with the tissue.FIG.77Bshows that the sample obtained from a wound or wounds created by tissue penetrating members1292may flow through channel(s), capillary tube(s), or other pathways as indicated by arrow1295to a channel1299or other inlet to a separation device. In one embodiment, the channel1299may be coated with at least one anticoagulant. Optionally, some embodiments may have two channels1299that may draw sample along two pathways, wherein each channel may have the same, or optionally different, coatings on the surface of the channels1299. Optionally, some embodiments may have surfaces of the device uncoated but instead have the additive material in the container1297. As seen inFIG.77B, the sample may flow to a location such as but not limited to a chamber (shown in phantom), one end of the channel1299or other location wherein a conduit such as pathway1301or1303(shown in phantom) may be used to fluidically couple the sample collected in channel1299to transfer the sample container1296or1297. Motive force can be provided to move the sample as indicated by arrow1030along a horizontal path over the separator, a path from the plane of above the separator to a plane below the separator, and then laterally towards at least one sample container. In this non-limiting example, the pathway is a zig-zag path from one side of the separator to the other side which carries the liquid portion to an intermediate chamber or directly to one or more containers. As described, the container may be one with a sub atmospheric condition therein (prior to being fluidically engaged to the fluid pathway), one with a reverse syringe design as found in U.S. Provisional Application Ser. No. 62/051,906 filed Sep. 17, 2014, a container may be one that is un-pressurized, without a movable plunger but with a septa cap, or other suitable container for sample as currently known or may be developed in the future. It should be understood that some embodiments may have containers1296in both locations as shown inFIG.77Bor only at one but not the other. Optionally, some may have multiple containers at one location and none or fewer containers at the other location. Optionally, some of these may be unitized so that multiple vessels are integrally formed or otherwise joined together. As seen inFIG.77B, the container1296may be actuated by sliding the container1296to contact the pathway1301in a manner that allows sub-atmospheric environment inside the container1296to draw sample therein. Optionally, other actuation methods such as but not limited to using a valve, breaking a seal, or the like can be used to activate sample transfer from the device to the container1296. Some embodiments may keep the channel1299in one horizontal plane or may optionally have portions in one plane and portions in another plane. Optionally, instead of or in combination with capillary action from channel1299for drawing sample therein from the wound site, a suction or other sample pulling device can be used to draw sample into the channel1299. The embodiment ofFIG.77Bmay optionally be modified to locate the entry port of channel1299closer to the wound site such as but not limited a channel extension1305, forming the channel closer to the wound site, or positioning or orienting the tissue penetration members to form a wound closer to the inlet of channel1299. It should be understood that devices herein may be configured to include features from U.S. Provisional Application Ser. No. 62/051,906 filed Sep. 17, 2014, fully incorporated herein by reference for all purposes. It should be understood that devices in U.S. Provisional Application Ser. No. 62/051,906 filed Sep. 17, 2014, may be configured to include a formed component separation apparatus as described in this application. FIG.77Balso shows a still further embodiment using container1297having a reverse-syringe design is used. As seen herein, the movement of engaging the container1297with pathway1301or1303can be used to push the plunger2828to create a reduced pressure environment that draws sample into the container1297. It should be understood that some embodiments may have containers1297in both locations as shown inFIG.77Bor only at one but not the other. Optionally, some may have multiple containers at one location and none or fewer containers at the other location. Optionally, some of these may be unitized so that multiple vessels are integrally formed or otherwise joined together. Optionally, some embodiments may have one type of container1296at one location and a different type of container1297at a different location shown inFIG.77B. Optionally, some may have at least two different types of container at one location. Referring still toFIG.77B, some embodiments may use a push element1307that provide a cap or other seal that when moved as indicated over feature1305will cause a pressurized air bolus to push sample in the channel1299outward into the containers1297that may be attached to1301or1303. Optionally, it should be understood that some embodiments may have at least one formed component separation pathway for use in a non-diagnostic device. By way of non-limiting example, the device may be for sample collection, where no diagnosis occur on the device. Optionally, it should be understood that some embodiments may have at least one formed component separation pathway and at least one non-separation pathway for use in a non-diagnostic device. Optionally, it should be understood that some embodiments may have at least two formed component separation pathway and at least one non-separation pathway for use in a non-diagnostic device. Optionally, it should be understood that some embodiments may have at least one formed component separation pathway and at least two non-separation pathways, all for use in a non-diagnostic device. Of course, some alternative embodiments may have one or more pathways for use for diagnosis. Optionally, some embodiments may use this type of separation device with lateral flow strip wherein the fluid, after formed component separation, may be moved such as but not limited to wicking or other capillary flow onto a second region such as but not limited to an analyte-detecting region on a device such as but not limited to a test strip for analysis. Optionally, some embodiments may provide a vibration motion source, such as but not limited to one built into the device and/or in an external device use to process the sample container, to assist in fluid flow within device, during the collection, or post-collection. Some embodiments may use this vibration to assist flow or to remove any air pockets that may be created, such as but not limited to when doing a top-down fill. Optionally, some embodiments may provide more periodic or pulse type force to assist in fluid flow. It should be understood that although many components herein are shown to be in alignment in the same plane or parallel planes, some embodiments may be configured to have one or more component in a plane angled to or orthogonal to a plane of the fluid collection circuit in portion800. The fluid collection circuit in portion800does not need to be a flat planar device and may be in a curved configuration. Optionally, some embodiments may have it a cone configuration. Optionally, some embodiments may have it device with a polygonal cross-sectional shape. As seen, the fluid collection circuit in portion800is not limited to a planar shape. It should also be understood that in many embodiments, the portion800may be made of a transparent material. Optionally, the portion800may be made of a translucent material. Optionally, portions of the portion800may be covered with paint or other opaque material, be formed of an opaque material, or the like such that only portions that may contain fluid are transparent or translucent so as to provide an indicator of fill level. Such an embodiment may have all or only a portion of the fluid path visible to the user. In one non-limiting example, bar codes, color-coding, visual information, instructions, instructions for use, fill-indicator, advertising, child-appealing aesthetics, texturing, texturing for grip purpose, texturing for contour, texturing to provide feedback such as orientation of the front of the device, or other coating may be used hereon. Optionally, some embodiments may include an intermediary structure between the fluid circuit in portion800and the sample collection unit824. This intermediary structure can be in the fluid pathway and provide certain function such as but not limited to introducing a material into the collected fluid such as but not limited to anti-coagulant. Optionally, the intermediary structure in the fluid path may provide another route, such as switch or connection pathway, to add additional sample or other liquid material into the collected fluid. Optionally, some embodiments may have disposable portion(s) and reusable portions, wherein the reusable portions can be mated with the disposable portion(s) to form another collection device. By way of non-limiting example, a reusable portion may be one that does not directly contact the sample fluid or filtered fluid. Although embodiments herein show the separation member as part of a handheld device, it should be understood that other embodiments may incorporate the device as part of a non-handheld benchtop device, a non-portable device, or the like and the disclosures herein are not limited to handheld or disposable units. Some embodiments may also include features for collection sample from a plurality of sample processing devices. In this manner, an increased amount of filtered sample can be collected, simply by using more devices for use with more samples which in one embodiment may all be from one subject. Optionally, samples in multiple devices may be from multiple subjects. As used herein, the terms “substantial” means more than a minimal or insignificant amount; and “substantially” means more than a minimally or insignificantly. Thus, for example, the phrase “substantially different”, as used herein, denotes a sufficiently high degree of difference between two numeric values such that one of skill in the art would consider the difference between the two values to be of statistical significance within the context of the characteristic measured by said values. Thus, the difference between two values that are substantially different from each other is typically greater than about 10%, and may be greater than about 20%, preferably greater than about 30%, preferably greater than about 40%, preferably greater than about 50% as a function of the reference value or comparator value. As used herein, a “surfactant” is a compound effective to reduce the surface tension of a liquid, such as water. A surfactant is typically an amphiphilic compound, possessing both hydrophilic and hydrophobic properties, and may be effective to aid in the solubilization of other compounds. A surfactant may be, e.g., a hydrophilic surfactant, a lipophilic surfactant, or other compound, or mixtures thereof. Some surfactants comprise salts of long-chain aliphatic bases or acids, or hydrophilic moieties such as sugars. Surfactants include anionic, cationic, zwitterionic, and non-ionic compounds (where the term “non-ionic” refers to a molecule that does not ionize in solution, i.e., is “ionically” inert). For example, surfactants useful in the reagents, assays, methods, kits, and for use in the devices and systems disclosed herein include, for example, Tergitol™ nonionic surfactants and Dowfax™ anionic surfactants (Dow Chemical Company, Midland, Michigan 48642); polysorbates (polyoxyethylenesorbitans), e.g., polysorbate 20, polysorbate 80, e.g., sold as TWEEN© surfactants (ICI Americas, New Jersey, 08807); poloxamers (e.g., ethylene oxide/propylene oxide block copolymers) such as Pluronics® compounds (BASF, Florham Park, N.J); polyethylene glycols and derivatives thereof, including Triton™ surfactants (e.g., Triton™ X-100; Dow Chemical Company, Midland, Michigan 48642) and other polyethylene glycols, including PEG-10 laurate, PEG-12 laurate, PEG-20 laurate, PEG-32 laurate, PEG-32 dilaurate, PEG-12 oleate, PEG-15 oleate, PEG-20 oleate, PEG-20 dioleate, PEG-32 oleate, PEG-200 oleate, PEG-400 oleate, PEG-15 stearate, PEG-32 distearate, PEG-40 stearate, PEG-100 stearate, PEG-20 dilaurate, PEG-25 glyceryl trioleate, PEG-32 dioleate, PEG-20 glyceryl laurate, PEG-30 glyceryl laurate, PEG-20 glyceryl stearate, PEG-20 glyceryl oleate, PEG-30 glyceryl oleate, PEG-30 glyceryl laurate, PEG-40 glyceryl laurate, PEG-40 palm kernel oil, PEG-50 hydrogenated castor oil, PEG-40 castor oil, PEG-35 castor oil, PEG-60 castor oil, PEG-40 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-60 corn oil, PEG-6 caprate/caprylate glycerides, PEG-8 caprate/caprylate glycerides, polyglyceryl-10 laurate, PEG-30 cholesterol, PEG-25 phyto sterol, PEG-30 soya sterol, PEG-20 trioleate, PEG-40 sorbitan oleate, PEG-80 sorbitan laurate, polysorbate 20, polysorbate 80, POE-9 lauryl ether, POE-23 lauryl ether, POE-10 oleyl ether, POE-20 oleyl ether, POE-20 stearyl ether, tocopheryl PEG-100 succinate, PEG-24 cholesterol, polyglyceryl-10oleate, sucrose monostearate, sucrose monolaurate, sucrose monopalmitate, PEG 10-100 nonyl phenol series, PEG 15-100 octyl phenol series, and poloxamers; polyoxyalkylene alkyl ethers such as polyethylene glycol alkyl ethers; polyoxyalkylene alkylphenols such as polyethylene glycol alkyl phenols; polyoxyalkylene alkyl phenol fatty acid esters such as polyethylene glycol fatty acids monoesters and polyethylene glycol fatty acids diesters; polyethylene glycol glycerol fatty acid esters; polyglycerol fatty acid esters; polyoxyalkylene sorbitan fatty acid esters such as polyethylene glycol sorbitan fatty acid esters; phosphocholines, such as n-dodecylphosphocholine, (DDPC); sodium dodecyl sulfate (SDS); n-lauryl sarcosine; n-dodecyl-N,N-dimethylamine-N-oxide (LADO); n-dodecyl-β-D-maltoside (DDM); decyl maltoside (DM), n-dodecyl-N,N-dimethylamine N-oxide (LADO); n-decyl-N,N-dimethylamine-N-oxide, 1,2-diheptanoyl-sn-glycero-3-phosphocholine (DHPC); 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC); 2-methacryloyloxyethyl phosphorylcholine (MPC); 1-oleoyl-2-hydroxy-sn-glycero-3-[phospho-RAC-(1-glycerol)] (LOPC); 1-palmitoyl-2-hydroxy-sn-glycero-3-[phospho-RAC-(1-glycerol)] (LLPG); 3-[(3-cholamidopropyl) dimethylammonio]-1-propanesulfonate (CHAPS); n-Octyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; n-Decyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; n-Dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; n-Hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; Tetradecanoylamidopropyl-dimethylammonio-propanesulfonate; Hexadedecanoylamidopropyl-dimethylammonio-propanesulfonate; 4-n-Octylbenzoylamido-propyl-dimethylammonio Sulfobetaine; a Poly(maleic anhydride-alt-1-tetradecene), 3-(dimethylamino)-1-propylamine derivative; a nonyl phenoxylpolyethoxylethanol (NP40) surfactant; alkylammonium salts; fusidic acid salts; fatty acid derivatives of amino acids, oligopeptides, and polypeptides; glyceride derivatives of amino acids, oligopeptides, and polypeptides; lecithins and hydrogenated lecithins, including lecithin, lysolecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, phosphatidic acid, phosphatidylserine; lysolecithins and hydrogenated lysolecithins; phospholipids and derivatives thereof; lysophospholipids and derivatives thereof, including lysophosphatidylcholine, lysophosphatidylethanolamine, lysophosphatidylglycerol, lysophosphatidic acid, lysophosphatidylserine, PEG-phosphatidylethanolamine, PVP-phosphatidylethanolamine; carnitine fatty acid ester salts; salts of alkylsulfates; fatty acid salts; sodium docusate; acyl lactylates; mono- and di-acetylated tartaric acid esters of mono- and di-glycerides; succinylated mono- and di-glycerides; citric acid esters of mono- and di-glycerides; lactylic esters of fatty acids, stearoyl-2-lactylate, stearoyl lactylate, succinylated monoglycerides, mono/diacetylated tartaric acid esters of mono/diglycerides, citric acid esters of mono/diglycerides, cholylsarcosine, caproate, caprylate, caprate, laurate, myristate, palmitate, oleate, ricinoleate, linoleate, linolenate, stearate, lauryl sulfate, teracecyl sulfate, docusate, lauroyl carnitines, palmitoyl carnitines, myristoyl carnitines, and salts and mixtures thereof; alkylmaltosides; alkylthioglucosides; lauryl macrogolglycerides; hydrophilic transesterification products of a polyol with at least one member of the group consisting of glycerides, vegetable oils, hydrogenated vegetable oils, fatty acids, and sterols; polyoxyethylene sterols, derivatives, and analogues thereof; polyoxyethylated vitamins and derivatives thereof; polyoxyethylene-polyoxypropylene block copolymers; and mixtures thereof; fatty alcohols; glycerol fatty acid esters; acetylated glycerol fatty acid esters; lower alcohol fatty acids esters; propylene glycol fatty acid esters; sorbitan fatty acid esters; polyethylene glycol sorbitan fatty acid esters; sterols and sterol derivatives; polyoxyethylated sterols and sterol derivatives; polyethylene glycol alkyl ethers; sugar esters; sugar ethers; lactic acid derivatives of mono- and di-glycerides; hydrophobic transesterification products of a polyol with at least one member of the group consisting of glycerides, vegetable oils, hydrogenated vegetable oils, fatty acids and sterols; oil-soluble vitamins/vitamin derivatives; and combinations thereof. Referring now toFIG.78, one embodiment of a filtering device such as but not limited to a bodily fluid separation material3100will now be described.FIG.78shows a side cross-sectional view of the separation material3100, showing cross-sections of the structures3102of the separation material. By way of non-limiting example, the separation material3100may be a size-exclusion barrier such as but not limited to a porous membrane with size-exclusion properties. Other embodiments may use other types of size-exclusion barrier(s). In one embodiment described herein, the structures3102are fibers in the separation material with their cross-sectional views shown inFIG.78. Optionally, the structures3102are mesh portions of the separation material. Optionally, the structures3102are pore walls or pore-defining structures of the separation material. Optionally, the structures3102may be a percolating network of connected fibers, elongate members, or the like. Some embodiments may combine one or more of the foregoing to form the separation material. Although the descriptions herein are written in the context of a separation material, other filter materials or structures in sheet-like or other shapes are not excluded material.FIG.78shows that for the present embodiment, formed components3106such as but not limited to red blood cells, white blood cells, platelet, or other formed components of the bodily fluid can enter the separation material3100in a variety of directions, including from a top-down manner, and will continue to pass through the separation material until the component reaches a size-constrained area where the spacing becomes too small for the formed component3106to proceed any further. In this embodiment, operating under the principle of size exclusion, the formed component3106will then be constrained in the separation material3100while liquid portions and/or those components not size excluded can continue to pass through the separation material. In one non-limiting example, arrows3104show movement of formed components through the separation material3100ofFIG.78. Other movement, such as but not limited to lateral, side-ways, and/or diagonal movement, is not excluded. Referring still to the embodiment ofFIG.78, the dotted line3120shows that in this embodiment, there are at least two regions3122and3124for the separation material3100. It should be understood that other embodiments can have even more regions. In this current embodiment, the region3122comprises a formed component capture region. In some specific embodiments as will be discussed in more detail below, it may be an anti-hemolytic, formed component capture region. By way non-limiting example, the region3124comprises a pass-through region that has structural elements spaced closely enough that formed components of the bodily fluid sample cannot completely pass through that region3124. In at least some embodiments, the sizing and/or spacing of elements is selected such that the size-restriction technique of separation material components prevents the formed components from continuing through the separation material. This filters out the formed components from the liquid components of the bodily fluid. In one embodiment, because region3122can be configured to be a formed component capture region, structures in the region3122will have more potential direct contact with the formed components3106and be in contact with them for a longer period of time, relative to structures in the second region3124. Due at least in part to the greater direct contact physically and temporally, it may be desirable in it at least some embodiments described herein to treat the structures3102of the region3122to minimize undesirable breakdown, spoilage, or other detrimental effect that may result from the formed components being captured in the region3122. In one non-limiting example, the structures3102may be coated with an anti-hemolytic coating to prevent breakdown of red blood cell when the bodily fluid being processed is blood. One embodiment of an anti-hemolytic coating may be an NTA coating. Optionally, other anti-hemolytic treatments in layer or other form may use material such as but not limited to n-Octyl-β-D-Glucopyranoside (OG), cell lipid bilayer intercalating material, phosphate ester containing at least two ester linkages comprising fatty hydrocarbon groups, tri-2-ethylhexylphosphate, di-2-ethylhexylphthalate, dioctylterephthalate, anti-hemolytic surfactant(s), a surfactant such as but not limited to polysorbate 80 mixed with any of the foregoing, and/or other anti-hemolytic material. Other anti-hemolytic material used with embodiments herein includes but is not limited to one or more of the following: anti-coagulants, proteins (such as but not limited to BSA, HSA, Heparin, Casein, etc.), surfactants (such as but not limited to Tween, Silwet, SDS, etc.), sugars (such as but not limited to sucrose, trealose, etc.), and/or the like. In one embodiment, the region3124may be configured to be a liquid pass-through region positioned after the bodily fluid has passed through region3122. AlthoughFIG.78illustrates region3124to be next to region3122, it should be understood that embodiments having intermediate region(s) and/or space between the regions are not excluded. By way of non-limiting example, the pass-through region3124may be configured not have direct contact with the formed components. Optionally, only structures3108defining part of the upper portion of the region3124may be in contact with any formed components3106. Optionally, only structures3108defining part of the upper surface of the region3124may be in contact with any formed components3106. In one embodiment, the region3124may be have a selected structure size, spacing, and/or other property that prevents formed components3106from passing through the region3124so as to enable a size restriction filtering technique for removing formed components from the bodily sample. In at least some embodiments, because the formed components are not in direct contact with the region3124or are only in minimal contact with region3124, the separation material of region3124may not be coated with the material used in the region3122. Optionally, region3124may be selective coated with the materials used in region3122in a manner such as but not limited to only those portions that might still be in contact with formed components may be coated, which others portions of region3122are uncoated. Optionally, at least some embodiments may have some or all of region3124coated with a material different from that of the region3122. Optionally, at least some embodiments may have some or all of region3124covered with the material of region3122and then adding a second layer of the second material over the material of region3122. In one non-limiting example, this second material may be selected to prevent the first material leaching or otherwise entering the bodily fluid when the liquid passes through the region3124. In at least some embodiments, the portions of region3124covered with the material of region3122is covered with the second material while other areas of region3124are substantially or at least partially uncovered by either material. By way of example and not limitation, some embodiments may use Heparin and/or other anti-coagulant as the material for the second layer. Optionally, the material for the second layer may be a material that is already in the bodily fluid sample. By way of non-limiting example, the material may be EDTA if the bodily fluid sample has already been or will be treated with EDTA. Optionally, for the second layer, some embodiments may use inert materials alone or in combination with any of the other materials listed herein. Referring now toFIG.79, a still further embodiment will now be described. This embodiment shows a first separation material3200and a second separation material3210. Although only two separation materials are shown, it should be understood that other embodiments having additional separation materials above, between, and/or below the separation materials shown inFIG.79are not excluded. It should also be understood that one or more of the separation materials3200and3210can, within the separation materials themselves, each have additional regions therein for different properties. As seen in the embodiment ofFIG.79, the separation material200functions as a capture region similar to the capture region3122of the embodiment ofFIG.78. In the current embodiment, the separation material3210functions as a pass-through region similar to region3124of the embodiment ofFIG.78. Referring now toFIG.80, this embodiment shows a tri-layer filter assembly with a first layer3300, a second layer3310, and a third layer3320. For ease of illustration, the layers are shown to be similar in thickness, but configurations where all three are of different thicknesses, or only are of different thicknesses are not excluded. Embodiments with additional layers are also not excluded. Layers can also be formed of different materials. It should be understood that any of the layers3300,3310, or3320can be configured as a capture region, a pass-through region, or neither. In one non-limiting example, at least the upper two layers3300and3310are capture regions. They can have similar capture capabilities, or optionally, one can be configured to be preferential capture of components while the other layer has preferential capture of components in a different size and/or shape regime. In another non-limiting example, at least the upper two layers3300and3310are captures regions, but only one of them is coated with a material to prevent degradation of the formed component(s). Optionally, both of them are coated with a material to prevent degradation of the formed component(s). Another embodiment may have two layers such as layers3310and3320that are both configured as pass-through layers. In one embodiment, neither of the layers3310or3320have structures that are coated with a material to prevent degradation of the formed component(s). Optionally, at least one of the layers3310or3320has structures that are coated with a material to prevent degradation of the formed component(s). Optionally, some embodiments have both of the layers3310or3320have structures that are coated with a material to prevent degradation of the formed component(s). Separation Material Treatment By way of example and not limitation, in order to be able to use separation materials for producing plasma suitable for a greater range of assays, several separation material treatment methods have been identified. Some of these techniques may involve treatment of separation materials after they are formed. Some of the techniques may involve forming the separation materials in a way that does not involve additional treatment after separation material formation. Optionally, some techniques may use both separation material formation and post-formation treatment to create a desired configuration.1. Separation material wash: In one embodiment described herein, by controlled washing of the coated plasma separation material by water and/or buffer solutions, most of the hemolysis-preventing agents can be removed.FIG.81shows that a washing mechanism, such as but not limited to a nozzle3400directing washing fluid (as indicated by the arrows) towards the target separation material3402, can be used to reduce at least some of the coating off of the separation material. This can create a preferential change in the amount of coating in selected areas of the separation material. One example may show removal or at least reduction of coating on one side of the separation material. Optionally, some may direct the wash fluid to wash coating off of an interior region of the separation material. Other configurations where portions of coating are removed from other select areas are not excluded. In one embodiment described herein, a carefully controlled washing is desirable so as to not completely remove the hemolysis preventing agent—which would result in hemolysis. In contrast, insufficient wash will result in sufficient amount of the hemolysis preventing agent leaching into the plasma and causing hemolysis. Thus, in one non-limiting example, a reduced amount of coating, or coating in interior portions of the separation material can be acceptable. Optionally, as seen inFIG.82, some embodiments may also use a bath3410of wash fluid that preferentially removes coating material from certain areas of the separation material. Optionally, spray washing and bath soaking, or vice versa, may be combined for use on a separation material. This processing may occur sequentially or simultaneously.2. Custom separation material coating: In another embodiment described herein, both coated and uncoated versions of the plasma separation material can be coated using a custom formulation which is compatible with assay chemistries. The coating may contain one or more of the following: proteins, surfactants, sugars, organic and inorganic salts, anti-coagulants, etc. In one non-limiting example, the coating could be applied to an initially un-coated separation material to prevent hemolysis. Optionally, an initially coated separation material may be further coated to prevent assay interfering substances from leaching into the bodily fluid from the separation material.3. Charge Neutralization: In one embodiment described herein, separation material surface charge can be neutralized to prevent retention of small, oppositely charged ions. For example, the separation material with NTA coating has a negatively-charged surface, which can be neutralized to prevent retention of positively charged Ca++ ions. Optionally, if a coating has a positively-charged surface and is in turn attracting negatively charged ions in a detrimental manner, the member will be treated to neutralize the undesired charge condition.4. Other techniques and/or materials may also be used to create a filter such as a separation material that has anti-hemolytic qualities on the capture surfaces of the filter and non-leaching qualities on other surfaces of the filter. Some embodiments may combine one or more of the foregoing techniques on a separation material. By way of non-limiting example, one embodiment may have coated and uncoated regions on a separation material along with having been treated to achieve charge neutralization before, during, and/or after coating. Examples: Using a dynamic wash technique, asymmetric membranes were washed with high performance liquid chromatography (HPLC) grade water and then tested. In one non-limiting example, the membrane has a pore volume of 2 μL per 10 mm2of membrane. The pore loading is defined as the ratio of the total volume of blood to the pore volume. For a blood volume of 40 μL with membrane surface area of 100 mm2, this corresponds to a pore loading of2X. The wash procedure comprised pre-mounting membrane in a fixture for filtration. In this particular example, about 600 uL of water is directed through the membrane and then the water is discarded. This wash process of directing water through the membrane was repeated, which in this particular example, involved repeating the wash five (5) times. After washing, the membranes are allowed to dry. Filtration of the dynamically washed membranes were then tested. Washing by way of soaking (“static wash”) rather than the flow-through technique (“dynamic wash”) can create differences in the performance of the resulting membrane. In at least some static washed membranes, anti-hemolytic is preferentially removed from the large pore region. In at least some dynamic wash membranes, anti-hemolytic is preferentially removed from the small pore region. This asymmetry in coating material may be desirable when the formed blood components contact the membrane where the pores are larger while only plasma contacts the smallest pores. Hemolysis prevention happens only in the regions where RBCs can enter or be contacted (i.e. the large pore region). It is not possible to hemolyze plasma and thus coating the small pore region with anti-hemolytic does not result in noticeable performance benefit. As noted herein, the excess anti-hemolytic may have adverse impact on assay results for the assays sensitive to excess anti-hemolytic coating. In static wash, diffusion dominates removal of anti-hemolytic. In some embodiments of the membrane, large pores may be ˜50× bigger than small pores. Mass diffusion rate is proportional to cross sectional flow area. Thus diffusion rate of anti-hemolytic away from membrane on large pore side may be ˜2500× greater than on small pore side. Thus, without being bound to any particular theory, total removal should be much greater on large pore side, where the RBCs contact the membrane. In dynamic wash, shear dominates removal of anti-hemolytic. Shear increases dramatically with decreasing diameter. Without being bound to any particular theory, total removal should be greater in small pore regions, where shear is most significant. In yet another embodiment, the coating on the membrane can be a material that provides a negative charge. Without being bound to any particular theory, a negative charge repels formed blood component that have a negative polarity, and thereby reduces mechanical trauma inflicted on such formed blood components via contact with the membrane during filtration. Some embodiments may use formulations with negatively charged substances to coat all or optionally selective areas on the membrane. One embodiment may use casein 0.5%, Tween 20 1.35%, sucrose 5%, 15 minute soak time. Optionally, one embodiment may use Li-Heparin 50 mg/mL, sucrose 5%. Optionally, one embodiment may use Li-Heparin 50 mg/mL, Tween 80 1.35%, sucrose 5%. Optionally, one embodiment may use Casein 1.0%, Tween 20 2.70%, sucrose 5%. Optionally, one embodiment may use Li-Heparin 100 mg/mL, Tween 20 2.70%, sucrose 5%. Sample Processing Referring now toFIG.83, one embodiment of bodily fluid sample collection and transport system will now be described.FIG.83shows a bodily fluid sample B on a skin surface S of the subject. In the non-limiting example ofFIG.83, the bodily fluid sample B can be collected by one of a variety of devices. By way of non-limiting example, collection device1530may be but is not limited to those described herein. In the present embodiment, the bodily fluid sample B is collected by one or more capillary channels and then directed into sample vessels1540. The sample B forms through a wound that may be formed on the subject. This may be by way of fingerstick or wound created at other alternate sites on the body. By way of non-limiting example, a lancet, a needle, other penetrating device, or other technique may be used to release the bodily fluid sample from the subject. By way of non-limiting example, at least one of the sample vessels1540may have an interior that is initially under a partial vacuum that is used to draw bodily fluid sample into the sample vessel1540. Some embodiments may simultaneously draw sample from the sample collection device into the sample vessels1540from the same or different collection channels in the sample collection device. Optionally, some embodiments may simultaneous draw sample into the sample vessels. In the present embodiment after the bodily fluid sample is inside the sample vessels1540, the sample vessels1540in their holder1542(or optionally, removed from their holder1542) may placed in the sample verification device or directly into a storage device in a temperature controlled environment. In the present embodiment after the sample verification is completed, the sample vessels1540in their holder1542(or optionally, removed from their holder1542) are loaded into the transport container1500. In one non-limiting example, one of the sample vessels1540may contain only liquid portions of the sample (no formed blood components) which the other may contain sample with both liquid portion and formed component portion. In another non-limiting example, at least two of the sample vessels1540may contain only liquid portions of the sample (no formed blood components). In this embodiment, there may be one or more slots sized for the sample vessel holder1542or slots for the sample vessels in the transport container1500. By way of non-limiting example, they may hold the sample vessels in an arrayed configuration and oriented to be vertical or some other pre-determined orientation. It should be understood that some embodiments of the sample vessels1540are configured so that they hold different amount of sample in each of the vessels. By way of non-limiting example, this can be controlled based on the amount of vacuum force in each of the sample vessels, the amount of sample collected in the sample collection channel(s) of the collection device, and/or other factors. Optionally, different pre-treatments such as but not limited to different anti-coagulants or the like can also be present in the sample vessels. As seen inFIG.83, the sample vessels1540are collecting sample at a first location such as but not limited to a sample collection site. By way of non-limiting example, the bodily fluid samples are then transported in the transport container1500to a second location such as but not limited to an analysis site. The method of transport may be by courier, postal delivery, or other shipping technique. In many embodiments, the transport may be implemented by having a yet another container that holds the transport container therein. In one embodiment, the sample collection site may be a point-of-care. Optionally, the sample collection site is a point-of-service. Optionally, the sample collection site is remote from the sample analysis site. Although the present embodiment ofFIG.83shows the collection of bodily fluid sample from a surface of the subject, other alternative embodiments may use collection techniques for collecting sample from other areas of the subject, such as by venipuncture, to fill the sample vessel(s)1540. Such other collection techniques are not excluded for use as alternative to or in conjunction with surface collection. Surface collection may be on exterior surfaces of the subject. Optionally, some embodiments may collect from accessible surfaces on the interior of the subject. Presence of bodily fluid sample B on these surfaces may be naturally occurring or may occur through wound creation or other techniques to make the bodily fluid surface accessible. Referring now toFIGS.84to99, still other embodiments of manifolds and distribution patterns of the channels to the separator will now be described. In one embodiment, the device is configured for transverse filling of the channels along a shorter planar dimension of the separator versus along a lengthwise filling direction along a long dimension of the separator, particularly in a separator with an aspect ratio where at least one dimension along one axis is shorter than another dimension along another axis in the same plane. In one embodiment as seen in the cross-sectional view ofFIG.84, whether the plenum4000is separate from the whole blood channel or not, the lead-ins will be angled through channel(s)4002that route blood flow to distribution channel(s)4004over a separator4006, such as but not limited to the membrane. Optionally, some embodiments may include a vent4008at one end or other position along the distribution channel4004. As seen in this embodiment inFIG.84, the channel(s)4002from the plenum may be angled (from above or below) and not horizontal like the distribution channel4004. By way of non-limiting example, the angled conduit form plenum to distribution channels and membrane is only one embodiment of how sample may be transported from the plenum. Optionally, some embodiments may have both the channel4002and the distribution channel(s)4004parallel to each other and in the same plane. As seen inFIG.84, there may be a narrow area4010along the transition between the channel4002and the distribution channel(s)4004. A perspective view may be found inFIG.27D. As seen inFIGS.84and27D, an upper portion of sample in plenum4000is drawn into the channels4002to be moved along a path to separation such as into plasma when the sample is blood. A portion of sample that remains in the plenum4000travels along a different path and is collected without going through a separator. As seen inFIG.27D, on path exits via arrow4022(separated plasma) and the other pathway exits via arrow4024(whole blood). FIGS.85A-85Dshow various filling patterns. Illustrations of different filling scenarios in the manifold is shown with combined plenum.FIG.85A: Flow is essentially even and parallel. Sometimes there is a lag between the completion of plenum filling, and initiation of the lead-in flow.FIG.85B: Filling of the distribution channels and membrane occurs from upstream end to downstream. Based on previous observations, this type of behavior frequently corresponds to a situation where the lead-ins direct flow to the membrane as the plenum fills, rather than after the plenum filling has completed.FIG.85C: Filling order is from downstream to upstream, which is the reverse of what is shown inFIG.85B.FIG.85(d): One group of channels lags the others. FIG.86shows one embodiment where the plenum runs over the top of the separator and not through it or to the side. The membrane may be compressed to seal around the plenum4030. A separate channel4020in the device may be used for whole blood that will not be separated into plasma. Unlike the embodiment ofFIG.84where a single channel extends from an entrance to an exit containing both sample that will be separated and sample that will exit without being separated, this embodiment ofFIG.86uses separate channels4020and4030for the samples, depending on how the sample will be processed. FIGS.87and88show embodiments where additional membrane compression is employed around the perimeter of the plenum4030(except in the regions where that compression cannot be achieved due to the presence of the lead-ins). In this non-limiting example, this creates a membrane compression zone4050. Referring now to the embodiment ofFIG.89, one modification if the uncompressed membrane under the lead-ins is problematic is to use a thin film4040placed onto the bottom of the plenum area to create a “floor” for this channel, which separates the blood entirely from the non-functional region of the membrane underneath. The film may be formed from an inert material that does not interact with sample in the plenum4030. Optionally, the film may be Teflon film, a polymer film, a plastic film, or other material configured to not impact sample quality. Referring now toFIG.90, an additional variation of the device comprises placing the plenum on top of the membrane. In this variation the distribution channels do not branch, but rather they all connect directly to the plenum. Because angled through channels are not used when the plenum4030is directly on top of the membrane, it is not necessary to minimize the number of lead-ins by means of branching: there are no small, angled core pins or flash to worry about. Provided that the plenum region of the membrane can be adequately decoupled from the functional region of the membrane, each distribution channel4036could be directly fed by the plenum4030. In this non-limiting example, the benefit of this configuration is that it would enable better uniformity in the distribution of the blood over the membrane, and better control of the distribution of blood over the membrane. Referring now toFIG.91, the configurations with the plenum separate from the membrane use angled through channels for their lead-ins. This is noted inFIG.91. In this embodiment, the whole blood to exit from exit4024is drawn from the same plenum4000as sample on a path to exit a separate sample from exit4022.FIG.91shows that in some embodiments a common channel is used to provide sample to an outlet for outputting unseparated sample through outlet4024and for directing a portion of the sample along a path to a second outlet4022.FIG.91shows that the pathway through the separator may be by way of a single channel4002(angled or not) from the common channel and that this single channel may then spread to form multiple channels4004over the separation material. The transition from a single channel4002to multiple channels4004may more evenly distribute the sample. As seen inFIG.91, the channels4004may have different shapes depending on the desired distribution pattern.FIG.91shows that channels4004may form a “fork” pattern as they extend away from the channel4002. Some embodiments may form other patterns such as curved, spiral, star, radial tire spoke, or other geometric pattern. Most of these patterns are in direction lateral to, orthogonal to, or along the short axis, relative to a long longitudinal axis of the separation material. Referring now toFIGS.92and93, there are two layouts shown with the plenum on the side nearest the whole blood channel.FIG.92shows a version in which the plenum is centered on the inlet. There are advantages to the in-line configuration, such as simplicity and the fact that this layout will probably encourage rapid filling of the membrane.FIG.94shows a still further perspective view of the FIG.93shows yet another embodiment with the plenum adjacent to the whole blood channel. Here is that the plenum4030is not directly in line with the inlet. Rather, there is a curve just downstream of the intersection between the plenum and the inlet. What is gained is more range in the membrane aspect ratios that fit on the device. FIGS.95A to95Dshow various embodiments of distribution channel variation, from large and widely spaced, to no channels at all. As seen in thoseFIGS.95A to95D, there may be a vent4008at the end of the various distribution channels. FIGS.96and97show two possible configurations that employ deliberately unequal distribution of the blood over a separator such as but not limited to the membrane.FIG.96shows that the pitch between distribution channels4036can be reduced at one of end of the device.FIG.97shows that in addition to pitch variation between distribution channels, some embodiments may also various the diameter or cross-sectional area so that some channels have reduced size closer to where the sample is entering the plenum, so that more is directed towards those channels located further away from the inlet of the plenum. This may more preferentially direct sample flow so that the distribution of the sample is more even, without an initial rush that mainly fills the channels closest to the inlet of the plenum as seen inFIG.85B. Optionally, some embodiments may combine the features ofFIGS.96and97. Referring now toFIG.98, in one embodiment, the bed of capillary channels at the back of the membrane serves the dual purposes of helping the plasma to wick through the membrane, and providing a low-resistance flow pathway external to the membrane for the plasma to flow through during the extraction process.FIG.98shows perspective view of a “lower” portion of the device that is typically on the underside of the membrane, showing those structures that handle the fluid that has passed through the separation membrane. Optionally, capillary surfaces may be configured to exhibit the behavior known as “total wetting” in the presence of plasma. This corresponds to a contact angle of zero, meaning that the liquid will continue to spread until the volume of the capillaries is filled with plasma. This helps to achieve even flow through the membrane both prior to and during the extraction process. As seen in the magnified view ofFIG.98, at one end of the capillary channels near the extraction port to exit4022, the channels extend to an area just short of the end, so that a channel area4060is formed to route separated sample such as but not limited to plasms to the extraction port. FIG.99shows one embodiment where the membrane is compressed at location4100to provide a sealed perimeter. In one embodiment, the thickness used for compression is 100 μm. In one embodiment, the thickness used for compression is at least 100 μm. In one embodiment, the thickness used for compression is at least 90 μm but less than 110 μm. In one embodiment, the thickness used for compression is at least 80 μm but less than 110 μm. In one embodiment, the thickness used for compression is at least 70 μm but less than 110 μm. In one embodiment, the thickness used for compression is at least 60 μm but less than 110 μm. In one embodiment, the thickness used for compression is at least 50 μm but less than 110 μm. While the teachings has been described and illustrated with reference to certain particular embodiments thereof, those skilled in the art will appreciate that various adaptations, changes, modifications, substitutions, deletions, or additions of procedures and protocols may be made without departing from the spirit and scope of the invention. For example, with any of the above embodiments, it should be understood that the fluid sample may be whole blood, diluted blood, interstitial fluid, sample collected directly from the patient, sample that is on a surface, sample after some pre-treatment, or the like. Although the embodiments herein are described in the context of an anti-hemolytic coating, it should be understood that these embodiments may also be configured for use with other types of coatings, including but not limited to other coatings which may undesirably mix into the bodily fluid upon prolonged fluid exposure. Other material used with embodiments herein may include but is not limited to one or more of the following: anti-coagulants, proteins (BSA, HSA, Heparin, Casein, etc.), surfactants (Tween, Silwet, SDS, etc.), sugars (sucrose, trealose, etc.). It should be understood that in some embodiments, coatings of one or more of the following may be used to coat portions of fluid pathways of the device, only the channels of the distributor, only the non-channel portions of the distributor, sample collection areas, sample distributor area(s), channels, tubes, chambers, or other features of the device with: anti-hemolytic, anti-coagulants, proteins (BSA, HSA, Heparin, Casein, etc.), surfactants (Tween, Silwet, SDS, etc.), sugars (sucrose, trealose, etc.), or other coatings. Although the embodiments herein are described in the context of capturing formed components such as blood cells or platelets, it should be understood that these embodiments can also be adapted for use with fluid containing other solid, semi-solid, or formed components or particles. Although the embodiments herein are described in the context of separation material, it should be understood that these embodiments can also be adapted for use other filter materials such as meshes, porous layers, or other layer like materials or structures. In one embodiment described herein, a bodily fluid separation material is provided comprising a formed component capture region and a bodily fluid pass-through region. The pass-through region has structures with a reduced liquid leaching quality relative to than the capture region, wherein during separation material use, bodily fluid enters the capture region prior to entering the pass-through region. Optionally, a bodily fluid pass-through region has a reduced amount of liquid leaching material relative to than the capture region. In another embodiment described herein, a bodily fluid separation material is provided comprising an anti-hemolytic and formed component capture region; and a bodily fluid pass-through region having less anti-hemolytic material than the capture region, wherein during separation material use, bodily fluid enters the capture region prior to entering the pass-through region. In yet embodiment described herein, a bodily fluid separation material is provided comprising a first filter region of the separation material having an anti-hemolytic coating and mesh spacing sized to constrain formed blood components therein; a second filter region of the separation material having mesh spacing smaller than mesh spacing of the first filter region and configured to have an amount of anti-hemolytic coating less than that of the first region. In a still further embodiment described herein, a bodily fluid separation material is provided comprising a percolating network of structures wherein a first region of the percolating network with an anti-hemolytic coating on structures in the region, said structures sized and spaced to allow formed blood components to enter the first region but constraining blood components therein from passing completely through the first region; and a second region of the percolating network with a reduced anti-hemolytic coating on structures sized and spaced to prevent formed blood components from entering the second region, wherein bodily fluid passes through the first region prior to reaching the second region. It should be understood that embodiments herein may be adapted to include one or more of the following features. For example, the separation material may be an asymmetric separation material. Optionally, the anti-hemolytic material on the separation material comprises single and/or double alkyl chain N-oxides of tertiary amines (NTA). Optionally, the first region comprises a first separation material layer and the second region comprises a second separation material layer. Optionally, the separation material comprises a first separation material coupled to a second separation material. Optionally, the separation material comprises at least two separate separation materials. Optionally, there may be at least another region of the separation material between the first region and the second region. Optionally, the first region of the separation material may be in fluid communication with the second region. Optionally, the first region may be spaced apart from the second region. In yet another embodiment described herein, a method is provided for forming a bodily fluid separation material. The method comprises coating the separation material with an anti-hemolytic coating on a first region and a second region of the separation material; reducing anti-hemolytic effect of the second region of the separation material relative to the first region, wherein when the separation material is in operation, bodily fluid passes through the first region prior to reaching the second region. It should be understood that embodiments herein may be adapted to include one or more of the following features. For example, the method may include reducing the anti-hemolytic effect by washing off at least a portion of the anti-hemolytic coating on the second region. Optionally, washing off comprises directing solvent through the separation material. Optionally, washing off comprises soaking only a portion of the separation material in a solvent. Optionally, reducing the anti-hemolytic effect comprises adding another coating of a different material over the anti-hemolytic coating on the second region. Optionally, reducing the anti-hemolytic effect comprises treating the separation material to bring its electrical charge state to a neutral state and thus reduce the attraction of ions that increase the anti-hemolytic effect. In yet another embodiment described herein, a method is provided for forming a bodily fluid separation material. The method comprises coating at least a first region of the separation material with an anti-hemolytic coating; not coating at least second region of the separation material with the anti-hemolytic coating. Optionally, some embodiments have a bilayer structure based on a substantially even coating of anti-hemolytic material, but instead has a region of substantially greater pore size than another region. Although the material may be asymmetric, it is a not a linear gradient, but instead has a rapid change in pore size at an inflection point when pore size is graphed in depth from top of the layer to bottom of the layer. Additionally, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a size range of about 1 nm to about 200 nm should be interpreted to include not only the explicitly recited limits of about 1 nm and about 200 nm, but also to include individual sizes such as 2 nm, 3 nm, 4 nm, and sub-ranges such as 10 nm to 50 nm, 20 nm to 100 nm, etc . . . . The publications discussed or cited herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided may be different from the actual publication dates which may need to be independently confirmed. All publications mentioned herein are incorporated herein by reference to disclose and describe the structures and/or methods in connection with which the publications are cited. The following applications are fully incorporated herein by reference for all purposes: U.S. Pat. App. Ser. No. 62/051,929, filed Sep. 17, 2014; U.S. Pat. Nos. 8,088,593; 8,380,541; U.S. patent application Ser. No. 13/769,798, filed Feb. 18, 2013; U.S. patent application Ser. No. 13/769,779, filed Feb. 18, 2013; U.S. Pat. App. Ser. No. 61/766,113 filed Feb. 18, 2013, U.S. patent application Ser. No. 13/244,947 filed Sep. 26, 2011; PCT/US2012/57155, filed Sep. 25, 2012; U.S. application Ser. No. 13/244,946, filed Sep. 26, 2011; U.S. patent application Ser. No. 13/244,949, filed Sep. 26, 2011; U.S. Application Ser. No. 61/673,245, filed Sep. 26, 2011; U.S. Patent Application Ser. No. 61/786,351 filed Mar. 15, 2013; U.S. Patent Application Ser. No. 61/948,542 filed Mar. 5, 2014; U.S. Patent Application Ser. No. 61/952,112 filed Mar. 12, 2014; U.S. Patent Application Ser. No. 61/799,221 filed Mar. 15, 2013, U.S. Patent Application Ser. No. 61/697,797 filed Sep. 6, 2012, U.S. Provisional Patent Application, 62/216,359 filed Sep. 9, 2016, U.S. Patent Application Ser. No. 61/733,886 filed Dec. 5, 2012, U.S. Provisional Patent Application Ser. No. 62/471,918 filed Mar. 15, 2017, and U.S. Provisional Patent Application Ser. No. 62/468,905 filed Mar. 8, 2017, the disclosures of all of the foregoing are all hereby incorporated herein by reference in their entireties for all purposes. While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. Any feature, whether preferred or not, may be combined with any other feature, whether preferred or not. The appended claims are not to be interpreted as including means-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase “means for.” It should be understood that as used in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. For example, a reference to “an assay” may refer to a single assay or multiple assays. Also, as used in the description herein and throughout the claims that follow, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise. Finally, as used in the description herein and throughout the claims that follow, the meaning of “or” includes both the conjunctive and disjunctive unless the context expressly dictates otherwise. Thus, the term “or” includes “and/or” unless the context expressly dictates otherwise.
149,981
11857967
Like reference numerals have been used to identify like elements throughout this disclosure. DETAILED DESCRIPTION As described herein, porous monolithic structures are formed which can be integrated within microfluidic systems to facilitate processing of fluids such as bodily fluids (e.g., fluids including blood) and other types of fluids. The microfluidic systems incorporating monolithic structures can be configured to isolate and concentrate different types of bacteria for further analysis, where the monolithic structures are configured to separate components (e.g., by lysing and/or separating blood cells and/or other components) within a fluid passing through the monolithic structures while substantially permitting passage of intact bacteria within the fluid for further analysis downstream from the monolithic structures. In certain embodiments, porous monolithic structures are initially formed within capillaries and are then integrated within a microfluidic system utilizing one or more capillary clamps that effectively maintain the capillaries in position while the capillaries are secured at selected locations of the system. In such embodiments, the one or more capillary clamps effectively hold the capillaries in proper position or alignment with one or more channels of the microfluidic system while a thermoplastic material is melted to flow or reflow around the capillaries such that, upon solidification of the material, the capillaries are effectively secured to a support of the system (e.g., a microfluidic chip). Further, at least some of the capillary clamps can comprise the thermoplastic material that is melted to flow around capillaries and then solidified to secure the capillaries to the support. Utilizing thermoplastic flow material to secure the capillaries in position with the microfluidic support further effectively seals the capillaries with low dead volume. The sealing further provides a substantially fluid tight barrier between the flowed clamp structure and a portion of the capillary to which the clamp structure is connected so as to ensure fluid flows through (and not around) the capillary and porous monolithic structure disposed within the capillary. In other embodiments, porous monolithic structures are initially formed as rod like structures within channels defined in a mold, where the rod like structures are subsequently removed from the mold. In such embodiments, individual monolithic structures can be cut from the rod like structures to form smaller porous monolithic structures or “bricks”. The monolithic brick structures can have any suitable sizes and cross-sectional shapes (e.g., cross-sectional shapes that are circular or round, polygonal such as rectangular or square, elliptical or oval, etc.), including long brick structures having large length to diameter (or transverse cross-sectional dimension) ratios, as well as small brick structures that have a surface area that is much larger than the thickness/length of each brick. When the monolithic brick structure is integrated within a microfluidic system, the thickness of the monolithic brick defines the flow path of fluid or path length through the brick. In small sized brick structures, the surface area of the fluid flow path (defined by the surface area of the brick) is much greater than the length of the fluid flow path through the monolithic brick. In particular, the flow path surface area (SA) is defined as the area of the monolithic brick structure that is orthogonal to the flow path through which fluid flows through the brick structure, while the flow path length (L) is the length of the fluid flow path through the brick structure. The porous monolithic brick structure can be dimensioned such that the ratio of SA/L is greater than 1. This facilitates a greater throughput of fluid to be processed by the brick structure during operation in relation to standard or conventional sized filtration or separation columns (which typically have high length to diameter or L/D ratios that are greater than 1). In other embodiments, a porous monolithic brick structure can have a SA/L ratio that is no greater than 1 (e.g., greater than 0.1 but no greater than 1.0), where the brick structure can have a length that is much greater than its transverse cross-sectional dimension. As used herein, the term “microfluidic system” refers to a fluid processing system including components having sizes on the sub-millimeter scale. For example, a microfluidic system can include a chip (e.g., a small scale component having a “lab-on-a-chip” configuration) having sub-millimeter or micron size components including channels having dimensions (e.g., length, diameter/width and/or depth) on the order of 10,000 microns (micrometers) or less, 1,000 microns or less, 100 microns or less, or even 10 microns or less. The microfluidic systems can further process fluids at flow rates from, e.g., about 5 microliters per minute to about 1 milliliter per minute or greater. The present invention can integrate monolithic structures within one or more supports of any suitable microfluidic system. In example embodiments, the microfluidic system comprises one or more base platforms or chips. The microfluidic chips can be formed from any thermoplastic and/or other suitable materials including, without limitation, glass, silicon or silane based materials such as PDMS (polydimethylsiloxane), cyclic olefin polymer (COP) materials, etc. The chips are configured to include channels that facilitate flow of fluids through the channels (e.g., via micro-pumping or capillary action) in small volumetric sizes (e.g., in μL) so as to facilitate a variety of different operations for the microfluidic system (e.g., for DNA or other molecular screening, separation and/or analysis for a variety of different applications). In example embodiments, the microfluidic chips may be configured for insertion within an instrument within a laboratory environment or for field use in which fluids are analyzed and/or processed for different applications. Examples of microfluidic systems including one or more chips within which monolithic structures may be integrated in accordance with techniques as described herein are described in U.S. patent application Ser. No. 14/893,689 (published as US Patent Publication No. US 2016/0115520 A1), the disclosure of which is incorporated herein by reference in its entirety. The chips of the microfluidic systems can include one or more different process areas or stations which process fluids flowing through the channels of the chip. Monolithic structures that are integrated within a chip of the microfluidic system can be configured as a process station for the chip, where the monolithic structures perform a particular processing function for fluid flowing through the monolithic structures. The monolithic structures can perform a variety of different processing operations for fluids flowing within the chip including, without limitation, separation of analytes within the fluid, filtration of the fluid, biosensing of components within the fluid, and lysing of components within the fluid. The monolithic structures can be formed of any suitable materials (e.g., silica based materials acrylate materials such as methacrylates, etc.) and via any suitable techniques to obtain a suitable porosity with desired pore dimensions throughout the structures. The pore dimensions are preferably sized to be sufficiently large to accommodate passage of intact bacteria of interest through the pores while lysing and/or separating blood cells or other components from a fluid flowing through the monolithic structures. The types of blood cells that can be lysed and/or separated from the fluid within the monolithic structures include red blood cells, white blood cells and platelets. Example pore sizes for the monolithic structures can range from about 0.5 μm to about 10 μm, such as from about 1 μm to about 5 μm. The monolithic structures can be suitably configured such that the passage rate of bacterial components (i.e., bacteria) within a fluid flowing through the monolithic structures is at least about 90%, at least about 95%, at least about 99% and very nearly 100%. The passage rate of bacteria is determined as (((number of bacteria in fluid exiting a monolithic structure)−(number of bacteria in fluid entering monolithic structure))/(number of bacteria in fluid entering monolithic structure))×100. The monolithic structures can further be suitably configured such that the passage rate of certain components, such as blood cells (e.g., red blood cells) within a fluid flowing through the monolithic structures no greater than about 10%, such as no greater than about 5% or even no greater than about 1%. The passage rate of components (e.g., red blood cells) is determined as (((number of components in fluid exiting a monolithic structure)−(number of components in fluid entering monolithic structure))/(number of components in fluid entering monolithic structure))×100. In example embodiments, monolithic structures are formed via a sol-gel process within small diameter tubes or capillaries, where the capillaries are then segmented for integration/connection with one or more microfluidic chips. In other example embodiments, monolithic structures are formed via a sol-gel process within channels of a mold, where rod-like monolithic structures can then be removed from the mold for integration within a microfluidic system as described herein. Porous silica synthesis involves a competitive process of sol-gel transition and separation into a co-continuous binary phase via spinodal decomposition of a liquid mixture of alkyl silicates and porogen in acidic solution. Hydrolysis and condensation of silica are the major reactions which enable the formation of silica glass from liquid alkyl silicate at relatively low temperature. As the chemical reactions progress, entropic loss from the condensation of two silanol groups increases the Gibbs free energy, leading to separation into silicate-rich and solvent-rich phases. Slow hydrolysis under acidic conditions is required to uniformly hydrolyze all alkyl silicates, followed by a gradual increase in pH to trigger the condensation reaction to induce homogeneous phase separation in the mixture, resulting in the formation of the single porous monolithic structure. As further described herein, techniques are provided for selective lysing of components within a fluid utilizing one or more monolithic structures integrated within a microchip of a fluid processing system, where a monolithic structure selectively separates and/or lyses certain components from a fluid flowing through the monolithic structure while facilitating pass through flow of certain bacteria such that the bacteria remains intact within the fluid after passing through the monolithic structure. The intact bacteria can then be separated from the other components (e.g., based upon a size difference between lysed components and the intact bacteria), where the intact bacteria is then detected and identified within the fluid in a rapid manner within the microchip and/or fluid processing system, e.g., utilizing methods as described in U.S. patent application Ser. No. 14/893,689. It is noted that this is a significant distinction from previous attempts to utilize porous monolith structures to process bacteria, where the monolith structures were used to lyse the bacterial cells, e.g., in order to access markers such as DNA and/or other components of the bacterial cells. In contrast, in accordance with the present invention, porous monolithic structures are utilized to separate bacterial cells from other components within a fluid by maintaining the bacterial cells intact (i.e., substantially no lysis of the bacterial cells occurs during process of the fluid flowing through the porous monolithic structures). In particular, selective cell lysis utilizing a porous monolithic structure (e.g., a silica monolith) provides a simple flow-through method for intact bacteria isolation. This technique is very effective for identifying particular types of bacteria in a blood sample analyzed utilizing a microfluidic system as described herein. Further, porous monolithic structures can be integrated within a microfluidic system to provide high throughput processing of samples (i.e., a further advantage in relation to conventional blood or other fluid processing systems). However, the techniques enabled by the present invention are not limited to processing/analyzing blood samples. The present invention also facilitates processing/analysis of other types of fluids including, without limitation, urine, sputum, pharmaceutical processing streams, cerebrospinal fluid, etc. Other example processes that can be implemented utilizing the present invention include food safety testing, water testing, pharmaceutical production, etc. The porous monolith structure serves to induce high mechanical shear stress during cell perfusion through the monolith, enabling efficient lysis and/or separation of certain components, e.g., blood cells including erythrocytes or red blood cells, leukocytes or white blood cells, and platelets, while maintaining the integrity of bacteria (e.g., gram positive, gram negative and/or gram variable bacteria, or other micro-organisms, viruses, fungi, etc.) traversing the porous flow path. The components can have sizes larger than, smaller than and/or similar in size as the bacteria, where larger sized components can be lysed by shear stresses applied when passing through smaller sized pores, and smaller sized components (e.g., components at about the same size or smaller in relation to the bacteria of interest) can also be lysed based upon the fragility of the outer surface or cell membrane of the components in relation to the more rigid or robust bacteria of interest within the fluid being processed. Utilizing techniques as described herein, efficient selective lysis can also be achieved for certain gram negative as well as gram positive and gram variable bacteria which may be more prone to unwanted shear-induced lysis due to the lack of an outer lipopolysaccharide cell membrane. Robust operation over a wide range of bulk flow rates and flow velocities is enabled utilizing the techniques as described herein. The use of selective mechanical lysis is also shown to result in smaller blood cell fragments than chemical lysis, thereby conferring a greater size difference between bacteria and lysate particles for improved downstream separation. As used herein, the term “bacteria” is understood to generally represent all forms of bacterial, fungal, viral, and other microorganisms (unless it is clear from the context that only bacteria or some other microorganism is being discussed). Formation of a Monolithic Structure within a Capillary or a Mold An example embodiment of a process for formation of a monolithic structure within a capillary or a mold via a sol-gel process is described with reference toFIGS.1and2. The silica monolith was prepared from a precursor solution (Step2inFIGS.1and2) comprising alkyl silicates, with PEG (polyethylene glycol) as a porogen, urea as a source of hydroxyl ions, and acetic acid as a solvent. The addition of urea in the starting mixture is effective in minimizing heterogeneity of gel that forms. Unlike conventional methods for forming porous silica, which increase pH of the system by direct infusion of basic solution, urea can be thermally decomposed at temperatures above 80° C. leaving ammonia and methanol as products. Use of urea thus obviates the need for physical infusion of basic solution which can disrupt the soft gel phase. The source of silica for the process was provided using a mixture of TMOS (tetramethoxysilane) and MTMS (methyltrimethoxysilane). This mixture was selected as the source of silica to overcome the intrinsic volume contraction associated with a pure TMOS recipe, in which four methoxyl groups serve as crosslinking points during the condensation reaction. By using MTMS as an alkyl silicate with only three crosslinking points and one inert group, volume contraction was suppressed so that porous morphology can be uniformly formed without localized shrinkage. The precursor mixture was prepared by adding PEG and urea into acetic acid solution and stirred in an ice bath (e.g., 0.5 g PEG and 1.02 g urea added to 10 mL of 0.01 M acetic acid, depicted as step2inFIG.2). The silica source compounds, TMOS and MTMS, were then added (e.g., in an amount of 85:15 v/v ratio of TMOS to MTMS) to the solution (e.g., 4.5 mL of the TMOS/MTMS solution added to the acetic acid mixture) and stirred for a suitable time period (e.g., about 30 minutes). After mixing, the solution was loaded into a suitable structure (Step4ofFIGS.1and2). In some embodiments, the solution was loaded into a selected length of glass capillary tubing on the micron size internal diameter (e.g., capillary tubing from Polymicro Technologies having a 100 μm internal diameter, 360 μm outer diameter) and using a 0.45 μm PTFE (polytetrafluoroethylene) syringe filter. In other embodiments, the syringe filter was utilized to inject the solution into channels of a poly methyl methacrylate (PMMA) mold. The ends of the capillary and the mold were sealed and the solution was gelled by being heat treated at a suitable temperature (e.g., at 40° C. for about 10 hours), with further heat treatment (e.g., about 85° C. for about a 24 hour period), in which hydrolysis and condensation reactions occur (depicted as step6inFIGS.1and2). Further heat treatment (e.g., calcination, depicted as step8inFIGS.1and2) was also applied as needed to remove any excess solvent and organic compounds and solidify/form the monolithic structure within the capillary and within the channels of the mold. The monolith formation process can be selectively optimized so that the monolithic structure is homogeneous and further well-anchored to the silica capillary walls. In particular, attachment of porous silica to the glass capillary during the process is the result of covalent bonding during condensation reaction between silanol groups on the capillary wall and the growing silica gel phase within the monolith (forming Si—O—Si covalent bonding between monolithic structure and interior wall surface portions of the capillary). Thus, a fluid tight connection can be achieved between the monolithic structure and the interior walls of the capillary solely by bonding during the condensation reaction such that no shrinking process step is required to shrink the internal diameter of the capillary against the monolithic structure formed therein. In an example embodiment in which a monolithic structure is formed within a glass capillary utilizing the techniques described herein, the monolithic structure formed was characterized having a thickness of 2.0 μm±0.3 μm and with average pore dimensions within the structure of 2.4 μm±0.8 μm. An electron micrograph image showing a cross-section of the silica monolith formed within the glass capillary is depicted inFIG.3and shows a substantially uniform porosity with excellent wall anchoring of the monolithic structure. In an example embodiment in which a monolithic “brick” structure is formed utilizing the PMMA mold, a rod-like structure can be removed from the PMMA mold and cut into one or more monolithic bricks, where each brick can be formed having a surface area that is significantly greater than its thickness (resulting in a flow path surface area to length ratio for the monolithic brick that is greater than 1). In other embodiments, longer brick structures can be cut from the rod-like structures so as to have a length dimension that is much greater than the transverse cross-sectional dimension (e.g., width or diameter dimension). Formation of a Capillary Encased Monolithic Structure within a Microfluidic Chip Utilizing Clamping Structures The capillary encased monolithic structures are incorporated within a microfluidic chip as described herein and with reference toFIGS.4and5. In example embodiments, thermoplastic chips are formed of a cyclic olefin polymer (COP), such as a cyclic olefin copolymer, and capillary encased monolithic structures are integrated within such COP chips. Referring to Step70(FIG.4) andFIG.5A, a capillary encased monolithic structure40formed, e.g., utilizing a technique such as previously described herein, is cut into suitably sized segments42(e.g., segment sizes ranging from about 250 μm to about 5 mm), where each segment42includes an opening at each of its lengthwise ends and with a monolithic structure44disposed within the segment42. At Step72(FIG.4), a chip structure including first (upper) and second (lower) chip substrate portions is provided for integrating one or more monolithic structure segments42into the chip. In particular, referring toFIG.5B, a chip10includes a first or upper COP substrate20and a second or lower COP substrate30(e.g., 1020R chip substrates available from Zeon Chemicals, Kentucky) that combine at their facing surfaces22,32(e.g., a first surface22and a second surface32) to provide a fluid tight interface when brought together and bonded and sealed to form the chip. At Step74(FIG.4), the chip substrates20,30are processed to form channels and clamping structures along facing surfaces of the chip substrates. For example, the chip substrates22,32are suitably milled in an aligned manner (e.g., utilizing a CNC milling machine) to include suitable micron sized grooves along one or both of their facing surfaces22,32(FIG.5B) such that, when combined, the substrates define enclosed microfluidic channels60and other features. In particular, each chip substrate20,30can be milled at its first surface22/second surface32to a depth of about 250 μm or less (e.g., about 180 μm or less, where depths can be varied along each chip substrate for a particular application). The milling of each substrate20,30can include a raised surface portion25,35that serves as a COP clamp for securing a capillary segment within the formed chip10as described herein. In particular, the raised surface portions25,35can be formed by milling short regions to a depth that is less than the depth of the surrounding area forming a channel. For example, milling short regions to a depth of about 75 μm or less in relation to other portions of a channel (milled, e.g., to a depth of about 250 μm or less) results in the formation of the raised surface portions within the formed channels. Thus, the clamp structures are integral with and part of the chip substrates (since they are formed as material portions of the chip substrate that are within a formed groove or channel of the substrate). In other embodiments, the clamp structures can instead be provided as separate structures added into a formed groove or channel along a chip substrate surface (where the reflow steps as described herein facilitate securing of the clamp structures within the chip substrate channels). After machining/milling of the substrates20,30, the raised surfaces25,35are processed (e.g., cleaned, polished, etc.) at Step76(FIG.4) and prior to securing a capillary encased monolithic structure44between the substrates. For example, the raised surfaces25,35of the substrates can be cleaned and/or polished by sonication in methanol, acetone, and deionized water and then dried (e.g., in a vacuum oven). The substrates20,30can then be exposed to a decalin/ethanol (33/67 vol %) solution for a suitable time period (e.g., about 1.5 minutes) so as to enable solvent bonding of the COP components and to soften the raised surface portions25,35(also referred to herein as the capillary clamp structures) to support polymer reflow during the bonding process as described herein. As depicted inFIG.5B, the raised surface portions or clamp structures25,35for the upper and lower chip substrates20,30are aligned so as to be in a vertically stacked orientation in relation to each other (with clamp structure25being located directly over clamp structure35) when the substrates20,30are brought together to form the chip10. However, in alternative embodiments and depending upon a particular desired configuration, clamp structures for the upper and lower chip substrates20,30can also be offset from each other. At Step78(FIG.4), a capillary segment42is inserted between the chip substrates20,30and the clamp structures25,35are melted and reflowed, where portions of the melted clamp structures flow around and secure the capillary segment42in place within one or more channels60of the chip. Referring toFIG.5C, a capillary segment42is inserted against the surface32of the lower substrate30so as to further align and engage with the clamp structure35defined along the substrate surface32. The upper substrate20can then be placed on the lower substrate30such that the upper clamp structure25engages the capillary segment42. Referring toFIG.5D, the clamp structures25,35are then melted to deform and enable a COP flow or reflow of the clamp structure material around the capillary segment42that effectively secures or locks the capillary42segment in place within the chip10. In an example embodiment, the assembled components (upper substrate20, capillary segment42and lower substrate30) are placed within a hot press (e.g., an AutoFour/15 press available from Carver Inc., Indiana) and a suitable temperature (also referred to herein as a reflow temperature) and pressure are applied to effectively melt and flow the COP clamp material around the capillary segment42as well as bond other surface portions22,32of the upper and lower substrates20,30together thus forming the chip10. While temperatures and pressures can vary based upon the materials used and geometric configuration of the clamping structures, chip, capillary, etc., some example temperatures and pressures that can be utilized to reflow the COP clamp material around a capillary segment and/or bond other surface portions of the chip substrates together can include reflow temperatures ranging from about 80° C. to about 100° C. (e.g., from about 85° C. to about 95° C.) and pressures ranging from about 3000 kPa to about 6000 kPa (e.g., from about 3400 kPA to about 5500 kpA). This combined melt deformation of the clamp structures25,35and bonding of the upper and lower substrates20,30together at the interface defined by their facing surface portions22,32effectively provides a fluid tight seal for the chip10. The deforming of the clamp structures25,35by melting and flowing or reflowing the COP chip material results in bonding the capillary segment42in place within the chip10and also provides a fluid tight seal within microfluidic channels around the capillary segment42(i.e., not permitting fluid flow between the outer wall portions of the capillary segment42and the surface portions22,32of the substrates20,30at the locations of the clamp structures25,35that have now been deformed/melted). A magnified view is shown in the image ofFIG.6of a portion of a microfluidic chip including a capillary segment secured between upper and lower substrates using clamping structures that are melted and reflowed around the segment as described herein and depicted inFIGS.4and5. As shown in the magnified image ofFIG.6, the COP deformed/reflow material50provides an effective seal around the entire circumference of an outer surface portion of the capillary segment42. The location and alignment of the clamp structures25,35also facilitate suitable alignment of the open ends of the capillary segment42with fluid channels60defined in the chip10between the two substrates20,30. By integrating a monolithic structure within a capillary segment, the capillary wall provides a rigid protective barrier for the monolithic structure thus allowing sufficiently high pressures for bonding the two chip substrates together without the risk of fracturing portions of one or more monolithic structures during assembly. The capillary clamps25,35further provide an effective and relatively easy alignment and sealing (with melting, deformation and flow or reflow of the clamp material) around the capillary so as to ensure that fluid flows through only the capillary segment42(and thus through the monolithic structure44disposed therein) at such channel portion within the chip. Further, due to the Si—O—Si bonding between the monolithic structure44and the interior wall surface portions of the segment42, the fluid is also substantially forced through the monolithic structure44(i.e. substantially no fluid flows completely around the monolithic structure44at a location between the monolithic structure44and an interior wall surface portion of the segment42). While the example embodiment ofFIGS.5and6include clamp structures25,35at both the upper and lower substrates20,30of the chip10, the present invention is not limited to such embodiment but instead can include a single clamp structure at only one of the two substrates while still effectively aligning and sealing the channel when the capillary encased monolithic structure is integrated within the chip. Alternatively, the chip10can include a plurality of clamp structures to support and secure a capillary segment therein, where one or more clamp structures are configured to melt and deform during the chip formation while other clamp structures are not melted/deformed but instead maintain their original configurations. For example, certain clamp structures can be formed of a suitable thermoplastic material (e.g., COP) while other clamp structures are formed of different materials (e.g., silica) that maintain their shape during the melt/deformation of the thermoplastic clamp structures. Clamp structures disposed on the upper and lower chip substrates can be aligned to correspond with each other (e.g., as in the embodiment ofFIGS.5and6) or, alternatively be offset from each other. Further, any selected number of clamp structures (e.g., one or more) having any suitable one or more different shapes and sizes can be provided to clamp or secure one or more capillary encased monolithic structures within channels of the chip. In particular, the clamp structures can have any suitable shapes and/or dimensions that facilitate easy engagement with and alignment of a capillary segment between two chip substrates. The capillary used to encase the monolithic structure can further have any suitable dimensions and/or cross-sectional shapes including, without limitation, circular/round, elliptical, square or multi-faceted, etc. The clamp structures can also be provided with one or more capillary engaging surfaces that correspond with the outer surface contour of the capillary so as to facilitate easy engagement with a capillary segment inserted against the clamp structure. For example, a clamp structure can have a capillary engaging surface with a cross-sectional shape that is concave so as to facilitate nesting of a portion of a capillary segment having a rounded or circular cross-sectional shape within the engaging surface of the clamp structure. While at least some of the clamp structures25,35for the chip10are preferably formed from thermoplastic materials so as to facilitate a melting deformation and reflow of the material around the capillary encased monolithic structures as described herein, the chip substrates that define portions of the chip can be formed from the same or different materials as the thermoplastic clamp structures. For example, the chip substrates can be formed from the same material (e.g., a COP) as the clamp structures as described in the example embodiments. Alternatively, the chip substrates can be formed from a different material such as a material having a much higher melting point than the clamp structure material (e.g., the chip substrates can be formed from silica or glass), with channels formed (e.g., machined or etched) in the substrate surfaces and further with thermoplastic clamp structures provided in such channels (e.g., via a deposition process that forms a thermoplastic clamp structure within a channel). For example, a microfluidic chip may be formed of a silica based material and have channels and silica based clamp structures formed within the channels via an etching or other suitable process, where thermoplastic clamp structures can then also be formed within the channels by deposition of a suitable thermoplastic material (e.g., COP) within the channels. The chip substrates used to form the chip can include channels formed along a surface such that, when the chip substrates are combined with each (e.g., as in the embodiment ofFIG.3), the channels of each chip substrate correspond so as to define a microfluidic channel within the formed chip. In alternative embodiments, a single chip substrate can include a channel with no corresponding channel on the other chip substrate such that the microfluidic channel is defined solely by the channel of the single chip substrate. In such embodiments, clamp structures can still be provided for either or both chip substrates that secure a capillary segment within the formed chip in a similar manner as described for the embodiments ofFIGS.3and4. As previously noted, one or more porous monolithic structures can be integrated into a microfluidic chip so as to define a particular station within the chip for performing a particular processing function on a fluid flowing through the microfluidic channels of the chip. For example, a plurality of porous monolithic structures can be integrated within the microfluidic chip in a continuous flow pattern (i.e., in series) or in a parallel configuration. The integration of porous monolithic structures encased with capillaries within a microfluidic chip as described herein provides a number of advantages over conventional techniques for providing porous monoliths within a chip. For example, conventional methods for providing porous monoliths within channels of a chip, where a porous monolithic structure can be formed in situ within a channel of the chip can lead to issues such as incomplete sidewall anchoring, large variations in pore size and density within the monolith, etc. In addition, in methods where a porous monolith is prepared and then inserted within a channel of a chip, the porous monolith can be damaged when subjected to high temperatures and/or pressures during bonding/securing of the monolith within the channel of the chip. In the present invention, by forming the porous monolithic structure within a capillary and then securing a capillary encased monolithic segment in a chip channel, the capillary protects the monolithic structure during application of heat and pressure to secure the structure within the chip channel. In addition, the use of clamp structures within the chip channel that are melted provide a flow of the clamp structures around so as to secure the capillary encased monolithic segment in place within the chip channel while ensuring fluid flow is through (and not around) the porous monolithic structure within the capillary segment. Formation of a Monolithic Brick Structure within a Microfluidic Chip Porous silica monolithic bricks were obtained from the silica rod-like structures formed in channels of the PMMA mold (as previously described herein with reference toFIGS.1and2). After formation of the monolithic structures within the PMMA mold, the mold is opened and silica monolithic rods are removed from the mold and cut into segments or bricks. For example, the rods can be formed in square channels so as to have square cross-sections, and bricks can be formed having 3 mm×3 mm surface area dimensions and a thickness dimension of about 2 mm. However, it is noted that the bricks can formed having any suitable cross-sectional shapes (e.g., circular, polygonal, elliptical, etc.) and dimensions as desired for a particular process (where the shapes and dimensions can be defined by the channel shapes and dimensions formed in the PMMA mold and also the length at which the bricks are cut from the monolithic rods removed from the mold). The formed silica monolith bricks were integrated into COP thermoplastic chips in the following manner. Prior to milling, COP pellets were formed into 4 mm and 2 mm thick substrates using a hot press. Using a CNC milling machine, a 2 mm diameter and 3 mm deep hole was first formed in a 4 mm thick lower substrate, together with a 3 mm square and 2 mm deep depression or socket for the monolith brick, resulting in a square socket for monolith insertion and a 1 mm deep, 2 mm diameter indentation at the bottom of the socket. An additional 3.2 mm wide and 100 μm deep slot was milled around the perimeter of the socket. This slot served as a receptacle to receive solvated COP after insertion of the monolithic brick into the socket (so as to improve sealing of monolith during the final bonding step). A 2 mm diameter and 1 mm deep hole was then milled in a 2 mm thick upper COP substrate, and needle sized ports or channels extending through both substrates for external fluidic interfacing were formed on both substrates using a 650 um drill bit. The needle sized ports provide a connection with inlet and outlet channels or conduits of the formed chip so as to facilitate a fluid flow path from an exterior surface of one substrate to the slot formed on the interior surface of the substrate, through the monolithic brick, to the slot formed on the interior surface of the substrate and then to the exterior surface of the other substrate. In other words, each of the first and second substrates includes a channel extending through the substrate to the brick structure to provide a fluid flow path through the each of the first substrate, the second substrate and the brick structure. The needle sized ports can have cross-sectional channel (e.g., diameter) dimensions that are 10,000 microns (micrometers) or less, 1,000 microns or less, 100 microns or less, or even 10 microns or less. Each COP substrate was sonicated in methanol, acetone, and deionized water, and dried in a vacuum oven. A 2 mm diameter circular section of pressure-sensitive wafer dicing tape was patterned using a 2 mm diameter PDMS punch and adhered to the center of a porous silica brick to protect the fluidic path during monolith integration. In this process, the lower COP substrate was exposed to a decalin/ethanol (33/67 vol %) solution for 2 minutes, and the silica monolith brick was manually inserted into the monolith socket. After insertion, a solvated COP solution, prepared by slowly dissolving COP pellets in decalin to a concentration of 30 wt %, was applied using a doctor blade into the slot of the lower substrate defined around the slot into which the silica monolithic brick was inserted. The lower substrate was sufficiently dried at room temperature to evaporate decalin and to solidify the solvated COP, after which the protection tape was carefully removed from the monolith. Next, the lower and upper substrates were exposed to the same decalin/ethanol solution and bonded together in a hot press at 300 psi for 5 minutes at 35° C. Bonded devices were dried overnight in a 60° C. oven to remove excess solvent. The formed structure defines a monolithic brick encased microfluidic chip100as depicted inFIG.7. In particular, the chip100includes the lower substrate102and the upper substrate104, each including a needle sized port (e.g., port106defined in upper substrate104, the lower substrate102has a similar port not visible in the view ofFIG.7) extending through the substrate to provide inlet and outlet fluid connections for the monolithic brick110disposed within the socket formed on the surface of the lower substrate102. The solidified COP layer120is formed in the slot and also over a portion of the brick110on the surface of the lower substrate, where a portion130of the brick110is exposed (i.e., not covered by the COP layer120) as a result of the protection tape that was applied and then removed from the brick110as previously described herein. The upper substrate104is connected with the lower substrate102to seal the brick110between the two substrates in a fluid tight manner. The formed chip can be integrated within a microfluidic system in any suitable configuration and with any other desired components. The surface area of the brick110(surface area of fluid flow path through the brick) was 9 mm2(3 mm×3 mm) and the thickness of the brick (flow path length through the brick) was 2 mm. The 2 mm diameter depression provided within each substrate on either side of the brick110provided a surface area opening to each side of the brick of about 3.14 mm2. The ratio of fluid flow path surface area to flow path length through the brick (SA/L ratio) was at least about 1.5 and as large as about 4.5. Monolithic bricks formed in accordance with the present invention can have any suitable dimensions, including thickness, length, width and/or diameter dimensions from 10 μm to 100 mm, e.g., from about 100 μm to about 10 mm, or from about 1 mm to about 5 mm. The dimensions are chosen depending upon a particular microfluidic system in which the structures are to be implemented and for a particular process application. The dimensions of the brick structures can be selected such that the SQ/L ratio is greater than 1. Alternatively, larger length brick structures can also be formed having SQ/L ratios no greater than 1 (e.g., greater than 0.1 but no greater than 1.0). Integration of Microfluidic Chip within Fluid Processing Systems A microfluidic chip can include a capillary encased monolithic structure, a monolithic brick structure, or combinations of each. The microfluidic chip can be formed in a manner as described herein and can be implemented in a variety of different fluid processing systems, including isolation and/or detection of various forms of bacteria from bodily and/or other fluids, food safety testing, water testing, pharmaceutical production, etc. An example embodiment for implementation of a microfluidic chip with porous monolithic structure formed therein is described in detail in U.S. patent application Ser. No. 14/893,689 and further with reference toFIG.8, monolithic structures can be integrated within a microfluidic chip as part of a separation station of a fluid processing system200. The system200provides a process in which bacteria or other components from a blood (or other fluid) sample are analyzed. For example, the chip can be configured to receive and process a fluid sample (e.g., via an inlet of the chip to receive the fluid and an outlet from the chip to output processed fluid and/or other processed components). The chip includes a separation stage210in which certain non-bacterial components (e.g., red blood cells) that are larger in size than bacteria are first separated from intact bacteria (e.g., a separation stage that uses inertial focusing to achieve separation), followed by selective lysis of the remaining non-bacterial cells in a lysis stage220using one or more chips containing porous monolithic structures (formed in accordance with techniques as described herein), where the porous monolithic structures can be utilized to achieve selective lysis. The result of the selective lysis of the fluid flowing through the porous monolithic structures is that the fluid contains intact bacteria and non-bacterial cell debris. The debris can then be separated from the intact bacteria at a lysis debris removal stage230. An example embodiment of a lysis debris removal stage suitable for use in system200is a stage that separates intact bacteria from debris based upon differences in hydrodynamic sizes of components in the fluid (e.g., utilizing deterministic lateral displacement). Upon selective lysis and separation of intact bacteria from certain lysed debris via the porous monolithic structures, the fluid can be filtered at a filtration stage240within the chip and/or at another portion of the microfluidic system200. This allows the intact bacteria to be analyzed for identification and/or concentration within the fluid (e.g., utilizing infrared analysis, such as infrared spectroscopy, in a manner such as described by U.S. patent application Ser. No. 14/893,689). For example, a detector can be provided at a downstream location from the monolithic structure to facilitate identification and analysis of the separated and intact bacteria within a fluid stream that has exited from an outlet of the monolithic structure. The entire separation, concentration and identification of bacteria can be accomplished without the use of reagents such as DNA sequences or antibodies. Further, a plurality of porous monolithic structures (e.g., at least two monolithic structures, as many as 100 monolithic structures or more) can be integrated within a chip (e.g., at the separation stage220) in a parallel fluid flow arrangement (e.g., in a manner similar to that which is described by U.S. patent application Ser. No. 14/893,689 and depicted inFIG.8). This allows fluid to flow through multiple monolithic structures at the same time to rapidly process larger volumes of fluid. For example, consider a conventional microfluidic system that processes a blood culture analysis for blood samples of 5-10 mL. The conventional microfluidic system can handle a fluid flow rate of about 0.1 mL/minute, such that it would take several minutes (e.g., about 100 minutes) to process the blood sample. Consider further the fact that a blood sample is typically diluted by 10× or greater, which would of course increase the process time considerably to process a diluted sample via a conventional microfluidic system. By providing a plurality of porous monolithic structures in parallel, the fluid flow rate through a microfluidic system of the present invention can rapidly process fluid samples at much higher fluid flow rates so as to provide an analysis of a fluid sample in a much shorter time period. A plurality of monolithic structures can also be combined in parallel so as to serve as a filter or membrane structure (where the membrane thickness is defined by the monolith lengths). In other embodiments, a plurality of monolithic structures can be arranged in fluidic series with each other. Monolithic structures can further be of any suitable sizes, diameters (or cross-sectional dimensions) and lengths. For the capillary encased monolithic structures, such structures can be formed with length-to-diameter (L/D) ratios of at least 10, e.g., a L/D ratio of at least 100, a L/D ratio of at least 1000, a L/D ratio of at least 10000, etc. For monolithic brick structures, such structures can be formed having a flow path defined through the structure with a flow path surface area to flow path length (SA/L) ratio that is greater than 0.1 but no greater than 1.0, or greater than 1 (e.g., a SA/L ratio of at least 2, a SA/L ratio of at least 3, a SA/L ratio of at least 4, a SA/L ratio of at least 5, a SA/L ratio of at least 10, etc.). Accordingly, any number of potential arrangements and/or dimensions of monolithic structures are possible for integration within a microfluidic chip in accordance with the present invention. Performance of Capillary Encased Porous Monolithic Structures for Isolation of Bacteria within Fluid Samples Capillary encased porous monolithic structures integrated within a chip in accordance with the methods described herein were tested for their ability to successfully isolate certain bacterial strains within blood samples. In particular, monolithic structures formed and having varying geometries (e.g., geometries having pore sizes ranging from about 1.6 μm to about 3.2 μm) were evaluated with blood samples infiltrated with different bacterial strains and passed through the monolithic structures at varying flow conditions. The following bacteria were selected to validate the selective isolation performance of the monolithic structures in certain tests:A. aceti(gram negative, 0.6-0.8 μm diameter and 1-4 μm length),E. cloacae(gram negative, 0.3-0.6 μm diameter and 1-2 μm length), andB. subtilis(gram positive, 0.25-1.0 μm diameter and 4-10 μm length). Each bacteria sample was obtained as lyophilized powder (ARL Culture Collection Center for Agricultural Utilization Research, Peoria, Ill.) and grown in a suitable culture. Resulting bacteria suspension was pelletized by centrifugation, and re-suspended with 1× phosphate buffered saline (PBS) solution after discarding supernatant. For blood lysis testing, human whole blood was collected and diluted with 1× PBS solution to specified levels before use. Samples were analyzed before and after monolith processing (i.e., at the monolith inlet and at the monolith outlet) and passage rate of the three bacteria was determined based upon cell counts analyzed for the samples. At various trials for each bacterial species, passage rate was determined to be at least 90%, in many tests nearly 100% (refer toFIG.9, showing images for each bacteria sample at the inlet and outlet of the monolithic structure and further a chart showing the pass rate percentage through the monolithic structure for each sample based upon a difference in cell count for the sample at the inlet and outlet). This indicates that both gram positive and gram negative strains with rod-like shape can effectively pass through the pores of the monolithic structures while remaining intact. Further testing of the bacteria samples and blood samples was conducted where such samples were processed by the monolithic structures. Samples were analyzed at the monolith inlet and outlet utilizing an optical microscope and dynamic light scattering (DLS). Size differences were determined at the monolith inlet and outlet between erythrocyte material and intact bacterial cells. For example, size differences within the sample prior to lysis processing were observed between erythrocytes andE. cloacae, with erythrocytes having radius sizes at the monolith inlet in a range of a 3-4 μm whereas bacterial cells had radius sizes in a 0.8-1 μm range (see the data plotted in the charts inFIG.10). At the monolith outlet, the bacterial cells had the same or substantially similar size (as indicated by substantially similar peaks of the same size/intensity and at the same 0.8-1 μm location), while the size of erythrocytes varied in size under 1 μm in diameter (peaks at the monolith outlet smaller in size and varied in location), which indicates lysis of at least some erythrocyte cells into smaller fragments. This was compared with chemical lysis of a similar blood sample, where the chemical lysis of the blood sample had fragments varying from tens of nanometers to a few microns. These tests indicate an isolation of bacterial cells from erythrocytes in a blood sample by one or more of the following: i) blood cell retention at or near the inlet of monolithic structure due to size restriction of the erythrocytes; ii) entrapment of erythrocytes within the monolithic structure; and iii) stress induced mechanical lysis and release of membrane fragments and cytoplasm of erythrocytes by pressure driven flow into small pores of the monolithic structure. It was therefore demonstrated that the porous monolithic structure can isolate bacterial cells while selectively removing blood cells from a blood sample, thus allowing for bacterial detection without the addition of any chemical reagents or external stimuli. Similar results were observed when tested using 100× diluted blood spiked withE. cloacae, as shown inFIG.11. Two significant peaks at around 100 nm and around 1 μm for the monolith outlet match closely with peaks for the analyses providing the results ofFIG.10. Both DLS results and optical microscopic images revealed that porous silica monoliths can isolate bacterial cells while selectively removing blood cells from a mixed clinical matrix. In other tests,L. lactisandM. luteus(both gram positive) were also utilized along withE. cloacaeandB. subtilisto demonstrate effect of lysis efficiency of erythrocytes by the porous monolithic structures encased within capillaries as formed in accordance with the invention. The human erythrocyte is a discoid shaped cell with sizes of approximately 2-3 μm in thickness and 8 μm in diameter. Given the nature of its viscoelastic cell membrane, red blood cells (RBCs) can tolerate a high degree deformation at a constant volume and surface area. However, when the deformation exceeds a threshold beyond which the membrane surface area must expand to accommodate further deformation, the RBCs rupture and lyse. When the pore radius is small enough to confine a RBC into a sphero-cylindrical shape with a given cylindrical radius (rc) determined as about 1.53 μm, the RBC can flow freely while deforming to fit within a pore when the pore radius is less than rc. However, upon reaching a critical pore radius r* of about 1.48 μm, the flow resistance for the RBC rapidly increases with increasing tension on the RBC membrane thus causing mechanical hemolysis of the RBC. Since the pores in the porous monolithic structures have an average through-pore radius of no greater than about 1.2 μm, such structures provide a high lysis efficiency even when there is a large variance in pore size distribution. However, even for capillary encased monolith structures having larger pore size distributions in which there are a number of pores greater than 1.2 μm, it has been determined that varying the length of the capillary segment that is secured in the microfluidic chip can influence the lysis efficiency. Referring toFIG.12, the length of the capillary encased porous monolithic structure segment was varied and tested with solutions flowed through the segments that included RBCs and different bacterial strains (L. lactis, M luteus, E. cloacaeandB. subtilis). The tests were also conducted at two different flow rates (10 μL/min and 50 μL/min). For segment lengths of about 500 μm or less, the RBC passage rate was as large as about 30% at the varying flow rates. However, as segment lengths were increased above 500 μm, the RBC passage rate dropped to about 5% or less (with decreasing RBC passage rate with increasing segment size). The bacterial passage rate for the different strains remained about the same or similar at the different segment lengths and varying flow rates, with passage rates of 90% or greater. Performance of Porous Monolithic Brick Structures for Isolation of Bacteria within Fluid Samples Monolithic brick structures provide a greater throughput of fluid to be processed through the structures due to the high SA/L ratio provided by such structures. For example, microfluidic chips incorporating the porous monolithic bricks in accordance with the invention are capable of processing >400 μL of whole blood without losing separation efficiency and without exhibiting a significant increase in back pressure while operating at a flow rate of 10 μL/min. As indicated by the tests conducted for the capillary encased porous monolithic structures, such structures can successfully reduce RBC population to a significant degree (e.g., up to 99% or greater RBCs removed from a fluid) while substantially maintaining intact bacteria within the fluid for further analysis. While lysis efficiency can also be increased by increasing the length of the capillary and monolith encased therein, this can also lead to higher fluidic back pressure required to pump fluid through the monolithic structure (particularly when lysed RBC and/or other matter becomes lodged within pores of the monolithic structure). Passage through monolithic brick structures formed in accordance with the invention can also achieve a high rate of lysis efficiency while maintaining passage of intact bacteria at high flow rates and without significant increase in back pressure (due to the greater SA/L ratio in comparison to the capillary encased monolithic structures). Further, the combination of two or more monolithic brick structures (e.g., incorporated in series or consecutively within the fluid flow path) has been found to further increase the degree of RBC removal from a fluid sample to as much as 99.99% or greater. Thus, the present invention facilitates the integration of a capillary encased porous monolithic structure and/or a porous monolithic brick structure within a microfluidic chip. The capillary encased monolithic brick structure is integrated within a chip utilizing one or more thermoplastic clamp structures configured to suitably align or position the monolithic structure within a portion of the chip and further secure the monolithic structure at such suitable alignment or position upon melting and flowing or reflowing/deformation of the clamp structure(s) via the application of heat and/or pressure to the clamp structure(s). During melting and deformation of the clamp structure(s), the clamp structure material flow/reflows around a circumferential or exterior surface portion of the capillary and then solidifies upon cooling to effectively secure the capillary in position as well as provide a fluid tight barrier between a portion of the capillary exterior and the chip such that fluid flowing within a channel of the chip passes through the capillary and monolithic structure disposed within the capillary (i.e., the fluid passes between open ends of the capillary) with substantially no fluid passing around the exterior of the capillary during operation of the microfluidic chip. The monolithic brick structure is also integrated within a chip and provides a high throughput through the structure due to the high SA/L ratio for fluid flowing through the structure (e.g., SA greater than 1). The present invention further facilitates the integration of such monolithic structures within one or more microfluidic chips for performing operations to effectively isolate bacterial cells and/or other components from other components (e.g., components that may be larger in size, smaller in size or about the same size as the bacteria of interest). Any combinations of capillary encased monolithic structures with monolithic brick structures can be designed in series and/or parallel flow paths as desired for a particular fluid processing operation. For example, this can facilitate a rapid identification of a particular bacterial strain within a fluid sample. While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. For example, Thus, it is intended that the present invention covers the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. It is to be understood that terms such as “top”, “bottom”, “front”, “rear”, “side”, “height”, “length”, “width”, “upper”, “lower”, “interior”, “exterior”, and the like as may be used herein, merely describe points of reference and do not limit the present invention to any particular orientation or configuration.
59,310
11857968
DETAILED DESCRIPTION The present disclosure provides microfluidic systems and methods for arranging a set of objects. In an exemplary method, the set of objects may be transported in carrier fluid along a microfluidic channel structure having a reformatting zone including an object-accessible region and at least one object-excluding region. A portion of the carrier fluid may be moved from the object-accessible region to the at least one object-excluding region in an upstream section of the reformatting zone, to reduce a spacing of objects of the set. The portion of the carrier fluid may be directed into the object-accessible region from the at least one object-excluding region in a downstream section of the reformatting zone, to increase a spacing of objects of the set. The steps of moving and directing in combination may increase the spacing between objects disproportionately for a subset of the objects that are closest to one another. The method may produce a more uniform spacing of objects and/or a lower incidence of objects in close proximity to one another. The present disclosure provides an exemplary method of altering the spacing of a stream of objects. The stream of objects may be transported in carrier fluid along a microfluidic channel structure defining an object-excluding flow path for the objects and having a reformatting zone including an upstream section and a downstream section. A portion of the carrier fluid may be moved out of the flow path in the upstream section such that objects within the stream move closer to one another. The portion of the carrier fluid may be directed into the flow path in the downstream section to increase a distance between objects within the stream. The stream may have a more uniform spacing of the objects downstream of the downstream section compared to upstream of the upstream section, and/or a lower incidence of objects in close proximity to one another downstream relative to upstream of the reformatting zone. The general concept is to have a stream of carrier fluid (e.g., a liquid stream) flowing in a microfluidic channel and carrying objects (e.g. droplets, particles, etc.). The objects may have a size in the same range as a transverse dimension of the microfluidic channel (e.g., 1-500 micrometers). Various exemplary microfluidic designs are disclosed which alter the spacing between these objects within the channel. An exemplary purpose is to reduce the likelihood of two adjacent objects traveling in close proximity to one another in the stream of carrier fluid, and/or to render the spacing of the objects more uniform within the stream of carrier fluid. Close proximity may be defined as a percentage of the average spacing between objects, such as less than 100%, 80% 60%, 50%, 40%, 30%, 25%, 20%, or 10% of the average spacing. Altering the spacing of the objects could be beneficial for various applications. For example, the application could be spacing of a fluorescent readout from the objects. Other applications involve partitioning a liquid stream carrying the objects. For example, if the liquid stream is to be partitioned into a plurality of isolated (separate) fluid volumes, there is a certain probability (typically, a Poisson distribution) that a given number of objects (i.e., 0, 1, 2, 3, etc.) will end up in the same fluid volume. By altering the spacing of the objects, and particularly objects that are in close proximity to one another, the probability of having two objects very close to one another can be reduced. As a result, the altered spacing creates a lower probability of having two or more objects within the same fluid volume. Essentially, this may overcome an underlying Poisson probability. Exemplary microfluidic channel structures disclosed herein may utilize a similar concept. In these designs, a portion of the carrier fluid may be drained away from the objects by moving the portion to one or more object-excluding regions of the channel structure. This movement of carrier fluid concentrates objects within an object-accessible region of the channel structure. Objects that are farther apart get closer to one another. Objects that already are close to one another may get even closer. However, since the objects have a finite size, there is a physical limit to how closely the centers of the objects can approach one another before further approach is mutually obstructed. Accordingly, the objects may be concentrated differentially, with a subset of the objects that are closest together being concentrated less than objects that are farther apart. The portion of carrier fluid may be reintroduced into the object-accessible region of the channel structure, thereby diluting objects within the channel to increase the spacing thereof. The objects may be diluted equally. Therefore, the spacing between a subset of the objects, namely, each adjacent pair of objects that exhibited mutual obstruction during concentration, may be increased disproportionately by concentration and dilution. Furthermore, concentrating and diluting objects may create a larger minimum spacing between the objects. The minimum spacing may be determined by the size of the objects and the amount of carrier fluid that was drained from and reintroduced into the channel. The minimum spacing between objects before concentration may be about the same as the diameter of the objects. The minimum spacing after dilution may be at least about 125%, 150%, 175%, 200%, or 250%, among others, of the diameter of the objects. The minimum spacing between objects may be increased at least 25%, 50%, 75%, 100%, or 150%, among others, by concentration and dilution. Further aspects of the present disclosure are described in the following sections: (I) definitions, (II) overview of microfluidic systems and methods for arranging objects, (III) reformatting zones, and (IV) examples. I. DEFINITIONS Technical terms used in this disclosure have meanings that are commonly recognized by those skilled in the art. However, the following terms may be further defined as described below. Object—any entity having a diameter of less than one millimeter. The objects of a set or object stream may have any suitable diameter, such less than 500, 200, or 100 micrometers and/or greater than 1, 2, 5, 10, or 20 micrometers, among others. In exemplary embodiments, the objects may have a width of 1-500 micrometers, 5-500 micrometers, 10-200 micrometers, or the like. The objects of a set or object stream may be about the same size. For example, the objects may have a standard deviation of their respective diameters that is less than about 40%, 30%, 20%, 15% or 10% of the mean of the diameters. A “stream” of objects may be a substantially single-file arrangement of the objects, whether or not the objects are exactly aligned with one another along a flow axis. Accordingly, the objects of an object stream may be offset somewhat from one another laterally, such as offset from a flow axis by less than about 75%, 50%, or 25% of the diameter of the objects. An object stream interchangeably may be described as a line, train, succession, or series of objects. The objects may have any suitable shape. The objects of a set or line may or may not be rounded and/or elongated. The present disclosure utilizes spherical objects to illustrate the systems and methods, and the term “diameter” to describe the width of the objects. However, the term “diameter” is intended to mean width (e.g., an average width) for any shape of object. The objects may be composed of matter having any suitable state, such as solid, liquid, gas, or a combination thereof. However, the objects may be predominantly solid, predominantly liquid, and/or predominantly a combination of solid and liquid, in some embodiments. The objects may be substantially incompressible and/or rigid when subjected to the microfluidic manipulations disclosed herein. Exemplary objects include particles, droplets, and the like. The particles may be biological cells or beads, among others. The droplets may be composed at least predominantly of liquid. Spacing—a distance between an adjacent pair of objects, a set of individual distances between adjacent objects of a group, object stream, or set, or an average distance between adjacent objects of a group, object stream, or set. The distance (a center-to-center spacing) between an adjacent pair of objects may be measured from the center of one of the objects to the center of the other object. This distance may be described as a separation or separation distance between the objects, whether or not there is any space between the objects. Microfluidic—involving fluid manipulation on a sub-millimeter scale. For example, a microfluidic channel may have a characteristic dimension, such as a width or depth, of less than one millimeter. Microfluidic systems, and channels thereof, may produce and guide a laminar flow of fluid, and/or may operate with a Reynolds number of less than about 500, 200, 100, or 50, among others. Carrier fluid—a fluid in which objects are transported in a microfluidic system, channel structure, and/or channel. The carrier fluid may be liquid. In some embodiments, the carrier fluid may be aqueous (or may be non-aqueous). The carrier fluid may be immiscible with liquid of the objects, if the objects include liquid. If the objects are solid, the objects may be substantially insoluble in the carrier fluid. In some embodiments, the carrier fluid may comprise oil, and the objects may be aqueous droplets, or the carrier fluid may be aqueous, and the objects may be droplets comprising oil, among others. Channel—an elongated, fluid-guiding structure. A channel may be enclosed radially along most or all of its longitudinal extent. Channel structure—a fluid-guiding structure including a single channel or two or more channels that communicate with one another. The channel structure may be unbranched or branched. Each of the channels may be a microfluidic channel. The channel structure may be configured to guide fluid from an inlet to an outlet, without any substantial addition or loss of fluid. The channel structure may have a cross-sectional area for fluid flow at each position between the inlet and the outlet. The cross-sectional area may be defined at each position by a single channel, or collectively by two or more channels configured to carry fluid in parallel. II. OVERVIEW OF MICROFLUIDIC SYSTEMS AND METHODS FOR ARRANGING OBJECTS This section provides an overview of exemplary microfluidic systems and methods for arranging objects; seeFIGS.1-10. FIG.1shows a schematic view of an exemplary microfluidic system50for arranging objects, and particularly for reformatting a stream52of objects54to space the objects more uniformly. The system includes a channel structure56having an inlet58(e.g., a single inlet), an outlet60(e.g., a single outlet), and a reformatting zone62located on an object-accessible flow path63that connects the inlet to the outlet. The channel structure may have only one channel64extending between the inlet and outlet and forming the reformatting zone, as in the depicted embodiment. In other embodiments, channel structure56may branch upstream and merge downstream to create the reformatting zone (see Section II). Channel structure56may be configured to direct a stream66of carrier fluid68transporting objects54from inlet58to outlet60, with the objects following, and substantially restricted to, flow path63. The objects may be arranged in object stream52, which may be straight, bent, curved, or the like. In other embodiments described below, the objects may be placed into single file by the reformatting zone, and thus the objects may enter the reformatting zone laterally spread out. Reformatting zone62may have a fixed geometry that passively (e.g., without valves, feedback, electrical signals, etc.) adjusts the spacing between at least a subset of the objects, to make the spacing less stochastic (such as to make the spacing less of a Poisson distribution). For example, in the depicted embodiment, objects54located upstream of reformatting zone62in an inflow region70of the channel structure have a more variable spacing than objects54located downstream of reformatting zone62in an outflow region72of the channel structure. More particularly, inflow region70contains two unseparated pairs74a,74bof objects, while all of objects54in outflow region72are well separated from one another. As described further below, the reformatting zone may be configured to disproportionately increase the relative and/or absolute spacing between adjacent objects that are spaced from one another by less than a threshold distance. Reformatting zone62may be configured to concentrate and dilute objects, to produce a change in the spacing between the objects. The zone may have an object-accessible region76(e.g., the part of flow path63passing through zone62) in which objects54can travel, and one or more object-excluding regions77that selectively and/or substantially exclusively permit entry of carrier fluid68relative to objects54. Object-excluding regions77may be configured to exclude a majority of the objects from entering the region, such as more than about 70%, 80%, 90%, 95%, 98% or 99% of the objects, among others. Reformatting zone62may have a concentration section78, interchangeably called an upstream section, in which a portion of carrier fluid68is moved from flow path63, indicated by arrows at80. The portion of carrier fluid is moved from object-accessible region76to object-excluding regions77. The portion of carrier fluid may be moved into one or more wings82(i.e., one or more lateral areas) of channel64(and/or into one or more by-pass channels) that branch from the channel and are separate from one another. Reformatting zone62also may have a dilution section84, interchangeably called a downstream section or re-entry section, in which the portion of carrier fluid68may be reintroduced into flow path63(and thus into object-accessible region76) from object-excluding regions77(e.g., from one or more wings82), indicated by arrows at86. The velocity of objects54may (or may not) decrease in concentration section78, and/or carrier fluid may be drained from the object-accessible region of the reformatting zone, which may cause objects54to be concentrated locally. The local spacing of objects54in the reformatting zone may decrease, relative to their spacing in inflow region70. The velocity of objects54may increase, and/or carrier fluid68may be reintroduced into object-accessible region76in dilution section84, which may cause the spacing between objects54, such as the spacing for each adjacent pair74a,74b, to be increased from the more concentrated configuration in the reformatting zone. Reformatting zone62may have any suitable length. For example, the length may be at least about 2, 3, 4, 5, 10, or 20 object diameters, among others. FIG.2shows an exemplary geometry for channel structure56upstream (and/or downstream) of reformatting zone62. The channel structure may be formed by a channel-defining device87having a plurality of layers, such as layers88,90, bonded to one another and defining a plane92. Channel64, in inflow region70, and/or outflow region72, may be sized in correspondence with objects54(seeFIGS.1and2). The channel may have a depth94(measured orthogonal to plane92) and a width96(measured parallel to plane92) that are about the same as one another, such as less than about 100%, 75%, 50%, or 25% different. The size of channel64in inflow region70and outflow region72may be the same, or may be different. For example, the outflow region may have a smaller cross-sectional area, depth, and/or width than the inflow region (also see below). The depth and/or width of the outflow region and/or inflow region may be only somewhat larger than the diameter of objects54, such as less than about 100%, 75%, 50%, or 25% larger, among others, to reduce lateral migration of the objects out of alignment with one another. FIG.3shows an exemplary geometry for channel structure56within reformatting zone62. Channel64may (or may not) have an expanded region98(also seeFIG.1) at which a width100of the channel increases relative to width96of inflow region70and/or outflow region72. Whether or not the channel has an expanded region, a depth104of object-excluding region(s)77(e.g., depth104of each wing82) may be less than a depth106of object-accessible region76, to form a shelf on one or both sides of object-accessible region76. Depth104of each object-excluding region77may be less than the diameter of objects54, to substantially exclude objects54from the object-excluding region. Accordingly, each object-excluding region77may be configured to permit selective movement of only carrier fluid68, and not objects54, from object-accessible region76, making the process of draining carrier fluid from around objects54more efficient. Each object-excluding region77may have a substantially uniform depth, or the depth may vary stepwise or via a taper, among others, within the object-excluding region. Object-excluding regions77ofFIGS.1-3and elsewhere herein are shown as being symmetrical, with object-accessible region76located between, contiguous with, and separating, a pair of object-excluding regions. However, in other embodiments, only a single object-excluding region77may be located on only one side of object-accessible region76, the object-excluding regions may be asymmetrically arranged, or three or more object-excluding regions may be present. Object-accessible region76may be formed adjacent each object-excluding region77at least in part by a groove108. The object-accessible region may include laterally unbounded space above the groove, as indicated by a pair of dashed boundaries extending upward from the walls of the groove between wings82. The amount of increase and decrease in cross-sectional area of the channel structure created by expanded region98(and/or by one or more by-pass channels) may directly related to the fraction of carrier fluid that is drained from the object-accessible flow path and reintroduced to the flow path. Accordingly, a larger increase and decrease in cross-sectional area may provide a greater deceleration and acceleration of objects, and a larger effect on object spacing. The amount of increase in cross-sectional area may set a threshold separation distance between objects, below which the relative or absolute spacing within object pairs is increased disproportionately by the reformatting zone. With a smaller increase in cross-sectional area, the spacing between only closely paired objects may be affected disproportionately, while with a larger increase in cross-sectional area, the spacing within a greater percentage of the object pairs may be altered disproportionately. FIG.1shows other exemplary aspects of system50. One or more sources of positive/negative pressure, such as at least one pump110, may be operatively connected to channel structure56upstream of inlet58and/or downstream of outlet60. The pump(s) creates a pressure differential to move fluid within the channel structure. Each pressure source may be any device or mechanism configured to drive flow of carrier fluid68and objects54from inlet58to outlet60. Each pump may, for example, apply positive pressure upstream of inlet58, indicated at112, to push carrier fluid, or may apply negative pressure (suction) downstream of outlet60, indicated at114, to pull carrier fluid. Exemplary pumps may include syringe pumps, peristaltic pumps, diaphragm pumps, piston pumps, and the like. A source116of objects54and carrier fluid68may be connected to channel structure56. Source116may be connected removably or integrally, among others. Objects54may be placed into single file as the objects enter channel structure56. For example, the objects may travel through a tapered alignment region118leading to inlet58. In other embodiments, alignment region118may be provided by reformatting zone62(see below). System50may have a partitioning structure120located at or downstream of outlet60. The partitioning structure may be configured to divide carrier fluid stream66into a plurality of isolated volumes122(interchangeably called partitions), optionally of equal size. The size of the volumes may be selected such that a majority of the volumes contain either no object54or only one object54. Passing carrier fluid stream66through reformatting zone62before partitioning can make partitioning less random, by decreasing the percentage of volumes containing two or more objects54and increasing the percentage of volumes122containing only one object. Partitioning structure120may have any suitable mechanism of operation. The partitioning structure may be a dispenser that dispenses volumes122into separate containers or as an aerosol. In other embodiments, the partitioning structure may form volumes122encapsulated by a continuous liquid phase. Accordingly, the partitioning structure may be a droplet generator. Exemplary droplet generators form droplets by flow focusing, shearing, co-flow, a confinement gradient, etc. In some embodiments, system50may include a detector124operatively located downstream of reformatting zone62. Detector124may be configured to detect a signal from a detection zone126of channel64as objects54pass therethrough. The reformatting zone increases the separation between closely paired objects and thus may reduce the incidence of signal overlap between detected waveforms corresponding to the objects. The detector may, for example, be configured to detect light from detection zone126. In some embodiments, a light source128may be configured to irradiate the detection zone, such as to produce photoluminescence from the objects. The light source may provide epi- or trans-illumination of the detection zone. Partitioning structure120may or may not be omitted from embodiments including detector124. FIGS.4-7show part of channel structure56of system50ofFIG.1in the presence of a pair of objects54(“A” and “B”). The upstream, center-to-center distance, spacing S1, between the objects in inflow region70is different in each figure to illustrate how reformatting zone62may operate on objects of different initial spacing. The same pair of objects54in each figure is shown as dashed inside reformatting zone62, and in dash-dot-dot outline in outflow region72after passing through the reformatting zone. The spacing for the pair of objects at each of the three positions along the flow path is labeled as S1, S2, and S3, respectively. The changes in spacing shown inFIGS.4-7are exemplary; other channel geometries may produce larger or smaller changes. Furthermore, the reversible changes in separation shown inFIGS.6and7for S1greater than the threshold distance may not apply in some case, such as if the cross-sectional areas of inflow region70and outflow region72are different. FIG.4shows a configuration in which S1is approximately equal to the diameter of the pair of objects. In other words, the objects are very close to one another before entering reformatting zone62. Accordingly, although moving carrier fluid into object-excluding regions77in concentration section78urges the objects toward one another, the objects cannot move substantially closer to one another, and S1substantially equals S2, because the objects mutually obstruct one another. However, the dilution produced by dilution section84causes the objects to move apart from one another, such that S3is greater than S1(and S2). FIG.5shows a configuration in which S1is greater than inFIG.4, but the two objects are still relatively close (e.g., S1may be less than two object diameters). Moving carrier fluid into object-excluding regions77in concentration section78may urge the objects closer together until the objects mutually obstruct further movement toward one another. At this point, S2is substantially equal to the diameter of the objects (i.e., S1), and no further movement toward each other is permitted without object deformation. As inFIG.4, the dilution produced by dilution section84causes the objects to move apart from one another, such that S3is greater than S1(and S2). S3inFIGS.4and5may be the same, since S2is the same, even though S1is different. Accordingly, each pair of objects having less than a threshold spacing for S1may have the same spacing S3as one another after passing through the reformatting zone. The threshold spacing may be determined by the diameter of the objects, and a ratio of the amount of concentration and the amount of dilution produced by the reformatting zone. FIGS.6and7show configurations in which S1is greater than inFIG.5(and greater than the threshold spacing). More particularly, S1is large enough that moving carrier fluid into object-excluding regions77in concentration section78urges the objects closer together but not close enough for the objects to obstruct movement toward one another. Accordingly, the dilution produced by dilution section84causes the objects to move apart from one another to their original spacing (i.e., S1equals S3). At the threshold spacing (e.g., intermediate S1ofFIGS.5and6), the objects may move to the closest approach ofFIGS.4and5but still may return to their original spacing. Any adjacent objects having less than the threshold spacing for S1leave the reformatting zone with substantially the same spacing S3, which is the reformatted minimum spacing between objects. FIG.8shows a histogram presenting an exemplary distribution of the spacing between objects54upstream of reformatting zone62. Objects that are relatively closer together (e.g., represented by the bar on the left) may be undesirable for applications in which the objects should be well singulated. FIG.9shows a histogram presenting an exemplary change in the distribution ofFIG.8produced by passing the objects through reformatting zone62of system50. InFIG.9, the threshold spacing for reformatting zone62(seeFIGS.5and6) is between two and three. Accordingly, the object pairs that were represented by the bar on the left (inFIG.8) have been spaced farther from one another and are now represented by the middle bar of the histogram. However, the spacing of the rest of the object pairs may not have changed significantly. Accordingly, the spacing of the objects has been adjusted to increase the average distance between objects, by selectively (and/or disproportionately) increasing the spacing between a subset of the objects that are closest to one another. FIG.10shows another exemplary microfluidic system50′ for arranging objects54. System50′ may have any suitable combination of features described above for system50(seeFIG.1), such as a pump110to drive flow of carrier fluid68and objects54, a partitioning structure120, a detector124in communication with a detection zone126, and the like. The system also may include a channel structure56forming a reformatting zone62. The reformatting zone may be created by a single channel64or by two or more channels of the channel structure, as described below in Section III. The reformatting zone may include an object-accessible region76and one or more object-excluding regions77, which may be of different depth from one another, as described above for system50(seeFIG.3). Moreover, the reformatting zone may have a concentration section78in which a portion of carrier fluid68is moved from object-accessible region76to object-excluding regions77, indicated by arrows at80. Reformatting zone62also may have a dilution section84in which the portion of carrier fluid is reintroduced to object-accessible region76from object-excluding regions77, indicated by arrows at86. However, reformatting zone62of system50′ may not be formed by an expanded region of channel64(compare with expanded region98ofFIG.1). Instead, channel64, at the upstream end of reformatting zone62, may be much wider than the diameter of objects54(e.g., more than 2, 3, 4, or 5 times the diameter of the objects), and may narrow toward the downstream end of reformatting zone62. The objects may enter the reformatting zone spread out laterally from one another in a disordered arrangement (and not aligned). Objects54may be aligned with one another and placed into single file by tapered alignment region118of reformatting zone62(namely, object-accessible region76thereof) as the objects travel downstream through the reformatting zone. Alignment region118thus may be contiguous with each object-excluding region77(and one or more wings82). The cross-sectional area for fluid flow may taper from the upstream end to the downstream end of the reformatting zone. Accordingly, in contrast to system50, carrier fluid68may not be decelerated as it enters the reformatting zone. III. REFORMATTING ZONES This section describes other exemplary channel geometries for reformatting zone62of system50and/or50′; seeFIGS.11-18(also seeFIGS.1-10). The outline convention for each pair of objects “A” and “B” inFIGS.11-18is as described above in Section II. FIGS.11-16show three different geometries for reformatting zone62, namely rectangular (FIGS.11and12), round (FIGS.13and14), and tapered (FIGS.15and16). For each type of geometry, two embodiments are illustrated: one having uniform channel depth (FIGS.11,13, and15), and the other having a deeper object-accessible region76and shallower object-excluding regions77. FIG.11shows an exemplary rectangular geometry for reformatting zone62of system50. The zone has an expanded region98to create upstream deceleration and downstream acceleration within the zone. However, the depth of reformatting zone62is uniform, such that carrier fluid68is not drained away from objects54efficiently. FIG.12shows another exemplary rectangular geometry for reformatting zone62of system50. The perimeter of the zone has the same shape as inFIG.11. However, the depth of zone62varies, as described above for system50ofFIG.1, to create object-accessible region76and object-excluding regions77. The presence of object-excluding regions77allows the geometry ofFIG.12to drain carrier fluid away from objects54much more efficiently than inFIG.11, to produce a much greater concentration and dilution of objects by the zone.FIGS.13and14have the same general relation to one another asFIGS.11and12, as doFIGS.15and16. FIG.17shows an exemplary branched geometry130for reformatting zone62of system50. The zone has a primary channel132and one or more lateral by-pass channels134. Each by-pass channel branches from primary channel132and rejoins the primary channel downstream. The primary channel forms object-accessible region76, and the by-pass channels form object-excluding regions77. Carrier fluid68may enter by-pass channels134in concentration section78, to concentrate objects54in primary channel132. Carrier fluid68may be reintroduced in dilution section84to dilute the objects. An inlet136of each by-pass channel134, formed at the downstream end of an inflow channel138, may be configured to exclude objects54. For example, the inlet may have a width and/or a depth that is less than the diameter of the objects, and/or the inlet may include one or more pillars or other barriers to object entry. An outflow channel140may extend downstream from reformatting zone62. FIG.18shows another exemplary branched geometry130for reformatting zone62of system50. The geometry of the reformatting zone ofFIG.18is similar to that ofFIG.17except that inflow channel138is much wider than the diameter of objects54(as in system50′ ofFIG.10). Also, primary channel132within zone62forms a tapered alignment region118(as in system50′ ofFIG.10). IV. EXAMPLES The following examples describe selected aspects and embodiments of microfluidic systems and methods for arranging objects. These aspects and embodiments are intended for illustration and should not limit the entire scope of the present disclosure. Example 1. System and Method for Next Generation Sequencing This example describes an exemplary system150and method for generating an emulsion152to enable next generation sequencing. The emulsion may include isolated volumes (droplets154) of carrier fluid68encapsulated by an immiscible continuous phase liquid156(e.g., oil). Droplets154may contain beads158(as objects54) and biological cells160at partial occupancy; seeFIGS.19and20. Beads158may carry oligonucleotides, which may be configured to function as primers and/or barcodes. System has a channel structure including bead channel162, at least one cell channel164, at least one bead-and-cell channel166, one or more oil channels168, and a droplet channel170. Bead channel162carries beads158through reformatting zone62to a junction with cell channel164. Cells160are introduced to a bead-containing stream172at the junction to produce bead-and-cell-containing stream174. Stream174travels to a channel junction176at which the stream may be segmented by at least one stream of continuous phase liquid156to generate droplets154. The goal is to have as many droplets as possible containing only one bead and only one cell, while minimizing the number of droplets containing two or more beads. With a Poisson distribution of the beads (no reformatting zone62), the percentage of droplets containing one bead is kept relatively low, to avoid an unacceptably high fraction of droplets with two beads. Zone62permits a greater percentage of droplets (e.g., ˜40%) to contain one bead, while fewer (e.g., ˜5%) contain two beads. The percentage with three beads may be negligible. FIG.20shows a bottom section of a channel-defining microfluidic device178of an embodiment of system150. Reformatting zone62has a wide expanded region98with a deep entry region180of uniform depth in which objects may accumulate. The expanded region becomes shallower to form a downstream portion of object-accessible region76, and even shallower still to form lateral object-excluding regions77. The downstream portion of object-accessible region76tapers to create alignment region118for the objects. A pair of cell channels164a,164bintersect the outlet of reformatting zone62, to add biological cells to the outflowing stream of carrier fluid and beads. A resulting stream of carrier fluid transporting beads and biological cells travels along bead-and-cell channel166. Example 2. Selected Embodiments This example describes selected embodiments of the present disclosure presented as a series of indexed paragraphs. Paragraph A1. A method of arranging objects, the method comprising: (a) transporting a set of objects in carrier fluid along a microfluidic channel structure having a reformatting zone including an object-accessible region and at least one object-excluding region; (b) moving a portion of the carrier fluid from the object-accessible region to the object-excluding region(s) in an upstream section of the reformatting zone, to reduce a spacing of objects of the set; and (c) directing the portion of the carrier fluid into the object-accessible region from the object-excluding region(s) in a downstream section of the reformatting zone, to increase a spacing of objects of the set. Paragraph A2. The method of paragraph A1, wherein at least one pair of objects of the set are in sufficiently close proximity to one another in the reformatting zone that the objects of the pair mutually obstruct a closer approach to one another encouraged by the step of moving. Paragraph A3. The method of paragraph A1 or A2, wherein a spacing between a subset of the objects of the set that are closest together is increased disproportionately by the steps of moving and directing in combination. Paragraph A4. The method of any of paragraphs A1 to A3, wherein objects of the set leave the reformatting zone in single file. Paragraph A5. The method of any of paragraphs A1 to A4, further comprising a step of arranging objects of the set in single file. Paragraph A6. The method of paragraph A5, wherein objects of the set are arranged in single file by an alignment region of the channel structure that does not overlap the upstream section. Paragraph A7. The method of paragraph A5, wherein objects of the set are arranged in single file by an alignment region of the channel structure located in the upstream section. Paragraph A8. The method of paragraph A6 or A7, wherein the alignment region tapers to a width that is less than twice an average diameter of the objects. Paragraph A9. The method of any of paragraphs A1 to A8, wherein the object-accessible region is deeper than each object-excluding region of the at least one objection-excluding region. Paragraph A10. The method of paragraph A9, wherein the object-excluding region has a depth that is less than an average diameter of the objects of the set. Paragraph A11. The method of paragraph A9 or A10, wherein the object-accessible region and each object-excluding region of the at least one object-excluding region are formed by a same channel of the channel structure. Paragraph A12. The method of paragraph A11, wherein each object-excluding region of the at least one object-excluding region is continuously contiguous with the object-accessible region between the upstream section and the downstream section. Paragraph A13. The method of any of paragraphs A9 to A12, wherein the object-accessible region includes an object-accessible groove, and wherein the at least one object-excluding region includes one or more wings located adjacent the object-accessible groove. Paragraph A14. The method of any of paragraphs A9 to A13, wherein the at least one object-excluding region includes a pair of object-excluding regions that are separated from one another by the object-accessible region, and optionally separated from one another only by the object-accessible region. Paragraph A15. The method of any one of paragraphs A1 to A14, wherein the object-accessible region is formed by a primary channel of the channel structure, and wherein the step of moving includes a step of moving at least part of the portion of the carrier fluid to one or more by-pass channels defined by the channel structure. Paragraph A16. The method of paragraph A15, wherein each by-pass channel branches from the primary channel in the upstream section and merges with the primary channel in downstream section. Paragraph A17. The method of paragraph A15 or A16, wherein the one or more by-pass channels include a pair of by-pass channels, and wherein the primary channel is located between the pair of by-pass channels. Paragraph A18. The method of any one of paragraphs A15 to A17, wherein each by-pass channel has an inlet configured to prevent entry of objects of the set into the by-pass channel. Paragraph A19. The method of paragraph A18, wherein the inlet is sized to prevent entry of objects of the set into the by-pass channel. Paragraph A20. The method of any one of paragraphs A1 to A19, wherein a plurality of objects of the set travel through the upstream section during the step of moving, and wherein only a subset of the plurality of objects move closer to an adjacent object of the set during the step of moving without being stopped by a periphery of the adjacent object. Paragraph A21. The method of paragraph A20, wherein at least a pair of the plurality of objects do not move substantially closer to one another during the step of moving due to mutual obstruction. Paragraph A22. The method of any one of paragraphs A1 to A21, wherein a plurality of objects of the set travel through the downstream section during the step of directing, wherein each object of the plurality of objects moves farther from each adjacent object of the plurality during the step of directing, Paragraph A23. The method of any one of paragraphs A1 to A22, wherein the steps of moving and directing, in combination, create substantially the same spacing for a subset of pairs of the objects that are closest to one another. Paragraph A24. The method of paragraph A23, wherein objects of each of the pairs are spaced from one another by less than a threshold spacing before traveling through the formatting zone. Paragraph A25. The method of any one of paragraphs A1 to A24, wherein the carrier fluid is an aqueous carrier fluid. Paragraph A26. The method of any one of paragraphs A1 to A25, wherein the objects include liquid that is immiscible with the carrier fluid, and wherein, optionally, each of the objects is formed at least predominantly of liquid. Paragraph A27. The method of any one of paragraphs A1 to A26, wherein the objects are selected from the group consisting of beads, droplets, and biological cells. Paragraph A28. The method of any one of paragraphs A1 to A27, further comprising a step of partitioning a stream including the carrier fluid and carrying objects of the set at a position downstream of the downstream section to form isolated volumes. Paragraph A29. The method of paragraph A28, wherein each isolated volume of a majority of the isolated volumes contains none or only one of the objects of the set. Paragraph A30. The method of paragraph A28 or A29, wherein the step of partitioning includes a step of encapsulating the isolated volumes with a liquid that is immiscible with the carrier fluid. Paragraph A31. The method of any one of paragraphs A28 to A30, wherein the step of partitioning includes a step of forming droplets. Paragraph A32. The method of any one of paragraphs A28 to A31, wherein the objects are beads, further comprising a step of adding biological cells to the carrier fluid. Paragraph A33. The method of paragraph A32, wherein each isolated volume of a plurality of the isolated volumes contains only one of the beads and only one biological cell. Paragraph A34. The method of any one of paragraphs A1 to A33, further comprising a step of moving one or more of the objects of the set through a detection zone downstream of the downstream section, and a step of detecting a signal from the detection zone. Paragraph A35. The method of paragraph A34, wherein the step of detecting a signal includes a step of detecting light. Paragraph B1. A method of altering the spacing of a stream of objects, the method comprising: (a) transporting objects of the object stream in carrier fluid along an object-accessible flow path, the flow path being defined by a microfluidic channel structure and extending through a reformatting zone including an upstream section and a downstream section; (b) moving a portion of the carrier fluid out of the flow path in the upstream section such that objects within the object stream move closer to one another; and (c) directing the portion of the carrier fluid into the flow path in the downstream section to increase a distance between objects within the object stream. Paragraph B2. The method of paragraph B1, wherein the object stream has a more uniform spacing of objects downstream of the downstream section compared to upstream of the upstream section, and/or wherein a distance between object pairs of the object stream that are closest together upstream of the upstream section is increased disproportionately by the steps of moving and directing in combination. Paragraph B3. The method of paragraph B1 or paragraph B2, wherein the channel structure includes an object-accessible groove and at least one object-excluding wing located adjacent the groove. Paragraph B4. The method of paragraph B3, wherein the step of moving includes a step of moving the portion of the carrier fluid from a deeper region to at least one shallower region of the channel structure. Paragraph B5. The method of paragraph B4, wherein the step of moving includes a step of moving the portion of the carrier fluid to a pair of shallower regions of the channel structure that are separated from one another by a deeper, object-accessible groove. Paragraph B6. The method of paragraph B4 or B5, wherein the step of moving includes a step of moving the portion of the carrier fluid to at least one shallower region having a depth that is less than a diameter of the objects, such that a majority of objects of the object stream are excluded from the at least one shallower region. Paragraph B7. The method of any one of paragraphs B1 to B6, wherein the step of moving includes a step of moving the portion of the carrier fluid from a primary channel to one or more by-pass channels defined by the channel structure. Paragraph B8. The method of paragraph B7, wherein the channel structure has a primary channel, and wherein each by-pass channel branches from the primary channel in the upstream section and merges with the primary channel in the downstream section. Paragraph B9. The method of paragraph B8, wherein the one or more by-pass channels include a pair of by-pass channels. Paragraph B10. The method of any one of paragraphs B7 to B9, wherein each by-pass channel has an inlet configured to prevent entry of objects of the object stream into the by-pass channel. Paragraph B11. The method of paragraph B10, wherein the inlet is sized to prevent entry of objects of the object stream into the by-pass channel. Paragraph B12. The method of any of paragraphs B1 to B11, wherein a plurality of the objects of the object stream travel through the upstream section during the step of moving, and wherein only a subset of the plurality of objects move closer to an adjacent object of the object stream during the step of moving until closer approach is obstructed by a periphery of the adjacent object. Paragraph B13. The method of any of paragraphs B1 to B12, wherein at least a pair of the plurality of objects do not move substantially closer to one another during the step of moving due to mutual obstruction. Paragraph B14. The method of any one of paragraphs B1 to B13, wherein a plurality of the objects travel through the downstream section during the step of directing, and wherein each object of the plurality of objects moves farther from each adjacent object of the object stream during the step of directing. Paragraph B15. The method of any one of paragraphs B1 to B14, wherein the carrier fluid is an aqueous carrier fluid. Paragraph B16. The method of any one of paragraphs B1 to B15, wherein the objects are formed at least predominantly of liquid that is immiscible with the carrier fluid. Paragraph B17. The method of any one of paragraphs B1 to B16, wherein the objects are selected from the group consisting of beads, droplets, and biological cells. Paragraph B18. The method of any one of paragraphs B1 to B17, further comprising a step of forming partitions from a stream including the carrier fluid and carrying a plurality of the objects at a position of the channel structure downstream of the downstream section. Paragraph B19. The method of paragraph B18, wherein each partition of a majority of the partitions contains none or only one of the objects. Paragraph B20. The method of paragraph B18 or B19, wherein the step of forming partitions includes a step of encapsulating volumes of the stream with an immiscible liquid. Paragraph B21. The method of any one of paragraphs B18 to B20, wherein the step of forming partitions includes a step of forming droplets. Paragraph B22. The method of any one of paragraphs B18 to B21, wherein the objects are beads, further comprising a step of adding biological cells to the carrier fluid. Paragraph B23. The method of paragraph B22, wherein each partition of a plurality of the partitions contains only one of the beads and only one biological cell. Paragraph B24. The method of any one of paragraphs B1 to B23, further comprising a step of passing one or more of the objects through a detection zone downstream of the downstream section, and a step of detecting a signal from the detection zone. Paragraph B25. The method of paragraph B24, wherein the step of detecting a signal includes a step of detecting light. Paragraph C1. A method of altering the spacing of a stream of objects, the method comprising: (a) transporting objects of the object stream in carrier fluid along a microfluidic channel structure having a deceleration region upstream of an acceleration region; (b) slowing down objects within the object stream at the deceleration region such that at least a subset of such objects are moved closer to one another; and (c) speeding up objects of the object stream at the acceleration region to increase a distance between such objects; wherein the object stream has a lower incidence of closely-spaced pairs of the objects downstream of the acceleration region compared to upstream of the deceleration region. Paragraph C2. The method of paragraph C1, further comprising any one or combination of the limitations from paragraphs A1 to A35 and B1 to B25. Paragraph D1. A method of altering the spacing of a stream of objects, the method comprising: (a) transporting the objects of the object stream in carrier fluid along a microfluidic channel structure having an inflow region, an outflow region, and an expanded region extending from the inflow region to the outflow region, wherein the expanded region has a greater cross-sectional area for fluid flow than the inflow region and the outflow region; (b) moving objects of the object stream from the inflow region to the expanded region such that at least a subset of such objects are moved closer to one another; and (c) passing objects of the object stream from the expanded region to the outflow region to increase a distance between such objects. Paragraph E1. A system for arranging a set of objects, comprising: (a) a microfluidic channel structure having a reformatting zone including an object-accessible region and at least one object-excluding region; and (b) at least one source of positive/negative pressure operatively connected to the channel structure and configured to form a stream of carrier fluid transporting objects of the set in the channel structure; wherein the channel structure is configured such that a portion of the carrier fluid is moved from the object-accessible region to the at least one object-excluding region in an upstream section of the reformatting zone, to reduce a spacing between objects of the set, and such that the portion of the carrier fluid is directed into the object-accessible region from the at least one object-excluding region in a downstream section of the reformatting zone, to increase a spacing between objects of the set. Paragraph E2. The system of paragraph E1, further comprising any one or combination of the limitations from paragraphs A1 to A35, B1 to B25, C1 to C2, and D1. Paragraph F1. A system for altering the spacing of a stream of objects, comprising: (a) a microfluidic channel structure having an inflow region, an outflow region, and an expanded region extending from the inflow region to the outflow region, wherein the expanded region has a greater cross-sectional area for fluid flow than the inflow region and the outflow region; (b) a source of carrier fluid and objects in communication with the inflow region of the channel structure; and (c) at least one source of positive/negative pressure operatively connected to the channel structure and configured to form a stream of carrier fluid transporting a stream of objects, such that objects of the object stream pass from the inflow region to the expanded region and at least a subset of such objects are moved closer to one another, such that objects of the object stream are directed from the expanded region to the outflow region to increase a distance between such objects, and such that the object stream has a more uniform spacing of the objects downstream of the expanded region compared to upstream of the expanded region. The disclosure set forth above may encompass multiple distinct inventions with independent utility. Although each of these inventions has been disclosed in its preferred form(s), the specific embodiments thereof as disclosed and illustrated herein are not to be considered in a limiting sense, because numerous variations are possible. The subject matter of the inventions includes all novel and nonobvious combinations and subcombinations of the various elements, features, functions, and/or properties disclosed herein. The following claims particularly point out certain combinations and subcombinations regarded as novel and nonobvious. Inventions embodied in other combinations and subcombinations of features, functions, elements, and/or properties may be claimed in applications claiming priority from this or a related application. Such claims, whether directed to a different invention or to the same invention, and whether broader, narrower, equal, or different in scope to the original claims, also are regarded as included within the subject matter of the inventions of the present disclosure. Further, ordinal indicators, such as first, second, or third, for identified elements are used to distinguish between the elements, and do not indicate a particular position or order of such elements, unless otherwise specifically stated. Finally, the present disclosure incorporates material by reference. If any ambiguity or conflict in the meaning of a term results from this incorporation by reference, the literal contents of the application govern construction of the term.
53,394
11857969
DETAILED DESCRIPTION Described herein are air-matrix digital microfluidics (DMF) methods and apparatuses that may be used with a fresh or stored (e.g., frozen) blood same, including blood samples taken directly from a patient. An air-matrix DMF apparatus as described herein may be particularly useful for use with immediately processing blood samples as part of the DMF process. In particular, described herein are air-matrix DMF apparatuses including a plasma separation membrane as part of the apparatus, including as part of a cartridge that may be applied to a DMF driving apparatus. The plasma separation membrane may be formed as part of the top (e.g., top surface, or top plate) of the DMF apparatus. The apparatus may be configured to enhance the capillary forces drawing plasma through the plasma separation membrane and into the air gap of the DMF apparatus. Without the enhancements described herein, the rate of flow of plasma through a typically membrane (e.g., filter, separation membrane, etc.) would be rate limiting and slow, and would further limit the usefulness of the apparatus for directly processing blood without the need for separation or other pre-treatments. For example, in any of the apparatuses described herein, a plasma separation membrane may be included on the top plate of the digital microfluidic (DMF) apparatus. The apparatus may be configured to pre-wet the separation membrane and/or a method of using the apparatus may include prewetting the separation membrane, to enhanced capillary forces and achieve faster flow through membrane. The apparatus may be configured so that, upon contact of plasma with DMF surface, the electrode(s) is/are actuated to pull the plasma to the DMF device using electro wetting forces. For example, the apparatus may be configured to detect plasma contacting the one or more electrodes within a plasma loading region of the air gap, for example, by electrical detection (e.g., change of an electrical property of the electrode(s)), optical detection (e.g., an optical sensor aimed at the air gap region at or near the plasma loading region), etc. Once fluid, e.g., plasma, is detected within this region, the DM apparatus may electrically modify the electrowetting forces and move the droplet. Pulling the droplet away by adjusting the electrowetting force may increase the flow of plasma through the membrane and into the air gap. In any of the apparatuses and methods described herein, the plasma separation membrane may be sandwiched between super hydrophobic surfaces. The loading region on the outward-facing side of the apparatus may be a super-hydrophobic surface (e.g., including super hydrophobic coatings). The super hydrophobic environment surrounding the membrane may prevent a blood sample from overflowing the edges of the separation membrane, and may help achieve a maximum volume flow through membrane. Any of the methods (including user interfaces) described herein may be implemented as software, hardware or firmware, and may be described as a non-transitory computer-readable storage medium storing a set of instructions capable of being executed by a processor (e.g., computer, tablet, smartphone, etc.), that when executed by the processor causes the processor to control perform any of the steps, including but not limited to: displaying, communicating with the user, analyzing, modifying parameters (including timing, frequency, intensity, etc.), determining, alerting, or the like. In general, an air-matrix DMF apparatus as disclosed herein may have any appropriate shape or size. The air-matrix DMF apparatuses described herein generally include at least one hydrophobic surface and a plurality of activation electrodes adjacent to the surface; either the hydrophobic surface may also be a dielectric material or an additional dielectric material/layer may be positioned between the actuation electrodes and the hydrophobic surface. For example, in some variations, the air-matrix DMF includes a series of layers on a printed circuit board (PCB) forming a first or bottom plate. The outer (top) surface of this plate is the hydrophobic layer. Above this layer is the air gap (air gap region) along which a reaction droplet may be manipulated. In some variations a second plate may be positioned opposite from the first plate, forming the air gap region between the two. The second plate may also include a hydrophobic coating and in some variations may also include a ground electrode or multiple ground electrodes opposite the actuation electrodes. The actuation electrodes may be configured for moving droplets from one region to another within the DMF device, and may be electrically coupled to a controller (e.g., control circuitry) for applying energy to drive movement of the droplets in the air gap. As mentioned, this plate may also include a dielectric layer for increasing the capacitance between the reaction droplet and the actuation electrodes. The reaction starting materials and reagents, as well as additional additive reagents may be in reservoirs that may be dispensed into the air gap, where the reaction mixture is typically held during the reaction. In some instances the starting materials, reagents, and components needed in subsequent steps may be stored in separate areas of the air gap layer such that their proximity from each other prevents them from prematurely mixing with each other. In other instances, the air gap layer may include features that are able to compartmentalize different reaction mixtures such that they may be close in proximity to each other but separated by a physical barrier. In general, the floor of the air gap is in the first plate, and is in electrical contact with a series of actuation electrodes. In some embodiments, one of the plates can be integrated into a reader device, and the other plate can be integrated into a removable, disposable cartridge, that when attached to the reader, form a two plate digital microfluidics system similar to that described herein. The reader device can be a permanent, reusable device that contains all or a bulk of the electronics for controlling the DMF system, and may optionally also containing sensors (i.e. sensors for measuring color and/or light, temperature or pH) for analyzing the droplets in the device. In addition, the actuation electrodes can be disposed on a film, which can also be made of a dielectric material. The film can be removably attached to one of the plates, such as the plate on the reader or the plate on the cartridge, while the other plate can have the ground electrode(s). For example, U.S. Pat. Nos. 8,187,864; 8,470,153; 8,821,705; 8,993,348; and 9,377,439, which are hereby incorporated by reference in their entireties, describe cartridge based DMF systems. FIG.10is a schematic depicting a removable film or sheet with electrodes and/or pre-loaded with reagents that can be removably attached to one of the plates. The film10may optionally have an at least one pre-loaded reagent depot12mounted (i.e. spotted and dried/frozen) on a hydrophobic front surface of the film10. This disposable substrate10may be any thin dielectric sheet or film so long as it is chemically stable toward the reagents pre-loaded thereon. For example, any polymer based plastic may be used, such as for example saran wrap. In addition to plastic food-wrap, other substrates, including generic/clerical adhesive tapes and stretched sheets of paraffin, were also evaluated for use as replaceable DMF substrates. As shown, the disposable sheet10can be affixed to the electrode array16of the DMF device14with a back surface of the sheet10adhered or suctioned to the electrode array16in which the reagent depot12deposited on the surface of the sheet10(across which the reagent droplets are translated) is aligned with pre-selected individual electrode18of the electrode array16as shown in steps (1) and (2) ofFIG.10. One or more reagents droplets20and22can deposited onto the device prior to or during an assay. As can be seen from step3ofFIG.10, during the assay reagent droplets20and22can be actuated over the top of film10to facilitate mixing and merging of the assay reagent droplets20and22with the desired reagent depot12over electrode18. After the reaction has been completed, the disposable film10may then be peeled off as shown in step (4) and the resultant reaction products26analyzed if desired as shown in step (5). A fresh disposable film10may then be attached to the DMF device14for the next round of analysis. The product26can be also analyzed while the removable substrate is still attached to the device DMF device14. This process can be recycled by using additional pre-loaded substrates. In addition, the droplets containing reaction product(s) may be split, mixed with additional droplets, incubated for cell culture if they contain cells. In some embodiments as shown inFIG.11, the film10may also have a plurality of electrodes23that are attached and/or embedded within the film10. The film10may have electrical contacts and/or junctions that electrically couple the film10and electrodes23to complementary electrical contacts and junctions on the top or bottom plate of the DMF device. In this embodiment, the plate to which the film10is attached may not have any electrodes and instead may only have electrical contacts and/or junctions for electrically coupling with the film10. The air gap DMF apparatuses described herein may also include other elements for providing the needed reaction conditions. For instance, the air gap DMF apparatuses may include one or more thermal regulators (e.g., heating or cooling element such as thermoelectric modules) for heating and cooling all or a region (thermal zone) of the air gap. In other instances, heating or cooling may be provided by controlling endothermic or exothermic reactions to regulate temperature. The air gap DMF apparatuses may also include temperature detectors (e.g., resistive temperature detector) for monitoring the temperature during a reaction run. In addition, the DMF apparatuses may also include one or more magnets that can be used to manipulate magnetic beads in an on demand fashion. For example, the magnet(s) can be an electromagnet that is controlled by a controller to generate a magnetic field that can agitate or immobilize magnetic beads. Thus, the air gap DMF apparatuses described herein may include one or more thermal zones. Thermal zones are regions on the air gap DMF apparatuses (e.g., the air gap) that may be heated or cooled, where the thermal zones may transfer the heating or cooling to a droplet within the thermal zone through one or more surfaces in contact with the air gap region in the zone (e.g., the first plate). Heating and cooling may be through a thermal regulator such as a thermoelectric module or other type of temperature-modulating component. The temperature of one or many thermal zones may be monitored through a temperature detector or sensor, where the temperature information may be communicated to a computer or other telecommunication device. The temperature is typically regulated between 4° C. and 100° C., as when these apparatuses are configured to perform one or more reactions such as, but not limited to: nucleic acid amplifications, like LAMP, PCR, molecular assays, cDNA synthesis, organic synthesis, etc. An air gap DMF apparatus may also include one or more thermal voids. Thermal voids may be disposed adjacent to the different thermal zones. The thermal voids are typically regions in which heat conduction is limited, e.g., by removing part of the plate (e.g., first plate) (forming the “void”). These voids may be strategically placed to isolate one thermal zone from another which allows the correct temperatures to be maintained within each thermal zone. In general, any of the air-matrix DMF apparatuses described herein may include a separate reaction chamber that is separate or separable from the air gap of the apparatus, but may be accessed through the air gap region. The reaction chamber typically includes a reaction chamber opening that is continuous with the lower surface of the air gap (e.g., the first plate), and a reaction chamber well that forms a cup-like region in which a droplet may be controllably placed (and in some variations, removed) by the apparatus to perform a reaction when covered. The cover may be a mechanical cover (e.g., a cover the seals or partially seals the reaction chamber opening, or a cover that encapsulates, encloses or otherwise surrounds the reaction droplet, such as an oil or wax material that mixes with (then separates from and surrounds) the reaction droplet when the two are combined in the reaction chamber. In general, the reaction chamber opening may be any shape or size (e.g., round, square, rectangular, hexagonal, octagonal, etc.) and may pass through the first (e.g., lower) plate, and into the reaction chamber well. In some variations, the reaction chamber opening passes through one or more actuation electrodes; in particular, the reaction chamber opening may be completely or partially surrounded by an actuation electrode. FIG.1shows a top view of an exemplary air-matrix DMF apparatus101. As shown, the DMF device may include a series of paths defined by actuation electrodes. The actuation electrodes103are shown inFIG.1as a series of squares, each defining a unit cell. These actuation electrodes may have any appropriate shape and size, and are not limited to squares. For example, the unit cells formed by the actuation electrodes in the first layer may be round, hexagonal, triangular, rectangular, octagonal, parallelogram-shaped, etc. In the example ofFIG.1, the squares representing the unit cells may indicate the physical location of the actuation electrodes in the DMF device or may indicate the area where the actuation electrode has an effect (e.g., an effective area such that when a droplet is situated over the denoted area, the corresponding actuation electrode may affect the droplet's movement or other physical property). The actuation electrodes103may be placed in any pattern. In some examples, actuation electrodes may span the entire corresponding bottom or top surface the air gap of the DMF apparatus. The actuation electrodes may be in electrical contact with starting sample chambers (not shown) as well as reagent chambers (not shown) for moving different droplets to different regions within the air gap to be mixed with reagent droplets or heated. In the air-matrix apparatuses described herein, the first (lower) plate may also include one or more reaction chamber openings (access holes)105,105′. Access to the reaction chamber wells may allow reaction droplets to be initially introduced or for allowing reagent droplets to be added later. In particular, one or more reaction droplets may be manipulate in the air gap (moved, mixed, heated, etc.) and temporarily or permanently moved out of the air gap and into a reaction chamber well though a reaction chamber opening. As shown, some of the reaction chamber openings105′ pass through an actuation electrode. As will be shown in greater detail herein, the reaction chamber may itself include additional actuation electrodes that may be used to move a reaction chamber droplet into/out of the reaction chamber well. In some variations one or more actuation electrodes may be continued (out of the plane of the air gap) into the reaction chamber well. In general, one or more additional reagents may be subsequently introduced either manually or by automated means in the air gap. In some instances, the access holes may be actual access ports that may couple to outside reservoirs of reagents or reaction components through tubing for introducing additional reaction components or reagents at a later time. As mentioned, the access holes (including reaction chamber openings) may be located in close proximity to a DMF actuation electrode(s). Access holes may also be disposed on the side or the bottom of the DMF apparatus. In general, the apparatus may include a controller110for controlling operation of the actuation electrodes, including moving droplets into and/or out of reaction chambers. The controller may be in electrical communication with the electrodes and it may apply power in a controlled manner to coordinate movement of droplets within the air gap and into/out of the reaction chambers. The controller may also be electrically connected to the one or more temperature regulators (thermal regulators120) to regulate temperature in the thermal zones115. One or more sensors (e.g., video sensors, electrical sensors, temperature sensors, etc.) may also be included (not shown) and may provide input to the controller which may use the input from these one or more sensors to control motion and temperature. As indicated above, surface fouling is an issue that has plagued microfluidics, including DMF devices. Surface fouling occurs when certain constituents of a reaction mixture irreversibly adsorbs onto a surface that the reaction mixture is in contact with. Surface fouling also appears more prevalent in samples containing proteins and other biological molecules. Increases in temperature may also contribute to surface fouling. The DMF apparatuses and methods described herein aim to minimize the effects of surface fouling. One such way is to perform the bulk of the reaction steps in a reaction chamber that is in fluid communication with the air gap layer. The reaction chamber may be an insert that fits into an aperture of the DMF device as shown inFIGS.2B and2C.FIG.2Bshows the floor (e.g., first plate) of an air gap region coupled to a centrifuge (e.g., Eppendorf) tube205whileFIG.2Cincorporates a well-plate207(e.g., of a single or multi-well plate) into the floor of the air gap region. A built-in well209may also be specifically fabricated to be included in the air-matrix DMF apparatus as shown inFIG.2D. When a separate or separable tube or plate is used, the tubes may be coupled to the DMF device using any suitable coupling or bonding means (e.g., snap-fit, friction fit, threading, adhesive such as glue, resin, etc., or the like). In general, having a dedicated reaction chamber within the DMF device minimizes surface fouling especially when the reaction is heated. Thus, while surface fouling may still occur within the reaction chamber, it may be mainly constrained to within the reaction chamber. This allows the majority of the air gap region floor to remain minimally contaminated by surface fouling and clear for use in subsequent transfer of reagents or additional reaction materials if needed, thus allowing for multi-step or more complex reactions to be performed. When the reaction step or in some instances, the entire reaction is completed, the droplet containing the product may be moved out of the reaction chamber to be analyzed. In some examples, the product droplet may be analyzed directly within the reaction chamber. In order to bring the droplet(s) containing the starting materials and the reagent droplets into the reaction chamber, additional actuation electrodes, which may also be covered/coated with a dielectric and a hydrophobic layer (or a combined hydrophobic/dielectric layer), may be used.FIGS.3A-3Eshows a series of drawings depicting droplet301movement into and out of an integrated well305. As this series of drawings show, in addition to lining the floor of the air gap layer, additional actuation electrodes307line the sides and the bottom of the well. In some variations, the same actuation electrode in the air gap may be extended into the reaction chamber opening. The actuation electrodes307(e.g., the reaction chamber actuation electrodes) may be embedded into or present on the sides and bottom of the well for driving the movement of the droplets into/out of the reaction chamber well. Actuation electrodes may also cover the opening of the reaction chamber. InFIG.3A, a droplet301(e.g., reaction droplet) in the air gap layer may be moved (using DMF) to the reaction chamber opening. The actuation electrodes307along the edge of the well and the sides of the well maintain contact with the droplet as it moved down the well walls to the bottom of the well (shown inFIGS.3B and3C). Once in the reaction chamber well, the droplet may be covered (as described in more detail below, either by placing a cover (e.g., lid, cap, etc.) over the reaction chamber opening and/or by mixing the droplet with a covering (e.g., encapsulating) material such as an oil or wax (e.g., when the droplet is aqueous). In general, the droplet may be allowed to react further within the well, and may be temperature-regulated (e.g., heated, cooled, etc.), additional material may be added (not shown) and/or it may be observed (to detect reaction product). Alternatively or additionally, the droplet may be moved out of the well using the actuation electrodes; if a mechanical cover (e.g., lid) has been used, it may be removed first. If an encapsulating material has been used it may be left on. In some variations contacts may penetrate the surfaces of the reaction chamber. For example, there may be at least ten electrical insertion points in order to provide sufficient electrical contact between the actuation electrodes and the interior of the reaction chamber. In other examples there may need to be at least 20, 30, or even 40 electrical insertion points to provide sufficient contact for all the interior surfaces of the reaction chamber. The interior of the reaction chamber may be hydrophobic or hydrophilic (e.g., to assist in accepting the droplet). As mentioned, an electrode (actuation electrode) may apply a potential to move the droplets into and/or out of the well. In general, the actuation electrodes may bring the droplet into the well in a controlled manner that minimizes dispersion of the droplet as it is moved into the well and thus maintaining as cohesive a sample droplet as possible.FIGS.3D and3Eshow the droplet being moved up the wall of the well and then out of the reaction chamber. This may be useful for performing additional subsequent steps or for detecting or analyzing the product of interest within the droplet, although these steps may also or alternatively be performed within the well. Actuation electrodes may be on the bottom surface, the sides and the lip of the well in contact with the air gap layer; some actuation electrodes may also or alternatively be present on the upper (top) layer. In instances where the reaction compartment is an independent structure integrated with the DMF devices as those shown inFIGS.2A and2B, the thickness of the substrate (e.g., PCB) may be similar to what is commonly used in DMF fabrication. When the reaction compartment is an integrated well structure fabricated in the bottom plate of the DMF device as shown inFIG.2D, the thickness of the substrate may be equivalent to the depth of the well. In another embodiment, the electrodes embedded in the reaction compartments can include electrodes for the electrical detection of the reaction outputs. Electrical detection methods include but are not limited to electrochemistry. In some instances, using the changes in electrical properties of the electrodes when the electrodes contact the reaction droplet, reagent droplet, or additional reaction component to obtain information about the reaction (e.g., changes in resistance correlated with position of a droplet). The apparatuses described herein may also prevent evaporation. Evaporation may result in concentrating the reaction mixture, which may be detrimental as a loss of reagents in the reaction mixture may alter the concentration of the reaction mixture and result in mismatched concentration between the intermediate reaction droplet with subsequent addition of other reaction materials of a given concentration. In some variations, such as with enzymatic reactions, enzymes are highly sensitive to changes in reaction environment and loss of reagent may alter the effectiveness of certain enzymes. Evaporation is especially problematic when the reaction mixture has to be heated to above ambient temperature for an extended period of time. In many instances, microfluidics and DMF devices utilize an oil-matrix for performing biochemical type reactions in microfluidic and DMF devices to address unwanted evaporation. One major drawback of using an oil matrix in the DMF reaction is the added complexity of incorporating additional structures to contain the oil. The methods and apparatuses described herein may prevent or limit evaporation by the use of wax (e.g., paraffin) in minimizing evaporation during a reaction. A wax substance may include substances that are composed of long alkyl chains. Waxes are typically solids at ambient temperatures and have a melting point of approximately 46° C. to approximately 68° C. depending upon the amount of substitution within the hydrocarbon chain. However, low melting point paraffins can have a melting point as low as about 37° C., and some high melting point waxes can have melting points about 70-80° C. In some instances higher melting point waxes may be purifying crude wax mixtures. As mentioned, wax is one type of sealing material that may be used as a cover (e.g., within a reaction chamber that is separate from the plane of the air gap). In some variations, wax may be used within the air gap. In particular, the wax may be beneficially kept solid until it is desired to mix it with the reaction droplet so that it may coat and protect the reaction droplet. Typically the wax material (or other coating material) may be mixed with the reaction droplet and enclose (e.g., encapsulate, surround, etc.) the aqueous reaction droplet. When a reaction droplet is maintained within a paraffin coating, not only is evaporation minimized, but the paraffin may also insulate the reaction droplet from other potentially reaction interfering factors. In some instances, a solid piece of paraffin or other wax substance may be placed within a thermal zone of the air gap layer of the DMF device. For example, during a reaction, actuation electrodes may move a reaction droplet to a wax (e.g., paraffin) body. Upon heating to a melting temperature, the wax body may melt and cover the reaction droplet. The reaction then may continue for an extended period of time (including at elevated temperatures) without need to replenish the reaction solvents, while preventing loss by evaporation. For example wax-encapsulated droplet may be held and/or moved to a thermal zone to control the temperature. The temperature may be decreased or increased (allowing control of the phase of the wax as well, as the wax is typically inert in the reactions being performed in the reaction droplet). The temperature at that particular thermal zone may be further increased to melt the paraffin and release the reaction droplet. The reaction droplet may be analyzed for the desired product when encapsulated by the liquid or solid wax, or it may be moved to another region of the DMF device for further reaction steps after removing it from the wax covering. Paraffins or other wax materials having the desired qualities (e.g. melting point above the reaction temperature) may be used. For example, paraffins typically have melting points between 50 and 70 degrees Celsius, but their melting points may be increased with increasing longer and heavier alkanes. FIG.4Ashows a time-sequence images (numbered 1-4) taken from an example using a wax body within the air matrix as discussed above, showing profound reduction in evaporation as compared to a control without wax (shown inFIG.4B, images 1-2). InFIG.4A, the first image, in the top right, shows an 8 μL reaction droplet603that has been moved by DMF in the air matrix apparatus to a thermal zone (“heating zone”) containing a solid wax body (e.g., paraffin wall601). Once in position, the reaction droplet may be merged with a solid paraffin wall (e.g., thermally printed onto DMF), as shown in image 2 ofFIG.4A, or the wax material may be melted first (not shown). InFIG.4Aimage 3, the thermal zone is heated (63° C.) to or above the melting point of the wax material thereby melting the paraffin around the reaction droplet, and the reaction droplet is surrounded/encapsulated by the wax material, thus preventing the droplet from evaporation as shown inFIG.4Aimages 3 and 4. Using this approach, in the example shown inFIG.4Aimage 4, the volume of reaction droplets was maintained roughly constant at 63° C. for an incubation time approximately two hours long (120 min). An equivalent experiment without the paraffin wall was performed, and shown inFIG.4B. The left picture (image 1) inFIG.4Bshows the reaction droplet603′ at time zero at 63° C. and the right picture ofFIG.4Bshows the reaction droplet after 60 minutes at 63° C. As shown, the reaction droplet almost completely evaporated within approximately an hour's time at 63° C. Through this approach of enclosing a droplet in a shell of liquid wax, the reaction volume and temperature are maintained constant without the use of oil, a humidified chamber, off-chip heating, or droplet replenishment methods. Waxes other than paraffin can be used to prevent droplet evaporation as long as their melting temperature is higher than the ambient temperature, but lower or equal to the reaction temperature. Examples of such waxes include paraffin, bees and palm waxes. The wax-like solids can be thermally printed on the DMF device surface by screen-, 2D- or 3D-printing. This wax-mediated evaporation prevention solution is an important advancement in developing air-matrix DMF devices for a wide variety of new high-impact applications. As mentioned, the wax-based evaporation methods described may be used in conjunction with the DMF devices having a reaction chamber feature, or they may be used without separate reaction chambers. When used within a reaction chamber, the wax may be present in the reaction chamber and the reaction droplet may be moved to the reaction chamber containing wax for performing the reaction steps requiring heating. Once the heating step has completed, the reaction droplet may be removed from the reaction chamber for detection or to perform subsequent reaction steps within the air gap layer of the DMF device. In other embodiments, the wax may be liquid at room temperature or an oil can be used instead of a wax or a solid wax can be heated until it is liquid. Instead of a heated reaction zone with wax, the liquid wax or oil can be mixed with a reagent before introducing the mixture into the DMF device in order to prevent the reagent from evaporating. The reagent droplet will then have a liquid wax or oil shell surrounding the reagent, which can be manipulated as described above. In some embodiments, the liquid wax/oil can be added manually to the reagent by the user. In other embodiments, the liquid wax/oil and the reagent can be dispensed from reservoirs, mixed together, and introduced into the DMF device using a pump by the DMF device. The methods and apparatuses described herein may be used for preventing evaporation in air-matrix DMF devices and may enable facile and reliable execution of any chemistry protocols on DMF with the requirement for a temperature higher than the ambient temperature. Such protocols include, but are not limited to, DNA/RNA digestion/fragmentation, cDNA synthesis, PCR, RT-PCR, isothermal reactions (LAMP, rolling circle amplification-RCA, Strand Displacement Amplification-SDA, Helicase Dependent Amplification-HDA, Nicking Enzyme Amplification reaction-NEAR, Nucleic acid sequence-based amplification-NASBA, Single primer isothermal amplification-SPIA, cross-priming amplification-CPA, Polymerase Spiral Reaction-PSR, Rolling circle replication-RCR), as well as ligation-based detection and amplification techniques (ligase chain reaction-LCR, ligation combined with reverse transcription polymerase chain reaction-RT PCR, ligation-mediated polymerase chain reaction-LMPCR, polymerase chain reaction/ligation detection reaction-PCR/LDR, ligation-dependent polymerase chain reaction-LD-PCR, oligonucleotide ligation assay-OLA, ligation-during-amplification-LDA, ligation of padlock probes, open circle probes, and other circularizable probes, and iterative gap ligation-IGL, ligase chain reaction-LCR, over a range of temperatures (37-100° C.) and incubation times (≥2 hr). Additional protocols that can be executed using the systems and methods described herein include hybridization procedures such as for hybrid capture and target enrichment applications in library preparation for new generation sequencing. For these types of applications, hybridization can last up to about 3 days (72 h). Other protocols include end-repair, which can be done, for example, with some or a combination of the following enzymes: DNA Polymerase I, Large (Klenow) Fragment (active at 25° C. for 15 minutes), T4 DNA Polymerase (active at 15° C. for 12 minutes), and T4 Polynucleotide Kinase (active at 37° C. for 30 minutes). Another protocol includes A-Tailing, which can be done with some or a combination of the following enzymes: Taq Polymerase (active at 72° C. for 20 minutes), and Klenow Fragment (3′→5′ exo-) (active at 37° C. for 30 minutes). Yet another protocol is ligation by DNA or RNA ligases. Manipulation and Processing of Encapsulated Droplets Although the encapsulation of droplets in wax may prevent or reduce evaporation while executing chemistry protocols at elevated temperatures, after protocol completion, it has been discovered that when the droplet is removed and separated from the wax, e.g., by driving the droplet using the electrodes of the DMF apparatus, a small amount of liquid wax remains with the droplet as a coating even when the aqueous droplet is moved away from the wax, and that this wax coating may prevent or interfere with subsequent processing and analysis of the reaction droplet, particularly as the droplet cools and the wax solidifies around the droplet after the droplet is moved out of the heating zone. Therefore, in some embodiments, the wax encapsulated reaction droplet can be accessed through the wax coating using the systems and methods described herein, which enables facile and reliable execution of downstream biochemical processes. To access the reaction droplet through the wax coating after the reaction droplet has been separated from the bulk liquid wax in the heating zone, an additional hydrophobic (e.g., oil) material may be added to the reaction droplet to help dissolve the solidified wax encapsulated the reaction droplet. For example, a carrier droplet (i.e., an aqueous droplet enclosed in a thin layer of oil) can be merged with the encapsulated reaction droplet. The carrier droplet gains access to the reaction droplet by having the oil from the carrier droplet dissolve and/or merge with the thin wax layer encapsulating the reaction droplet. Other materials other than oil may be used by the carrier droplet to break through the wax layer encapsulating the reaction droplet. For example, materials that are immiscible with aqueous reaction droplet and are capable of dissolving wax may be used, such as carbon tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, dichloromethane, diethyl ether, dimethyl formamide, ethyl acetate, heptane, hexane, methyl-tert-butyl ether, pentane, toluene, 2,2,4-trimethylpentane, and other organic solvents. Other materials that may be used to break through the wax layer include ionic detergents such as cetyltrimethylammonium bromide, Sodium deoxycholate, n-lauroylsarcosine sodium salt, sodium n-dodecyl Sulfate, sodium taurochenodeoxycholic; and non-ionic detergents such as dimethyldecylphosphine oxide (APO-10), dimethyldodecylphosphine oxide (APO-12), n-Dodecyl-β-D-maltoside (ULTROL®), n-dodecanoylsucrose, ELUGENT™ Detergent, GENAPOL® C-100, HECAMEG®, n-Heptyl β-D-glucopyranoside, n-Hexyl-b-D-glucopyranoside, n-Nonyl-b-D-glucopyranoside, NP-40 Alternative, n-Octanoylsucrose, n-Octyl-b-D-glucopyranoside, n-Octyl-b-D-thioglucopyranoside, PLURONIC® F-127, Saponin, TRITON® X-100, TRITON® X-114, TWEEN® 20, TWEEN® 80, Tetronic 90R4. At temperatures where a wax remains liquid, a carrier droplet encapsulated with wax may also be used to break through the wax encapsulating the reaction droplet. However, for lower temperatures where the wax solidifies, a carrier droplet coated with wax generally cannot be used since solid wax will prevent droplet movement. For example,FIG.7Aillustrates a setup similar or the same as that shown inFIG.4A. The setup includes a DMF device interfaced to a heating element placed below or within the bottom DMF substrate, hence generating discrete heating zones900on the bottom DMF substrate. Alternatively, the heating element can be placed above or within the top substrate to form a heating zone on the top substrate. However, forming the heating zone on the bottom substrate allows visual access. On the bottom substrate, a hydrophilic region902is printed or otherwise formed or disposed around the actuating electrodes in the electrode array904that are in the heating zone900. One or more wax walls906or wax structures, which can be solid at room temperature, can be assembled on the top substrate by, for example, thermal printing to overlay a portion of the hydrophilic region902adjacent to the electrodes in the heating zone900on the bottom plate when the DMF device is assembled. Alternatively, the wax walls906or wax structures can be formed directly on the bottom plate around the electrodes in the heating zone900. In yet another embodiment, the wax walls906can be placed on a removable sheet that can be removably attached to either the top plate or the bottom plate. The removable sheet can have a hydrophobic surface on one side for interacting with the droplet and an adhesive on the other side for adhering to the top or bottom plate. Reagents and other materials can also be placed on the removable sheet to interact with the droplets. In some embodiments, the top plate or the bottom plate can be part of a removable cartridge that is combined with the other plate and electronics to form the working DMF device. As described herein, a reaction droplet908can be transported to the heating zone900along a path of actuating electrodes, which may be a relatively narrow path formed by a single line of actuating electrodes to the heating zone900. Then the heating zone900is heated, and the wax wall906surrounding the heating zone900and reaction droplet908melts to encapsulate the reaction droplet908in liquid wax910as shown inFIG.7B(frame i), thereby preventing or reducing evaporation from the reaction droplet908during the reaction protocol. The hydrophilic region902surrounding the heating zone900functions to pin or localize the liquid wax910in place in the heating zone900and allows the reaction droplet908to break away as described below. As shown inFIG.7B(frames ii-iv), the process of breaking away or separating the encapsulated reaction droplet908from liquid wax910can be accomplished by driving the aqueous reaction droplet908away from the heating zone900and the liquid wax910by actuating the actuating electrodes in the heating zone and path. As the aqueous reaction droplet908is actuated away from the heating zone900, the hydrophilic region902surrounding the liquid wax910helps hold the liquid wax910in place as the reaction droplet908moves away from the heating zone900, which causes the liquid wax910encasing the droplet908to begin to neck and eventually break off from the droplet908, thereby leaving trace or small quantities of liquid wax910surrounding the separated reaction droplet908. In general, the heating zone900is single use only to avoid cross-contamination. However, in situations where cross-contamination is not an issue, the heating zone900may be reused by heating and melting the wax within the heating zone and then moving the next droplet into the reheated liquid wax910. Because the reaction droplet may be surrounded by a thin layer of liquid wax910after separation from the heating zone900, it may be difficult to merge the reaction droplet908with another aqueous droplet since the liquid wax910coating may act as a barrier. In addition, the liquid wax910may solidify as the droplet cools to form a physical barrier that impedes merger with another droplet. Therefore, to facilitate merging of a liquid wax910coated reaction droplet908or a cooled reaction droplet908with a solid wax coating with another droplet, a carrier droplet912can be used to merge with the reaction droplet908as shown inFIG.7B(frame v). The carrier droplet912can be an aqueous droplet that is coated with a thin layer of oil or another organic solvent as described above. The aqueous portion of the carrier droplet912can include additional reagents, beads coated (or not) with DNA/RNA probes or antibodies or antigens for performing separations, uncoated beads, magnetic beads, beads coated with a binding moiety, solid phase reversible immobilization (SPRI) beads, water for dilution of the reaction droplet, enzymes or other proteins, nanopores, wash buffers, ethanol or other alcohols, formamide, detergents, and/or other moieties for facilitating further processing of the reaction droplet908. As shown inFIG.8A(frames i-iv), when the carrier droplet912and the reaction droplet908are moved by the actuating electrodes to the same location, the thin layer of oil surrounding the carrier droplet912can merge with the thin layer of liquid wax surrounding the reaction droplet908, thereby facilitating the merger of the aqueous portions of the two droplets908,912to form a combined droplet914. After the carrier droplet912has been merged with the reaction droplet908, further processing of the combined droplet914can proceed, such as extracting an analyte from the combined droplet914and/or perform other steps such as hybridizing capture probes, digesting the reaction product using an enzyme, amplifying the reaction product with a set of primers, and the like. For example, the carrier droplet912can be carrying beads for extracting the analyte, e.g., DNA or RNA or proteins. When the droplets are merged, the beads, which can be magnetic, can be used to mix the combined droplet914by application of a magnetic field. The target analyte binds to the beads, which can be immobilized against the substrate by the magnetic field to form a bead pellet916, as shown inFIG.8B(frame i). Next, the combined droplet914can be moved away from the immobilized bead pellet916, leaving the bead pellet916with bound analyte on the substrate, as shown inFIG.8B(frames ii-iii). The combined droplet914can be moved away from the immobilized bead pellet916by actuating the electrodes. Alternatively, the combined droplet914can be held in place while the bead pellet916is moved away from the combined droplet914. The bead pellet916can be moved away and separated from the combined droplet914by, for example, moving the magnetic field (e.g., by moving the magnet generating the magnetic field) that is engaging the bead pellet916away from the combined droplet914. In some embodiments, the combined droplet914can be actively immobilized through actuation of the electrodes in contact with the droplet and/or surrounding the droplet. Alternatively or in addition, the droplet914can be passively immobilized through natural adhesive forces between the droplet and substrate on which the droplet is contacting, as well as physical structures, such as retaining walls that partially surround the combined droplet914while having an opening for passing the bead pellet916. As shown inFIG.8C(frames i and ii), an aqueous droplet918can be moved over the bead pellet916to resuspend the beads with the bound analyte. See Example 3 described below for an embodiment of this procedure used for miRNA purification. Plasma Extraction FIGS.9A-9Eillustrate a DMF device1000with a sample inlet1002for receiving a sample, such as whole blood, and a sample outlet1004that deposits a droplet of the sample into the air gap between the top plate1006and bottom plate1008for manipulation by the actuation electrodes1010. A separation membrane1012, such as plasma separation membrane for separating plasma from whole blood, can be positioned between the sample inlet1002and sample outlet1004for filtering the sample. To form the sample inlet1002, a cover plate1014, with a hole or port that can serve as the sample inlet1002, can be placed over a hole or port in the top plate1006that can serve as the sample outlet1004. The cover plate1014can be made of a hydrophobic or super-hydrophobic material or can be coated with a hydrophobic or super-hydrophobic layer1016, as shown inFIG.9B. A water droplet on a super-hydrophobic surface has a contact angle of greater than 150 degrees, while a water droplet on a hydrophobic surface has a contact angle greater than 90 degrees but less than 150 degrees. In addition, the top surface of the top plate1006can also be coated with a hydrophobic or super-hydrophobic material. The separation membrane1012can sandwiched between the hydrophobic surfaces of the cover plate1014and top surface of the top plate1006. Making these surfaces hydrophobic prevents or greatly reduces the spread of blood out of the sample inlet1002and over the cover plate1014. In addition, as the blood sample saturates and passes through the separation membrane1012, the hydrophobic surfaces prevent or greatly reduce the spread of blood out of the membrane and into the gap between the cover plate1014and top plate1006. The separation membrane1012can be made of a porous, hydrophilic material, with the pore size decreasing through the membrane thickness such that larger pores are located on the sample inlet1002side and smaller pores are located on the sample outlet1004side. In some embodiments, a gasket can be placed between the cover plate1014and top plate1006and around the separation membrane1012in order to prevent the spread of blood between the cover plate1014and top plate1006. The sample outlet1004, which can be formed as a hole in the top plate1006, can optionally have a hydrophilic surface, such as from a hydrophilic coating or layer or from constructing the top plate1006from a hydrophilic material. A hydrophilic coating or layer may help draw the plasma through the separation membrane1012and into the sample outlet1004. For example, in one embodiment, a cover plate1014having about a 1 mm to 10 mm ID hole (e.g. a 4 mm ID hole) can be spray-coated on both sides with a super-hydrophobic layer (e.g., ˜500 nm layer of NeverWet®) followed by post-baking in an oven (100° C., 10 min). The top plate1006of the DMF device1000can have about a 1 to 20 mm ID hole (e.g. a 10 mm ID hole) that is aligned with the hole in the cover plate1014. The hole in the top plate1006may be larger than the hole in the cover plate1014. For example, the hole in the top plate1006may be about 3 to 10 mm larger than the hole in the cover plate1014. The top surface of the top plate1006that faces the cover plate1014can also be coated with a super-hydrophobic layer (as above) and the other side of the top plate1006with the ground electrode can be spin-coated with a hydrophobic layer (e.g., a 50 nm layer of Teflon-AF1600) followed by post-baking as above. The bottom plate1008of the DMF device1000can be fabricated from a six-layer PCB substrate bearing copper electrodes (e.g., a 43 μm thick layer) plated with nickel (e.g., a 185 μm thick layer) and gold (e.g. a 3.6 μm thick layer) that can be formed by conventional photolithography and etching techniques, and covered with dielectric tape (e.g. a 25 μm thick layer) or coating. The PCB substrate can have an array of electrodes, such as one-hundred and twenty actuation electrodes (e.g. each 3.5 mm×3.5 mm) with inter-electrode gaps of about 10 to 100 μm (e.g. 40 μm). The cover plate1014and top plate100can be assembled using screws, bolts, snaps, adhesives and/or other fasteners, with the separation membrane (e.g. PALL plasma separation membrane, Ann Arbor, MI) sandwiched in between. The bottom plate1008and top plate1006can be assembled with one or more spacers disposed between the two plates that separates the two plates by about 100 to 1000 μm (e.g. about 300 μm). For example, the spacer can be formed from one or more layers of double-sided tape (e.g. three pieces of double-sided tape having a total thickness of ˜300 μm). The double-sided tape can provide dual functions of spacing and fastening the top plate to the bottom plate. As described above, in some embodiments, one of the plates can be integrated into a reader device, and the other plate can be integrated into a removable cartridge, that when attached to the reader, form a two plate digital microfluidics system similar to that described herein. In addition, the actuation electrodes can be disposed on a film, which can also be made of a dielectric material. The film can be removably attached to one of the plates, such as the plate on the reader or the plate on the cartridge, while the other plate can have the ground electrode(s). For example, the film can be attached to the PCB substrate of the bottom plate. The process for extracting plasma from whole blood samples into the DMF device and onto the electrodes is depicted inFIGS.9A-9E. As shown, a sample of whole blood (e.g. 300 μL) can be spotted directly onto a prewetted (e.g. with tris buffer) separation membrane1012—faster flow is achieved through the separation membrane1012as a result of enhanced capillary forces due to prewetting. The sample can have a volume less than 100 to 5000 μL, or between 100 to 500 μL. The sample can be incubated for less than about 1 to 10 minutes (e.g. 1, 2, 3, 4, or 5 min) or between 1 to 10 minutes, and during that time plasma transfers from the bottom of separation membrane1012to the receiving DMF device surface with the actuation electrodes (e.g. the surface of the bottom plate) by gravity and capillary forces of the receiving DMF surface. In some embodiments, negative and/or positive pressure can be used to drive the fluid through the membrane. For example, a negative pressure can be generated between the plates at the fluid outlet using a pump, such as a displacement pump, and/or a positive pressure can be generated at the fluid inlet using a pump. The pressure and enhanced flow rate can be maintained below a desired threshold to reduce or prevent hemolysis, which can interfere with some types of nucleic acid assays. In some embodiments, the base flow rate using a 2 cm diameter membrane without pressure enhancement is between about 50 to 200 microliters per minute (i.e., 50, 60, 70, 80, 90, 100, 110, or 120 microliters per minute). The flow rate can depend on the size and characteristics of the membrane (i.e., pore size and pore distribution) as well as the magnitude of the applied positive and/or negative pressure. In some embodiments, the enhanced flow rate through the membrane with pressure enhancement can be less than 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100% more than the base flow rate through the membrane without pressure enhancement. The positive and/or negative pressure used to enhance the flow rate can be set or modulated to achieve the above flow rates. Once the plasma contacts the DMF surface with the actuation electrodes1010, the actuation electrodes contacting the plasma and around the contact point are activated, thereby pulling the plasma towards the DMF surface using electrowetting forces, and then a volume between 10-250 μL (e.g., ˜70 μL) of the extracted plasma is actuated by actuation electrodes of the DMF device1000for further processing. In some embodiments, a sensor can be used for feedback control by detecting when the plasma contacts the bottom plate, and the actuation electrodes can be activated when the sensors detect the plasma on the plate. For example, the actuation electrodes and/or separate sensor electrodes can be used to measure capacitance, which changes when liquid covers the electrode. In some embodiments, the actuation electrodes1012below the sample outlet1004can be activated before the extracted plasma contacts the actuation electrodes and can be kept on until a sufficient amount of plasma has been extracted or can be kept on for a set or predetermined amount of time, such as about 1, 2, 3, 4, or 5 minutes. As mentioned above, one of the key features of the assembled architecture is the super hydrophobic environment surrounding the separation membrane1012which prevents or reduces the likelihood that blood sample overflows from the edge of the separation membrane and into the gap between the cover plate and top plate, which allows the DMF device to achieve a maximum or increased volume of plasma flow through the separation membrane. The systems and methods described herein result in extraction yields up to 2× the volume of plasma extraction from a given sample volume in comparison to benchtop lateral flow methods. Moreover, the quality of plasma collected using this DMF device is surprisingly comparable to plasma prepared by centrifugation and lateral-flow methods with respect to the degree of RBC hemolysis. The system is designed for facile reconfiguration and reprogramming, for accommodation of a wide range of blood volumes and plasma output. Example 1: Device Fabrication and Assembly DMF apparatuses that include embedded centrifuge tubes and/or well-plate wells (e.g.,FIGS.2B,2C) were constructed by drilling 5.5 mm diameter holes into 3 mm thick PCB substrates, bearing copper (43 μm thick) plated with nickel (185 μm) and gold (3.6 μm) for electrodes and conductive traces. Tubes and wells were then inserted into holes. DMF devices with embedded wells (e.g.,FIG.2D) were fabricated with holes (5 mm diameter, 10 mm depth) drilled in 15 mm thick PCB substrates. Actuation electrodes (each 10 mm×10 mm) were formed by conventional photolithography and etching, and were coated with soldermask (˜15 μm) as the dielectric. As shown inFIGS.3A-3E, some of the electrodes were formed around and adjacent to the hole which served as the access point to reaction compartments. The electrical contact pads were masked with polyimide tape (DuPont; Hayward, CA), and the substrate was spin-coated with a 50 nm layer of Teflon-AF (1% wt/wt in Fluorinert FC-40, 1500 rpm for 30 sec) and then baked at 100° C. for 3 h. The top plate of the DMF device, consisting of a glass substrate coated uniformly with unpatterned indium tin oxide (ITO) (Delta Technologies Ltd; Stillwater, MN) with 5.5 mm diameter PDMS plugs was spin-coated with 50 nm of Teflon-AF, as described above. Prototype devices fabricated as described above performed better or as well as air-gap DMF apparatuses without reaction chambers. Example 2: Quantifying Evaporation Prevention Using Waxes To qualitatively evaluate the effect of wax bodies to prevent evaporation in our assays, loop mediated amplification (LAMP) reactions were executed while covered in liquid paraffin wax in tubes on the benchtop using a real-time PCR Machine. As shown inFIG.5, the LAMP assay amplified miR-451, and the Ct values with and without paraffin were comparable (˜13 cycles), indicating no significant effect on the assay. For LAMP on DMF, the reaction droplet (8 μL) was driven to heating zone (as shown inFIG.4A). There, the droplet wets the solid paraffin wax wall which under conditional heating at 63° C. will melt into liquid wax to encircle the reaction volume and maintain it intact throughout the incubation time at 63° C.FIG.6Ashows a LAMP assay using paraffin-mediated methods, whileFIG.6Bshows a LAMP assay using conventional methods. InFIG.6A, the two upper traces are for a hemolyzed sampled while the two lower traces are for a non-hemolyzed sample. The two traces of each are to show repeatability of the runs using wax-mediated air matrix DMF. InFIG.6B, the conventional LAMP assay for a hemolyzed sample are shown in upper two traces while the non-hemolyzed LAMP runs are shown in lower two traces. Again, the two upper and two lower traces each are to show result repeatability. The wax-mediated approach on DMF generated results comparable in Ct values to those generated by conventional LAMP in tubes as shown inFIGS.6A and6B. Example 3: miRNA Purification Human Panel A beads from the TaqMan® miRNA ABC Purification Kit (Thermo Fisher Scientific). Aliquots of miRNA (4 ul), or “reaction droplets”, were loaded onto the DMF platform and brought to an array of electrodes overlaying the heating zone such that the droplet came into contact with the paraffin wall. The heating zone was then heated (65° C., 2 min) to melt the paraffin around the droplet. Once the paraffin melted, the reaction droplets were driven away from the heating zone and merged with miRNA Binding Beads (4×106 beads;FIG.3A) in 2 ul of mineral oil (i.e., carrier droplet). After mixing, the droplets were incubated (30° C., 30 min) to allow miRNA to bind to the miRNA Binding Beads. Beads were captured by engaging an external magnet positioned below the bottom plate. Once a pellet was formed, the beads were recovered from solution by moving the magnet laterally along the bottom plate while simultaneously actuating the electrodes positioned below the reaction droplet (FIG.3B). The miRNA Binding Beads were then resuspended in water (4 ul) using the DMF platform and transferred to a centrifuge tube for elution of miRNA (70° C., 3 min;FIG.3C). The efficiency of miRNA recovery from paraffin-encased miRNA droplets was evaluated against recovery from miRNA droplets without paraffin, but only in oil. RT-qPCR analysis of miRNA prepared by the system from samples with and without paraffin encasement generated comparable Ct values. Example 4: Plasma Separation Device Cover plates bearing 4 mm ID hole were spray-coated on both sides with a super-hydrophobic layer (˜500 nm, NeverWet®) followed by post-baking in an oven (100° C., 10 min). Device top plates with 10 mm ID holes were coated with a super-hydrophobic layer (as above) on one side and the side comprising of ground electrode was spin-coated with a hydrophobic layer (50 nm, Teflon-AF1600) followed by post-baking as above. The bottom plate of the DMF device was designed in CAD systems, and Gerber files were outsourced to a third-party company for fabrication. Briefly, a six-layer PCB substrate bearing copper electrodes (43 μm thick) plated with nickel (185 μm) and gold (3.6 μm) were formed by conventional photolithography and etching 15, and covered with dielectric tape (25 μm). The substrate featured an array of one-hundred and twenty actuation electrodes (each 3.5×3.5 mm) with inter-electrode gaps of 40 μm. The cover and top plates were assembled by means of screws with the plasma separation membrane (PALL, Ann Arbor, MI) sandwiched in between. The bottom and top plates were assembled with a spacer consisting of three pieces of double-sided tape (total thickness of ˜300 μm). A sample of whole blood (300 μL) was spotted directly onto a prewetted (with tris buffer) separation membrane. The sample was incubated for 3 minutes and during that time plasma transferred from the bottom of the separation membrane to the receiving DMF device surface by capillary forces of the receiving DMF surface. Once the plasma contacted the DMF surface, the actuation electrodes were activated, thereby pulling the plasma towards the DMF surface using electrowetting forces. Once a sufficient volume of plasma was collected (˜70 μL), the actuation electrodes were actuated by the DMF device for further processing of the collected plasma droplet. When a feature or element is herein referred to as being “on” another feature or element, it can be directly on the other feature or element or intervening features and/or elements may also be present. In contrast, when a feature or element is referred to as being “directly on” another feature or element, there are no intervening features or elements present. It will also be understood that, when a feature or element is referred to as being “connected”, “attached” or “coupled” to another feature or element, it can be directly connected, attached or coupled to the other feature or element or intervening features or elements may be present. In contrast, when a feature or element is referred to as being “directly connected”, “directly attached” or “directly coupled” to another feature or element, there are no intervening features or elements present. Although described or shown with respect to one embodiment, the features and elements so described or shown can apply to other embodiments. It will also be appreciated by those of skill in the art that references to a structure or feature that is disposed “adjacent” another feature may have portions that overlap or underlie the adjacent feature. Terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. For example, as used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items and may be abbreviated as “/”. Spatially relative terms, such as “under”, “below”, “lower”, “over”, “upper” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is inverted, elements described as “under” or “beneath” other elements or features would then be oriented “over” the other elements or features. Thus, the exemplary term “under” can encompass both an orientation of over and under. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. Similarly, the terms “upwardly”, “downwardly”, “vertical”, “horizontal” and the like are used herein for the purpose of explanation only unless specifically indicated otherwise. Although the terms “first” and “second” may be used herein to describe various features/elements (including steps), these features/elements should not be limited by these terms, unless the context indicates otherwise. These terms may be used to distinguish one feature/element from another feature/element. Thus, a first feature/element discussed below could be termed a second feature/element, and similarly, a second feature/element discussed below could be termed a first feature/element without departing from the teachings of the present invention. Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising” means various components can be co-jointly employed in the methods and articles (e.g., compositions and apparatuses including device and methods). For example, the term “comprising” will be understood to imply the inclusion of any stated elements or steps but not the exclusion of any other elements or steps. As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers may be read as if prefaced by the word “about” or “approximately,” even if the term does not expressly appear. The phrase “about” or “approximately” may be used when describing magnitude and/or position to indicate that the value and/or position described is within a reasonable expected range of values and/or positions. For example, a numeric value may have a value that is +/−0.1% of the stated value (or range of values), +/−1% of the stated value (or range of values), +/−2% of the stated value (or range of values), +/−5% of the stated value (or range of values), +/−10% of the stated value (or range of values), etc. Any numerical values given herein should also be understood to include about or approximately that value, unless the context indicates otherwise. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. It is also understood that when a value is disclosed that “less than or equal to” the value, “greater than or equal to the value” and possible ranges between values are also disclosed, as appropriately understood by the skilled artisan. For example, if the value “X” is disclosed the “less than or equal to X” as well as “greater than or equal to X” (e.g., where X is a numerical value) is also disclosed. It is also understood that the throughout the application, data is provided in a number of different formats, and that this data, represents endpoints and starting points, and ranges for any combination of the data points. For example, if a particular data point “10” and a particular data point “15” are disclosed, it is understood that greater than, greater than or equal to, less than, less than or equal to, and equal to 10 and 15 are considered disclosed as well as between 10 and 15. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed. Although various illustrative embodiments are described above, any of a number of changes may be made to various embodiments without departing from the scope of the invention as described by the claims. For example, the order in which various described method steps are performed may often be changed in alternative embodiments, and in other alternative embodiments one or more method steps may be skipped altogether. Optional features of various device and system embodiments may be included in some embodiments and not in others. Therefore, the foregoing description is provided primarily for exemplary purposes and should not be interpreted to limit the scope of the invention as it is set forth in the claims. The examples and illustrations included herein show, by way of illustration and not of limitation, specific embodiments in which the subject matter may be practiced. As mentioned, other embodiments may be utilized and derived there from, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. Such embodiments of the inventive subject matter may be referred to herein individually or collectively by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept, if more than one is, in fact, disclosed. Thus, although specific embodiments have been illustrated and described herein, any arrangement calculated to achieve the same purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description.
67,903
11857970
DETAILED DESCRIPTION Features will now be described more fully hereinafter with reference to the accompanying drawings in which exemplary embodiments of the disclosure are shown. Whenever possible, the same reference numerals are used throughout the drawings to refer to the same or like parts. However, this disclosure can be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. A cell culture vessel (e.g., flask) can provide a sterile cell culture chamber for culturing cells. In some embodiments, culturing cells can provide information related to the study of diseases and toxicology, the efficacy of medications and treatments, characteristics of tumors, organisms, genetics, and other scientific, biological, and chemical principles of and relating to cells. As compared to two-dimensional cell cultures, in some embodiments, three-dimensional cell cultures can produce multicellular structures that are more physiologically accurate and that more realistically represent an environment in which cells can exist and grow in real life applications as compared to simulated conditions in a laboratory. For example, three-dimensional cell cultures have been found to more closely provide a realistic environment simulating “in vivo” (i.e. within the living, in a real-life setting) cell growth; whereas two-dimensional cell-cultures have been found to provide an environment simulating “in vitro” (i.e., within the glass, in a laboratory setting) cell growth that is less representative of a real-life environment occurring outside of a laboratory. By interacting with and observing the properties and behavior of three-dimensional cell cultures, advancements in the understanding of cells relating to, for example, the study of diseases and toxicology, the efficacy of medications and treatments, characteristics of tumors, organisms, genetics, and other scientific, biological, and chemical principles of and relating to cells can be achieved. Under certain conditions, cells will clump together to form three dimensional “balls” of cells called spheroids or organoids. For these types of studies and uses, it is desirable to provide controlled, homogeneous populations of spheroids. Cell culture vessels can be structured and arranged to provide an appropriate environment for cells to form spheroids in culture. The cell culture vessel can include a cell culture surface including a plurality of microcavities (e.g., microcavities, micron-sized wells, submillimeter-sized wells). When these microcavities are arranged in an array, providing a large number of microcavities in a single cell culture vessel, it is possible to culture large numbers of spheroids, and therefore it is possible to carry out assays and experiments on a large number of cells. However, when flat surfaces are present in a cell culture vessel intended to grow spheroids, cells can settle onto these flat surfaces and form irregular cellular conglomerates. These are undesirable. In embodiments, the disclosure provides cell culture vessels that do not have flat surfaces that cells can settle on and grow in an irregular multicellular form. That is, the cell culture surface of the vessel consists substantially of microcavities. In embodiments, the cell culture surface can be an insert placed in the flask or the cell culture surface can be bonded to the wall of the cell culture vessel. A cell culture surface having an array of microcavities can be bonded to the wall of a cell culture vessel by, for example gluing, laser welding, ultrasonic welding, or some other method. The cell culture surface can include top and/or bottom sides that include undulating (e.g., sinusoidal) surfaces that form the plurality of microcavities. When culturing cells, the vessel can be filled with a material (e.g., media, solid, liquid, gas) that facilitates growth of three-dimensional cell cultures (e.g., cell aggregates, spheroids). For example, a media including cells suspended in a liquid can be added to the cell culture chamber of the vessel. The suspended cells can collect in the plurality of microcavities and can form (e.g., grow) into groups or clusters of cells. These groups or clusters are spheroids or organoids. For example, in some embodiments, a single spheroid can form in each microcavity of the plurality of microcavities based at least on gravity causing one or more cells suspended in a liquid to fall through the liquid and become deposited within each microcavity. The shape of the microcavity (e.g., a concave surface or bottom defining a well), and a surface coating of the microcavity that prevents the cells from attaching to the surface can also facilitate growth of three-dimensional cell cultures in each microcavity. That is, the cells form spheroids and are constrained by the dimensions of the microcavity to grow to a certain size. During culturing, the spheroids can consume media (e.g., food, nutrients) and produce metabolite (e.g., waste) as a byproduct. Thus, in some embodiments food media can be added to the cell culture chamber during culturing and waste media can be removed from the cell culture chamber during culturing. Attempts can be made when adding and removing media to avoid displacing the spheroids from the microcavities and promote desired cell culturing of the spheroids. Embodiments of cell culture vessel100and methods of culturing cells in the cell culture vessel100will now be described with reference toFIGS.1-37.FIG.1illustrates a side view of an embodiment of a cell culture vessel100, andFIG.2shows a plan view of the vessel100along line2-2ofFIG.1. In some embodiments, the cell culture vessel100can include a top101, a bottom108, a necked opening112and a port, shown inFIG.1covered by a cap104.FIG.2, a plan view, shows wall107surrounding the cell culture surface115. Each of these that features, top101bottom108, and wall107(shown inFIG.2) and the necked opening112have interior surfaces. That is, top101has an interior surface201, wall107has an interior surface207, bottom108has an interior surface208, and necked opening112has an interior surface212. These interior surfaces define the cell culture chamber103. The interior surface208of the bottom108of the vessel100is the cell culture surface115. This cell culture surface115has an array of microcavities (SeeFIGS.5-7) for containing and culturing spheroids. As shown inFIG.2, the interior surface of the wall abuts the cell culture surface115. In embodiments, there are no flat surfaces between the cell culture surface115and the interior surface207of wall107. That is, the cell culture surface115is substantially free of flat surfaces. Stated another way, the cell culture surface115is made up of microcavities entirely. The cell culture surface consists essentially of microcavities. The vessel can be manufactured from a material including, but not limited to, polymer, polycarbonate, glass, and plastic. In the drawing figures, the vessel100is illustrated as being manufactured from a clear (e.g., transparent) material; although, in some embodiments, the vessel100may, alternatively, be manufactured from a semi-transparent, semi-opaque, or opaque material without departing from the scope of the disclosure.FIG.3shows a cross-sectional view of the vessel100along line3-3ofFIG.1. In some embodiments, the cell culture surface115and the inner surface207of the wall107defines a cell culture chamber103of the vessel100, with an aperture105extending through the wall107in fluid communication with the cell culture chamber103. For example, in some embodiments, the cell culture chamber103can include an internal spatial volume of the vessel100. Turning back toFIG.1andFIG.2, in some embodiments, the vessel100can include a cap104oriented to cover the aperture105to at least one of seal and block the aperture105, thereby obstructing a path into the cell culture chamber103from outside the vessel100through the aperture105. For clarity purposes, the cap104is removed and, therefore, not shown in other drawing figures, although it is to be understood that the cap104can be provided and selectively added to or removed from the aperture105of the vessel100, in some embodiments, without departing from the scope of the disclosure. In some embodiments, the cap104can include a filter that permits the transfer of gas in to and/or out of the cell culture chamber103of the vessel100. For example, in some embodiments, the cap104can include a gas-permeable filter oriented to regulate a pressure of gas within the cell culture chamber103, thereby preventing pressurization (e.g., over-pressurization) of the cell culture chamber103relative to a pressure of the environment (e.g., atmosphere) outside the vessel100. As shown inFIG.3, which shows a cross-sectional view along line3-3ofFIG.2, and inFIG.4, which shows a cross-sectional view along line4-4ofFIG.1, in some embodiments, the cell culture surface115can span a length “L1” of the cell culture chamber103that extends along the axis510.FIG.5shows an enlarged schematic representation of a portion of the cell culture surface115taken at view5ofFIG.4. Additionally,FIG.6shows a cross-sectional view of the portion of the cell culture surface115along line6-6ofFIG.5, andFIG.7shows an alternative embodiment of the cross-sectional view ofFIG.6. As shown inFIG.5, in some embodiments, microcavities120can be arranged in a diagonal array, although other arrangements can be provided in other embodiments. Additionally, in some embodiments, each microcavity120a,120b,120ccan include a concave bottom121a,121b,121c(SeeFIG.6andFIG.7) defining a well122a,122b,122c. Further, each microcavity120a,120b,120ccan include an opening123a,123b,123cin the top of each microcavity120. As shown inFIG.6, in some embodiments, the first side125of the cell culture surface115can include a non-linear (e.g., undulating, sinusoidal) profile and a second side126of the cell culture surface115can be flat. Similarly, as shown inFIG.7, in some embodiments, both the first side125and the second side126of the cell culture surface115can include a non-planar (e.g., undulating, sinusoidal) profile. In some embodiments, the cell culture surface115, and the vessel100(as discussed inFIGS.1-16) and300(as discussed inFIG.17-34) can include a polymeric material including, but not limited to, polystyrene, polymethylmethacrylate, polyvinyl chloride, polycarbonate, polysulfone, polystyrene copolymers, fluoropolymers, polyesters, polyamides, polystyrene butadiene copolymers, fully hydrogenated styrenic polymers, polycarbonate PDMS copolymers, and polyolefins such as polyethylene, polypropylene, polymethyl pentene, polypropylene copolymers and cyclic olefin copolymers. Additionally, in some embodiments, at least a portion of the well122a,122b,122cdefined by the concave bottom121a,121b,121ccan be coated with an ultra-low binding material, thereby making the at least a portion of the well122a,122b,122cnon-adherent to cells. For example, in some embodiments, one or more of perfluorinated polymers, olefins, agarose, non-ionic hydrogels such as polyacrylamides, polyethers such as polyethyleneoxide, polyols such as polyvinylalcohol or mixtures thereof can be applied to at least a portion of the well122a,122b,122cdefined by the concave surface121a,121b,121c. Moreover, in some embodiments, each microcavity120a,120b,120cof the plurality of microcavities120(as discussed inFIGS.1-16) and320(as discussed inFIG.17-34) can include a variety of features and variations of those features without departing from the scope of the disclosure. For example, in some embodiments the plurality of microcavities120can be arranged in an array including a linear array (shown), a diagonal array, a rectangular array, a circular array, a radial array, a hexagonal close-packed arrangement, etc. Additionally, in some embodiments, the opening123a,123b,123ccan include a variety of shapes. In some embodiments, the opening123a,123b,123ccan include one or more of a circle, an oval, a rectangle, a quadrilateral, a hexagon, and other polygonal shapes. Additionally, in some embodiments, the opening123a,123b,123ccan include a dimension (e.g., diameter, width, diagonal of a square or rectangle, etc.) from about 100 microns (μm) to about 5000 μm. For example, in some embodiments, the opening123a,123b,123ccan include a dimension of 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm, 1000 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm, and any dimension or ranges of dimensions encompassed within the range of from about 100 μm to about 5000 μm. In some embodiments, the well122a,122b,122c(as discussed inFIGS.1-16) and322(as discussed inFIG.17-34) defined by the concave surface121a,121b,121ccan include a variety of shapes. In some embodiments, the well122a,122b,122cdefined by the concave surface121a,121b,121ccan include one or more of a circular, elliptical, parabolic, hyperbolic, chevron, sloped, or other cross-sectional profile shape. Additionally, in some embodiments, a depth of the well122a,122b,122c(e.g., depth from a plane defined by the opening123a,123b,123cto the concave surface121a,121b,121ccan include a dimension from about 100 microns (μm) to about 5000 μm. For example, in some embodiments, the depth of the well122a,122b,122ccan include a dimension of 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm, 1000 μm, 1500 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm, any dimension or ranges of dimensions encompassed within the range of from about 100 μm to about 5000 μm. In some embodiments, three-dimensional cells150(e.g., spheroids, organoids150a,150b,150c) (SeeFIG.16) (as discussed inFIGS.1-16) and350(as discussed inFIG.17-34) that can be cultured in at least one microcavity120a,120b,120cof the plurality of microcavities120can include a dimension (e.g., diameter) of from about 50 μm to about 5000 μm, and any dimension or ranges of dimensions encompassed within the range of from about 50 μm to about 5000 μm. In some embodiments, dimensions greater than or less than the explicit dimensions disclosed can be provided and, therefore, unless otherwise noted, dimensions greater than or less than the explicit dimensions disclosed are considered to be within the scope of the disclosure. For example, in some embodiments, one or more dimensions of the opening123a,123b,123c, the depth of the well122a,122b,122c, and the dimension of the three-dimensional cells150(e.g., spheroids150a,150b,150c) can be greater than or less than the explicit dimensions disclosed without departing from the scope of the disclosure. Turning back toFIGS.1-4, in some embodiments, the vessel100can include a neck portion555extending from the aperture105to the cell culture surface115. In some embodiments, the neck portion555can include one or more of an inclined (e.g., canted) profile, a profile that narrows in a direction toward and/or away from the aperture105, and a profile that widens in a direction toward and/or away from the cell culture surface115. As shown inFIG.3, in some embodiments, the neck portion555is angled with respect to the cell culture chamber103. Additionally, in some embodiments, the neck portion555of the vessel can have a bend158. In embodiments, the bend158is higher than the cell culture surface115. However, it is to be understood that, in some embodiments, the bend can be of any shape. For example, the bend158can be curved or sloped or angled or stepped. In addition or alternatively, as shown inFIG.3andFIG.4, in some embodiments, the cell culture vessel100can include a dam130extending from interior surface212of the neck portion112. In some embodiments, the dam130can include a port-facing surface131obstructing a path defined between the aperture105and the cell culture surface115. In some embodiments, the port-facing surface131of the dam130can be substantially perpendicular to the axis510of the vessel100. Moreover, as shown inFIG.3, in some embodiments, at least a portion of a free end135of the dam130can be spaced a distance “d10” from the inner surface201of the top101. In some embodiments, by spacing at least a portion of the free end135of the dam130from the inner surface201, in some embodiments, access to a rear portion of the vessel100(e.g., opposite the aperture105) can be provided. For example, in some embodiments, one or more instruments (not shown) can be inserted into the aperture105of the vessel100past the dam130(e.g., through the distance “d10”) to access a region of the cell culture chamber103positioned behind the dam130. Accordingly, as disclosed, for example, with respect to the dam130of the first exemplary cell culture vessel100, in some embodiments, the dam130of the cell culture vessel100can, likewise, at least one of obstruct and slow a velocity of material (e.g., food, nutrients) flowing in to and/or material (e.g., waste) flowing out of the vessel100while also permitting bulk access into the cell culture chamber103of the vessel100. As shown inFIG.1, in some embodiments, the vessel100can include a lid137. In some embodiments, the lid137, when closed, can be the top101of the vessel100. (see alsoFIG.3). In some embodiments, the first major surface538can define at least a portion of the cell culture chamber103. Additionally, in some embodiments, the lid137can be open or closed, or partially open (or partially closed). The lid137can be slidingly atached to the vessel100or, in embodiments, the lid137can be hingedly attached to the vessel100. In some embodiments, the aperture536can be in fluid communication with the cell culture chamber103. Moreover, as shown inFIG.3, in some embodiments, a first distance “d11” from the cell culture surface115to top101or lid137can be less than a second distance “d12” from the cell culture surface115to the opening507of the aperture105. In some embodiments, the second distance “d12” from the cell culture surface115to the opening507of the aperture105can be defined at any location of the opening507. However, in some embodiments, the second distance “d12” from cell culture surface115to the opening507of the aperture105can be defined as the closest location of the opening507of the aperture105relative to the cell culture surface115. For example, in some embodiments, when the vessel100is oriented with the axis510extending in a direction perpendicular to the direction of gravity “g” (SeeFIG.17), the second distance “d12” from the cell culture surface115to the opening507of the aperture105can be defined as the lowermost location of the opening507of the aperture105relative to the direction of gravity “g”. Accordingly, in some embodiments, as compared to a comparable vessel where, for example, a distance from the cell culture surface115extending to the lid portion137is greater than a second distance from the cell culture surface115to the opening507of the aperture105, one or more features of the vessel100, alone or in combination, can provide a cell culture chamber103including a larger volume in which material can be contained. That is, when the vessel100is oriented with the axis510extending in a direction perpendicular to the direction of gravity “g”, the second distance “d12” from the cell culture surface115to the opening507of the aperture105(defined as the lowermost location of the opening507of the aperture105relative to the direction of gravity “g”), can define a maximum fill line with respect to a volume of material that can be contained within the cell culture chamber103of the vessel100. For example, if the second distance “d12” is less than the first distance “d11”, and the vessel100is oriented with the axis510extending in a direction perpendicular to the direction of gravity “g”, the maximum fill line of a volume of material contained within the cell culture chamber103would be commensurate with the distance from the lid137as any additional material added to the cell culture chamber103would flow out of the opening of the aperture105rather than being contained within the cell culture chamber103. Thus, if the second distance “d12” is less than the first distance “d11”, and the vessel100is oriented with the axis510extending in a direction perpendicular to the direction of gravity “g”, the vessel100can include a volume including a portion of the cell culture chamber103that is not employed with respect to containing material. Accordingly, in some embodiments, by providing the vessel100, in accordance with embodiments of the disclosure, including the second distance “d12” that is greater than the first distance “d11”, the entire volume of the cell culture chamber103can be employed to contain material, a larger volume of material can be contained in the cell culture chamber103, and an efficient allocation of material and overall utilization of space of the vessel100can be achieved. Likewise, in some embodiments, the second distance “d12” can be equal to the first distance “d11”, without departing from the scope of the disclosure. Moreover, in some embodiments, with respect to a unit area of the cell culture surface115(e.g., a unit area providing a respective surface on which one or more cells can be cultured), three-dimensional cell culturing can consume more media (e.g., food, nutrients) and produce more media (e.g., waste) as a byproduct than, for example, a comparable two-dimensional cell culture. Thus, in some embodiments, as compared to, for example, a comparable two-dimensional cell culture, three-dimensional cell cultures in accordance with embodiments of the disclosure can include more frequent media exchanges (e.g., addition of food, nutrients and/or removal of waste) for a comparable period of time. In addition or alternatively, in some embodiments, as compared to, for example, a comparable two-dimensional cell culture, three-dimensional cell cultures in accordance with embodiments of the disclosure can include larger media volumes (e.g., consume more food, nutrients and/or produce more waste) for a comparable period of time. Accordingly, in some embodiments, one or more features of the cell culture vessel100and the methods of culturing cells150in the cell culture vessel100can provide advantages with respect to the frequency of media exchanges as well as the volume of media that can be one or more of contained within the cell culture chamber103of the vessel100, added to the cell culture chamber103, and removed from the cell culture chamber103, thereby providing a desirable, effective environment in which to culture three-dimensional cells. As shown inFIG.8which shows a partial cross-sectional view of the vessel100along line8-8ofFIG.2, in some embodiments, top wall101can include a groove180, and the lid137can be slideable within the groove180(as shown by arrow181inFIG.2) to selectively provide access to the cell culture chamber103, for example, through an opening of aperture136. In addition or alternatively, as shown inFIG.9which shows a partial cross-sectional view of the vessel100along line9-9ofFIG.2, in some embodiments, the vessel100can include a hinge182connecting the lid137to the wall101. In some embodiments, the lid137can be rotatable about the hinge182(as shown by arrow183) to selectively provide access to the cell culture chamber103, for example, through an opening of aperture136. Moreover, in some embodiments, the lid137can be connected to the wall101with one or more fasteners (not shown) and/or adhesives (not shown) including reusable and non-reusable adhesives to, for example, selectively provide access to the cell culture chamber103, for example, through an opening of aperture136. Additionally, in some embodiments, a length “L2” of the vessel100, measured from the port105to the end wall107extending along the axis510of the vessel can be equal to or greater than the length “L1” of the cell culture surface115. Accordingly, in some embodiments, a plurality of vessels100can be stacked (e.g., vertically relative to the direction of gravity) to, for example, reduce a surface area (e.g., laboratory surface area, table surface area) occupied by the plurality of vessels100. For example,FIG.10schematically illustrates a side view of a plurality of vessels100,100a,100bstacked together in accordance with embodiments of the disclosure. As shown schematically inFIG.10, in some embodiments, vessel100aincluding wall101a, cap104a, neck portion555a, lid137a, and a bottom108acan be stacked, one on top of the other. For example, in some embodiments, the bottom portion108bof vessel100b, with walls101,101a,101b, can be placed on a horizontal surface (not shown) that defines a major surface perpendicular to the direction of gravity. In some embodiments, the bottom portion108of vessel100can be positioned on (e.g., facing) the lid137bof the vessel100b. Likewise, in some embodiments, the bottom portion108aof vessel100acan be positioned on (e.g., facing) lid137of vessel100. By positioning (e.g., stacking) the plurality of vessels100,100a,100bin accordance with embodiments of the disclosure, the plurality of vessels100,100a,100bcan efficiently utilize a space (e.g., area, volume) in which the vessels100,100a,100bare provided, for example, during one or more of storage, cleaning, and culturing with respect to the vessels100,100a,100b. Although shown as a plurality of three stacked vessels100,100a,100b, it is to be understood that, in some embodiments, two vessels or more than three vessels can be stacked in accordance with embodiments of the disclosure, without departing from the scope of the disclosure. Moreover, in some embodiments the plurality of vessels100,100a,100bcan be positioned separately and/or together (e.g., stacked) in a variety of configurations including configurations not explicitly disclosed in the disclosure, without departing from the scope of the disclosure. In embodiments, the vessels are stackable. Moreover, based at least in part on one or more features of the bend158in the neck112, when stacked in accordance with embodiments of the disclosure, access to the ports105,105a,105bcan be maintained to, for example, permit addition of material (e.g., food, nutrients) and/or removal of material (e.g., waste) from the respective cell culture chambers103,103a,103bwhile the plurality of vessels100,100a,100bare stacked (e.g., stationary). For example, in some embodiments, stacking vessels that do not include one or more features of the disclosure could one or more of limit, obstruct, and prevent access to the openings of the apertures. In some embodiments, stacked vessels including openings of the apertures to which access is one or more of limited, obstructed, and prevented may be moved (e.g., at least one of translated and rotated) relative to each other during a culturing process to, for example, provide access to the openings of the apertures. However, in some embodiments, movement of vessels relative to each other during a culturing process may one or more of dislodge and disturb cells being cultured in the vessels, thereby negatively impacting the cell culture process. Accordingly, based at least in part on one or more features of the bend158,158a,158bof the neck555,555a,555bof the vessel100,100a,100b, when stacked in accordance with embodiments of the disclosure, access to the openings of the port can be achieved and advantages with respect to a cell culturing process can be obtained. Methods of culturing cells in cell culture vessel100will now be described with reference toFIGS.11-16. As shown inFIG.11, in some embodiments, a method of culturing cells150(SeeFIG.15) in the cell culture vessel100can include passing liquid (e.g., represented by arrow106) through the aperture105from outside the vessel100into the cell culture chamber103, thereby providing a predetermined amount of liquid140in the cell culture chamber103. In embodiments, the method can be performed in a vessel with or without the optional dam130. Also shown is the bend158of the neck112of the vessel100. In some embodiments, the method can include tilting the vessel100so that the bend158forms a low point in the neck112. Liquid140introduced into the vessel can accumulate in the neck112at the bend158. That is, the vessel can contain a predetermined amount of liquid140in the bend158of the neck112, without liquid140contacting the microcavity array115. As discussed more fully below, preventing liquid140from contacting one or more microcavities120of the cell culture surface115containing an array of microcavities120, at this stage of the method, can provide several advantages that, for example, facilitate improved culturing of the cells150(SeeFIG.15). Then the vessel can be tilted slowly back so that axis510is perpendicular to gravity “g”, allowing the liquid140to slowly flow across the cell culture surface115having an array of microcavities120, allowing the liquid to slowly fill the microcavities120. This step is shown schematically inFIG.12. For example,FIG.13illustrates an enlarged schematic representation of a cell culture vessel100taken at view13ofFIG.12showing at least a portion of the liquid140flowing from the neck112on to the cell culture surface115along the length “L1” of the cell culture chamber103and entering microcavities120a,120b,120cof the microcavity array120. In some embodiments, the movement of the vessel100to cause the liquid to flow can be controlled and slow (e.g., performed during a duration of time on the order of minutes). For example, it has been observed that directly filling the microcavities120a,120b,120cof the plurality of microcavities120with liquid (e.g., not based on the method of the disclosure) can result in bubbles forming in the microcavities. This slow introduction of liquid to the microcavities120allows liquid to flow into the microcavities with reduced bubble formation. Bubbles disrupt cell growth. Liquid media can have a high surface tension (it can be thick) and the microcavities120are very small. Without intending to be bound by theory, it is believed, when directly and quickly (e.g., performed during a duration of time on the order of seconds) filling the microcavities120a,120b,120cwith liquid, because of surface tension, bubbles may become trapped in the microcavities. However, by employing one or more features of the method of the disclosure, it has been observed that, for example, by introducing liquid into the bend158of the neck112and then slowly tilting the vessel100to it's cell culturing position (with the cell culture surface perpendicular to gravity “g”, bubble formation can be reduced. In addition, for long-term cell culture, media must be changed to ensure that the cells maintain a fresh supply of nutrients. This requires removing media and replacing the media while spheroids are in place in each microcavity120. It is important not to dislodge the spheroids from the microcavities120during media changes. When a spheroid150“hops” out of its microcavity, it can settle into another, already occupied microcavity. When spheroids touch each other, they form irregular cellular conglomerates801(seeFIGS.35and36), leading to inhomogeneous cell culture. In some embodiments, bend158of the neck112can abut the cell culture surface115and fluid140can flow from the bend158in the neck112and deposit into at microcavities120a,120b,120cwith controlled flow (e.g., reduced or no liquid splashing and reduced or no turbulent flow), thereby providing a steady flow of liquid depositing into the well122a,122b,122cof the microcavities120a,120b,120cthrough a portion of the respective opening123a,123b,123cof the microcavities120a,120b,120cwhile displacing gas from the well122a,122b,122c. In embodiments, the cell culture surface115extends from wall107to wall107. In embodiments, the cell culture surface115does not have any flat areas. That is, the cell culture surface is an array of microcavities from wall to wall with no border, no flat areas between the cell culture surface and walls107. In embodiments, the cell culture surface consisting essentially of a plurality of microcavities. In embodiments, there no flat areas in the cell culture chamber for cells to settle on. This is important to ensure that cells do not settle in the cell culture chamber outside of the microwells. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates, and create an inhomogeneous population of multicellular 3D structures in the vessel. In embodiments, a cell culture surface consisting essentially of a plurality of microcavities. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates801(SeeFIGS.35A and35B,36A and36B), and create an inhomogeneous population of multicellular 3D structures in the vessel. In embodiments, a cell culture surface consisting essentially of a plurality of microcavities. In embodiments, the cell culture surface115extends from wall107to wall107. In embodiments, the cell culture surface115does not have any flat areas. That is, the cell culture surface is an array of microcavities120extending from wall to wall with no border, no flat areas between the cell culture surface and walls107. In embodiments, the cell culture surface consisting essentially of a plurality of microcavities. In embodiments, there no flat areas in the cell culture chamber for cells to settle on. This is important to ensure that cells do not settle in the cell culture chamber outside of the microwells. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates801(SeeFIGS.35A and35B,36A and36B), and create an inhomogeneous population of multicellular 3D structures in the vessel. In embodiments, a cell culture surface consisting essentially of a plurality of microcavities. As shown inFIG.14, in some embodiments, the liquid140can be caused to flow from the neck112over the entire cell culture surface115based at least on the movement of the vessel100. Additionally,FIG.15illustrates an enlarged schematic representation of a cell culture vessel100taken at view15ofFIG.14including a method of culturing cells150in the cell culture vessel100. For example, in some embodiments, the method can include culturing cells150(e.g., spheroid150a, spheroid150b, spheroid150c) in the at least one microcavity120a,120b,120cof the plurality of microcavities120after depositing the at least a portion of the predetermined amount of liquid140in the at least one microcavity120a,120b,120c. As shown inFIG.14andFIG.15, in some embodiments, the axis510of the vessel100can be substantially perpendicular relative to the direction of gravity “g” while culturing cells150in the microcavities120. As shown schematically inFIG.16, in some embodiments, the method can further include adding additional liquid media140(as shown by arrow508) to the cell culture chamber103. For example, in some embodiments, while culturing cells150(SeeFIG.15) in the cell culture vessel100, liquid media140(cell food, liquid containing nutrients) can be added to the cell culture chamber103. Because the port105is raised and facing up, liquid140can be added to the vessel up to a distance “d13” from lowest point of the aperture507of the port105. That is, in embodiments, the vessel can be filled right up to the lid137or top101of the vessel100. In this way, the cell culture chamber103can contain larger volume of liquid140than it would be able to contain if the port were arranged lower with respect to the top101of the vessel100. In an additional embodiment of a cell culture vessel300and methods of culturing cells in the cell culture vessel300will now be described with reference toFIGS.17-34. While the embodiments shown inFIGS.17-34show an embodiments without a necked opening or a port, it is to be understood that the embodiments shown inFIGS.17-34can be incorporated into the embodiments illustrated inFIGS.1-16, a vessel with a port. For example,FIG.17schematically illustrates a side view of cell culture vessel300, andFIG.18schematically illustrates a plan view of the vessel300along line18-18ofFIG.17. In some embodiments, the cell culture vessel300can include a wall301and a lid304. In the drawing figures, the vessel300is illustrated as being manufactured from a clear (e.g., transparent) material; although, in some embodiments, the vessel300can, alternatively, be manufactured from a semi-transparent, semi-opaque, or opaque material without departing from the scope of the disclosure. In some embodiments, the lid304can be oriented to cover an opening of the vessel300to at least one of seal and block the opening, thereby obstructing a path into the cell culture chamber303from outside the vessel300through the opening. For clarity purposes, the lid304is removed and, therefore, not shown in other drawing figures, although it is to be understood that the lid304can be provided and selectively added to or removed from the opening of the vessel300, in some embodiments, without departing from the scope of the disclosure. In some embodiments, the lid304can include a filter that permits the transfer of gas in to and/or out of a cell culture chamber303(SeeFIG.19) of the vessel300. For example, in some embodiments, the lid304can include a gas-permeable filter oriented to regulate a pressure of gas within the cell culture chamber303, thereby preventing pressurization (e.g., over-pressurization) of the cell culture chamber303relative to a pressure of the environment (e.g., atmosphere) outside the vessel300. FIG.19shows a cross-sectional view of an exemplary embodiment of the cell culture vessel300along line19-19ofFIG.18, andFIG.20shows an alternative exemplary embodiment of the cross-sectional view of the cell culture vessel300ofFIG.19. Additionally,FIG.25shows an alternative exemplary embodiment of the cross-sectional view of the cell culture vessel300ofFIG.18, andFIG.26shows an alternative exemplary embodiment of the cross-sectional view of the cell culture vessel300ofFIG.25. In some embodiments, the wall301can include an inner surface302, and the vessel300can include a cell culture surface315including a plurality of microcavities320. As shown inFIG.19andFIG.25, in some embodiments, the cell culture surface315and the inner surface302of the wall301define the cell culture chamber303of the vessel300. Alternatively, as shown inFIG.20andFIG.26, in some embodiments, the inner surface302of the wall301can define a cell culture chamber303of the vessel300including, for example, a first region303aand a second region303b, and the cell culture surface315can be positioned in the cell culture chamber303, between the first region303aand the second region303b. As shown inFIG.19andFIG.20, in some embodiments, an outer perimeter330of the cell culture surface315can surround the plurality of microcavities320, and at least a portion331of the outer perimeter330can be positioned in a recess335of the inner surface302of the wall301of the vessel300. For example,FIG.24shows an exemplary cross-section view of the vessel300taken along line24-24ofFIG.30, where the entire outer perimeter330laterally circumscribes the plurality of microcavities320and the entire outer perimeter330is positioned in the recess335. Alternatively, as shown inFIG.25andFIG.26, in some embodiments, the outer perimeter330of the cell culture surface315can surrounds the plurality of microcavities320, and at least a portion331of the outer perimeter330can be positioned on a protrusion337of the inner surface302of the wall301of the vessel300. For example,FIG.29shows an alternative exemplary embodiment of the cross-sectional view of the third exemplary cell culture vessel300ofFIG.24, where the entire outer perimeter330laterally circumscribes the plurality of microcavities320and the entire outer perimeter330is positioned on the recess335protrusion337. Throughout the disclosure, “surrounds” means that, in a top or bottom view in a direction perpendicular to a major feature of the cell culture surface315, for example, an outer periphery defined by the first feature surrounds an outer periphery defined by the second feature. Thus, for example, as shown in the view ofFIG.24andFIG.42, an outer periphery (defined by the outer perimeter330) of the cell culture surface315surrounds an outer periphery (defined by the plurality of microcavities320) of the cell culture surface315. In embodiments, the cell culture surface315extends from wall301to wall301. In embodiments, the cell culture surface315does not have any flat areas. That is, the cell culture surface is an array of microcavities320extending from wall to wall with no border, no flat areas between the cell culture surface and walls301. In embodiments, the cell culture surface consisting essentially of a plurality of microcavities. In embodiments, there no flat areas in the cell culture chamber for cells to settle on. This is important to ensure that cells do not settle in the cell culture chamber outside of the microwells. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates801(SeeFIGS.35A and35B,36A and36B), and create an inhomogeneous population of multicellular 3D structures in the vessel. In embodiments, a cell culture surface consisting essentially of a plurality of microcavities. FIGS.21-23show exemplary embodiments of an enlarged view of a portion of the vessel300taken at view21ofFIG.19including the at least a portion331of the outer perimeter330of the cell culture surface315positioned in the recess335. Similarly,FIG.27andFIG.28show exemplary embodiments of an enlarged view of the vessel300taken at view28ofFIG.25including the at least a portion331of the outer perimeter330positioned on the protrusion337. In some embodiments, each microcavity320a,320b,320cof the plurality of microcavities320can include a concave surface321a,321b,321cdefining a well322a,322b,322cand an opening323a,323b,323cLiquid enters and exits the microcavities through the openings323a,323b,323c. In some embodiments, the cell culture surface315can be attached to the wall301of the vessel300. For example, in some embodiments the cell culture surface315can be attached to the wall301of the vessel300with an adhesive (not shown), a solvent (not shown), or a fastener (not shown), by welding (laser welding or ultrasonic welding) or the wall and the cell culture surface315can be molded together. In addition or alternatively, in some embodiments the cell culture surface315can be attached to the inner surface302of the wall301of the vessel300based at least in part on, for example, operation of a plastic welding process, a laser welding process, an ultrasonic welding process. In some embodiments, at least one of the wall301and the outer perimeter330can include an energy director (not shown) to facilitate bonding of the cell culture surface315to the wall301of the vessel300based at least in part on operation of the plastic welding process. Additionally, as shown inFIG.22, in some embodiments, the vessel300can include a stepped portion306extending outward from the cell culture surface315and forming the recess335. In some embodiments, the stepped portion306can increase at least one of a volume of the cell culture chamber303and a quantity of microcavities320a,320b,320cof the plurality of microcavities320within the cell culture chamber303. In addition or alternatively, the stepped portion306can provide a relatively larger recess335without increasing a thickness of the wall301of the vessel300as compared to the corresponding recess335and wall301thickness shown, for example, inFIG.21. In some embodiments, the recess335formed by the stepped portion306can be oriented to accommodate the at least a portion331of the outer perimeter330of the cell culture surface315positioned in the recess335. Similarly, as shown inFIG.28, in some embodiments, the vessel300can include a stepped portion308extending inward toward the cell culture surface315and forming the protrusion337. In some embodiments, the stepped portion308can provide a relatively larger protrusion337without increasing a thickness of the wall301of the vessel300as compared to the corresponding protrusion337and wall301thickness shown, for example, inFIG.28. In some embodiments, the protrusion337formed by the stepped portion308can be oriented to accommodate the at least a portion331of the outer perimeter330of the cell culture surface315positioned on the protrusion337. In embodiments, the cell culture surface315extends from wall301to wall301. In embodiments, the cell culture surface315does not have any flat areas. That is, the cell culture surface is an array of microcavities320extending from wall to wall with no border, no flat areas between the cell culture surface and walls301. In embodiments, the cell culture surface consisting essentially of a plurality of microcavities. In embodiments, there no flat areas in the cell culture chamber for cells to settle on. This is important to ensure that cells do not settle in the cell culture chamber outside of the microwells. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates801(SeeFIGS.35A and35B,36A and36B), and create an inhomogeneous population of multicellular 3D structures in the vessel. In embodiments, a cell culture surface consisting essentially of a plurality of microcavities. Additionally, as shown inFIG.23,FIG.25, andFIG.28, in some embodiments, the at least a portion331of the outer perimeter330of the cell culture surface315can be spaced from the portion of the cell culture surface315including the openings323a,323b,323cof the microcavities320a,320b,320cin a direction away from the concave surface321a,321b,321cof each microcavity320a,320b,320cof the plurality of microcavities320. For example, in some embodiments, the cell culture surface315can include a peripheral surface332extending from the at least a portion331of the outer perimeter330to the portion of the cell culture surface315including the openings323a,323b,323c. In some embodiments, the peripheral surface332can include a vertical orientation (e.g., extending in the direction of gravity); however, in some embodiments, the peripheral surface332can be inclined relative to the direction of gravity to, for example, direct cells toward the openings323a,323b,323cof the microcavities320a,320b,320c. Moreover, by positioning the at least a portion331of the outer perimeter330of the cell culture surface315in the recess335, in some embodiments, the opening323aof the microcavity320a, for example, can be positioned to abut the inner surface302of the wall301at the location of the recess335. For example, in some embodiments, the opening323aof the microcavity320acan be flush with the inner surface302of the wall301such that cells suspended in a liquid will fall (e.g., based at least on the force of gravity) and/or be directed by the inner surface302into the well322aof the microcavity320awithout settling on or adhering to a surface of the vessel300. Likewise, by positioning the at least a portion331of the outer perimeter330of the cell culture surface315on the protrusion337, in some embodiments, the opening323aof the microcavity320a, for example, can be positioned to abut the peripheral surface332of the cell culture surface315with the outer perimeter330supported by the protrusion337. For example, in some embodiments, the opening323aof the microcavity320acan be flush with the peripheral surface332of the cell culture surface315such that cells suspended in a liquid will fall (e.g., based at least on the force of gravity) and/or be directed by the peripheral surface332into the well322aof the microcavity320awithout settling on or adhering to any other surface of the vessel300. In embodiments, the cell culture surface315extends from wall301to wall301. In embodiments, the cell culture surface115does not have any flat areas. That is, the cell culture surface is an array of microcavities320extending from wall to wall with no border, no flat areas between the cell culture surface and walls301. In embodiments, the cell culture surface consisting essentially of a plurality of microcavities. In embodiments, there no flat areas in the cell culture chamber for cells to settle on. This is important to ensure that cells do not settle in the cell culture chamber outside of the microwells. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates201(SeeFIGS.35A and35B,36A and36B), and create an inhomogeneous population of multicellular 3D structures in the vessel. In embodiments, a cell culture surface consisting essentially of a plurality of microcavities. In some embodiments, cells that settle on or adhere to a surface of the vessel300can accumulate and grow (e.g., multiply) outside of the microcavities320a,320b,320ccausing problems with respect to desired growth of three-dimensional cells within the microcavities320a,320b,320c.FIG.35AandFIG.35Bare schematic drawings of cells accumulating in flat areas on the periphery of the microcavities. For example, in some embodiments, cells that do not fall (based at least on the force of gravity) into the well322a,322b,322cand that accumulate or attach to other surfaces of the vessel300can grow outside of the well322a,322b,322c. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates801which are undesirable. In addition, these irregular cellular conglomerates801can creep into neighboring microcavities and disrupt (e.g., discourage, alter, slow, or prevent) desired growth of three-dimensional cells within the well322a,322b,322c. Similarly, in some embodiments, cells that accumulate or attach to other surfaces of the vessel300can grow and dislodge three-dimensional cells in the well322a,322b,322c, thereby disrupting or destroying desired growth of three-dimensional cells within the well322a,322b,322cand altering desired size uniformity of the cells. Accordingly, in some embodiments, by positioning at least a portion331of the outer perimeter330of the cell culture surface315in the recess335or on the protrusion337, all cells suspended within the liquid can be directed into the wells322a,322b,322c, thus reducing and eliminating problems that can otherwise occur if cells attach to surfaces of the vessel300outside the wells322a,322b,322c. Another exemplary embodiment of the cell culture vessel300is shown in the cross-sectional view ofFIG.30. In some embodiments, the cell culture vessel300and the cell culture surface315can be manufactured from the same material. For example, in some embodiments, the cell culture surface315including the plurality of microcavities320can be manufactured (e.g., formed, machined, pressed, extruded, molded, printed by operation of 3D printing, etc.) as an integral part of the wall301of the vessel300, such that there is no distinct boundary between the cell culture surface315and the wall301of the vessel300. As shown inFIG.30, in some embodiments, the cell culture surface315and the inner surface302of the wall301(integrally formed together) can define the cell culture chamber303of the vessel300. Alternatively, as shown inFIG.31, in some embodiments, the inner surface302of the wall301can define the cell culture chamber303of the vessel300, including a first region303aand a second region303b, and the cell culture surface315(integrally formed with the wall301) can be positioned in the cell culture chamber303between the first region303aand the second region303b. In some embodiments, the vessel300including the wall301and cell culture surface315integrally manufactured together can include a material that is non-permeable. Alternatively, in some embodiments (e.g., where the cell culture surface315is attached to the wall301of the vessel300), the wall301of the vessel300can be manufactured from a non-permeable material, and the cell culture surface315can be manufactured from one or more of a non-permeable material, a non-porous material, a gas permeable material or a porous material, integrally formed with the wall301. In this embodiment, where the cell culture surface315and the wall301are manufactured as a single part, the cell culture surface315extends from wall301to wall301. In embodiments, the cell culture surface315does not have any flat areas. That is, the cell culture surface is an array of microcavities320extending from wall to wall with no border, no flat areas between the cell culture surface and walls301. In embodiments, the cell culture surface consisting essentially of a plurality of microcavities. In embodiments, there no flat areas in the cell culture chamber for cells to settle on. This is important to ensure that cells do not settle in the cell culture chamber outside of the microwells. When cells settle outside of microwells, on flat areas outside the cell culture surface, cells can grow as irregular cellular conglomerates201(SeeFIGS.35A and35B,36A and36B), and create an inhomogeneous population of multicellular 3D structures in the vessel. In embodiments, a cell culture surface consisting essentially of a plurality of microcavities. Additionally, in some embodiments, the vessel300can include a predetermined amount of liquid370, and a method of culturing cells in the cell culture vessel300can include depositing liquid370in at least one microcavity320a,320b,320cof the plurality of microcavities320and culturing cells in the at least one microcavity320a,320b,320cafter depositing the liquid370in the at least one microcavity320a,320b,320c. As shown inFIG.45, which shows an enlarged view of the integrally formed cell culture surface315and wall301of the vessel300at view45ofFIG.43, the predetermined amount of liquid370can contact submerged surfaces325of the vessel300and occupy a region of the cell culture chamber303of the vessel300.FIG.46, shows an alternate exemplary embodiment ofFIG.45, including features of the at least a portion331of the outer perimeter330of the cell culture surface315positioned in the recess335of the wall301of the vessel300with the predetermined amount of liquid contacting submerged surfaces325of the vessel300, including the peripheral surface332of the cell culture surface315, and occupying a region of the cell culture chamber303of the vessel300. Similarly,FIG.34, shows an alternate exemplary embodiment ofFIG.32, including features of the at least a portion331of the outer perimeter330of the cell culture surface315positioned on the protrusion337of the wall301of the vessel300with the predetermined amount of liquid370contacting submerged surfaces325of the vessel300, including the peripheral surface332of the cell culture surface315, and occupying a region of the cell culture chamber303of the vessel300. For illustrative purposes only, the submerged surfaces325are shown with thicker line weights inFIGS.32-34with the understanding that, in some embodiments, submerged surfaces325can include surfaces of the vessel300that are in contact with the predetermined amount of liquid370. In some embodiments, the submerged surfaces325can be defined relative to the direction of gravity “g” at or during a specified step of a method of culturing cells in the vessel300. For example, in some embodiments, the predetermined amount of liquid370can define a liquid level371, where the submerged surfaces325include surfaces of the vessel300in contact with the predetermined amount of liquid370that are, relative to the direction of gravity “g”, positioned below the liquid level371and, therefore, submerged in the predetermined amount of liquid370. In some embodiments, the level371of the predetermined amount of liquid370can define a planar free surface of the predetermined amount of liquid370spaced a distance from a portion375of the cell culture surface315. For example, the portion375of the cell culture surface315can include the openings323a,323b,323cand the planar free surface defined by the liquid level371of the predetermined amount of liquid370can be spaced a distance from the portion375in a direction away from the concave surface321a,321b,321cof each microcavity320a,320b,320cof the plurality of microcavities320. Additionally, in some embodiments, the submerged surfaces325of the vessel300do not include planar surface portions parallel to the planar free surface of the predetermined amount of liquid370. By providing submerged surfaces325that do not include planar surface portions parallel to the planar free surface of the level371of the predetermined amount of liquid370, cells suspended in the liquid370will fall (e.g., based at least on the force of gravity) and/or be directed by the submerged surfaces325into the wells322a,322b,322cof the microcavities320a,320b,320cbecause there are no submerged surfaces325on which the cells can settle or to which the cells can adhere. As noted above, in some embodiments, cells that settle on or adhere to a surface of the vessel300can accumulate and grow (e.g., multiply) outside of the microcavities320a,320b,320ccausing problems with respect to desired growth of three-dimensional cells within the microcavities320a,320b,320c. For example, in some embodiments, cells that do not fall (based at least on the force of gravity) into the well322a,322b,322cand that accumulate or attach to other surfaces of the vessel300(e.g., if the submerged surfaces325were to include planar surface portions parallel to the planar free surface of the predetermined amount of liquid370) can grow outside of the well322a,322b,322cand disrupt (e.g., discourage, alter, slow, or prevent) desired growth of three-dimensional cells within the well322a,322b,322c. Similarly, in some embodiments, if the submerged surfaces325were to include planar surface portions parallel to the planar free surface of the predetermined amount of liquid370, cells could accumulate or attach to the planar surface portions and could grow and dislodge three-dimensional cells in the well322a,322b,322c, thereby disrupting or destroying desired growth of three-dimensional cells within the well322a,322b,322c. Accordingly, in some embodiments, by providing submerged surfaces325that do not include planar surface portions parallel to the planar free surface of the level371of the predetermined amount of liquid370, all cells suspended within the liquid370can be directed into the wells322a,322b,322c, thus reducing and eliminating problems that can otherwise occur if cells attach to surfaces of the vessel300outside the wells322a,322b,322c. As shown inFIG.33, in some embodiments, at least a portion331of the outer perimeter330of the cell culture surface315can be spaced a distance “d4” from the portion375of the cell culture surface315in a direction away from the concave surface321a,321b,321cof each microcavity320a,320b,320cof the plurality of microcavities320. Additionally, the cell culture surface315can include the peripheral surface332extending from the at least a portion331of the outer perimeter330to the portion375of the cell culture surface315. In some embodiments, a depth “d5” of the predetermined amount of liquid370from the liquid level371defining the planar free surface to the portion375of the cell culture surface315along the direction can be less than the distance “d4”. Likewise, as shown inFIG.47, in some embodiments, at least a portion331of the outer perimeter330of the cell culture surface315can be spaced a distance “d6” from the portion375of the cell culture surface315in a direction away from the concave surface321a,321b,321cof each microcavity320a,320b,320cof the plurality of microcavities320. The cell culture surface315can include the peripheral surface332extending from the at least a portion331of the outer perimeter330to the portion375of the cell culture surface315. In some embodiments, a depth “d7” of the predetermined amount of liquid370from the liquid level371defining the planar free surface to the portion375of the cell culture surface315along the direction can be less than the distance “d6”. Accordingly, in some embodiments, by providing submerged surfaces325that do not include planar surface portions parallel to the planar free surface of the level371of the predetermined amount of liquid370, alone or in combination with, a depth “d5” of the predetermined amount of liquid370from the liquid level371defining the planar free surface to the portion375of the cell culture surface315along the direction can be less than the distance “d4” (e.g.,FIG.33, including the recess335) and a depth “d7” of the predetermined amount of liquid370from the liquid level371defining the planar free surface to the portion375of the cell culture surface315along the direction can be less than the distance “d6” (e.g.,FIG.34, including the protrusion337), all cells suspended within the liquid370can be directed into the wells322a,322b,322c, thus reducing and eliminating problems that can otherwise occur if cells attach to surfaces of the vessel300outside the wells322a,322b,322c. Moreover, although not explicitly illustrated, in some embodiments, a method of culturing cells (SeeFIG.16) in the vessel300can include depositing a portion of the predetermined amount of liquid370in at least one microcavity320a,320b,320cof the plurality of microcavities320a,320b,320c; and culturing cells in the at least one microcavity320a,320b,320cafter depositing the portion of the predetermined amount of liquid370in the at least one microcavity320a,320b,320c. Referring toFIGS.32-34, in some embodiments, a method of culturing cells in the cell culture vessel300can include filling a region of a cell culture chamber303of the vessel300with a predetermined amount of liquid370. In some embodiments, the cell culture chamber303can be defined at least in part by an inner surface302of the wall301of the vessel300, and the method can include depositing a portion of the predetermined amount of liquid370in at least one microcavity320a,320b,320cof the plurality of microcavities320of the cell culture surface315. The cell culture surface315can define at least a portion331of the region, and each microcavity320a,320b,320cof the plurality of microcavities320can include a concave surface321a,321b,321cdefining a well322a,322b,322cand an opening323a,323b,323cin a portion375of the cell culture surface315defining a path into the well322a,322b,322c. In some embodiments, the method can further include culturing cells in the at least one microcavity320a,320b,320cafter depositing the portion of the predetermined amount of liquid370in the at least one microcavity320a,320b,320c, with the predetermined amount of liquid370contacting submerged surfaces325of the vessel300. In some embodiments, while culturing the cells in the at least one microcavity320a,320b,320c, the submerged surfaces325do not include planar surface portions including a surface normal that is opposite the direction of gravity “g”. Optionally, in some embodiments, while culturing the cells in the at least one microcavity320a,320b,320cof the plurality of microcavities320, a level371of the predetermined amount of liquid370can define a planar free surface of the predetermined amount of liquid370that is perpendicular relative to the direction of gravity “g”. By providing submerged surfaces325that do not include planar surface portions including a surface normal that is opposite the direction of gravity “g”, cells suspended in the liquid370will fall (e.g., based at least on the force of gravity) and/or be directed by the submerged surfaces325into the wells322a,322b,322cof the microcavities320a,320b,320cbecause there are no submerged surfaces325on which the cells can settle or to which the cells can adhere. As noted above, in some embodiments, cells that settle on or adhere to a surface of the vessel300can accumulate and grow (e.g., multiply) outside of the microcavities320a,320b,320ccausing problems with respect to desired growth of three-dimensional cells within the microcavities320a,320b,320c. For example, in some embodiments, cells that do not fall (based at least on the force of gravity) into the well322a,322b,322cand that accumulate or attach to other surfaces of the vessel300(e.g., if the submerged surfaces325were to include planar surface portions including a surface normal that is opposite the direction of gravity “g”) can grow outside of the well322a,322b,322cand disrupt (e.g., discourage, alter, slow, or prevent) desired growth of three-dimensional cells within the well322a,322b,322c. Similarly, in some embodiments, if the submerged surfaces325were to include planar surface portions including a surface normal that is opposite the direction of gravity “g”, cells could accumulate or attach to the planar surface portions and could grow and dislodge three-dimensional cells in the well322a,322b,322c, thereby disrupting or destroying desired growth of three-dimensional cells within the well322a,322b,322c. Accordingly, in some embodiments, by providing submerged surfaces325that do not include planar surface portions including a surface normal that is opposite the direction of gravity “g”, all cells suspended within the liquid370can be directed into the wells322a,322b,322c, thus reducing and eliminating problems that can otherwise occur if cells settle on or attach to surfaces of the vessel300outside the wells322a,322b,322c. Moreover, for purposes of the disclosure, unless other noted, “planar surface portion” is intended to mean any planar surface portion including a planar dimension greater than about 5 microns. For example, in some embodiments, submerged surfaces325that do not include planar surface portions parallel to the planar free surface of the level371of the predetermined amount of liquid370can be defined as submerged surfaces325that do not include planar surface portions, including a planar dimension greater than about 5 microns, parallel to the planar free surface of the level371of the predetermined amount of liquid370. Similarly, in some embodiments, submerged surfaces325that do not include planar surface portions including a surface normal that is opposite the direction of gravity “g” can be defined as submerged surfaces325that do not include planar surface portions, including a planar dimension greater than about 5 microns, including a surface normal that is opposite the direction of gravity “g”. For example, in some embodiments, the submerged surfaces325can include a planar portion; however, if a planar dimension of the planar surface portion is, for example, less than or equal to 5 microns, in some embodiments, the planar surface portion is considered too small for cells to reasonably accumulate or attach. Accordingly, in some embodiments, by providing submerged surfaces325that do not include planar surface portions including a planar dimension greater than about 5 microns, all cells suspended within the liquid370can be directed into the wells322a,322b,322c, thus reducing and eliminating problems that can otherwise occur if cells settle on or attach to surfaces of the vessel300outside the wells322a,322b,322c. In some embodiments, however, the submerged surfaces325can be entirely free of planar surface portions, irrespective of a threshold dimension defining the planar surface portion. FIG.35AandFIG.35Bare drawings illustrating cells growing as spheroids in microcavities and cells growing as irregular cellular conglomerates201. These irregular cellular conglomerates can occur in the embodiments shown inFIG.1-16(cell culture surface115) or in the embodiments shown inFIG.17-34(cell culture surface315), where flat surfaces occur in a vessel. It is important to avoid flat surfaces in the cell culture chamber103or303, to avoid these irregular cellular conglomerates. FIG.36Ais a photograph of spheroids in an array of microcavities under suitable conditions provide a homogeneous population of spheroids in the vessel.FIG.36Bis a photograph of irregular cellular conglomerates801isolated from a vessel having flat surfaces in the cell growth chamber103,303. To avoid producing these irregular cellular conglomerates801, embodiments of a cell culture vessel are provided which do not have flat surfaces in the cell culture surface, or do not have flat surfaces in the submerged region of the cell culture surface. That is, in embodiments of a cell culture vessel, the cell culture surface consists essentially of an array of microcavities, and does not provide flat surfaces that can produce undesirable irregular cellular conglomerates801. Throughout the disclosure, the terms “material”, “liquid”, and “gas” can be used to describe properties of a material employed when, for example, culturing cells in the cell culture vessel. Unless otherwise noted, for purposes of the disclosure, “material” can include fluid material (e.g., liquid or gas). Additionally, material can include a culture solution or media including a liquid including solid particles (e.g., cells) suspended in the liquid. Unless otherwise noted, for purposes of the disclosure, “liquid” can include cleaning or rinsing solutions, aqueous solutions, or other liquid that can be added to or removed from the vessel to, for example, clean the cell culture chamber, sterilize one or more features of the cell culture surface and the vessel, prepare the cell culture surface for cellular growth and other uses of liquid. Additionally, liquid can include a culture solution or media including a liquid including solid particles (e.g., cells) suspended in the liquid. Unless otherwise noted, for purposes of the disclosure, “gas” can include air, filtered or treated air, or other gases. Throughout the disclosure, the terms “non-permeable”, “gas-permeable”, and “porous” can be used to describe properties (e.g., material properties, characteristics, parameters) of one or more features of a cell culture surface. Unless otherwise noted, for purposes of the disclosure, a “non-permeable” cell culture surface (e.g., material of a non-permeable cell culture surface) is considered to be impermeable to solid, liquid, and gas under normal conditions (e.g., no external influence including but not limited to pressure and force) and, therefore, does not permit the transfer of solid, liquid, or gas in to, through, or out of, the non-permeable cell culture surface under normal conditions. In some embodiments, a non-permeable cell culture surface can form a portion of the wall of the vessel. Additionally, the cell culture chamber of the vessel is considered to be sterile when a non-permeable cell culture surface forms a portion of the wall of the vessel because bacteria, for example, cannot pass through the non-permeable cell culture surface. However, when filling the plurality of microcavities of the cell culture surface with material, gas can become trapped within the microcavity of a non-permeable cell culture surface based on surface tension of the liquid, thereby, in some embodiments, preventing material from filling the microcavities and preventing growth of a spheroid. Unless otherwise noted, for purposes of the disclosure, a “gas-permeable” cell culture surface (e.g., material of a gas-permeable cell culture surface) is considered to be impermeable to solid and liquid, and permeable to gas under normal conditions. Therefore, a gas-permeable cell culture surface does not permit the transfer of solid and liquid in to, through, or out of, the gas-permeable cell culture surface and does permit the transfer of gas in to, through, or out of, the gas-permeable cell culture surface. In some embodiments, a gas-permeable cell culture surface can form a portion of the wall of the vessel. Additionally, the cell culture chamber of the vessel is considered to be sterile when a gas-permeable cell culture surface forms a portion of the wall of the vessel because bacteria, for example, cannot reasonably pass through the gas-permeable cell culture surface. However, although the cell culture surface is gas-permeable, gas can still become trapped in the microcavity during filling with material because gas-permeation rates through the gas-permeable cell culture surface can be slower than the rate required to displace gas from the cavity under ordinary operating conditions and can therefore take an unacceptably long amount of time to permeate through the cell culture surface. Thus, in some embodiments, slowly filling the microcavities allows the liquid front to enter each microcavity at an angle, thereby displacing gas as the liquid fills the microcavity. In some embodiments, after filling the cavity with liquid, gas can permeate (slowly) through the gas-permeable cell culture surface. Unless otherwise noted, for purposes of the disclosure, a “porous” cell culture surface (e.g., material of a porous cell culture surface) is considered to be impermeable to solid and permeable to liquid and gas under normal conditions. Therefore, a porous cell culture surface does not permit the transfer of solid in to, through, or out of, the porous cell culture surface and does permit the transfer of liquid and gas in to, through, or out of, the porous cell culture surface. A porous cell culture surface cannot form a portion of the vessel because bacteria can pass through a porous cell culture surface, thus causing sterility issues in the cell culture chamber. Thus, when using a porous cell culture surface, the cell culture surface must be enclosed (entirely enclosed) in the sterile cell culture chamber of the vessel. During filling of the microcavities with material, however, gas can escape (e.g., pass) through the porous cell culture surface. Thus, filling of the microcavities can be performed rapidly without concern for entrapping gas in the microcavities. In some embodiments, liquid can only pass through the porous cell culture surface with added pressure or physical contact and disturbance of the cell culture surface. Thus, in some embodiments, material including liquid can be contained in the microcavities of the cell culture surface so long as the cell culture surface is not exposed to added pressure or physical contact and disturbance. For example, in some embodiments, the porous cell culture surface can be supported in the cell culture chamber to allow gas to pass through the cell culture surface during filling as well as during culturing and to isolate the cell culture surface from added pressure or physical contact and disturbance from external forces (e.g., outside the cell culture chamber). A number of aspects of cell culture vessels and methods of culturing cells have been disclosed herein. A summary of some selected aspects is presented below. In a first aspect, the disclosure provides a cell culture vessel comprising: a cell culture surface consisting essentially of a plurality of microcavities; a wall attached to the cell culture surface, the cell culture surface and an inner surface of the wall define a cell culture chamber of the vessel. In a second aspect, the disclosure provides the cell culture vessel of aspect 1, each microcavity of the plurality of microcavities comprises a concave bottom and an opening. In a third aspect, the disclosure provides the cell culture vessel of aspect 1 or 2, further comprising a necked opening. In a fourth aspect, the disclosure provides the cell culture vessel of aspect 3 further comprising and dam in the necked opening. In a fifth aspect, the disclosure provides the cell culture vessel of aspect 1 or 2 further comprising a lid. In a sixth aspect, the disclosure provides the cell culture vessel of aspect 3 or 4 further comprising a lid. In a seventh aspect, the disclosure provides the cell culture vessel of aspect 6 wherein the lid comprises a hinged opening. In an eighth aspect, the disclosure provides the cell culture vessel of aspect 4 wherein the lid comprises a sliding opening. In a ninth aspect, the disclosure provides the cell culture vessel of aspect 3, 4, or 6-8 wherein the necked opening comprises a bend. In a tenth aspect, the disclosure provides the cell culture vessel of any one of aspects 1-9 wherein the wall comprises a recess and the cell culture surface is attached to the recess. In an eleventh aspect, the disclosure provides the cell culture vessel of any one of aspects 1-9 wherein the wall comprises a protrusion and the cell culture surface is attached to the protrusion. In a twelfth aspect, the disclosure provides a cell culture vessel comprising: a cell culture surface comprising a plurality of microcavities, the microcavities having a non-flat sinusoidal shape; a wall attached to the cell culture surface, the cell culture surface and an inner surface of the wall define a cell culture chamber of the vessel; wherein the cell culture surface is substantially free of flat areas. In a thirteenth aspect, the disclosure provides the cell culture vessel of aspect 12, each microcavity of the plurality of microcavities comprises a concave bottom and an opening. In a fourteenth aspect, the disclosure provides the cell culture vessel of aspect 12 or 13, further comprising a necked opening. In a fifteenth aspect, the disclosure provides the cell culture vessel of aspect 14 further comprising and dam in the necked opening. In a sixteenth aspect, the disclosure provides the cell culture vessel of aspect 12 or 13 further comprising a lid. In a seventeenth aspect, the disclosure provides the cell culture vessel of aspect 14 or 15 further comprising a lid. In an eighteenth aspect, the disclosure provides the cell culture vessel of aspect 17 wherein the lid comprises a hinged opening. In a nineteenth aspect, the disclosure provides the cell culture vessel of aspect 17 wherein the lid comprises a sliding opening. In a twentieth aspect, the disclosure provides the cell culture vessel of any one of aspects 14, 15, or 17-19 wherein the necked opening comprises a bend. In a twenty-first aspect, the disclosure provides the cell culture vessel of any one of aspects 12-17 wherein the wall comprises a recess and the cell culture surface is attached to the recess. In a twenty-second aspect, the disclosure provides the cell culture vessel of any one of claims12-17wherein the wall comprises a protrusion and the cell culture surface is attached to the protrusion. It will be appreciated that the various disclosed embodiments can involve particular features, elements or steps that are described in connection with that particular embodiment. It will also be appreciated that a particular feature, element or step, although described in relation to one particular embodiment, can be interchanged or combined with alternate embodiments in various non-illustrated combinations or permutations. It is to be understood that, as used herein the terms “the,” “a,” or “an,” mean “at least one,” and should not be limited to “only one” unless explicitly indicated to the contrary. Thus, for example, reference to “a component” includes embodiments having two or more such components unless the context clearly indicates otherwise. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, embodiments include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that any particular order be inferred. While various features, elements or steps of particular embodiments can be disclosed using the transitional phrase “comprising,” it is to be understood that alternative embodiments, including those that can be described using the transitional phrases “consisting” or “consisting essentially of,” are implied. Thus, for example, implied alternative embodiments to an apparatus that comprises A+B+C include embodiments where an apparatus consists of A+B+C and embodiments where an apparatus consists essentially of A+B+C. It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure cover the modifications and variations of this disclosure provided they come within the scope of the appended claims and their equivalents.
81,450
11857971
DETAILED DESCRIPTION Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Test Device FIG.1AtoFIG.6Dare views illustrating examples of the embodiment of the present invention. Portions assigned with the same reference numeral in the drawings indicate the same member. It is noted that in the drawings, some of the structures are appropriately omitted for the simplification of the drawings. The size, shape, thickness, and the like of the members are appropriately exaggerated. FIGS.1A-1Dincludes views illustrating a test device10according to the present embodiment.FIG.1Ais a top view illustrating its appearance,FIG.1Bis a top view illustrating an example of a test piece13,FIG.1Cis a side view of the test piece13, andFIG.1Dis a side cross-sectional view illustrating a state before testing (before a specimen liquid S2drops on the test piece13) as well as an unused state of the test device10. As illustrated inFIGS.1A-1D, the test device10of the present embodiment includes a culturing unit11, a test piece13, a separating unit15, an opening unit17, and a case19. As illustrated inFIG.1D, the culturing unit11includes, for example, a solution housing part19C, a flow path23of a specimen liquid S2, and a sealing unit (for example, a screw cap)25to seal the solution housing part19C. In the solution housing part19C, a culture solution S1is housed before testing. The culture solution S1can culture a specimen to a considerable number (for example, 1000 times). Also, the solution housing part19C can subsequently house a solution (hereinafter, referred to as a “specimen liquid S2”) containing a considerable number of specimens after cultured. More specifically, the solution housing part19C can house a sampling unit27(in this example, a cotton swab or the like) with a sampled specimen as it is. The sampling unit27is, for example, a rod-like member (in this example, a cotton swab or the like) having a sampling part27A on one end thereof. According to the culturing unit11, the sampling unit27is housed in the solution housing part19C such that the sampling part27A (the tip of the cotton swab) is immersed in the culture solution S1. Furthermore, the sampling unit27is sealed by the sealing unit (cap)25so as to be housed in a sealed state, so that the specimen can be cultured. A metal plate31having high thermal conductivity or the like may be disposed on a portion of the outer surface of the solution housing part19C. The metal plate31facilitates the transmission of exterior heat to the inside of the solution housing part19C during culture. Accordingly, the responsivity of the culture temperature control improves, so that the culture can be easily facilitated. It is noted that in this example, the cap25is mounted to the rear end portion (an end portion opposite to the sampling part27A) of the sampling unit27. Thus, the test device is configured such that when the sampling unit27with a sampled specimen is housed in the solution housing part19C and the cap25is fitted to the rear end portion of the solution housing part19C, the sampling part27A is immersed in the culture solution S1. The test piece13is, for example, a band-like porous member that can absorb the specimen liquid S2cultured by the culturing unit11. In this example, the test piece13is a known test piece used in an immunochromatographic assay. More specifically, for example, as illustrated inFIG.1BandFIG.1C, the test piece13is a member that includes a sample pad131to serve as a dropped portion of the specimen liquid S2, a conjugate pad133containing antibodies (labeled antibodies) labeled with colored particles such as gold nanoparticles, a membrane filter135containing capture antibodies (T) and control antibodies (C), for example, linearly applied and immobilized in the width direction of the band, and an absorption pad137to absorb the dropped specimen liquid S2. These constituents are laminated such that their end portions superimpose each other in the band lengthwise direction. The specimen liquid S2dropped on the sample pad131migrates in the arrow direction toward the absorption pad137. It is noted that the test piece13is not limited to a laminated structure in which the sample pad131, the conjugate pad133, the membrane filter135, and the absorption pad137each partly superimpose each other as illustrated inFIG.1C. For example, the test piece13may have a structure of a single band-like porous member in which the sample pad131, the conjugate pad133, the membrane filter135, and the absorption pad137are continuously disposed along the band lengthwise direction such that their respective corresponding regions are next to each other or a structure in which some of these constituents are laminated. In the following description, the test piece13having a laminated structure as illustrated inFIG.1Cwill be described as an example. However, when the test piece13has a shape of a single band (or a band in which some of the constituents superimpose each other), the constituents described as the sample pad131, the conjugate pad133, the membrane filter135, and the absorption pad137should be read as regions corresponding to the respective constituents. For example, when “the sample pad131” is described, it should be read as “a region corresponding to the sample pad131”. In this example, the case19includes a test piece housing part19A, a linking unit19B, and the solution housing part19C. In brief, the solution housing part19C of the culturing unit11is disposed integrally with the test piece housing part19A without any space therebetween. The test piece housing part19A has a shape of, for example, a substantially rectangular parallelepiped inside which the test piece13is housed. Also, a determination window191through which a determination region (that is, the membrane filter135) of the test piece13can be determined (viewed) from the outside and an evaporation window193that prevents the specimen liquid S2from flowing back in the test piece13are provided to a surface (the upper surface inFIG.1D) facing to the test piece13of the test piece housing part19A. The determination window191is covered with a transparent resin, glass, or the like. The evaporation window193opens and communicates with (opens to) the inside, but is sufficiently small to such a degree that allows the evaporation of the vaporized specimen liquid S2. With this configuration, the test piece13in the inside cannot be touched through these windows. It is noted that a guide G for visual determination may be provided to a portion of the determination window191by, for example, affixing a sticker or printing. As the guide G, a scale of a plurality of settings (for example, 10 settings) which represents color shading levels is indicated so that the guide G serves as an index of the colored state of (the control antibodies of) the membrane filter135. Alternatively, only one color as a criterion may be indicated instead of the color shading levels. The linking unit19B is a site where it is in intimate contact with both the test piece housing part19A and the solution housing part19C without any space and integrally links the test piece housing part19A and the solution housing part19C. Also, the linking unit19B is configured to be, for example, bendable and deformable. Here, as an example, the linking unit19B has a bellows structure such that the test piece housing part19A and the solution housing part19C are linked and retained in a relatively foldable manner. In the test device10of the present embodiment, the culturing unit11and the test piece13are aligned along the lengthwise direction of the case19. The culture solution S1or the specimen liquid S2in the culturing unit11after culture and the test piece13are sealed and retained integrally by the case19(the test piece housing part19A, the linking unit19B, and the solution housing part19C). However, before testing by the test device10(before the specimen liquid S2drops on the test piece13), the culture solution S1or the specimen liquid S2and the test piece13are separated by the separating unit15in a non-contact state as illustrated inFIG.1D. The separating unit15is, for example, a sealing member that is housed inside the linking unit19B of the case19and prevents the specimen liquid S2from being brought into contact with the test piece13until a prescribed time (a timing of testing). In this example, the separating unit15is provided as a portion of the case19(integrally with the case19). More specifically, the flow path23of the specimen liquid S2is formed in the solution housing part19C on a side closer to the test piece13(a side opposite to the cap25). In this example, the flow path23is, for example, smaller in diameter than the cylindrical solution housing part19C and narrower toward a direction away from the solution housing part19C. With this configuration, an appropriate amount of the specimen liquid S2in the solution housing part19C can drop on the end portion (the sample pad131) of the test piece13. It is noted that the shape of the flow path23is not limited to that illustrated in the drawing. The flow path23may have any shape and structure as long as the specimen liquid S2can flow out toward the test piece13. In this case, the separating unit15is in contact with the outflow-side end portion (opening) of the flow path23of the culturing unit11to seal the opening, above the end portion (the sample pad131) of the test piece13on a side closer to the culturing unit11. The separating unit15is, for example, a sealing member formed in such a manner that a portion (the inner wall of the test piece housing part19A) of the case19is pulled into the inner space of the linking unit19B. It is noted that the contact region between the flow path23and the separating unit (sealing member)15and/or its vicinity has a fragile structure V that is more likely to be broken than other regions, such that the flow path23and the separating unit (sealing member)15can be separated by, for example, applying an (slight) external force. For example, in this example, at least one of the flow path23and the separating unit (sealing member)15or the contact portion therebetween, and/or its vicinity have a thin structure (seeFIG.3B). This thin structure is, for example, a structure in which the member is thinner than other sites to reduce its strength or a structure in which the member has a notch to guide the folding and separation into a prescribed direction. For example, inFIG.1D, the contact portion between the separating unit15and the flow path23has the fragile structure V. For example, the contact portion is folded and broken (separated) with such an external force as bending, folding, or pinching by the operator's hand and fingers. Accordingly, the separating unit (sealing member)15detaches from the flow path23. Thus, the flow path23and the test piece housing part19A communicate with each other, and the specimen liquid S2drops on the sample pad131of the test piece13. In the example illustrated inFIG.1, the opening unit17is the linking unit19B which links the test piece housing part19A and the solution housing part19C and retains the both in a foldable manner. Specifically, for example, the operator can fold the solution housing part19C with respect to the test piece housing part19A (for example, fold the solution housing part19C toward the upper side ofFIG.1D) around the opening unit17(linking unit19B) of the bellows structure. Accordingly, the separating unit15opens from the flow path23. Thus, in the test device10of the present embodiment, the case19integrally seals at least a portion (the sample pad131portion that is a region on which the specimen liquid S2drops) of the test piece13on the side closer to the separating unit15, at least a portion (the solution housing part19C, the flow path23, and the tip opening of the flow path23) of the culturing unit11, and the separating unit (sealing member)15. In a state before the start of testing, the culture solution S1or the specimen liquid S2and the test piece13are separated by the separating unit15. Furthermore, the test device10includes the opening unit17that can release the separated state (sealed state) between the specimen liquid S2and the test piece13by the separating unit (sealing member)15to be capable of forming the flow path through which the specimen liquid S2housed in the solution housing part19C of the culturing unit11reaches the test piece13. As already described, the opening unit17of this example is a portion (the linking unit19B), which can deform in a state in which the sealing is maintained, of the case19. During testing, the opening unit17(linking unit19B) changes its state thereby to open the separating unit15while the sealed state inside the case19is maintained. For example, the opening unit17can be deformed by applying an external force in a state in which the sealing is maintained. Accordingly, the separating unit15opens in the state of being sealed inside the case19. When the separating unit15opens, the flow path23and the inside of the test piece housing part19A communicate with each other. Then, the specimen liquid S2drops on the sample pad131of the test piece13without being exposed to the outside of the case19. It is noted that the separating unit15and/or the fragile structure V near the separating unit15are more likely to be broken than other regions such that the flow path23and the separating unit15can be easily separated. In the present embodiment, a structure (here, including the fragile structure V) which contributes to the opening by the opening unit17in this manner is also a part of the opening unit17. Although the opening unit17(linking unit19B) has the bellows structure in this example, it may have, for example, a tube structure which is inwardly bendable or foldable with an external force or the like. Also, at least the opening unit17may preferably be transparent such that the separating unit15and its vicinity can be viewed from the outside. Accordingly, the operator can easily check the opening state of the separating unit15, which enables a reliable opening work. According to such a structure, the process from the culturing of the specimen to the dropping of the specimen liquid S2on the test piece13can be performed in a sealed environment. In particular, the step of dropping the specimen liquid S2, which had the risk that the specimen liquid S2may be exposed, can be completed inside the case19under a substantially sealed environment. Therefore, even when the specimen liquid S2contains a high concentration of bacteria, the specimen liquid S2will not be exposed to the outside, and the specimen liquid S2can be prevented from splattering and leaking. Moreover, secondary contamination and infection to the operator and the work environment can be prevented. Furthermore, since the examination can be performed simply and safely, it can also be performed, for example, by employees of restaurants in the premises of restaurants or the like without resort to specialized institutions and skilled operators. In the above-described example, the evaporation window193is provided to the case19for preventing the specimen liquid S2from flowing back in the test piece13. The evaporation window193, however, may not be provided if the outflow can be prevented by, for example, observing a determination time or devising the shape of the test piece13(for example, sufficiently increasing the length in the lengthwise direction). When the evaporation window193is not provided, a substantially complete sealed space can be realized in the case19. Specifically, the test piece13, the solution housing part19C and the flow path23of the culturing unit11, and the separating unit15can be sealed, which is further suitable in terms of the prevention of the splattering and leaking of the specimen liquid S2. Detection Test Method of Biomolecules By referring toFIG.2AtoFIG.3D, a detection test method of biomolecules using the test device10of the present embodiment will be described. It is noted thatFIG.3BandFIG.3Care an enlarged view near the linking unit19B. First, a specimen is sampled in a sampling environment (for example, a kitchen of a restaurant) where the existence of biomolecules to be intended (detected) (for example, pathogenicEscherichia colisuch as O157) is suspected. Specifically, an unused test device10of the present embodiment is prepared. As described above, the test device10includes the culturing unit11and the test piece13which are retained in the integral-type case19(FIG.2A). A specimen is sampled in a state in which the culturing unit11and the test piece13are separated. The sampled specimen is cultured in the culturing unit11in a sealed state. Specifically, the cap25at the end portion of the culturing unit11is removed, and the sampling unit27is pulled out. A desired site is wiped with the sampling part27A of the sampling unit27such that a specimen adheres to the sampling part27A (FIG.2B). Thereafter, the sampling unit27is housed back in the culturing unit11and closed and sealed with the cap25. The sampling part27A (the tip of a cotton swab) is configured to be immersed in the culture solution S1in the state of being sealed with the cap25. Thus, the specimen can be cultured while the sampling unit27is housed in the sealed state. During culture, the test device10is stored in, for example, a constant-temperature incubator50and left to stand for a prescribed time (FIG.2C). For example, when antigens areE. colisuch as O157, the antigens are, for example, cultured at 37° C. for 3 hours to about 1000 times. After the completion of culture, the separation between the culturing unit11and the test piece13is released while the sealed state by the case19is maintained. Thus, the specimen liquid S2is absorbed by the test piece13without being exposed to the outside. Specifically, the test device10is removed from the constant-temperature incubator50or the like. Then, the opening unit17(linking unit19B) portion in the bellows structure is folded in the sealed state (without removing the cap25) (FIG.3A). Accordingly, as illustrated in the enlarged views ofFIG.3BandFIG.3C, the separating unit15is folded and broken to release the separated state inside the linking unit19B while the sealed state by the case19is maintained. Specifically, the separating unit (sealing unit)15detaches from the flow path23, so that the flow path23and the inside of the test piece housing part19A communicate with each other. Accordingly, while the sealed state by the case19is maintained, the specimen liquid S2drops on the sample pad131of the test piece13(FIG.3A). The specimen liquid S2passes through the sample pad131and the conjugate pad133and then is absorbed by the membrane filter135(seeFIG.1BandFIG.1C). When antigens exist in the specimen liquid S2, the antigens migrate by capillary action in the membrane filter135while forming immune complexes with labeled antibodies. Since the immune complexes are colored when captured by capture antibodies to become a state in which colored particles derived from the labeled antibodies are concentrated, the coloring is viewed as the degree of the antigens contained in the specimen for determination. As illustrated inFIG.3D, determination is performed by, for example, comparing the colored state of the membrane filter135to the guide G for visual determination disposed on a portion of the determination window191. Alternatively, comparison may be performed using, other than the test device10, a guide plate on which one or a plurality of color shading levels is printed. Still alternatively, an image of the colored state of the membrane filter135and the guide (guide plate) taken by a mobile terminal (for example, a smartphone) may be transmitted to a determination institution for determination. Also, the taken image may be caught using a determination application program or the like for instant determination. As described above, according to the test method using the test device10of the present embodiment, the process from the culturing of the specimen to the dropping of the specimen liquid S2on the test piece13can be performed in a sealed environment. In particular, the step of dropping the specimen liquid S2, which had the risk that the specimen liquid S2may be exposed, can be completed inside the case19under a substantially sealed environment. Therefore, even when the specimen liquid S2contains a high concentration of bacteria, the specimen liquid S2will not be exposed to the outside, and the specimen liquid S2can be prevented from splattering and leaking. Moreover, secondary contamination and infection to the operator and the work environment can be prevented. Furthermore, since the examination can be performed simply and safely, it can also be performed, for example, by employees of restaurants in the premises of restaurants or the like without resort to specialized institutions and skilled operators. Also, when a comparison image of the colored state of the membrane filter135and the guide (guide plate) is transmitted to a specialized institution or captured in a specialized application program or the like for determination, unevenness in determination among operators is avoided, and accurate determination can be performed. Modified Examples FIG.4AtoFIG.6Dare schematic views of side cross sections mainly illustrating modified examples of the separating unit15and the opening unit17in the test device10of the present embodiment. It is noted that although the structures such as the test piece13and the test piece housing part19A are partly omitted inFIG.4AtoFIG.6D, the omitted structures (the test piece13and the test piece housing part19A) are the same as those illustrated inFIG.1. As illustrated inFIGS.4A-4B, in the test device10of the present embodiment, the test piece13and the specimen liquid S2are housed integrally in the case19, and the separating unit15can separate at least the test piece13and the specimen liquid S2in a non-contact state (FIG.4A). During testing, (at least a portion of) the separating unit15opens when the operator manipulates the opening unit17at an optional timing. This enables the formation of a flow path through which the specimen liquid S2reaches the test piece13without being exposed to the outside of the case19(FIG.4B). For example, as illustrated inFIG.5A, the fragile structure V of the opening unit17may have a structure in which a notch to facilitate folding and separating in a prescribed direction (upward inFIGS.5A-5C) is formed to one of the separating unit15(a portion of the test piece housing part19A) and the flow path23or to their nearby member. Also, as illustrated inFIG.5B, the opening unit17may be, for example, the linking unit19B (17A) stretchably disposed in the lengthwise direction of the case19and a needle-like member17B protruding from the side closer to the test piece13to the side closer to the flow path23of the culturing unit11, and the separating unit15may be the bottom of the solution housing part19C. In this case, although omitted in the drawing, the needle-like member17B is, for example, linked integrally with the test piece housing part19A, and the needle-like member17B and the separating unit15are separated in an unused state. Then, when the linking unit19B is shrunk after culture, the needle-like member17B breaks (chips, or sticks to break) at least a portion of the separating unit15. Also, inFIG.5B, the needle-like member17B may be advanced solely toward the separating unit15by a manipulation from the outside. For example, the other end (the end portion away from the separating unit15) of the needle-like member17B is led to the outside of the case19, and the operator manipulates the led end portion thereof to move the needle-like member17B toward the separating unit15. In this case, the linking unit19B of the case19may be configured not to deform. Also, the needle-like member17B may be a needle-like member that advances from the side closer to the solution housing part19C to the side closer to the test piece housing part19A to break (chip) at least a portion of the separating unit15. Also, as illustrated inFIG.5C, the opening unit17may be formed integrally to, for example, the bottom, which serves as the separating unit15, of the solution housing part19C. Such an opening unit17may be, for example, folded and broken with respect to the separating unit15to chip a portion (joining part with the opening unit17) of the separating unit15such that the solution housing part19C and the test piece housing part19A communicate with each other. In this case, for example, the end portion opposite to the separating unit15of the opening unit17is led to the outside of the case19, and the led portion is manipulated to fold the opening unit17. Alternatively, although omitted in the drawing, the linking unit19B of the case19may have a shape of bellows, a tube, or the like so as to be bendable and deformable as illustrated inFIG.5A. Such a linking unit19B may be deformed to fold the opening unit17. In this manner, at least a portion of the opening unit17of the present embodiment may be housed in the case19(linking unit19B). In both cases ofFIG.5BandFIG.5C, the fragile structure V is provided to only a portion of the solution housing part19C thereby to chip the separating unit15. Thus, the opening region can be controlled (concentrated in the fragile structure V and its vicinity). Also, in bothFIG.5BandFIG.5C, the flow path23as illustrated inFIG.5Ais formed, and the separating unit15may be a sealing member covering the flow path23. Also, as illustrated inFIG.6AandFIG.6B, the separating unit15may be a stopper member that plugs the tip of the flow path23. InFIG.6A, the separating unit (stopper member)15is inserted into the flow path23. InFIG.6B, the tip of the flow path23is inserted into the separating unit (stopper member)15. The separating unit15and the flow path23may removably fit together by relatively moving the both in the lengthwise direction of the case19or may be linked together by thrusting one into the other. In this case, although omitted in the drawing, the separating unit15may be linked with the test piece housing part19A, and the separating unit (stopper member)15may be attachable and detachable by the manipulation of the opening unit (linking unit19B). The opening unit17is, for example, the linking unit19B, which is bendable and deformable and stretches and shrinks in the lengthwise direction of the case19or rotates around the rotation axis along the lengthwise direction, of the case19. The linking unit19B is manipulated from the outside of the case19, so that the separating unit15is detached from the flow path23. Alternatively, a portion of the separating unit15may be led to the outside of the case19, and the led portion is manipulated to attach or detach the separating unit15. Also, as illustrated inFIG.6C, at least a portion of the solution housing part19C of the culturing unit11may be bendable and deformable. According to such a structure, when an external force is applied from the outside of the solution housing part19C (when the solution housing part19C is pressed), the fragile structure V provided to a portion (for example, the bottom on the side closer to the test piece13or the wall) of the flow path23or the solution housing part19C chips (breaks). In this case, the fragile structure V and a portion of the flow path23or the solution housing part19C near the fragile structure V to be chipped serve as the separating unit15, and a bendable and deformable region of the culturing unit11(solution housing part19C) capable of being pressed serves as the opening unit17. In the present embodiment, when the amount of the specimen liquid S2dropping on the test piece13is excessively large, a stable result may not be obtained depending on the specimen and the structure of the test piece13. The dropping amount of the specimen liquid S2is, as an example, 100 μL to 140 μL, and preferably 250 μL to 500 μL in some cases depending on the shape of the test piece13. In the above-described test device10, the shape of the flow path23, the opened position when the solution housing part19C is directly opened, the position and shape of the fragile structure V, the shapes of the opening unit17and the separating unit15, and the aspect of opening are appropriately selected such that when an appropriate dropping amount of the specimen liquid S2is specified, the appropriate amount can be dropped. It is noted that the test device10of the present invention is not limited to the structure in which a portion of the specimen liquid S2housed in the solution housing part19C drops on the test piece13. The test device10may be configured such that when the separating unit15is opened by the opening unit17, a portion (for example, only the sample pad131) of the test piece13is entirely immersed in the specimen liquid S2as illustrated inFIG.6D. In this case, a partition19D is provided in the test piece housing part19A. Accordingly, the test piece13other than the sample pad131is not immersed in the specimen liquid S2, and the specimen liquid S2migrates in the test piece13. Also, although the determination window191is provided to the test piece housing part19A in the above-described example, the determination window191may not be provided, and the test piece housing part19A or the entire case may be transparent such that the inside can be viewed. Also, although the test device10used in the detection test of biomolecules by immunochromatography has been described as an example in the above-mentioned embodiment, the test device10of the present invention may also be, without limited to immunochromatography, a test device using the test piece13that absorbs the specimen liquid S2cultured by the culturing unit11to be capable of displaying some kind of a result or the test piece13that absorbs the specimen liquid S2(in the culturing unit11) housed in the culturing unit11to be capable of displaying some kind of a result. It should be noted that the test device10of the present invention is not limited to the above-described embodiment and can be variously modified without departing from the scope of the present invention.
30,368
11857972
Similar reference characters denote corresponding features consistently throughout the attached drawings. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring toFIGS.1and2, the core sample holder for microwave heating of a core sample, designated generally as10in the drawings, uses microwave-based heating of a reservoir rock core sample S or the like during testing. The core sample holder10includes a hollow housing12having opposed open first and second ends14,16, respectively, having at least one pressurized fluid port34formed through a wall36of the hollow housing12. InFIG.2, two such pressurized fluid ports34are shown. However, it should be understood that any suitable number of pressurized fluid ports34may be utilized. It should be further understood that the hollow housing12may be formed from any suitable material that can withstand the hydrostatic confining pressure required therein during testing of core sample S. For example, the hollow housing12may be formed from a carbon fiber composite material with an aluminum liner. Alternatively, the hollow housing12may be formed from steel, a nickel-chromium-molybdenum-tungsten alloy, or a ceramic zirconia material. A resilient sleeve18is disposed within the hollow housing12. The resilient sleeve18is adapted for releasably holding the core sample S during testing. The hollow housing12may be a cylindrical housing, and the resilient sleeve18may be elongated and axially aligned with an axis of the cylindrical housing12. However, it should be understood that the overall shape and relative dimensions of the hollow housing12and the resilient sleeve18are shown inFIGS.1and2for exemplary purposes only, and may be varied dependent upon the size, shape and type of samples being tested. It should be further understood that resilient sleeve18may be formed from any suitable type of resilient material. For example, resilient sleeve18may be formed from neoprene with an internal Teflon® (polytetrafluoroethylene, or PTFE) lining. The resilient sleeve18is adapted for securely and releasably retaining the core sample S within an interior region72of the sleeve18. An annular bladder20is also disposed within the hollow housing12and surrounds the resilient sleeve18. The annular bladder20is adapted for receiving a liquid22. The liquid22may be water, for example, although it should be understood that any suitable liquid that can be heated by applied microwave radiation may be used. The annular bladder20may completely cover an outer surface28of the resilient sleeve18to provide full and even heating of the resilient sleeve18and the core sample S disposed therein. The annular bladder18may be formed from silicone rubber, for example, which has a melting temperature ranging between from 200° C. and 450° C. However, it should be understood that the annular bladder20may be formed from any suitable material that will not melt or degrade at or near the boiling point of the liquid22within the bladder20. An annular cavity74is defined between an outer surface24of the annular bladder20and an inner surface26of the hollow housing12. The annular cavity74is adapted for receiving a pressurized fluid, such as pressurized air or the like, through the at least one pressurized fluid port34. During testing, the pressurized fluid within the annular cavity74simulates the native pressure within the rock at the depth from which the core sample S was extracted. A pressure sensor70may be coupled to one of the pressurized fluid ports34for monitoring the pressurized fluid within the annular cavity74. First and second caps30,32, respectively, releasably cover and seal the first and second ends14,16of the hollow housing12, respectively. An inlet channel38is formed through the first cap30for injecting a testing fluid into the core sample S, and an outlet channel40is formed through the second cap32for discharging the testing fluid from the core sample S. InFIG.2, exemplary inlet and outlet ports42,44are shown connected to inlet channel38and outlet channel40, respectively, although it should be understood that any suitable type of fluid connection may be used. As shown, each of the first and second caps30,32may have an interior portion48,50, respectively, having a reduced diameter. This allows each of the interior portions48,50to releasably cover and seal the corresponding open end52,54of the resilient sleeve18, as shown inFIG.2. First and second sand screens60,62may be attached to the interior portions48,50of the first and second caps30,32, respectively, such that, in use, the first and second sand screens60,62contact opposed ends of the core sample S during testing. The first and second sand screens60,62restrict migration of fine particles from the core sample S during testing. InFIG.2, the first cap30has external threads76for engaging corresponding internal threads formed about the open end14of the hollow housing12. Similarly, the second cap32has external threads78for engaging corresponding internal threads formed about the open end16of the hollow housing12. It should be understood that the threads76,78are shown for exemplary purposes only, and that any suitable type of fastener or engagement may be used to effect releasable covering and sealing of the open ends14,16by the first and second caps30,32, respectively. Additional seals, such as O-rings80,82, or the like, may also be used to effect a tight and fluid-proof seal. A microwave waveguide46passes through the wall36of the hollow housing12and the annular cavity74, such that the microwave waveguide46terminates within the annular bladder20. The microwave waveguide46is adapted for transmitting microwave radiation from an external microwave source M into the liquid22contained within the annular bladder20to heat the liquid. It should be understood that any suitable type of source of microwave radiation may be used, such as a magnetron or the like. A temperature sensor56, such as a thermocouple or the like, may be embedded in the first cap30for monitoring the temperature during testing. During testing, the liquid22is heated to a temperature that simulates the native temperature within the rock at the depth from which the core sample S was extracted. In use, the microwave radiation heats the liquid22, and the heat is transferred by conduction through the wall of the annular bladder20to the resilient sleeve18, and from the resilient sleeve18into the core sample S. It is to be understood that the core sample holder for microwave heating of a core sample is not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.
6,897
11857973
DETAILED DESCRIPTION OF THE EMBODIMENTS A clear and complete description of technical solutions in the embodiments of the present disclosure will be given below, in combination with the drawings in the embodiments of the present disclosure. Apparently, the embodiments described below are merely a part, but not all, of the embodiments of the present disclosure. The following description of at least one exemplary embodiment is merely illustrative and is in no way used as any limitation to the present disclosure and its application or use. All of other embodiments, obtained by those of ordinary skill in the art based on the embodiments in the present disclosure without any creative effort, fall into the protection scope of the present disclosure. Unless otherwise specified, the relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments are not intended to limit the scope of the present disclosure. In the meantime, it should be understood that the dimensions of various parts shown in the drawings are not drawn in the actual scale relationship for the convenience of description. Techniques, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the techniques, methods and devices should be considered as a part of the authorized specification. In all of examples shown and discussed herein, any specific value should be construed as illustrative only and not as a limitation. Accordingly, other examples of the exemplary embodiments may have different values. It should be noted that: similar reference numerals and letters indicate similar items in the following drawings, therefore, once an item is defined in one drawing, it is not required to be further discussed in the subsequent drawings. In the description of the present disclosure, it should be understood that, the terms “first”, “second” and the like are used for defining components and parts, and are merely for the convenience of distinguishing the corresponding components and parts, and unless otherwise stated, the above words have no special meaning, and thus cannot be construed as limiting the protection scope of the present disclosure. In the description of the present disclosure, it should be understood that, orientation or position relationships indicated by orientation words such as “front, back, upper, lower, left, right”, “lateral, longitudinal, vertical, horizontal” and “top, bottom” and the like are generally orientation or position relationships shown on the basis of the drawings, and are merely for the convenience of describing the present disclosure and simplifying the description, in the absence of opposite statement, these orientation words do not indicate or imply that the referred apparatuses or elements must have specific orientations or must be constructed and operated in specific orientations, and thus cannot be construed as limiting the protection scope of the present disclosure; and the orientation words “inside and outside” refer to the inside and outside of the contours of the components themselves. A “lateral direction” used in the following description refers to a left-right direction of the gene sequencing reaction device as shown inFIG.1toFIG.3, a “longitudinal direction” refers to a front-back direction of the gene sequencing reaction device as shown inFIG.1toFIG.3, and a “vertical direction” refers to an up and down direction of the gene sequencing reaction device as shown inFIG.1toFIG.3. FIG.1toFIG.11show the structure of a gene sequencing reaction device1in an embodiment of the present disclosure. As shown inFIG.1toFIG.11, the embodiment of the present disclosure discloses a gene sequencing reaction device1. The gene sequencing reaction device1includes a supporting platform8, a dipping container, a temperature control apparatus5, and a transfer apparatus6. The dipping container is disposed on the supporting platform8. The dipping container has a dipping reaction area, and the dipping reaction area is used for holding a chemical reagent for gene sequencing reaction and dipping a sequencing chip2having a DNA sample loading structure on the surface and having a DNA sample loaded thereon in the chemical reagent to perform a gene sequencing reaction. The temperature control apparatus5is configured to control the temperature of the chemical reagent in the dipping reaction area. The transfer apparatus6is configured to insert the sequencing chip2into the dipping reaction area or pull out the sequencing chip from the dipping reaction area. The DNA sample in the present embodiment is a sequencing reaction template, and labeled nucleotides may be added to the sequencing reaction template. The gene sequencing reaction device1provided by the present disclosure may realize the gene sequencing reaction in a dipping manner. The sequencing chip2is dipped in the chemical reagents in different dipping reaction areas to complete various steps required for the sequencing reaction. The chemical reagent in the dipping reaction area may be reused, thereby reducing the cost of consumables. There is no problem of uneven liquid flow rate in the dipping manner, and bubbles are unlikely to be generated on the surface of the sequencing chip2, so that a more uniform and sufficient chemical reaction may be ensured. The sequencing chip2is subjected to uniform pressure and uniform heating in the dipping reaction area, thereby generating no deformation. No complicated fluid system is needed, few parts and components are used, the assembly is easy, and the manufacturing cost is low. Multiple sequencing chips2may be dipped at the same time, thereby having the advantages of high throughput. The gene sequencing reaction device1may be automatically controlled by the controller23, so that automated operation may be achieved. The embodiment of the present disclosure will be described in detail below in combination withFIG.1toFIG.11. As shown inFIG.1toFIG.11, the gene sequencing reaction device1of the embodiment of the present disclosure includes a sequencing chip2, a dipping container, a temperature control apparatus5, a transfer apparatus6, a chip holding apparatus, an chip supplying storage apparatus14, a chip unloading storage apparatus15, a container cover4, a cover overturning mechanism22, an air blowing apparatus25, a controller23, and a supporting platform8. The surface of the sequencing chip2is provided with a DNA sample loading structure, and before the gene sequencing reaction is performed, a DNA sample has been loaded on the DNA sample loading structure of the sequencing chip2. In the present embodiment, the sequencing chip2is a silicon chip, and linkers capable of capturing DNA molecules are preset on surfaces of both sides of the silicon chip. After a series of chemical reactions, the DNA molecules may be captured by these linkers and eventually adhered to the surface of the silicon chip. The linkers may be formed, for example, by modifying the surface of the silicon chip with amino group. During the gene sequencing reaction, the DNA sample is always attached to the sequencing chip2. The so called DNA sample in the present embodiment may be a nanosphere molecule disclosed in U.S. Pat. No. 8,445,197 B2, which may also be referred to as DNB. A genomic DNA is fragmented at first, a sequence of linkers is added then, and cyclizing is performed to form a single-stranded circular DNA, the single-stranded circular DNA is amplified to 2-3 orders of magnitudes by using the rolling circle amplification technology to form the DNB. The dipping container has a dipping reaction area, and the dipping reaction area is used for holding a chemical reagent for gene sequencing reaction and dipping a sequencing chip2having a DNA sample loading structure on the surface and having a DNA sample loaded thereon in the chemical reagent to perform the gene sequencing reaction. The sequencing chip2is dipped in the chemical reagent for gene sequencing reaction in the dipping reaction area to complete the steps of the gene sequencing reaction. The temperature control apparatus5may control the temperature of the chemical reagent in the dipping reaction area to provide a suitable temperature condition for the gene sequencing reaction. In the present embodiment, the gene sequencing reaction device1includes a plurality of dipping containers. As shown inFIG.1toFIG.3, the dipping container is specifically a dipping cylinder3. Each dipping cylinder3has a dipping reaction area. A plurality of dipping cylinders3are disposed on the temperature control apparatus5. The temperature control apparatus5is disposed on the supporting platform8. The transfer apparatus6may insert the sequencing chip2into the dipping cylinder3and pull out the sequencing chip2from the dipping cylinder3. In the present embodiment, each dipping cylinder3is filled with a chemical reagent, and different dipping cylinders are filled with chemical reagents required for each gene sequencing link. After the transfer apparatus6clamps the sequencing chip2for dipping in the dipping cylinders3for a predetermined time, nucleotides may be added to the DNA sample (the sequencing reaction template) of the sequencing chip2. Thereafter, the sequencing chip2is placed on an external optical imaging device for imaging, and then the type of the added nucleotides may be detected. The sequence of the gene may be read by continuously circulating the above steps. In other embodiments not shown, the dipping cylinders3may also be grouped, and each group of dipping cylinders3is filled with a chemical reagent. Referring toFIG.1toFIG.3, in the present embodiment, the gene sequencing reaction device1includes two rows of dipping cylinders3disposed laterally, and each row includes 17 dipping cylinders3. In other embodiments not shown, the dipping container may also include a plurality of dipping reaction areas isolated from one another, and each or each group of dipping reaction areas is filled with a chemical reagent. As shown inFIG.10, in the present embodiment, the dipping cylinder3includes an overflow port29. When the liquid in the dipping cylinder3exceeds a certain water level, it overflows from the overflow port29, so that the liquid level in the dipping cylinder3may be prevented from being excessively high. The temperature control apparatus5is configured to control the temperature of the chemical reagent in the dipping reaction area. The temperature control apparatus5is disposed on the supporting platform8, and the dipping container is disposed on the supporting platform8through the temperature control apparatus5. In the present embodiment, as shown inFIG.1toFIG.3, the temperature control apparatus5includes a temperature control portion and a water bath kettle. The water bath kettle is configured to hold liquid capable of transferring heat. The dipping container is disposed in the water bath kettle. The temperature control portion controls the temperature of the liquid in the water bath kettle to control the temperature of the chemical reagent in the dipping container. In the present embodiment, the temperature control portion is a heat exchange tube disposed in the wall of the water bath kettle, and the heat exchange tube may input heat to the liquid in the water bath kettle or absorb heat from the liquid in the water bath kettle, so that the heat conduction liquid in the water bath kettle may be heated or cooled down accordingly. By inputting or outputting the heat to the wall of the water bath kettle or the liquid in the water bath kettle, the heat conduction liquid in the water bath kettle may be heated or cooled down accordingly, and the dipping cylinder3is dipped in the heat conduction liquid, so that the temperature of the chemical reagent in the dipping cylinder3may be controlled. By using the liquid as a heat conducting medium, the temperature of the chemical reagent in each dipping cylinder3may be controlled more uniformly. Furthermore, the temperature of the chemical reagent is more stable and is unlikely to change quickly. In other embodiments not shown, a direct temperature control manner of directly heating or cooling the dipping cylinder3or the liquid therein may also be adopted by a temperature controller (for example, a Peltier temperature controller), but the direct temperature control manner is prone to a phenomenon of uneven heating and cooling compared with the indirect temperature control manner of the water bath kettle. The chip supplying storage apparatus14is configured to contain the sequencing chip2on which the gene sequencing reaction is about to be performed. The chip unloading storage apparatus15is configured to contain the sequencing chip2on which the gene sequencing reaction has been completed. As shown inFIG.8andFIG.9, in the present embodiment, each of the chip supplying storage apparatus14and the chip unloading storage apparatus15includes a chip storage box and a liquid storage box18. The top of the chip storage box is open and is provided with a slot16and a drain hole17. The slot16is formed in an inner surface of a side wall of the chip storage box configured to position and contain the sequencing chip2. The drain hole17is formed in a bottom wall of the chip storage box for discharging the liquid in the chip storage box. In the present embodiment, the drain hole17may drain the chemical reagent flowing down from the surfaces of the chip framework9and the sequencing chip2. In the present embodiment, in a gene sequencing reaction process, the sequencing chip2is mounted on the chip framework9, and the sequencing chip2is moved by moving the chip framework9. The slot16is configured to position and contain the chip framework9so as to position and contain the sequencing chip2through the chip framework9. The chip framework9is inserted into the slot16to position and contain the sequencing chip2thereon in the chip storage box. The number of slots16of the chip supplying storage apparatus14and the chip unloading storage apparatus15optionally corresponds to the number of positioning holes13on a clamping jaw7which will be described later, to ensure that the clamping jaw7accurately clamp and place the chip framework9. As shown inFIG.4toFIG.7, in the present embodiment, the number of positioning holes13of the clamping jaw7is 3; and as shown inFIG.8andFIG.9, the number of slots16of the chip supplying storage apparatus14and the chip unloading storage apparatus15is also3. The liquid storage box18is disposed below the drain hole17for receiving the liquid discharged from the drain hole17. The liquid storage box18in the present embodiment is made into a drawer type box body, which may be taken out to pour the liquid, when the liquid storage box18is filled with liquid or the use of the gene sequencing reaction device1is stopped. It should be noted that, although each of the chip supplying storage apparatus14and the chip unloading storage apparatus15of the gene sequencing reaction device1in the present embodiment include the chip storage box and the liquid storage box18, in other embodiments not shown, the specific structures of the chip supplying storage apparatus14and the chip unloading storage apparatus15may also be set in other manners. The structures of the chip supplying storage apparatus14and the chip unloading storage apparatus15may be the same or different. In addition, neither the chip supplying storage apparatus14nor the chip unloading storage apparatus15is necessary. For example, after the sequencing chip2is mounted on the chip holding apparatus, it may be directly placed in the dipping reaction area corresponding to a first reaction link of the gene sequencing reaction, and the chip supplying storage apparatus14is not disposed. As another example, after the sequencing chip2completes the sequencing reaction, it may be directly sent to the external optical imaging device for imaging, and the chip unloading storage apparatus15is not disposed. The container cover4is configured to be capable of being opened and closed and covered on the dipping container to prevent the evaporation of the chemical reagent. As shown inFIG.1,FIG.2andFIG.11, optionally, the container cover4comprises a plurality of cover bodies, and each of the cover bodies is correspondingly disposed with one or more dipping reaction areas to prevent the evaporation of the chemical reagent in the corresponding dipping reaction areas. At least one of the cover bodies may be opened and closed independently relative to other cover bodies. In the present embodiment, corresponding to the two rows of dipping cylinders3, the container cover4includes two rows of cover bodies, and each row includes6cover bodies. And each cover body covers a plurality of dipping cylinders3. The cover overturning mechanism22is in driving connection with the container cover4to drive the container cover4to open and close. As shown inFIG.1toFIG.3, the cover overturning mechanism22is disposed on the supporting platform8. Referring toFIG.11, the cover overturning mechanism22includes a push-pull rod26correspondingly arranged with the cover body, the push-pull rod26is connected with the cover body of the container cover4, when the push-pull rod26pulls the cover body, the cover body is opened, and when the push-pull rod26pushes the cover body, the cover body is closed. The transfer apparatus6is configured to insert the sequencing chip2into the dipping reaction area or pull out the sequencing chip2from the dipping reaction area. In the present embodiment, the transfer apparatus6is configured to move the sequencing chip2to insert the sequencing chip2into each dipping reaction area or pull out the sequencing chip from each dipping reaction area. The transfer apparatus6of the present embodiment may move the sequencing chip2in any dipping cylinder3into another dipping cylinder3. In the present embodiment, the sequencing chip2on which the gene sequencing reaction is about to be performed may be contained in the slot16of the chip supplying storage apparatus14by another external transfer apparatus, and the sequencing chip2may also be manually contained in the slot16of the chip supplying storage apparatus14. Similarly, the sequencing chip2on which the gene sequencing reaction has been completed may be taken away by another external transfer apparatus, and the sequencing chip2may also be manually taken away. By disposing the transfer apparatus6, the automation degree of the gene sequencing reaction device1may be improved, the error rate caused by the manual operation may be reduced, and the dipping sequence and the dipping time may also be accurately controlled by cooperation with the controller23, thereby facilitating the high-quality completion of the gene sequencing reaction. In the present embodiment, the transfer apparatus6is configured to move the sequencing chip2, and includes a connecting portion connected with the sequencing chip2, and a movement mechanism that is in driving connection with the connecting portion to change a working position of the connecting portion. The transfer apparatus6is mounted on the supporting platform8. In other embodiments not shown, the transfer apparatus6may also be mounted on other supports, as long as the function of connecting and moving the sequencing chip2may be achieved. In the present embodiment, as shown inFIG.1toFIG.3, the movement mechanism includes a lateral movement mechanism19, a longitudinal movement mechanism20and a vertical movement mechanism21. The longitudinal movement mechanism20is disposed on the supporting platform8. The lateral movement mechanism19is disposed on the longitudinal movement mechanism20. The vertical movement mechanism21is disposed on the lateral movement mechanism19. The connecting portion is disposed on the vertical movement mechanism21. The longitudinal movement mechanism21drives the lateral movement mechanism19to perform longitudinal movement. The lateral movement mechanism19drives the vertical movement mechanism21to perform lateral movement. The vertical movement mechanism21drives the connecting portion to perform vertical movement. The connecting portion in the present embodiment includes a clamping jaw7for clamping the sequencing chip2. As described above, the plurality of dipping cylinders3are arranged in two rows along the lateral direction. By the combined use of the lateral movement mechanism19, the longitudinal movement mechanism20and the vertical movement mechanism21, it may be ensured that the clamping jaw7may insert the sequencing chip2into and pull out the sequencing chip2from any one of the dipping cylinders3. In addition, the dipping cylinders3may also be arranged in a ring shape, at this time, the movement mechanism may include a rotating mechanism. The connecting portion may also be in other forms, for example, a vacuum chuck, an electromagnetic chuck or the like that cooperates with the chip holding apparatus for supporting the sequencing chip2. In addition, although the movement of the sequencing chip2between different dipping cylinders3is realized by moving the sequencing chip2through the movement mechanism and the connecting portion in the present embodiment, in other embodiments not shown, a required position relationship change between the sequencing chip2and the dipping cylinder may be achieved just by purely moving the dipping container or simultaneously moving the dipping container and the sequencing chip2. The chip holding apparatus is configured to hold the sequencing chip2, so that the sequencing chip2moves along with the chip holding apparatus. The chip holding apparatus includes one or more connecting portions24, and the sequencing chip2is mounted on the chip mounting position so as to move the sequencing chip2by moving the chip holding apparatus. By disposing the chip holding apparatus, on one hand, the pollution caused by directly operating the sequencing chip2may be reduced, and on the other hand, a plurality of sequencing chips2are simultaneously moved by the chip holding apparatus as needed, and the plurality of sequencing chips2keep a predetermined interval, thereby improving the throughput of the sequencing chip2. In the present embodiment, surfaces on both sides of the sequencing chip2are provided with the DNA sample loading structures. As shown inFIG.4toFIG.7, the chip mounting position includes a chip mounting opening, the sequencing chip2is mounted in the chip mounting opening, and the chip mounting opening is a through opening with both open sides. Due to such setting, both surfaces of the sequencing chip2may be dipped, so that the number of DNA sample molecules loaded by the single sequencing chip2may be increased. In addition, the chip framework9is transferred between different dipping cylinders3. In order to reduce the cross contamination between different chemical reagents as much as possible, it is generally required that the chip framework9is transferred into the next dipping cylinder3after all liquid remaining on the surface of the chip framework9drops. In order to speed up the dripping speed of the liquid on the surface of the chip framework9, as shown inFIG.4toFIG.7, in the present embodiment, a lower end of the chip framework9is gradually tapered from top to bottom. In an alternative embodiment, the surface of the chip framework9may be set as a hydrophobic surface. Of course, the chip framework9may be set as the hydrophobic surface while the lower end of the chip framework9is gradually tapered from top to bottom, thereby achieving faster dripping of the chemical reagent. As shown inFIG.5toFIG.7, an upper end of the chip framework9is provided with a jaw fitting opening10; and a movement mechanism of the transfer apparatus6is in driving connection with the clamping jaw7to change the working position of the clamping jaw7, and the clamping jaw7is connected with the chip framework9. In the present embodiment, the clamping jaw7includes a positioning frame11and a clamping block12, the positioning frame11is connected with the movement mechanism, the clamping block12is movably disposed on the positioning frame11, the positioning frame11is provided with a positioning hole13for inserting the upper end of the chip framework9, and the clamping jaw7is clamped with the jaw fitting opening10of the chip framework9inserted into the positioning hole13so as to clamp the chip framework9. As shown inFIG.4toFIG.7, each chip framework9is provided with two jaw fitting openings10oppositely. The clamping jaw7is also correspondingly provided with two opposite clamping blocks12. The clamping blocks12are located above the positioning hole13. After the chip framework9passes through the positioning hole13upward, the two clamping blocks12move toward each other and are respectively clamped in the two jaw fitting openings10of the chip framework9, so as to fix the chip framework9in the positioning hole13. The positioning frame11of the present embodiment is designed with three positioning holes13, and the three positioning holes13are arranged equidistantly. In other embodiments not shown, the number of positioning holes13may be set to be more or less, for example, may be set as 1, 2, 4, 5 and the like, so as to simultaneously operate the corresponding number of sequencing chips2. The number and positions of the dipping reaction areas and the number and positions of the slots16vary depending on the number of positioning holes13. In the present embodiment, the clamping jaw7of the transfer apparatus6indirectly holds the sequencing chip2through the chip holding apparatus to realize the connection between the transfer apparatus6and the sequencing chip2. Through the indirect clamping of the sequencing chip2, cross contamination generated after the clamping jaw7clamps different sequencing chips2may be prevented. In addition, the clamping jaw7indirectly clamps the sequencing chip2by clamping the chip framework9, so a clamping structure only needs to be processed on the chip framework9, and the clamping structure does not need to be processed on the sequencing chip2, thereby reducing the processing cost of the sequencing chip2, and maximally utilizing the surface area of the sequencing chip2. Of course, in other embodiments not shown, the transfer apparatus6and the sequencing chip2may also be connected by directly clamping the sequencing chip2via the clamping jaw7. Optionally, the gene sequencing reaction device1includes a protective cover, and the dipping container is disposed in the protective cover. The sequencing reaction process may be completely open if environmental conditions permit, for example, during operation in a sterile environment. However, in many cases, in order to avoid external interference, the sequencing reaction process needs to be carried out in a closed environment, the dipping container is located in the protective cover to provide a closed reaction environment to ensure the quality of the gene sequencing reaction. The transfer apparatus6may also be disposed in the protective cover or not as needed. The air blowing apparatus25is configured to blow off the chemical reagent on the surface of the sequencing chip2and/or the surface of the chip holding apparatus on which the sequencing chip is mounted. In the present embodiment, the air blowing apparatus25is configured to blow off the residual chemical reagent on the surfaces of the sequencing chip2and the chip framework9. By blowing off the residual chemical reagent on the surfaces of the sequencing chip2and the chip framework9, the cross contamination generated when the sequencing chip2is dipped in the next dipping reaction area may be avoided as much as possible. Referring toFIG.11, in the present embodiment, the air blowing apparatus25includes a nozzle. The nozzle is configured to eject a gas, and the ejected gas blows off the residual chemical reagent on the surfaces of the sequencing chip2and the chip framework9. The controller23is configured to control and monitor the work of the gene sequencing reaction device1. In the present embodiment, the controller23is coupled with the temperature control apparatus5to control the temperature of the chemical reagent, and is also coupled with the transfer apparatus6to control the dipping time and/or dipping sequence of the sequencing chip2in the dipping reaction area. In the present embodiment, the controller23is a built-in controller and is disposed on the supporting platform8. In other embodiments not shown, an external controller may also be coupled with the gene sequencing reaction device1to control and monitor the work of the gene sequencing reaction device1. By controlling the temperature control apparatus5and the transfer apparatus6by the controller23, automatic operation of the gene sequencing reaction device1may be realized, and the quality and efficiency of gene sequencing may be improved. As shown inFIG.1toFIG.3, the supporting platform8in the present embodiment includes a box. The aforementioned dipping container, the temperature control apparatus5, the transfer apparatus6, the chip supplying storage apparatus14, the chip unloading storage apparatus15, the container cover4, the cover overturning mechanism22, the air blowing apparatus25and the controller23are all disposed on a top face of the box. Reagents and tools and the like required for the gene sequencing reaction may also be stored and accommodated in the box. In order to facilitate the movement of the gene sequencing reaction device1, rollers27are mounted below the cabinet. In other embodiments not shown, the supporting platform8may also be a supporting plate. As shown inFIG.1toFIG.3, in the present embodiment, the gene sequencing reaction device1may include a signal lamp28for alarming when the gene sequencing reaction device1is abnormal. In the present embodiment, a chemical reagent for gene sequencing reaction is loaded in each dipping reaction area, the transfer apparatus6holds a group of sequencing chips2for dipping the same in a group of dipping reaction areas for a period of time, then transfers the group of sequencing chips2into the next group of dipping reaction areas to be dipped for a period of time, and the circulation is accordingly. After any one of the group of sequencing chip2is dipped in the plurality of dipping reaction areas, once sequencing reaction process may be completed. For example, in the embodiment shown inFIG.1toFIG.3, each three sequencing chips are clamped as a group and may be numbered as No. 1 chip, No. 2 chip and No. 3 chip from right to left, the dipping cylinders3are sequentially numbered from right to left to the last one starting from the back row, and are sequentially numbered from left to right to the last one starting from the front row, which are respectively No. 1 dipping cylinder (the rightmost side on the back row), No. 2 dipping cylinder, No. 3 dipping cylinder, . . . , No. 17 dipping cylinder (the leftmost side on the back row), No. 18 dipping cylinder (the leftmost side on the front row), No. 19 dipping cylinder, . . . , No. 34 dipping cylinder (the rightmost side on the front row). When the gene sequencing reaction is started, the No. 3 chip is dipped in the No. 1 dipping cylinder; after being dipped for a predetermined time, the No. 3 chip is transferred into the No. 2 dipping cylinder to be continuously dipped, meanwhile, after the No. 2 chip is dipped in the No. 1 dipping cylinder for the predetermined time, the No. 3 chip is transferred into the No. 3 dipping cylinder to be continuously dipped, meanwhile, the No. 2 chip is dipped in the No. 2 dipping cylinder to be continuously dipped, and the No. 1 chip is dipped in the No. 1 dipping cylinder to start dipping. And so on, after a group of chips is dipped in a group of dipping cylinders, the sequencing chips2are sequentially transferred into the dipping cylinders with numbers greater than the respective dipping cylinders by 1 to be continuously dipped, until corresponding dipping processes of all sequencing chips2in the dipping cylinders are completed. The dipping processes in the No. 16 to No. 17 dipping cylinders, the No. 18 to No. 19 dipping cylinders and the No. 33 to No. 34 dipping cylinders are similar to the dipping processes in the No. 1 to No. 2 dipping cylinders, and a part of the sequencing chips2are dipped, while a part of the sequencing chips2is not dipped. In some embodiments, one or more dipping cylinders at the head and/or the tail of at least one row of dipping cylinders (the specific number may be set according to the number of sequencing chips clamped every time) may be set as empty containers, or are filled with the same chemical reagent as the adjacent dipping cylinder or are filled with reagents that have no effect on the gene sequencing reaction, so that the sequencing chip2that does not participate in the dipping is also in the dipping cylinder. In some embodiments, the dipping cylinders (or the dipping reaction areas) may also be grouped, for example, the dipping cylinders (or the dipping reaction areas) may be grouped according to the number of sequencing chips clamped every time, and each group of dipping cylinders (or the dipping reaction areas) holds the same chemical reagent, and during every dipping, a group of sequencing chips is dipped in a group of dipping cylinders holding the same chemical reagent. This setup may improve the efficiency of the gene sequencing reaction, but requires more dipping cylinders (or dipping reaction areas). A gene sequencing system of the present embodiment includes a DNA sample loading device and a gene sequencing reaction device1, and the gene sequencing reaction device1is the aforementioned gene sequencing reaction device1. A gene sequencing reaction method of the present embodiment includes: adding a chemical reagent for gene sequencing reaction into a dipping reaction area of a dipping container; controlling the temperature of the chemical reagent in the dipping reaction area; and dipping a sequencing chip2having a DNA sample loading structure on the surface and having a DNA sample loaded thereon in the chemical reagent for a predetermined time, and taking out the sequencing chip. Optionally, different chemical reagents for gene sequencing reaction are injected in a plurality of dipping reaction areas, and the sequencing chip2is sequentially dipped in the plurality of dipping reaction areas for a predetermined time according to a predetermined sequence. The working process of performing a gene sequencing reaction by using the gene sequencing reaction device1and the gene sequencing reaction method in the above embodiments will be briefly described below with reference toFIG.1toFIG.3.1. At an initial state, the chemical reagent for gene sequencing reaction is added into the dipping cylinders3, the heat conduction liquid in the water bath kettle is adjusted to a suitable temperature, the sequencing chips2on which the gene sequencing reaction is about to be performed are mounted on the chip frameworks9, all chip frameworks9are contained in the chip supplying storage apparatus14.2. The clamping jaws7of the transfer apparatus6clamp the chip frameworks9and dip the chip frameworks9in the dipping cylinders3for a period of time one by one; when the chip frameworks9are completely dipped in a row of dipping cylinders3, the longitudinal movement mechanism20drives the lateral movement mechanism19to perform longitudinal movement, so that the chip frameworks9may be dipped in other row of dipping cylinders3one by one, until the chip frameworks9are dipped in all dipping cylinders3.3. After the chip frameworks9are dipped in all dipping cylinders3, the transfer apparatus6places the chip frameworks9in the chip unloading storage apparatus15, and DNA samples on the sequencing chips2complete the sequencing reaction process and wait for removal. After the DNA samples on the sequencing chips2complete the sequencing reaction process, the DNA samples are transferred to an optical imaging device for imaging. It should be understood that, the above steps are only one of the working processes that may be implemented by the gene sequencing reaction device1, it does not indicate that the gene sequencing reaction device1may only implement these steps, nor is intended to limit the protection scope of the present disclosure. In addition, since the chemical reaction involved in the present disclosure does not belong to the content claimed in the present disclosure, and the non disclosure of the content does not affect the understanding of the present disclosure by those skilled in the art, therefore above chemical reaction is not disclosed herein. The gene sequencing system and the gene sequencing reaction method of the present disclosure have similar technical effects as the gene sequencing reaction device1of the present disclosure. It can be seen according to the above descriptions, the above embodiments of the present disclosure may achieve at least one of the following technical effects: The gene sequencing reaction device1may achieve the gene sequencing reaction in the dipping manner. The sequencing chip2is dipped in the chemical reagents in different dipping reaction areas to complete various steps required for the sequencing reaction. The chemical reagent in the dipping reaction area may be reused, thereby reducing the cost of consumables. There is no problem of uneven liquid flow rate in the dipping manner, and bubbles are unlikely to be generated on the surface of the sequencing chip2, so that a more uniform and sufficient chemical reaction may be ensured. The sequencing chip2is subjected to uniform pressure and uniform heating in the dipping cylinder3, thereby generating no deformation. Multiple sequencing chips2may be dipped at the same time, thereby having the advantages of high throughput. No complicated fluid system is needed, few parts and components are used, the assembly is easy, and the manufacturing cost is low. The gene sequencing reaction device1is automatically controlled by the controller23to realize automatic operation. Finally, it should be noted that the above-mentioned embodiments are merely used for illustrating the technical solutions of the present disclosure, rather than limiting them. Although the present disclosure has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art to which the present disclosure belongs should understand that: modifications may still be made to the specific embodiments of the present disclosure, or equivalent substitutions may be made to a part of technical features, and these modifications and equivalent substitutions shall fall within the scope of the technical solutions claimed by the present disclosure.
38,971
11857974
DETAILED DESCRIPTION The present disclosure provides methods and systems for thermally controlling a chemical reaction in droplets. In an exemplary method, a first thermal zone and a second thermal zone having different temperatures from one another may be created in a reaction chamber. An emulsion including droplets encapsulated by a carrier fluid may be held in the reaction chamber. The droplets may have a density mismatch with the carrier fluid, and each droplet may include one or more reactants for the chemical reaction. An orientation of the reaction chamber may be changed to move the droplets from the first thermal zone to the second thermal zone, such that a rate of the chemical reaction changes in at least a subset of the droplets. The methods and systems described herein offer various advantages, such as greater simplicity, more rapid and precise thermal control of chemical reactions, faster thermal cycling, and/or the like. Further aspects of the present disclosure are described in the following sections: (I) definitions, (II) overview of the methods and systems, (III) examples, and (IV) selected aspects. I. DEFINITIONS Technical terms used in this disclosure have meanings that are commonly recognized by those skilled in the art. However, the following terms may be further defined as follows. Amplicon—a product of an amplification reaction. Amplification—a process whereby multiple copies are made of an amplicon matching and/or complementary to a target sequence. The process interchangeably may be called an amplification reaction. Amplification may, for example, generate an exponential or linear increase in the number of copies as amplification proceeds. Typical amplifications may produce a greater than 1,000-fold increase in the number of copies of an amplicon. Exemplary amplification reactions for the methods disclosed herein may include a polymerase chain reaction (PCR) or a ligase chain reaction (LCR), each of which is driven by thermal cycling (e.g., 2-step, 3-step, or >3-step thermal cycling). The methods also or alternatively may use other amplification reactions, which may be performed isothermally, such as branched-probe DNA assays, cascade-RCA, helicase-dependent amplification, loop-mediated isothermal amplification (LAMP), nucleic acid based amplification (NASBA), nicking enzyme amplification reaction (NEAR), PAN-AC, Q-beta replicase amplification, rolling circle replication (RCA), self-sustaining sequence replication, strand-displacement amplification, and/or the like. Amplification may utilize a linear or circular template. Amplification reagents—any reagents that promote or affect amplification of a target sequence. The reagents may include any combination of at least one primer or primer pair for amplification of at least one target sequence, at least one label for detecting amplification of the at least one target sequence (e.g., at least one probe including a label and/or a DNA intercalating dye as a label), at least one polymerase enzyme and/or ligase enzyme (which may be heat-stable), and nucleoside triphosphates (dNTPs and/or NTPs), among others. Analyte—a chemical substance or region thereof that is the subject of an analysis to detect, quantify, and/or characterize the chemical substance or region thereof. Exemplary analytes include a reactant, catalyst, cofactor, or the like, for a chemical reaction. Suitable analytes may include nucleic acids, nucleic acid target sequences, proteins (e.g., enzymes), carbohydrates, lipids, and the like. Chemical reaction—a process that involves rearrangement of the molecular or ionic structure of one or more substances. Each of the substances is referred to as “reactant” for the chemical reaction. A chemical reaction may be unimolecular (only one chemical reactant that reacts with itself), bimolecular (two chemical reactants that react with one another), trimolecular (three chemical reactants that react with one another), etc. Exemplary classes of chemical reactions that may be suitable include oxidation-reduction, direct combination, decomposition, single displacement/substitution, double displacement/substitution, acid-base, isomerization, racemization, ring opening, cyclization, and hydrolysis reactions, among others. The chemical reaction may or may not be performed in the presence of an enzyme that catalyzes the chemical reaction. Complementary—related by the rules of base pairing. A first nucleic acid, or region thereof, is “complementary” to a second nucleic acid if the first nucleic acid or region is capable of hybridizing with the second nucleic acid in an antiparallel fashion by forming a consecutive or nearly consecutive series of base pairs. The first nucleic acid (or region thereof) is termed “perfectly complementary” to the second nucleic acid if hybridization of the first nucleic acid (or region thereof) to the second nucleic acid forms a consecutive series of base pairs using every nucleotide of the first nucleic acid or region thereof. A “complement” of a first nucleic acid is a second nucleic acid that is perfectly complementary to the first nucleic acid for at least ten consecutive nucleotides. The “complementarity” between a first nucleic acid (or region thereof) and a second nucleic acid (or region thereof) refers to the number or percentage of base pairs that can be formed when the first nucleic acid (or region thereof) is optimally aligned for hybridization in an antiparallel fashion with the second nucleic acid (or region thereof). A first nucleic acid or region thereof that is complementary to a second nucleic acid or region thereof generally has a complementarity of at least 80% or 90%. Droplet—a small volume of liquid encapsulated by an immiscible fluid (e.g., encapsulated by an immiscible liquid, which may form a continuous phase of an emulsion). The immiscible liquid may include oil and/or may be composed predominantly of oil. Droplets for the methods disclosed herein may, for example, have an average size of less than about 1 μL, 500 nL, 100 nL, 10 nL, or 1 nL, among others. The droplets may, for example, be aqueous droplets. Inversion—reorientation of greater than 90 degrees and less than 270 degrees with respect to a vertical axis (defined by gravity) or with respect to a g-force vector. The verb “invert” refers to the process of producing this reorientation. Label—an identifying and/or distinguishing marker or identifier associated with a structure, such as a primer, probe, amplicon, droplet, or the like. The label may be associated covalently with the structure, such as a label that is covalently attached to an oligonucleotide, or associated non-covalently (e.g., by intercalation, hydrogen bonding, electrostatic interaction, encapsulation, etc.). Exemplary labels include optical labels, radioactive labels, magnetic labels, electrical labels, epitopes, enzymes, antibodies, etc. Optical labels are detectable optically via their interaction with light. Exemplary optical labels that may be suitable include photoluminophores, quenchers, and intercalating dyes, among others. Light—optical radiation including ultraviolet light, visible light, and/or infrared light. Nucleic acid—a polymer of any length composed of naturally-occurring nucleotides (e.g., where the polymer is DNA or RNA), or a substance produced synthetically that can hybridize with DNA or RNA in a sequence-specific manner analogous to that of two naturally occurring nucleic acids, e.g., can participate in Watson-Crick base pairing interactions. A nucleic acid may be composed of any suitable number of nucleotides, such as at least about 5, 10, 100, or 1000, among others. Generally, the length of a nucleic acid corresponds to its source, with synthetic nucleic acids (e.g., oligonucleotides) typically being shorter, and biologically/enzymatically generated nucleic acids (e.g., genomic fragments) typically being longer. A nucleic acid may have a natural or artificial structure, or a combination thereof. Nucleic acids with a natural structure, namely, deoxyribonucleic acid (DNA) and ribonucleic acid (RNA), generally have a backbone of alternating pentose sugar groups and phosphate groups. Each pentose group is linked to a nucleobase (e.g., a purine (such as adenine (A) or guanine (G)) or a pyrimidine (such as cytosine (C), thymine (T), or uracil (U))). Nucleic acids with an artificial structure are analogs of natural nucleic acids and may, for example, be created by changes to the pentose and/or phosphate groups of the natural backbone and/or to one or more nucleobases. Exemplary artificial nucleic acids include glycol nucleic acids (GNAs), peptide nucleic acids (PNAs), locked nucleic acids (LNAs), threose nucleic acids (TNAs), xeno nucleic acids (XNA), and the like. The sequence of a nucleic acid is defined by the order in which nucleobases are arranged along the backbone. This sequence generally determines the ability of the nucleic acid to hybridize with another nucleic acid by hydrogen bonding. In particular, adenine pairs with thymine (or uracil) and guanine pairs with cytosine. Oligonucleotide—a relatively short and/or chemically synthesized nucleic acid. The length of an oligonucleotide may, for example, be 3 to 1000 nucleotides, among others. Partial occupancy—present in each droplet of only a subset of droplets. An analyte at partial occupancy within a set of droplets refers to a configuration in which one or more of the droplets each contains no copy of the analyte and one or more of the droplets each contains at least one copy of the analyte. In some cases, one or more of the droplets each contains exactly one copy of the analyte. The analyte may or may not have a Poisson distribution among the droplets. Photoluminescence—emission of light induced by electromagnetic radiation. Photoluminescence may be produced by any form of matter in response to absorption of photons of electromagnetic radiation, such as light. Exemplary forms of photoluminescence include fluorescence and phosphorescence, among others. Primer—an oligonucleotide capable of serving as a point of initiation of template-directed nucleic acid synthesis under appropriate reaction conditions (e.g., in the presence of a template to which the oligonucleotide anneals, nucleoside triphosphates, and a polymerization catalyst (such as a DNA or RNA polymerase or a reverse transcriptase), in an appropriate buffer and at a suitable temperature). The primer may have any suitable length, such as 5 to 500 nucleotides, among others. The primer may be a member of a “primer pair” including a “forward primer” and a “reverse primer” that define the ends of an amplicon generated in an amplification reaction. (The adjectives “forward” and “reverse” are arbitrary designations relative to one another.) The forward primer hybridizes with a complement of the 5′-end region of a target sequence to be amplified, and the reverse primer hybridizes with the 3′-end region of the target sequence. The term “primer binding site” refers to a portion of a template (or its complement) to which a primer anneals. The full sequence of the primer need not be perfectly complementary to the primer binding site, just sufficiently complementary to anneal under the conditions of the reaction. Accordingly, the primer may have a 3′-end region that is complementary to the primer binding site, and a 5′-end region that is not complementary to the primer binding site (and forms a “5′-tail”). Probe—a labeled oligonucleotide configured to report the occurrence of an amplification reaction and/or formation of an amplicon by the amplification reaction. A probe may, for example, be a photoluminescent probe including an oligonucleotide labeled with a photoluminophore. A probe may be configured to hybridize with at least a portion of an amplicon generated by amplification. The probe (e.g., a hydrolysis probe) may be configured to hybridize with at least a portion of an amplicon during an annealing/extension phase of amplification cycles of an amplification reaction, or the probe (e.g., a molecular beacon probe) may be configured to hybridize with the amplicon after the amplification reaction has been completed, among others. Reaction chamber—a substantially or completely enclosed space inside a container for performing a chemical reaction. A reaction chamber may or may not include one or more channels and/or distinct subchambers. The reaction chamber may be designed to hold an emulsion and particularly droplets thereof and retain the droplets in the reaction chamber while the reaction chamber is being reoriented to control a chemical reaction in the droplets. The reaction chamber may or may not be elongated between a pair of opposite ends, and may or may not have a uniform cross section or diameter intermediate the opposite ends. In some cases, it may be preferable to have a non-uniform reaction chamber with a larger volume at opposite ends and a smaller volume intermediate the opposite ends. This configuration allows the separation distance between the opposite ends to be increased to better maintain the temperature difference between the opposite ends. The reaction chamber may or may not be axially symmetric. In some cases, the reaction chamber may be or include a channel of elliptical (e.g., circular) or polygonal (e.g., rectangular) cross-section. The reaction chamber may be formed by, and/or cladded with, one or more metals or plastics that are machined, molded, fused, brazed, or the like. In some cases, it may be advantageous to use a combination of high thermal conductivity and low thermal conductivity materials, to encourage conduction of heat within each thermal zone while discouraging conduction of heat between thermal zones. Sensed zone—a space from which a reaction signal is detected. The term “reaction signal” refers to any detectable signal that is sensitive to the occurrence of a chemical reaction in droplets. Target sequence—a sequence of or within a template providing a pattern for synthesis of a complementary sequence. Template—a nucleic acid that serves as a pattern for synthesis of a complementary strand. The template may provide a primer binding site for a primer, which is extended by sequential addition of complementary nucleotides according to the pattern. Thermal zone—an area having a controlled temperature, such as a temperature actively maintained at a selected set point. The area may be only a portion of the space defined by a reaction chamber. A thermal zone may include an end or recess of the reaction chamber at which droplets can accumulate when the reaction chamber is reoriented. II. OVERVIEW OF THE METHODS AND SYSTEMS This section provides an overview of the methods and systems of the present disclosure for thermally controlling a chemical reaction in droplets; seeFIGS.2-5. FIG.2shows an exemplary reaction control device50having a reaction chamber52to hold an emulsion53. The emulsion includes droplets54containing reactants55for a chemical reaction (see panel A). Each droplet54is encapsulated by an immiscible carrier fluid56(a liquid) and has a different density than the carrier fluid. (The droplets may have the same density as one another.) This density mismatch between the droplets and the carrier fluid causes the droplets to either move to the top of reaction chamber52(i.e., if the droplets are less dense than the carrier fluid) or to the bottom of reaction chamber52(i.e., if the droplets are denser than the carrier fluid). For consistency, in each of the depicted embodiments of the present disclosure, the droplets have a lower density than the carrier fluid and thus are buoyant in the carrier fluid. The direction of the force of gravity, g, for panels A-D is indicated with an arrow at the top center ofFIG.2and is opposite the buoyant force that urges droplets54toward the top of reaction chamber52. In other embodiments, each droplet54has a higher density than carrier fluid56and is urged downward in reaction chamber52by gravity. In some examples, a g-force larger than gravity may be applied to reaction chamber52by centrifugation, to increase the buoyant (or sedimenting) force on the droplets, thereby driving faster travel of droplets within the reaction chamber (see Example 5). Reaction control device50is configured to create two or more thermal zones in reaction chamber52. Here, a pair of thermal zones58a,58bare created at opposite ends of reaction chamber52and have different temperatures, T1and T2, respectively. In other examples, three or more thermal zones are created having three or more different temperatures (see Example 3). Panels A-D illustrate changing the orientation of reaction chamber52, indicated by turning arrows at60, to move droplets54as a group from thermal zone58ato thermal zone58b. More specifically, the orientation of reaction chamber52is changed with respect to the direction of gravity (and/or an additional g-force) to encourage the desired migration of droplets54. In the depicted embodiment, reaction chamber52is inverted to produce this migration. Thermal zone58ais at the top of reaction chamber52in panel A, while thermal zone58bhas this position in panel D. Accordingly, droplets54have temperature T1in panel A and temperature T2in panel D. T2can be less than T1, such that reorientation cools the droplets (i.e., lowers their temperature), which may slow or stop (or start or speed up) the chemical reaction with reactants55in the droplets (i.e., in at least a subset (one or more) of the droplets). Alternatively, T2can be greater than T1, such that reorientation heats the droplets (i.e., raises their temperature), which may start or speed up (or slow or stop) the chemical reaction in the droplets (i.e., in at least a subset (one or more) of the droplets). Once reorientation is completed, rotation of reaction chamber52may be paused for any suitable dwell time, to permit incubation of the droplets at temperature T2in thermal zone58b. If desired, reaction chamber52then may be reoriented further, such as to move droplets54back to thermal zone58a(or to a third thermal zone within the reaction chamber). When this process is used to thermally cycle the droplets, the cycle number, each temperature, and the dwell time of the droplets at each temperature are readily controlled. Movement of droplets54toward thermal zone58b, as reaction chamber52is being reoriented, is indicated with a motion arrow61in panels B and C. This movement is accompanied by a net flow of carrier fluid56that is displaced by droplets54, indicated by a flow arrow at62, in the opposite direction toward thermal zone58a. Droplets54and carrier fluid56can enter and leave reaction chamber52, at the appropriate times, via one or more ports, such as an inlet64and an outlet66. In some examples, inlet64may function as both an inlet and an outlet for the emulsion, and outlet66may function only as a vent. An upstream valve and a downstream valve may be operatively connected to inlet64and outlet66, respectively, to control when fluid flow through either or both the inlet and the outlet is permitted. In some examples, both valves may remain closed while emulsion53is being processed in reaction chamber52(e.g., when reaction chamber52is being reoriented). In some examples, both valves may be opened to allow preheated carrier fluid to be added to reaction chamber52during processing of emulsion53(e.g., see Example 4). Reaction control device50may have a respective gate68associated with each port to limit travel of droplets54out of reaction chamber52. Gate68may, for example, be a structure that passively blocks travel of droplets54out of reaction chamber52until a sufficient pressure differential is created with a pump to force the droplets past the gate. FIG.3shows reaction control device50being used to expose droplets54to a series of different temperatures (T1-T5). The different temperatures may, for example, be a series of increasing temperatures or decreasing temperatures, to respectively step up or step down the temperature of the droplets. Stepping up or down the droplet temperature may be used to generate a melting curve or an annealing curve for one or more nucleic acid duplexes in the droplets (e.g., see Example 5). The melting/annealing curve may allow amplification of two or more different target sequences to be distinguished from one another using the same probe and/or label. Panels A-D illustrate an exemplary series of configurations. In panel A, droplets54are located in thermal zone58aat a temperature of T1. In panel B, reaction chamber52has been reoriented to move droplets54to thermal zone58bhaving temperature T2. While droplets54are being incubated in thermal zone58b, the other thermal zone,58a, is being changed to temperature T3. In panel C, reaction chamber52has been reoriented again to move droplets54back to thermal zone58a, for incubation at T3. While droplets54are located in thermal zone58a, the other thermal zone,58b, is being changed to temperature T4. In panel D, reaction chamber52has been reoriented yet again to move droplets54back to thermal zone58b, for incubation at T4. During this incubation, the other thermal zone,58a, is being changed to temperature T5to further extend the temperature series over which the droplets are incubated. In other examples, the temperature of only one of the thermal zones may be changed. FIG.4shows a flowchart listing exemplary steps for a method70of thermally controlling a chemical reaction in droplets. The steps listed may be performed in any suitable order and combination, and may be modified as described elsewhere herein. The steps shown in dashed boxes and connected by dashed arrows provide exemplary options for modifying the basic method. Droplets of an emulsion may be generated, indicated at step71. The droplets may be generated outside the reaction chamber and then introduced into the reaction chamber, or may be generated inside the reaction chamber (e.g., see Examples 5 and 6). Each droplet, or only a subset of the droplets, may contain each reactant required for the chemical reaction. The droplets may be sample-containing droplets each containing a portion of the same sample. The droplets may contain an analyte at partial occupancy, which means that each droplet of only a subset of the droplets contains at least one copy of analyte, and, optionally, each droplet of only a subset of the droplets contains no copies of the analyte. The analyte may, for example, be a nucleic acid, nucleic acid target sequence, protein, carbohydrate, lipid, or the like. The droplets may be generated by any suitable procedure and/or device. In some examples, the droplets may be generated by dividing a bulk phase mixture, which may contain the reactant(s), the sample, and any other suitable reagents for performing the chemical reaction and/or detecting occurrence of the chemical reaction. In some examples, the droplets may be generated by fusing other droplets with one another. Two or more thermal zones may be created in a reaction chamber, indicated at72. The thermal zones may have different, individually selectable and controllable temperatures. Creating the thermal zones may be performed before or after the droplets are present in the reaction chamber. Each thermal zone may represent any suitable portion of the reaction chamber by volume, such as at least about 10%, 20%, 30%, 40%, or 50% of the volume. In some examples, the thermal zones, collectively, may represent more than 50%, 60%, 70%, or 80% of the total volume of the reaction chamber. The temperature of each thermal zone may remain substantially constant until droplet processing is completed, or may be adjusted to a different temperature at any suitable time after the droplets are located in the reaction chamber. The droplets may be held in the reaction chamber, indicated at73. Holding the droplets means that the droplets are contained in the reaction chamber, and may be moving, stationary, or a combination thereof, while being held. The reaction chamber may be reoriented to move the droplets between at least two of the thermal zones, indicated74. Reorienting the reaction chamber means changing the orientation of the reaction chamber sufficiently with respect to gravity or a g-force, to produce migration of the droplets en masse to a different thermal zone of the reaction chamber. Reorienting may, for example, include turning the reaction chamber at least about one-fourth or one-half turn, or about one full turn, among others (e.g., see Examples 2-5). A plurality of the droplets may be read, indicated at75. Reading means collecting reaction data from the plurality of droplets, where the reaction data relates to occurrence of the chemical reaction. The reaction data may be collected by detecting a reaction signal that reflects whether or not the chemical reaction has occurred and/or the extent of occurrence. Detecting a reaction signal may include detecting any suitable type of signal, such as an optical or other electromagnetic signal, an electrical signal, a magnetic signal, radioactive decay, or the like. In some embodiments, the reaction signal may be an amplification signal for an amplification reaction performed in the droplets. The step of reading may be performed any suitable number of times. In some examples, a plurality of the droplets may be read only once. For example, the droplets may be read inside the reaction chamber (e.g., see Example 5) or removed from the reaction chamber and read outside the reaction chamber (e.g., see Example 6). In other examples, the droplets may be read multiple times, such as inside the reaction chamber, where the temperature of the droplets is changed between each reading (e.g., see Example 5). If performed inside the reaction chamber, reading may be performed on droplets that are moving in response to reorientation of the reaction chamber, such as on droplets passing through a sensed zone of a channel within the reaction chamber. The temperature of one of more of the thermal zones may be changed, indicated at76. In other words, the droplets may be exposed serially to two or more different selected temperatures in the same thermal zone. Changing the temperature of a thermal zone permits, for example, a thermal cycling profile to be changed between different thermal cycles of an amplification reaction, or generation of a melting curve or an annealing curve for an amplicon generated in an amplification reaction that includes the chemical reaction. The reaction chamber may be reoriented multiple times, indicated by a return arrow at77. For example, the reaction chamber may be reoriented multiple times to thermally cycle the droplets to promote a polymerase chain reaction (PCR) or a ligase chain reaction (LCR), among others. The droplets may be thermally cycled for any suitable number of cycles, such as at least 10, 20, 25, or 30, among others. The thermal cycling may be two-step thermal cycling, in which each cycle has only two temperature steps (e.g., a denaturation temperature and an annealing/extension temperature). In other examples, the thermal cycling may be at least three-step thermal cycling, in which each thermal cycle has three or more temperature steps (e.g., a denaturation temperature, an annealing temperature, and an extension temperature). FIG.5shows a block diagram of an exemplary system80for thermally controlling a chemical reaction in droplets. System80may include an encapsulation portion81, a reaction portion82, and a detection portion83. Here, portions81-83are shown as being separate and operating in series (also see Example 6). However, portions81-83may have any suitable overlap with one another. For example, encapsulation portion81may be incorporated into reaction portion82(e.g., see Example 5), and/or detection portion83may include a part of reaction portion82(e.g., see Example 5). Encapsulation portion81generates droplets of an emulsion. The encapsulation portion may include at least one droplet generator84. Droplet generator84may receive a reaction mixture and a carrier fluid, and form droplets of the reaction mixture surrounded by the carrier fluid. The droplet generator may operate by any suitable mechanism, such as cross-flow, co-flow, flow-focusing, or a confinement gradient, among others. The mechanism may operate in any suitable mode, such as dripping, squeezing, jetting, tip-streaming, tip-multi-breaking, or the like. Reaction portion82includes a reaction chamber52, which may be operatively connected to a thermal control system86, an orienting drive87, a pump(s)88, and/or a centrifuge (e.g., see Example 5), among others. Reaction portion82is exemplified by various reaction control devices disclosed herein, such as in Examples 1-6. Thermal control system86provides temperature control of reaction chamber52to create two or more thermal zones therein. The thermal control system may include any suitable number of heaters89in thermal communication with each thermal zone of reaction chamber52. Exemplary heaters (also called heating devices) may be conductive, convective, and/or radiative heaters, and may be located outside (or inside) the reaction chamber. At least one temperature sensor90may be operatively associated with each thermal zone of the reaction chamber52. At least one controller91may be in communication with heaters89and sensors90to form a feedback loop for maintaining the temperature of each thermal zone based on a set point. Orienting drive87is a device operatively connected to reaction chamber52and configured to turn reaction chamber52with respect to a gravity vector or a g-force vector, to change the orientation of reaction chamber52. A motor92of the orienting drive may generate torque, which may drive rotation of reaction chamber52about a rotation axis. Orienting drive87may turn reaction chamber52in only one rotational direction or in opposite rotational directions, among others. At least one pump88may be operatively connected to reaction chamber52. Operation of the pump(s) may drive fluid, such as preheated carrier fluid, into and/or out of the reaction chamber. The reaction chamber may be isolated from pump(s)88by a valve(s), which may be opened and closed, at any suitable times. Detection portion83may be configured to detect any suitable light from the droplets, such as emitted light, scattered light, polarized light, and/or the like. The light detected may, for example, include luminescence emitted from a luminescent label present in the droplets. The label may be photoluminescent or chemiluminescent, among others. A light source93may generate light for irradiating droplets located in a sensed zone94. The light from light source93may propagate to sensed zone94via any suitable irradiation optics. Sensed zone94may be formed by a channel or a chamber, among others. In some embodiments, sensed zone94may be at least a portion of a channel or a chamber that is irradiated by light source93and that is optically coupled to at least one photosensor95. Sensed zone94may be located inside or outside reaction chamber52. Reaction control devices having a sensed zone inside a reaction chamber are described elsewhere herein, such as in Examples 2 and 5. III. EXAMPLES This section describes additional aspects and features of methods and systems for thermally controlling a chemical reaction in droplets. Any suitable aspects and features of this section may be combined with one another and with any suitable aspects and features described elsewhere in the present disclosure, such as in Sections I, II, and IV, in any suitable combination. The examples of this section are intended for illustration and should not limit the entire scope of the present disclosure. Example 1. Droplet-Retention Gates for Reaction Chambers This example describes exemplary droplet-retention gates for reaction chambers; seeFIGS.6and7. FIG.6shows selected aspects of an exemplary reaction control device150, which is an embodiment of reaction control device50of Section II. Reaction control device150includes a reaction chamber152holding droplets154encapsulated by a carrier fluid156. A pair of thermal zones158a,158bare located at opposite ends of the reaction chamber. Reaction chamber152has a curved inlet164and a curved outlet166each having a radial curvature forming a droplet-retention gate168shaped like a swan's neck. The curvature of inlet164and outlet166prevents droplets154from becoming trapped at either end of reaction chamber152, such that substantially all of droplets154move as a group between thermal zones of reaction chamber152when the reaction chamber is properly reoriented. FIG.7shows selected aspects of an exemplary reaction control device250, which is an embodiment of reaction control device50of Section II. Reaction control device250includes a reaction chamber252holding droplets254encapsulated by a carrier fluid256. Reaction chamber has an inlet264and an outlet266each having an indented droplet-retention gate268. The width of droplet-retention gate268is less than the diameter of each droplet254. Accordingly, droplets254do not pass through gate268when they migrate between thermal zones of the reaction chamber, but can be forced through gate268by a connected pump in order to enter and/or leave reaction chamber252. Example 2. Device and System Embodiments This example describes exemplary device and system embodiments for controlling a chemical reaction in droplets; seeFIGS.8-11. FIG.8shows selected aspects of an exemplary reaction control device350, which is an embodiment of reaction control device50of Section II. Reaction control device350includes a reaction chamber352holding droplets354encapsulated by a carrier fluid356. Reaction chamber352has a pair of thermal zones358a,358bmaintained at different temperatures, T1and T2, and located at opposite ends of the chamber. The extent of each thermal zone is indicated generally with a dashed box. Reaction chamber352forms a pair of wider subchambers367a,367bconnected to one another via a narrower channel370. Thermal zones358a,358bgenerally correspond to subchambers367a,367b, respectively. FIG.9shows selected aspects of an exemplary reaction control device450, which is an embodiment of reaction control device50of Section II. Reaction control device450includes a reaction chamber452holding droplets454encapsulated by a carrier fluid456. Reaction chamber452has a pair of thermal zones458a,458bmaintained at different temperatures, T1and T2, and located at opposite ends of the reaction chamber. The extent of each thermal zone is indicated generally with a dashed box. Reaction chamber452forms a pair of subchambers467a,467bconnected to one another separately by a droplet channel470aand a carrier fluid channel470b. Carrier fluid channel470bhas a pair of meandering portions471a,471battached to subchambers467a,467b, respectively. Reaction chamber452may be reoriented to move droplets454from subchamber467ato subchamber467b(or vice versa), predominantly or exclusively via droplet channel470a. At the same time, a matching volume of carrier fluid456travels from subchamber467bto subchamber467a(or vice versa) via carrier fluid channel470b. Each meandering portion471a,471bis located in the same thermal zone458aor458bas subchamber467aor467b. Accordingly, the matching volume of carrier fluid456that enters the subchamber is already preheated to the correct temperature, which helps to reduce temperature fluctuations in the subchambers and permits droplets454to reach each desired temperature more quickly. FIG.10shows selected aspects of an exemplary system580for thermally controlling a chemical reaction in droplets. System580is an embodiment of system80of Section II and includes a reaction control device550optically coupled to a detection module578. Reaction control device550includes a reaction chamber552holding droplets554encapsulated by a carrier fluid556. Reaction chamber552has a pair of thermal zones558a,558bmaintained at different temperatures, T1and T2, and located at opposite ends of the chamber. The extent of each thermal zone is indicated generally with a dashed box. Reaction chamber552forms a pair of subchambers567a,567bconnected to one another separately by a droplet channel570aand a carrier fluid channel570b. A detection portion583of system580includes detection module578and a sensed zone594within droplet channel570athat are optically coupled to one another. Detection module578is configured to detect light, such as photoluminescence, from droplets554as they travel along droplet channel570aand through sensed zone594in response to reorientation of reaction chamber552. The detection module578includes a light source593, a photosensor595, a beamsplitter596, and an objective597. Light source593generates optical radiation that propagates to sensed zone594via beamsplitter596and objective597and irradiates sensed zone594. This irradiation may induce photoluminescence from a photoluminescent label in droplets554. The photoluminescence is collected by objective597, propagates through beamsplitter596, and is incident on and detected by photosensor595. Detection module578may, for example, be utilized to collect amplification data from droplets554during or after each of a plurality of thermal cycles to which the droplets are subjected in reaction chamber552. FIG.11shows an exemplary reaction control device650, which is an embodiment of reaction control device50of Section II. Reaction control device650includes a reaction chamber652holding droplets654encapsulated by a carrier fluid656. Reaction chamber652has a pair of thermal zones658a,658bmaintained at different temperatures, T1and T2, and demarcated generally in dashed outline. Reaction chamber652includes a pair of subchambers667a,667bconnected to one another via a pair of channels670a,670b. Panels A-D show reaction chamber652being reoriented through a full turn, indicated by turning arrows at660, in a plane parallel to channels670a,670b, to move droplets654as a group from subchamber667ato667b. Droplets654can be returned to subchamber667aby another full turn in the same or the opposite rotational direction. Example 3. Thermal Zones Offset by Less than 180 Degrees This example describes exemplary reaction control devices having thermal zones that are rotationally offset from one another by less than 180 degrees; seeFIGS.12and13. FIG.12shows an exemplary reaction control device750including a rectangular reaction chamber752holding an emulsion of droplets754encapsulated by a carrier fluid756. Reaction chamber752has a pair of thermal zones758a,758bthat are rotationally offset from one another by 90 degrees in the plane of the image. In other words, rotating reaction chamber752by 90 degrees about an axis orthogonal to the plane of the image can move droplets754from thermal zone758ato thermal zone758bor vice versa. Accordingly, reaction chamber752may be configured to have up to four thermal zones each located generally at a different corner of the reaction chamber. An inlet764and an outlet766are in fluid communication with thermal zones758a,758b, respectively, but in other embodiments, one or both of the inlet and outlet may be placed instead at a different corner(s) of reaction chamber752. FIG.13shows an exemplary reaction control device850including a triangular reaction chamber852holding an emulsion of droplets854encapsulated by a carrier fluid856. Reaction chamber852has three thermal zones858a-c, at respective temperatures T1-T3, that are rotationally offset from one another by 120 degrees in the plane of the image. In other words, rotating reaction chamber852by 120 degrees about an axis orthogonal to the plane of the image can move droplets854from thermal zone858ato either thermal zone858bor thermal zone858c. Droplets854can be moved to each of three thermal zones858a-cin succession by rotating the reaction chamber one full turn or 120 degrees per thermal zone. An inlet864and an outlet866are in fluid communication with thermal zones858a,858brespectively, but in other embodiments, one or both of the inlet and outlet may be placed instead at a different corner(s) of reaction chamber852. In other embodiments, the reaction chamber may have any suitable polygonal shape, such as a pentagon (having up to five thermal zones), a hexagon (up to six thermal zones), etc. Example 4. Addition of Pre-Heated Carrier Fluid This example describes an exemplary system980including reaction control device150ofFIG.6and a pair of pumps, T1pump999aand T2pump999b, to drive preheated carrier fluid156into reaction chamber152holding droplets154; seeFIGS.14and15. System980has a pair of thermal zones958a,958bmaintained at different temperatures T1and T2. The thermal zones are demarcated generally by dashed boxes. Thermal zones958a,958bencompass thermal zones158a,158bof reaction chamber152and lengths of tubing1001a,1001brespectively connected to inlet164and outlet166of reaction chamber152. Accordingly, lengths of tubing1001a,1001bserve as reservoirs holding preheated carrier fluid156. In other embodiments, thermal zones958a,958bmay encompass carrier fluid156held by chambers of pumps999a,999band/or other chambers located along the flow paths intermediate pumps999a,999band reaction chamber152. FIGS.14and15show reaction chamber152in a pair of configurations that are inverted relative to one another. InFIG.14, droplets154have reached thermal zone158aafter migration from thermal zone158b(in which the temperature is T2). To accelerate heating or cooling droplets154to temperature T1, a volume of carrier fluid156preheated to T1is driven into reaction chamber152from length of tubing1001aby the action of T1pump999a. This flow of carrier fluid156may be encouraged by T2pump999b, which may actively urge a corresponding volume of carrier fluid156out of reaction chamber152via outlet166. Alternatively, T2pump999bmay be replaced by a chamber that passively expands and contracts in response to the action of T1pump999a. InFIG.15, droplets154have just reached thermal zone158bin response to inverting reaction chamber152about a horizontal axis located in the plane of the image. To accelerate heating or cooling of droplets to T2, a volume of carrier fluid156preheated to T2is driven into reaction chamber152from length of tubing1001bby the action of T2pump999b. This flow of carrier fluid156may be encouraged by T1pump999a, which may actively urge a corresponding volume of carrier fluid156out of reaction chamber152via inlet164. Example 5. Centrifugation System to Drive Droplet Travel This example describes a centrifugation system1080including a plurality of reaction control devices1050a-deach having a thermally-zoned reaction chamber1052to hold sample-containing droplets (e.g., including Samples1-4); seeFIGS.16-19. Centrifugation system1080is an embodiment of system80ofFIG.5. To increase the thermal cycling rate, the droplets are moved more rapidly between the different thermal zones. This can be achieved by using a centrifuge to generate a g-force to drive the prospective droplet fluid first to one end. To drive it back to the other end, the reaction chamber is flipped over while spinning. However, system1080alternatively can be operated without centrifugation, by using gravity instead of a g-force to drive travel of droplets between thermal zones. Reaction control devices1050a-dare supported by a rotor1110, which is rotated about an axis, indicated at1111(seeFIG.16). This rotation applies a g-force1112to an emulsion held by each reaction chamber1052. (Only the g-force for reaction control device1050ais shown inFIG.16.) The g-force1112may be at least about 2, 5, 10, 25, 50, or 100 times the force of gravity, to move droplets more rapidly between thermal zones, relative to gravity-driven migration. Each reaction control device1050a-dhas a pair of heaters1089a,1089bto create thermal zones1058a,1058bof different temperature (e.g., T1and T2respectively) in each reaction chamber1052(seeFIGS.16and17). A respective orienting drive1087is operatively associated with each reaction control device1050a-d(seeFIG.16). The orienting drive is configured to change the orientation of the reaction control device, indicated by turning arrows at1060for reaction control device1050a, to move droplets between the pair of thermal zones while rotor1110is spinning. This change in orientation is with respect to the g-force1112exerted on the reaction control device. Each orienting drive1087may rotate the corresponding reaction control device1050a-dby any suitable angle, such as flipping each device one-half turn in the depicted embodiment, about a respective rotation axis that is transverse or parallel to the rotation axis of rotor1110. This reorientation of each reaction chamber1052moves droplets from one thermal zone1058aor1058bto the other thermal zone1058bor1058a. FIG.17shows reaction control device1050aof system1080being used for two-step thermal cycling to promote nucleic acid amplification in droplets (e.g., in only a subset of the droplets in chamber1052that contain a target sequence). An amplification signal may be detected from droplets1054during or after each thermal cycle of any suitable number of thermal cycles, such as every thermal cycle, as shown. Reaction chamber1052has a pair of channels1070a,1070bthat separately connect a pair of subchambers1067a,1067bto one another. Subchamber1067amay be maintained at temperature T1and subchamber1067bat temperature T2by heaters1089a,1089b. During each thermal cycle, droplets1054migrate to thermal zone1058a(temperature T1) and to thermal zone1058b(temperature T2). Panel A ofFIG.17shows droplets1054in the process of migrating from subchamber1067a(thermal zone1058aat temperature T1) to subchamber1067b(thermal zone1058bat temperature T2) via channel1070b. A matching volume of carrier fluid1056is moving in the opposite direction via channel1070a. Panel B ofFIG.17shows reaction control device1050arotated one-half turn with respect to panel A (to change the orientation of reaction chamber1052relative to g-force1112). Droplets1054are migrating from subchamber1067b(thermal zone1058bat temperature T2) to subchamber1067a(thermal zone1058aat temperature T1) via channel1070a. In other words, droplets1054may migrate alternately via the two channels1070a,1070b(compare panels A and B). A detection module1078of system1080collects amplification data from droplets1054as each droplet passes through a sensed zone1094aof channel1070a. In other embodiments, reaction chamber1052may have only one channel connecting subchambers1067aand1067bto one another (e.g., see Section II). In other embodiments, reaction chamber1052may be configured such that droplets1054migrate back and forth between the thermal zones predominantly or exclusively via the same channel (of a pair of channels). FIG.17illustrates detection of an amplification signal at only one temperature. However, the amplification assay may be rendered more informative by detecting an amplification signal from droplets1054at two, three, or more different temperatures, to distinguish amplification products having different melting temperatures from one another. For example, panels A-D ofFIG.18show reaction control device1050abeing used to generate a melting/annealing curve for amplification products in the droplets. An amplification signal is detected from the droplets passing alternately through sensed zones1094aand1094busing detection module1078, in response to each inversion of reaction chamber1052. The droplets have an increasing or decreasing series of different temperatures T3-T6in panels A-D respectively (also seeFIG.3). Detection of the amplification signal may be performed before and/or after thermal cycling of the droplets has been completed. In panel A, droplets1054are passing through sensed zone1094bfrom thermal zone1058aat temperature T3to thermal zone1058bat temperature T4. In panel B, droplets1054are passing through sensed zone1094afrom thermal zone1058bat temperature T4to thermal zone1058a, which is now at temperature T5. In panel C, droplets1054are passing through sensed zone1094bfrom thermal zone1058aat temperature T5to thermal zone1058b, which is now at temperature T6. In panel D, droplets1054are passing through sensed zone1094afrom thermal zone1058aat temperature T6to thermal zone1058b(still at temperature T5). FIG.19shows reaction control device1050aofFIG.17being used for droplet generation (panels A and B), thermally cycling droplets (panels C and D), and detection of an amplification signal from the droplets (panel E). In panel A, reaction chamber1052contains carrier fluid1056and a (non-partitioned) reaction mixture1114that are immiscible with one another. In panel B, reaction chamber1052has been flipped relative to panel A. In response, reaction mixture1114travels from thermal zone1058ato thermal zone1058bvia channel1070a. Reaction mixture1114is partitioned into droplets1054as the reaction mixture leaves the outlet of channel1070a. In panels C and D, two-step thermal cycling is performed by flipping reaction chamber1052multiple times to move droplets1054back and forth between thermal zones1058aand1058b. In panel E, an amplification signal is detected by detection module1078from droplets1054passing through sensed zone1094a. Example 6. Flow-Through System for Thermal Control This example describes a flow-through system1180including an encapsulation assembly1181, a reaction control device1150, and a sensed zone1194arranged in series; seeFIG.20. Flow-through system1180is an embodiment of system80ofFIG.5. Encapsulation assembly1181has a droplet generator1184. The droplet generator receives a sample-containing reaction mixture1214via a sample inlet1216and carrier fluid1156, such as oil, via a carrier inlet1218. Reaction mixture1214and carrier fluid1156flow in different channels to a channel intersection1220at which an emulsion of droplets in carrier fluid1156is generated. The emulsion flows to reaction control device1150via an inflow channel1222. Reaction control device1150has a reaction chamber1152including at least two thermal zones1158a,1158b. Droplets of the emulsion can be heated to different temperatures, such as thermally cycled, in reaction chamber1152by changing its orientation with respect to gravity as described elsewhere herein. Changing the orientation controls a chemical reaction, such as amplification of a target sequence in the droplets. The emulsion then flows out of reaction chamber1152via an outflow channel1224and passes through a sensed zone1194that is optically coupled to a detection module1178. The detection module may have a light source1193to irradiate sensed zone1194and a photosensor1195to detect light from sensed zone1194. The emulsion flows to waste downstream of sensed zone1194. IV. SELECTED ASPECTS This section describes selected aspects of the present disclosure as a series of indexed paragraphs. A1. A method of controlling a chemical reaction, the method comprising: (i) creating a first thermal zone and a second thermal zone in a reaction chamber, the first and second thermal zones having different temperatures from one another; (ii) holding an emulsion in the reaction chamber, the emulsion including droplets encapsulated by a carrier fluid and having a density mismatch with the carrier fluid, each of the droplets including one or more reactants for the chemical reaction; and (iii) changing an orientation of the reaction chamber to move the droplets from the first thermal zone to the second thermal zone, such that a rate of the chemical reaction changes in at least a subset of the droplets. A2. The method of paragraph A1, wherein changing an orientation starts or speeds up the chemical reaction in the at least a subset of the droplets. A3. The method of paragraph A1 or A2, further comprising reorienting the reaction chamber to return the droplets to the first thermal zone. A4. The method of paragraph A3, further comprising changing a temperature of the first thermal zone while the droplets are located in the second thermal zone before reorienting. A5. The method of paragraph A3 or A4, wherein reorienting changes the rate of the chemical reaction again in the at least a subset of the droplets. A6. The method of paragraph A5, wherein reorienting slows or stops the chemical reaction in the at least a subset of the droplets. A7. The method of any of paragraphs A3 to A6, wherein reorienting causes a plurality of the droplets to pass through a sensed zone within the reaction chamber, the method further comprising detecting a signal related to the chemical reaction from the plurality of droplets passing through the sensed zone. A8. The method of paragraph A7, wherein detecting a signal includes detecting photoluminescence from the plurality of droplets. A9. The method of any of paragraphs A1 to A8, wherein the reaction chamber has at least three thermal zones including the first thermal zone and the second thermal zone, wherein the at least three thermal zones are individually maintained at selected temperatures that are different from one another, the method further comprising turning the reaction chamber such that the droplets move from the first thermal zone to each of the other at least three thermal zones. A10. The method of any of paragraphs A1 to A9, wherein the chemical reaction is catalyzed by an enzyme, and wherein the enzyme is present in only a subset of the droplets, optionally the enzyme has a Poisson distribution among the droplets. A11. The method of paragraph A10, wherein the one or more reactants include a reactant having a photoluminescence that is changed by the chemical reaction, the method further comprising detecting the photoluminescence from a plurality of the droplets. A12. The method of any of paragraphs A1 to A9, wherein changing an orientation encourages generation of an amplicon corresponding to a target sequence present in at least a subset of the droplets, and wherein, optionally, a reactant of the one or more reactants is an oligonucleotide that hybridizes with the amplicon or the target sequence at one or both of the different temperatures. A13. The method of paragraph A12, wherein the oligonucleotide hybridizes with the amplicon or target sequence at only one of the different temperatures. A14. The method of paragraph A12 or A13, wherein at least one of the droplets does not contain the target sequence. A15. The method of any of paragraphs A12 to A14, wherein at least one of the droplets contains only one copy of the target sequence before changing an orientation. A16. The method of any of paragraphs A12 to A15, wherein each of the droplets contains a polymerase, a ligase, and/or a reverse transcriptase. A17. The method of any of paragraphs A12 to A16, wherein each of the droplets includes one or more mononucleotides as a reactant for the chemical reaction. A18. The method of any of paragraphs A12 to A17, wherein the chemical reaction adds one or more nucleotides to the oligonucleotide. A19. The method of any of paragraphs A1 to A9 and A11 to A18, further comprising performing an isothermal amplification reaction in at least a subset of the droplets while the droplets are located in the second thermal zone, wherein the isothermal amplification reaction includes the chemical reaction. A20. The method of paragraph A19, further comprising reorienting the reaction chamber to move the droplets from the second thermal zone to the first thermal zone, to slow or stop the isothermal amplification reaction. A21. The method of any of paragraphs A1 to A9 and A11 to A18, further comprising performing PCR including the chemical reaction in at least a subset of the droplets while the droplets remain in the reaction chamber. A22. The method of paragraph A21, wherein performing PCR includes thermally cycling the droplets by reorienting the reaction chamber multiple times to move the droplets to each of the first and second thermal zones multiple times. A23. The method of paragraph A22, further comprising collecting amplification data from the droplets while the droplets remain in the reaction chamber. A24. The method of paragraph A23, wherein the amplification data is collected from a plurality of the droplets passing through a sensed zone within the reaction chamber. A25. The method of paragraph A23 or A24, wherein collecting amplification data includes detecting photoluminescence from the plurality of droplets. A26. The method of any of paragraphs A23 to A25, wherein thermally cycling includes subjecting the droplets to a plurality of thermal cycles, and wherein collecting amplification data includes collecting amplification data from at least a subset of the droplets during or after each thermal cycle of two or more of the plurality of thermal cycles, optionally after every thermal cycle of the plurality of thermal cycles. A27. The method of any of paragraphs A23 to A26, wherein collecting amplification data includes collecting amplification data from at least a subset of the droplets at each temperature of an increasing or decreasing series of temperatures, and generating a melting curve or an annealing curve using the amplification data. A28. The method of paragraph A27, further comprising changing a temperature of at least one of the first and second thermal zones between a pair of temperatures of the series of temperatures. A29. The method of any of paragraphs A21 to A28, wherein the PCR is driven by two-step thermal cycling using the first and second thermal zones. A30. The method of any of paragraphs A21 to A28, wherein the PCR is driven by subjecting the droplets to a series of thermal cycles, wherein the reaction chamber includes a third thermal zone having a selected temperature that is different from the first and second thermal zones, the method further comprising moving the droplets to each of the first, second, and third thermal zones in each thermal cycle. A31. The method of any of paragraphs A19 to A30, wherein the droplets contain a probe having a label, the method further comprising detecting an amplification signal from the label. A32. The method of paragraph A31, wherein each of the droplets includes a polymerase having an exonuclease activity to degrade copies of the probe during the isothermal amplification or PCR. A33. The method of paragraph A31, wherein the probe is not degraded by the isothermal amplification or PCR. A34. The method of any of paragraphs A18 to A33, wherein the droplets contain an intercalating dye, the method further comprising detecting an amplification signal from the intercalating dye. A35. The method of paragraphs A18 to A34, wherein the isothermal amplification or PCR amplifies a target sequence or a complement thereof, and wherein only a subset of the droplets contain the target sequence. A36. The method of any of paragraphs A1 to A35, wherein the first and second thermal zones are connected to one another via a channel, and wherein changing an orientation causes at least a subset of the droplets to move from the first thermal zone to the second thermal zone via the channel. A37. The method of paragraph A36, wherein a pair of channels separately connect the first and second thermal zones to one another. A38. The method of paragraph A37, wherein the pair of channels are a droplet channel and a carrier fluid channel, and wherein changing an orientation causes the droplets to travel between the first and second thermal zones predominantly or exclusively via the droplet channel. A39. The method of paragraph 38, wherein the carrier fluid channel has a first end located in the first thermal zone and a second end located in the second thermal zone. A40. The method of paragraph A39, wherein a first end portion of the carrier fluid channel adjacent the first end and/or a second portion of the carrier fluid channel adjacent the second end follows a meandering path. A41. The method of any of paragraphs A1 to A40, further comprising forming the droplets outside the reaction chamber; and introducing the formed droplets into the reaction chamber. A42. The method of any of paragraphs A1 to A40, further comprising forming the droplets inside the reaction chamber. A43. The method of any of paragraphs A1 to A42, wherein each of the droplets has a lower density than the carrier fluid. A44. The method of any of paragraphs A1 to A43, wherein each of the droplets has a higher density than the carrier fluid. A45. The method of any of paragraphs A1 to A44, further comprising rotating the reaction chamber a plurality of full turns to produce alternating movement of the droplets as a group between the first and second thermal zones. A46. The method of any of paragraphs A1 to A45, further comprising rotating the reaction chamber alternately in opposite rotational directions to produce alternating movement of the droplets as a group between the first and second thermal zones. A47. The method of any of paragraphs A1 to A46, further comprising rotating the reaction chamber during a series of rotation intervals each inducing relocation of the droplets as a group from one of the first and second thermal zones to the other of the first and second thermal zones, and wherein rotating the reaction chamber also includes pausing rotation of the reaction chamber between successive rotation intervals of the series of rotation intervals. A48. The method of paragraph A47, wherein rotating the reaction chamber includes pausing rotation of the container during a series of pause intervals of at least two different durations. A49. The method of any of paragraphs A1 to A48, further comprising driving preheated carrier fluid into the reaction chamber at the second thermal zone using a pump when the droplets reach the second thermal zone from the first thermal zone. A50. The method of paragraph A49, wherein the preheated carrier fluid is preheated to the temperature of the second thermal zone. A51. The method of paragraph A49 or A50, further comprising reorienting the reaction chamber to move the droplets from the second thermal zone to the first thermal zone, and driving preheated carrier fluid into the reaction chamber at the first thermal zone using a pump when the droplets reach the first thermal zone from the second thermal zone. A52. The method of paragraph A51, wherein the preheated carrier fluid driven into the first thermal zone is preheated to the temperature of the first thermal zone. A53. The method of any of paragraphs A1 to A52, wherein changing an orientation is performed while the reaction chamber is spinning in centrifuge. A54. The method of any of paragraphs A1 to A53, further comprising detecting a reaction signal from a plurality of the droplets. A55. The method of paragraph A54, wherein detecting a reaction signal includes detecting the reaction signal from each droplet of the plurality of the droplets passing through a sensed zone of the reaction chamber. A56. The method of paragraph A54 or A55, wherein detecting a reaction signal includes detecting an amplification signal from a plurality of droplets after each cycle of a plurality of thermal cycles. A57. The method of any of paragraphs A54 to A56, wherein detecting a reaction signal includes detecting an amplification signal from a plurality of the droplets at each of a series of increasing or decreasing temperatures in the reaction chamber to produce a melting curve or an annealing curve. A58. The method of any of paragraphs A1 to A57, wherein a first heating device and a second heating device remain associated with the first and second thermal zones, respectively, as the orientation of the reaction chamber is changed. A59. The method of any of paragraphs A1 to A58, wherein changing an orientation moves the first thermal zone from an elevation higher than the second thermal zone to an elevation lower than the second thermal zone if the droplets are less dense than the carrier fluid, or vice versa if the droplets are more dense than the carrier fluid. B1. A system for controlling a chemical reaction, the system comprising: (i) a reaction chamber to hold an emulsion including droplets encapsulated by a carrier fluid and having a density mismatch with the carrier fluid, each of the droplets containing one or more reactants for the chemical reaction; (ii) a thermal control system configured to create a first thermal zone and a second thermal zone having different temperatures from one another in the reaction chamber; and (iii) an orienting drive configured to change an orientation of the reaction chamber to move the droplets as a group between the first thermal zone and the second thermal zone. B2. The system of paragraph B1, further comprising a droplet generator configured to generate the droplets, the droplet generator being connected or connectable to the reaction chamber such that the droplets travel from the droplet generator to the reaction chamber. B3. The system of paragraph B1 or B2, further comprising a detection module configured to detect a reaction signal from a plurality of the droplets each located in a sensed zone within or downstream of the reaction chamber. B4. The system of paragraph B3, wherein the sensed zone is a region of a channel, wherein the detection module includes a light source to irradiate each droplet of the plurality of droplets passing through the sensed zone, and a detector to detect light from the sensed zone. The term “exemplary” as used in the present disclosure, means “illustrative” or “serving as an example.” Similarly, the term “exemplify” means “to illustrate by giving an example.” Neither term implies desirability or superiority. The disclosure set forth above may encompass multiple distinct inventions with independent utility. Although each of these inventions has been disclosed in its preferred form(s), the specific embodiments thereof as disclosed and illustrated herein are not to be considered in a limiting sense, because numerous variations are possible. The subject matter of the inventions includes all novel and nonobvious combinations and subcombinations of the various elements, features, functions, and/or properties disclosed herein. The following claims particularly point out certain combinations and subcombinations regarded as novel and nonobvious. Inventions embodied in other combinations and subcombinations of features, functions, elements, and/or properties may be claimed in applications claiming priority from this or a related application. Such claims, whether directed to a different invention or to the same invention, and whether broader, narrower, equal, or different in scope to the original claims, also are regarded as included within the subject matter of the inventions of the present disclosure. Further, ordinal indicators, such as first, second, or third, for identified elements are used to distinguish between the elements, and do not indicate a particular position or order of such elements, unless otherwise specifically stated.
67,243
11857975
DETAILED DESCRIPTION The present disclosure describes apparatus and methods related to automating the sequential loading and unloading of multiple carriers, thereby extending the duration of autonomous operation of an automated examination system. These same concepts and principles may be applied to other fields and apparatus that can benefit from the positioning and handling features disclosed herein. This description is not intended to be a detailed catalog of all the different ways in which the disclosure may be implemented, or all the features that may be added to the instant disclosure. For example, features illustrated with respect to one embodiment may be incorporated into other embodiments, and features illustrated with respect to a particular embodiment may be deleted from that embodiment. Thus, the disclosure contemplates that in some embodiments of the disclosure, any feature or combination of features set forth herein can be excluded or omitted. In addition, numerous variations and additions to the various embodiments suggested herein will be apparent to those skilled in the art in light of the instant disclosure, which do not depart from the instant disclosure. In other instances, well-known structures, interfaces, and processes have not been shown in detail in order not to unnecessarily obscure the invention. It is intended that no part of this specification be construed to effect a disavowal of any part of the full scope of the invention. Hence, the following descriptions are intended to illustrate some particular embodiments of the disclosure, and not to exhaustively specify all permutations, combinations and variations thereof. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for the purpose of describing particular aspects or embodiments only and is not intended to be limiting of the disclosure. References to techniques employed herein are intended to refer to the techniques as commonly understood in the art, including variations on those techniques or substitutions of equivalent techniques that would be apparent to one of skill in the art. Concepts and designs known to those of ordinary skill in the art may be referenced herein but are not described in detail. Unless the context indicates otherwise, it is specifically intended that the various features of the disclosure described herein can be used in any combination. Moreover, the present disclosure also contemplates that in some embodiments of the disclosure, any feature or combination of features set forth herein can be excluded or omitted. The methods disclosed herein include and comprise one or more steps or actions for achieving the described method. The method steps and/or actions may be interchanged with one another without departing from the scope of the present invention. In other words, unless a specific order of steps or actions is required for proper operation of the embodiment, the order and/or use of specific steps and/or actions may be modified without departing from the scope of the present invention. As used in the description of the disclosure and the appended claims, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, “and/or” and “or” refer to and encompass any and all possible combinations of one or more of the associated listed items. The terms “about” and “approximately” as used herein when referring to a measurable value, such as a length, is meant to encompass variations of ±20%, ±10%, ±5%, ±1%, ±0.5%, or even ±0.1% of the specified amount, and when referring to a condition, such as proximity, its meant to be encompass a range of values similar in magnitude, for example from 0% to 200%, 0% to 100%, 0% to 50%, or even 0% to 10%, of a characteristic, such as a diameter, of the referenced object. As used herein, phrases such as “between X and Y” and “between about X and Y” should be interpreted to include X and Y. As used herein, phrases such as “between about X and Y” mean “between about X and about Y” and phrases such as “from about X to Y” mean “from about X to about Y.” As used herein, a “system” may be a collection of devices that are physical coupled or separated while in wired or wireless communication with each other. As used herein, “optical” refers to a range of wavelengths of radiation that, in certain embodiments, comprises the “visible” spectrum of 380 to 740 nanometers (nm). In certain embodiments, this range may comprise a portion of the infrared spectrum above 740 nm. In certain embodiments, this range may comprise a portion of the ultraviolet spectrum below 380 nm. As used herein, “imaging system” refers to a system that comprises one or more of an image-forming element, a filtering element, an image-detecting element, an image-conversion element that converts an optical image into an analog or digital representation of the image, an element for converting the representation into data, a data processing capability, a data transmission capability, and/or a data storage capability. As used herein, “hole” refers to a void that passes partially or completely through an object. The hole may be uniform in profile along the depth of the hole or have a profile that varies along the depth. The profile of a hole may be geometric shape, for example a circle or oval or square, or an arbitrary shape defined by a closed line. As used herein, a “slide” refers to a sample substrate that carries a substance or object to be examined. A slide may be made of any material, for example glass or plastic or ceramic or metal, and have any geometric form, for example a planar rectangle of uniform thickness. As used herein, “camera” refers to a detection system that is sensitive to a portion of the optical energy provided to the camera, for example an optical image formed on an element of the camera. A camera may include elements to provide an output in optical or electronic form that is associated with an attribute of the optical energy. As used herein, a “spring element” may be a single item or multi-element assembly that provides an elastic force-displacement characteristic. For example, a spring may be provided as a piece of elastic foam or a metal cantilever or helical coil or a sealed container containing a compressible fluid. FIG.1is a perspective view of an example slide examination system100. The system100typically has a base110on which is mounted an imaging system120, which may include a magnification system122, an optical system124, and a camera126. This system100has a manual slide carrier10that is configured to accept two slides in the slide mounting area12. The system100also includes a carrier mount130, wherein for example the manual carrier10can be slid laterally into the mount130. The mount130is attached to a slide positioning system140that includes a lateral positioning stage142and a vertical positioning stage144. The slide positioning system140is configured to selectably place a portion of a slide that is accepted into the carrier under the magnification system122. FIG.2is a schematic representation of the imaging system120of the slide examination system100ofFIG.1. The magnification system122and the optical system124cooperate to form an optical image of an object (not visible inFIG.2) on the surface of the slide200on a sensitive portion of the camera226. FIGS.3A-3Bdepict an exemplary slide transport system300, according to the present disclosure. The system300comprises a carrier340and a cartridge310. The exemplary carrier340shown inFIG.3Ahas a body configured to accept a slide (not shown inFIG.3A), for example slide200ofFIG.1, in the slide mounting area348. Tabs349are configured to couple to a slide, which are discussed further with respect toFIGS.10A-10C. Carrier340also comprises a notch344in the body and linear engagement feature346formed along an edge of the body, which are discussed further with respect toFIGS.8A-8G. In certain embodiments, the linear engagement feature comprises gear teeth. In certain embodiments, the gear teeth have a pitch in the range of 2-20 teeth per inch, 3-10 teeth per inch, 4-8 teeth per inch, or 5-6 teeth per inch. Carrier340also comprises a retention hole342through the body, which is discussed further with respect toFIGS.12A-12F. The exemplary cartridge310comprises a top plate324, two side plates322, a bottom plate (not visible inFIG.3A) that is opposite the top plate324, and one or more separators330that together define a plurality of compartments312each configured to accept a carrier340. The top plate326has a guide hole326. A portion of the separators330also have a guide hole (not visible inFIG.3A) that is aligned with the guide hole326along a linear axis328. In certain embodiments, all of the separators330comprise a guide hole. In certain embodiments, the axis328is aligned perpendicular to the top surface of the top plate324. In certain embodiments, the axis328is aligned perpendicular to the top surface of the bottom plate. In certain embodiments, the compartments312are of a common configuration and have a “pitch,” or separation distance, of d1, as shown inFIG.3A. This can be considered to be a center-to-center distance or the distance between corresponding features, for example the surface of the separators330that forms the lower side of adjacent compartments312. A compartment312also has a height, being the open distance between the upper surface of the lower separator330and the lower surface of the upper separator330. This height plus the thickness of the separators330equals the pitch of the compartments. FIG.3Bdepicts a carrier340partially disposed in a compartment312of cartridge310. The carrier340moves parallel to an axis332as the carrier340is inserted into or removed from a compartment312. Whether the carrier340is “partially” inserted/withdrawn or “fully” inserted/withdrawn is discussed with respect toFIGS.12C-12D. FIG.4depicts an exemplary slide handling system400, according to the present disclosure. The slide handling system400comprises a cartridge310that is coupled to a cartridge positioning system410attached to a base402. In this example, the cartridge310contains a plurality of carriers340. A carrier mount430is attached to a slide examination system100(not shown inFIG.4for clarity) that is also coupled to the base402. The cartridge positioning system410further comprises a structure414and an actuator450coupled to the structure and positioned proximate to the installed cartridge310. The operation of the actuator450is discussed further with respect toFIGS.8A-8G. The carrier mount430comprises slide clamp432and a finger-actuation slide434, which are discussed in further detail with respect toFIGS.11A-11B. FIG.5depicts a portion of the exemplary cartridge positioning system410, according to the present disclosure. The structure414and other details have been omitted for clarity. The system410comprises a platform412that is configured to accept and fixedly retain a cartridge310, with a further ability to selectably release the cartridge310. The system410further comprises at least one collar440coupled to the platform412and at least one drive rod420,421coupled to base402. In the example ofFIG.5, there are four collars440. Within the system410, each collar440is further coupled to a drive rod420, which is threaded in a first spiral direction, or a drive rod421, which is threaded in a second spiral direction that is opposite to the first spiral direction. Each drive rod420,421has an axis422. Rotating drive rods420in a clockwise (as seen from above in the orientation shown inFIG.5) direction will cause the associated collar440to move downward along the axis422. Rotating drive rods421in a clockwise direction will cause the associated collar440to move upward along the axis422. When the set of drive rods420,421are simultaneously rotated in the appropriate directions, for example rotating drive rods420clockwise while rotating drive rods421counterclockwise, the platform will move parallel to axis422and the torques applied by the drive rods420,421to the platform412are balanced, i.e. sum to approximately zero. In certain embodiments, the drive rods420,421are coupled together to rotate in appropriate directions at a common rotational rate. FIG.6Ais an enlarged view of a portion of drive rod420and collar440. The drive rod420comprises one or more grooves428formed as a spiral around the first axis of the drive rod. Adjacent grooves428, whether portions of a single groove428or multiple parallel grooves428, are separately by a separation ridge429. A groove428comprises a first portion425having an angle, indicated by line424, to the first axis422. Groove428also comprise a second portion427that is perpendicular, indicated by line426, to the first axis422. Portion427has a width d3, as shown inFIG.6A. The width d3, in combination with the inner diameter of the groove428, determines a range of angular position of drive rod420within which the collar440does not move with respect to the drive rod420along the axis422. This range reduces the sensitivity of the vertical position of platform412to the angular position of the drive rods420. The groove428may have a variety of profiles, for example circular or square or triangular. The profile of the separation ridge may also have a variety of profiles, for example flat-topped or rounded or a sharp peak. In certain embodiments, the groove428has a pitch of d2, as shown inFIG.6A. In this example, the drive rod420has a single groove428formed in spiral such that adjacent grooves are the same groove428. If d2is equal to d1ofFIG.3A, which is the pitch of the compartments312, then each full rotation of the drive rods420incrementally moves the platform412upward, or downward, by one compartment312. In certain embodiments, d2is equal to other integral multiples of d1, wherein that multiple of rotations of the drive rods420will incrementally move the platform412by one compartment. Collar440is coupled to the drive rod420by housing442, which encircles drive rod420in this example, and an element444that is configured to engage the groove428of the drive rod420. In this example, groove428is formed with a circular profile while the element444is a sphere, thereby providing a high degree of contact between the element444and groove428. In certain embodiments, the element444has other profiles, for example a cylinder with a rounded nose. In certain embodiments, the element444comprises a moving aspect, for example a roller that makes rolling contact with the groove428. In certain embodiments, the collar440comprises a spring element446that is configured to urge the element444toward the drive rod420. While shown inFIG.6Aas a coil spring, spring element46may be of any construction or material. In certain embodiments, the cartridge positioning system410is configured such that a compartment312is aligned with the carrier mount430, which allows a carrier340to be moved from a compartment312to the carrier mount430, when the element444is engaged within a second portion427of the groove428. This allows a range of the rotational position of drive rod430within which the compartment312remains aligned with the carrier mount430. In certain embodiments, a full rotation of the drive rods430of system410will align an adjacent compartment312of the cartridge310with the carrier mount430. In certain embodiments, an integer number of full rotations of the drive rods430of system410will align an adjacent compartment312of the cartridge310with the carrier mount430. FIG.6Bdepicts a portion of drive rod420and collar440while a force F is being applied to the collar440in a direction parallel to axis422. If the force F is greater than or equal to the threshold value, the element444retracts and passes from groove428B over the separation ridge429to groove428A (which may be different portions of a single groove in certain embodiments). In certain embodiments, the element444moves along an axis423that is perpendicular to the axis422. If the force F is less than the threshold value, element444remains engaged with the groove428B. FIGS.7A-7Ddepict an exemplary sequence of operations of the slide handling system400ofFIG.4, according to the present disclosure. FIG.7Adepicts a cartridge310being loaded onto the platform412of the cartridge positioning system410. The cartridge310, in this example, contains a plurality of carriers340. The carrier mount430, with the associated slide clamp432, is shown in a loading position. Actuator450is shown positioned proximate to the loading position of the carrier mount430. FIG.7Bshows the cartridge310accepted by the platform412and the cartridge positioning system410activated to place compartment312A in alignment with the carrier mount430. A carrier340A has been removed from compartment312A of the cartridge310and accepted by the carrier mount430, including activation of the slide clamp432to move downward and clamp a slide (not visible inFIG.7B) carried by carrier340A against a stop (not visible inFIG.7B) of the carrier mount430. The function of slide clamp432is discussed further with respect toFIGS.11A-11B. FIG.7Cdepicts the cartridge positioning system410activated to move platform412so as to position a second compartment312B, in this example the top compartment of cartridge310, in alignment with carrier mount430. Carrier430A was, in this example, inserted into compartment312A from the configuration ofFIG.7Bprior to the activation of the cartridge positioning system410. This activation comprises rotation of drive rods420and421in opposite directions. FIG.7Ddepicts the cartridge positioning system410activated to move platform412so as to position a third compartment312C, in this example the bottom compartment of cartridge310, in alignment with carrier mount430. FIGS.8A-8Gdepict an exemplary sequence of operations of the cartridge positioning system410for removing a carrier340from a cartridge310, according to the present disclosure. FIG.8Ais a plan view of a cut-away as indicated by section C-C inFIG.4, with certain elements omitted for clarity. A carrier340is position in a “seated” position within a compartment312between sidewalls322of a cartridge310. An actuator450is attached to structure414at a corner of the compartment312. The actuator450is vertically clear of the cartridge310such that the cartridge positioning system410can raise and lower the cartridge310without striking the actuator450. In this example sequence, the actuator450is shown in a “9 o'clock” position inFIG.8A. FIGS.8B-8Fare a portion of the view ofFIG.8A. FIG.8Bshows the configuration of cartridge positioning system410after counterclockwise rotation of the actuator450, as indicated by the arrow451, to an approximately “10 o'clock” position. The actuator450is configured to rotate about a center453and comprises a rotary engagement feature452and a tab454. In certain embodiments, the rotary engagement feature452comprises gear teeth. In certain embodiments, the rotary engagement feature452may comprise an alternate profile and material, for example a rubber drive wheel, while the linear engagement feature322may comprise a mating feature, for example a flat textured surface providing a non-slip surface for a rubber wheel. In certain embodiments, the gear teeth of the rotary engagement feature452are configured to mate with gear teeth of the linear engagement feature346. In certain embodiments, the gear teeth of the rotary engagement feature452have a pitch in the range of 2-20 teeth per inch, 3-10 teeth per inch, 4-8 teeth per inch, or 5-6 teeth per inch. InFIG.8B, the tab454of the actuator450is in contact with a surface of the notch344that is formed in the body of carrier340. FIG.8Cshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450, as indicated by the arrow451, to an approximately “8 o'clock” position. The carrier340has been moved toward the carrier mount (not shown inFIGS.8A-8G) by the motion of the actuator450and the rotary engagement feature452of the actuator450has engaged the linear actuation feature346of the carrier340. FIG.8Dshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “4 o'clock” position. The rotation of the actuator450, through the engagement of the rotary engagement feature452with the linear engagement feature352, has moved the carrier340further toward the carrier mount. FIG.8Eshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “2 o'clock” position, which has further moved carrier340toward the carrier mount. FIG.8Fshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “1 o'clock” position, which has further moved carrier340toward the carrier mount. The rotary engagement feature452has reached an end of the linear engagement feature346and the tab454extends beyond the “back” surface of the carrier340. FIG.8Gshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “8 o'clock” position, whereupon the tab454has been pushing on the back surface of the carrier340since passing approximately the “10 o'clock” position, which has further moved carrier340toward the carrier mount and, in the configuration shown inFIG.8G, into an “accepted” position of the carrier340in the carrier mount. The carrier mount is now able to move the carrier340into a viewing position of a system such as the slide examination system100shown inFIG.1. FIGS.9A-9Fdepict an exemplary sequence of operations of the cartridge positioning system410for inserting a carrier340into a cartridge310, according to the present disclosure. FIG.9Ashows the cartridge positioning system410in the initial configuration when carrier340is presented for unloading by the carrier mount (omitted inFIGS.9A-9Ffor clarity). The actuator450is shown in a “5 o'clock” position that positions the tab454clear of the carrier340. FIGS.9B-9Eare a portion of the view ofFIG.9A. FIG.9Bshows the configuration of cartridge positioning system410after clockwise rotation of the actuator450, as indicated by the arrow451A, to an approximately “8 o'clock” position wherein the tab454of the actuator450is in contact with a surface of the notch344A. FIG.9Cshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “10 o'clock” position. The rotary engagement feature452of the actuator450has engaged the linear actuation feature346of the carrier340. The carrier340has been moved into the compartment312of cartridge310(not shown for clarity) by the motion of the actuator450. FIG.9Dshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “1 o'clock” position. This rotation while the rotary engagement feature452is engaged with the linear engagement feature346of the slide carrier340has caused the slide carrier340to be moved further into the compartment312by the motion of the actuator450. FIG.9Eshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “6 o'clock” position. The carrier340has been moved further into the compartment312by the motion of the actuator450. The rotary engagement feature452has reached an end of the linear engagement feature346and the tab454extends beyond the “front” surface of the carrier340. FIG.9Fshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “10 o'clock” position, whereupon the tab454has been pushing on the front surface of the slide carrier340since passing approximately the “7 o'clock” position, which has further moved slide carrier340into the compartment312and, in the configuration shown inFIG.9F, into the “seated” position of the carrier340in the cartridge310. The cartridge positioning system410is now able to move the cartridge310into a new position such as shown inFIGS.7C-7D. FIG.10Ais a plan view of the top surface of an exemplary slide carrier1000, according to the present disclosure. Tabs1010are coupled to the body1020of the carrier1000and configured to removably couple to slides200, shown as slides200A and200B in the two slide mounting areas of the example carrier1000. Each tab1010comprises a gripper portion1014and a flexible portion1012. The carrier1000also comprises a retention hole1032that, in this example, has entry ramps1032. In certain embodiments, the retention hole1032is a circular through hole. The carrier1000also comprises a front-entry ramp1034and a back-entry ramp1035on the top surface of the body1020. FIGS.10B-10Care cross-section views of carrier1000ofFIG.10A. FIG.10Bdepicts the carrier1000in a first configuration that is representative of the carrier1000as first loaded into a carrier mount (most of which has been omitted for clarity). The slide200B is separately from the stops436of the carrier mount to allow movement of the carrier1000relative to the carrier mount. FIG.10Cdepicts the carrier1000in a second position wherein the slide200B has been vertically displaced to contact the stops436. This contact positions the slide in a known vertical position to enable a system, such as the slide positioning system ofFIG.1, to precisely position the slide200B. FIGS.11A-11Bdepict an exemplary actuation finger1050, according to the present disclosure.FIG.11Ashows the actuation finger1050as configured while the carrier1000is in the first configuration ofFIG.10B. In certain embodiments, this configuration of the actuator finger1050is determined by a first position of the finger-actuation slide434ofFIG.4(not shown inFIG.11A). FIG.11Bshows the actuation finger1050as configured while the carrier1000is in the second configuration ofFIG.10C. In certain embodiments, this configuration of the actuator finger1050is determined by a second position of the finger-actuation slide434. In certain embodiments, the tip of finger1050contacts the gripper1014and moves the gripper1014downward until slide200B contacts the stop436. In certain embodiments, the finger1050continues to apply a determined force to hold the slide200B against the stop436during operation of the slide positions system100. FIGS.12A-12Fdepict cut-away views of an exemplary carrier locking system1200, according to the present disclosure. FIG.12Adepicts an example system1200comprising a cartridge310having five compartments312with carriers1000disposed within four of the compartments312. In this view, the groove1036formed on the bottom surface of body1020of the carrier100is visible. The locking system1200comprises guide hole1210in top plate324, guide hole1214in bottom plate325, and guide holes1212in each of the separators330. In certain embodiments, the guide holes1210,1212, and1214are disposed on an axis1220. In certain embodiments, the axis1220is generally perpendicular to the plane of the compartments312. In general, the locking system1200is configured to allow separations between the spacers1230wherein the total of the separations is more than one and less than two times the remaining thickness of a slide carrier body1020after subtracting the depth of the groove1036. The effect of this limitation is that any slide carrier1000in a cartridge310can be with withdrawn but a second slide carrier1000cannot be displaced from its seated position while the first slide carrier1000is still partially inserted within the cartridge310. The guide system1200comprises a plurality of spacers1230(including spacers1230A and1230B) disposed generally within one or more of the guide holes1210,1212, and1214. In certain embodiments, the spacers1230(including top spacer1230A and bottom spacer1230B) are all identical and have a height. In certain embodiments, the spacers1230are approximately spheres having a height that is the same as the diameter of the sphere. In certain embodiments, the spacers1230comprise one of more of a metal, a ceramic, a plastic or other polymeric material, a glass, or any other solid material. In certain embodiments, the spacers1230comprise a coating or surface treatment, for example a friction-reducing material such as polytetrafluoroethylene (PTFE) or a wear-reducing treatment such as anodization. A portion of the spacers1230can move along axis1220. In certain embodiments, the bottom spacer1230B is fixed in guide hole1214. In certain embodiments, the height of spacer1230A and/or1230B are different from the spacers1230disposed between spacers1230A and1230B. In certain embodiments, the configuration of the spacers1230may differ within a locking system1200. A carrier1000that is disposed such that its retention hole1030is disposed on axis1220is in a “seated” position. With the four carriers1000in their respective seated positions as shown inFIG.12A, adjacent spacers1230are in contact with each other. In certain embodiments, guide hole1214is configured as a pocket having a depth that is less than the height of spacer1230B. In certain embodiments, guide hole1214has a depth that is approximately half the height of spacer1230B such that approximately half the spacer1230B protrudes in the lowest compartment. In certain embodiments, the thickness of a separator330and the height of a compartment312are in the range of 50%-150% of the height of a spacer1230. In certain embodiments, the thickness of a separator330and the height of a compartment312are in the range of 75%-125% of the height of a spacer1230. In certain embodiments, the thickness of a separator330and the height of a compartment312are in the range of 90%-110% of the height of a spacer1230. In certain embodiments, the thickness of a separator330and the height of a compartment312are approximately equal to the height of a spacer1230. FIG.12Bis a view from the “front” of the cartridge310, showing how the spacers1230ride within the groove1036. FIG.12Cdepicts the configuration of system1200while a carrier1000A is partially removed from a compartment312, i.e. the body1020is still interposed between adjacent spacers1230but the retention hole1030is not disposed on axis1220. Spacer1230D, disposed under the carrier1000A, rides in groove1036while spacer1230C, disposed above the carrier1000A, rides on the top surface of the body1020. The spacers1230that are above the carrier1000A are displaced upward by the thickness of the carrier above the groove1036. In certain embodiments, a spring (not shown inFIG.12Cfor clarity) applies a bias force F is provided in a downward direction to maintain the spacers1230in contact with the objects, carriers1000or other spacers1230, above and below them. In certain embodiments, this bias force F is partially provided by the weight of the spacers themselves. While the carrier locking system1200is configured as shown inFIG.12C, with a carrier1000partially removed from the compartment312, removal of other carriers1000from other compartments312is prevented by the displaced position of the spacers1230each substantially blocking a compartment312, for compartments above the partially removed carrier1000, and by the inability of the spacers1230of compartments312below the carrier1000to move at all. In certain embodiments, the displaced spacers1230are approximately centered in the height of the proximate compartments312. In certain embodiments, guide hole1210is configured as a pocket having a depth that is sufficient to allow spacer1230A to move upwards while a single carrier1000is partially removed but insufficient to allow two carriers to simultaneously be partially removed. In certain embodiments, this limitation on upward motion of the spacer1230A is provided by a travel limiting feature (not shown inFIG.12C) that is coupled to the top plate324. FIG.12Ddepicts the configuration of the carrier locking system1200after carrier1000A is “fully removed,” i.e. the body of carrier1000A is not interposed between spacers1230C and1230D. Spacer1230C and all the other spacers1230above1230C have moved downward such that spacers1230C and1203D are in direct contact. Now that the carrier1000A is fully removed, any other seated carrier1000can be removed, or a new carrier1000can be inserted into an open compartment312. FIG.12Edepicts the configuration of the carrier locking system1200when a locking feature1240that is movably coupled to the top plate324. The locking feature1240has an unlocked position that allows a carrier1000to be withdrawn from the cartridge310and a locked position that prevents any carrier1000from being withdrawn from any compartment312of the cartridge312.FIG.12Edepicts an example locking feature1240as a plate that has been moved to cover the guide hole1210, wherein the thickness of top plate324is such that the top spacer1230A must protrude above the top surface of the top plate324while a carrier1000is partially removed, as shown inFIG.12C. The position of locking feature1240inFIG.12Eis an exemplary locked position. Preventing the spacer1230A from protruding locks all the lower spacers1230in place and thereby prevents a carrier1000from being able to be removed. While the invention has been described with reference to particular aspects, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to a particular situation or material to the teachings of the invention without departing from the scope of the invention. Therefore, it is intended that the invention not be limited to the particular aspects disclosed but that the invention will include all aspects falling within the scope and spirit of the appended claims.
34,233
11857976
DETAILED DESCRIPTION The present disclosure describes apparatus and methods related to automating the sequential loading and unloading of multiple carriers, thereby extending the duration of autonomous operation of an automated examination system. These same concepts and principles may be applied to other fields and apparatus that can benefit from the positioning and handling features disclosed herein. This description is not intended to be a detailed catalog of all the different ways in which the disclosure may be implemented, or all the features that may be added to the instant disclosure. For example, features illustrated with respect to one embodiment may be incorporated into other embodiments, and features illustrated with respect to a particular embodiment may be deleted from that embodiment. Thus, the disclosure contemplates that in some embodiments of the disclosure, any feature or combination of features set forth herein can be excluded or omitted. In addition, numerous variations and additions to the various embodiments suggested herein will be apparent to those skilled in the art in light of the instant disclosure, which do not depart from the instant disclosure. In other instances, well-known structures, interfaces, and processes have not been shown in detail in order not to unnecessarily obscure the invention. It is intended that no part of this specification be construed to effect a disavowal of any part of the full scope of the invention. Hence, the following descriptions are intended to illustrate some particular embodiments of the disclosure, and not to exhaustively specify all permutations, combinations and variations thereof. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for the purpose of describing particular aspects or embodiments only and is not intended to be limiting of the disclosure. References to techniques employed herein are intended to refer to the techniques as commonly understood in the art, including variations on those techniques or substitutions of equivalent techniques that would be apparent to one of skill in the art. Concepts and designs known to those of ordinary skill in the art may be referenced herein but are not described in detail. Unless the context indicates otherwise, it is specifically intended that the various features of the disclosure described herein can be used in any combination. Moreover, the present disclosure also contemplates that in some embodiments of the disclosure, any feature or combination of features set forth herein can be excluded or omitted. The methods disclosed herein include and comprise one or more steps or actions for achieving the described method. The method steps and/or actions may be interchanged with one another without departing from the scope of the present invention. In other words, unless a specific order of steps or actions is required for proper operation of the embodiment, the order and/or use of specific steps and/or actions may be modified without departing from the scope of the present invention. As used in the description of the disclosure and the appended claims, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. As used herein, “and/or” and “or” refer to and encompass any and all possible combinations of one or more of the associated listed items. The terms “about” and “approximately” as used herein when referring to a measurable value, such as a length, is meant to encompass variations of ±20%, ±10%, ±5%, ±1%, ±0.5%, or even ±0.1% of the specified amount, and when referring to a condition, such as proximity, its meant to be encompass a range of values similar in magnitude, for example from 0% to 200%, 0% to 100%, 0% to 50%, or even 0% to 10%, of a characteristic, such as a diameter, of the referenced object. As used herein, phrases such as “between X and Y” and “between about X and Y” should be interpreted to include X and Y. As used herein, phrases such as “between about X and Y” mean “between about X and about Y” and phrases such as “from about X to Y” mean “from about X to about Y.” As used herein, a “system” may be a collection of devices that are physical coupled or separated while in wired or wireless communication with each other. As used herein, “optical” refers to a range of wavelengths of radiation that, in certain embodiments, comprises the “visible” spectrum of 380 to 740 nanometers (nm). In certain embodiments, this range may comprise a portion of the infrared spectrum above 740 nm. In certain embodiments, this range may comprise a portion of the ultraviolet spectrum below 380 nm. As used herein, “imaging system” refers to a system that comprises one or more of an image-forming element, a filtering element, an image-detecting element, an image-conversion element that converts an optical image into an analog or digital representation of the image, an element for converting the representation into data, a data processing capability, a data transmission capability, and/or a data storage capability. As used herein, “hole” refers to a void that passes partially or completely through an object. The hole may be uniform in profile along the depth of the hole or have a profile that varies along the depth. The profile of a hole may be geometric shape, for example a circle or oval or square, or an arbitrary shape defined by a closed line. As used herein, a “slide” refers to a sample substrate that carries a substance or object to be examined. A slide may be made of any material, for example glass or plastic or ceramic or metal, and have any geometric form, for example a planar rectangle of uniform thickness. As used herein, “camera” refers to a detection system that is sensitive to a portion of the optical energy provided to the camera, for example an optical image formed on an element of the camera. A camera may include elements to provide an output in optical or electronic form that is associated with an attribute of the optical energy. As used herein, a “spring element” may be a single item or multi-element assembly that provides an elastic force-displacement characteristic. For example, a spring may be provided as a piece of elastic foam or a metal cantilever or helical coil or a sealed container containing a compressible fluid. FIG.1is a perspective view of an example slide examination system100. The system100typically has a base110on which is mounted an imaging system120, which may include a magnification system122, an optical system124, and a camera126. This system100has a manual slide carrier10that is configured to accept two slides in the slide mounting area12. The system100also includes a carrier mount130, wherein for example the manual carrier10can be slid laterally into the mount130. The mount130is attached to a slide positioning system140that includes a lateral positioning stage142and a vertical positioning stage144. The slide positioning system140is configured to selectably place a portion of a slide that is accepted into the carrier under the magnification system122. FIG.2is a schematic representation of the imaging system120of the slide examination system100ofFIG.1. The magnification system122and the optical system124cooperate to form an optical image of an object (not visible inFIG.2) on the surface of the slide200on a sensitive portion of the camera226. FIGS.3A-3Bdepict an exemplary slide transport system300, according to the present disclosure. The system300comprises a carrier340and a cartridge310. The exemplary carrier340shown inFIG.3Ahas a body configured to accept a slide (not shown inFIG.3A), for example slide200ofFIG.1, in the slide mounting area348. Tabs349are configured to couple to a slide, which are discussed further with respect toFIGS.10A-10C. Carrier340also comprises a notch344in the body and linear engagement feature346formed along an edge of the body, which are discussed further with respect toFIGS.8A-8G. In certain embodiments, the linear engagement feature comprises gear teeth. In certain embodiments, the gear teeth have a pitch in the range of 2-20 teeth per inch, 3-10 teeth per inch, 4-8 teeth per inch, or 5-6 teeth per inch. Carrier340also comprises a retention hole342through the body, which is discussed further with respect toFIGS.12A-12F. The exemplary cartridge310comprises a top plate324, two side plates322, a bottom plate (not visible inFIG.3A) that is opposite the top plate324, and one or more separators330that together define a plurality of compartments312each configured to accept a carrier340. The top plate326has a guide hole326. A portion of the separators330also have a guide hole (not visible inFIG.3A) that is aligned with the guide hole326along a linear axis328. In certain embodiments, all of the separators330comprise a guide hole. In certain embodiments, the axis328is aligned perpendicular to the top surface of the top plate324. In certain embodiments, the axis328is aligned perpendicular to the top surface of the bottom plate. In certain embodiments, the compartments312are of a common configuration and have a “pitch,” or separation distance, of d1, as shown inFIG.3A. This can be considered to be a center-to-center distance or the distance between corresponding features, for example the surface of the separators330that forms the lower side of adjacent compartments312. A compartment312also has a height, being the open distance between the upper surface of the lower separator330and the lower surface of the upper separator330. This height plus the thickness of the separators330equals the pitch of the compartments. FIG.3Bdepicts a carrier340partially disposed in a compartment312of cartridge310. The carrier340moves parallel to an axis332as the carrier340is inserted into or removed from a compartment312. Whether the carrier340is “partially” inserted/withdrawn or “fully” inserted/withdrawn is discussed with respect toFIGS.12C-12D. FIG.4depicts an exemplary slide handling system400, according to the present disclosure. The slide handling system400comprises a cartridge310that is coupled to a cartridge positioning system410attached to a base402. In this example, the cartridge310contains a plurality of carriers340. A carrier mount430is attached to a slide examination system100(not shown inFIG.4for clarity) that is also coupled to the base402. The cartridge positioning system410further comprises a structure414and an actuator450coupled to the structure and positioned proximate to the installed cartridge310. The operation of the actuator450is discussed further with respect toFIGS.8A-8G. The carrier mount430comprises slide clamp432and a finger-actuation slide434, which are discussed in further detail with respect toFIGS.11A-11B. FIG.5depicts a portion of the exemplary cartridge positioning system410, according to the present disclosure. The structure414and other details have been omitted for clarity. The system410comprises a platform412that is configured to accept and fixedly retain a cartridge310, with a further ability to selectably release the cartridge310. The system410further comprises at least one collar440coupled to the platform412and at least one drive rod420,421coupled to base402. In the example ofFIG.5, there are four collars440. Within the system410, each collar440is further coupled to a drive rod420, which is threaded in a first spiral direction, or a drive rod421, which is threaded in a second spiral direction that is opposite to the first spiral direction. Each drive rod420,421has an axis422. Rotating drive rods420in a clockwise (as seen from above in the orientation shown inFIG.5) direction will cause the associated collar440to move downward along the axis422. Rotating drive rods421in a clockwise direction will cause the associated collar440to move upward along the axis422. When the set of drive rods420,421are simultaneously rotated in the appropriate directions, for example rotating drive rods420clockwise while rotating drive rods421counterclockwise, the platform will move parallel to axis422and the torques applied by the drive rods420,421to the platform412are balanced, i.e. sum to approximately zero. In certain embodiments, the drive rods420,421are coupled together to rotate in appropriate directions at a common rotational rate. FIG.6Ais an enlarged view of a portion of drive rod420and collar440. The drive rod420comprises one or more grooves428formed as a spiral around the first axis of the drive rod. Adjacent grooves428, whether portions of a single groove428or multiple parallel grooves428, are separately by a separation ridge429. A groove428comprises a first portion425having an angle, indicated by line424, to the first axis422. Groove428also comprise a second portion427that is perpendicular, indicated by line426, to the first axis422. Portion427has a width d3, as shown inFIG.6A. The width d3, in combination with the inner diameter of the groove428, determines a range of angular position of drive rod420within which the collar440does not move with respect to the drive rod420along the axis422. This range reduces the sensitivity of the vertical position of platform412to the angular position of the drive rods420. The groove428may have a variety of profiles, for example circular or square or triangular. The profile of the separation ridge may also have a variety of profiles, for example flat-topped or rounded or a sharp peak. In certain embodiments, the groove428has a pitch of d2, as shown inFIG.6A. In this example, the drive rod420has a single groove428formed in spiral such that adjacent grooves are the same groove428. If d2 is equal to d1 ofFIG.3A, which is the pitch of the compartments312, then each full rotation of the drive rods420incrementally moves the platform412upward, or downward, by one compartment312. In certain embodiments, d2 is equal to other integral multiples of d1, wherein that multiple of rotations of the drive rods420will incrementally move the platform412by one compartment. Collar440is coupled to the drive rod420by housing442, which encircles drive rod420in this example, and an element444that is configured to engage the groove428of the drive rod420. In this example, groove428is formed with a circular profile while the element444is a sphere, thereby providing a high degree of contact between the element444and groove428. In certain embodiments, the element444has other profiles, for example a cylinder with a rounded nose. In certain embodiments, the element444comprises a moving aspect, for example a roller that makes rolling contact with the groove428. In certain embodiments, the collar440comprises a spring element446that is configured to urge the element444toward the drive rod420. While shown inFIG.6Aas a coil spring, spring element46may be of any construction or material. In certain embodiments, the cartridge positioning system410is configured such that a compartment312is aligned with the carrier mount430, which allows a carrier340to be moved from a compartment312to the carrier mount430, when the element444is engaged within a second portion427of the groove428. This allows a range of the rotational position of drive rod430within which the compartment312remains aligned with the carrier mount430. In certain embodiments, a full rotation of the drive rods430of system410will align an adjacent compartment312of the cartridge310with the carrier mount430. In certain embodiments, an integer number of full rotations of the drive rods430of system410will align an adjacent compartment312of the cartridge310with the carrier mount430. FIG.6Bdepicts a portion of drive rod420and collar440while a force F is being applied to the collar440in a direction parallel to axis422. If the force F is greater than or equal to the threshold value, the element444retracts and passes from groove428B over the separation ridge429to groove428A (which may be different portions of a single groove in certain embodiments). In certain embodiments, the element444moves along an axis423that is perpendicular to the axis422. If the force F is less than the threshold value, element444remains engaged with the groove428B. FIGS.7A-7Ddepict an exemplary sequence of operations of the slide handling system400ofFIG.4, according to the present disclosure. FIG.7Adepicts a cartridge310being loaded onto the platform412of the cartridge positioning system410. The cartridge310, in this example, contains a plurality of carriers340. The carrier mount430, with the associated slide clamp432, is shown in a loading position. Actuator450is shown positioned proximate to the loading position of the carrier mount430. FIG.7Bshows the cartridge310accepted by the platform412and the cartridge positioning system410activated to place compartment312A in alignment with the carrier mount430. A carrier340A has been removed from compartment312A of the cartridge310and accepted by the carrier mount430, including activation of the slide clamp432to move downward and clamp a slide (not visible inFIG.7B) carried by carrier340A against a stop (not visible inFIG.7B) of the carrier mount430. The function of slide clamp432is discussed further with respect toFIGS.11A-11B. FIG.7Cdepicts the cartridge positioning system410activated to move platform412so as to position a second compartment312B, in this example the top compartment of cartridge310, in alignment with carrier mount430. Carrier430A was, in this example, inserted into compartment312A from the configuration ofFIG.7Bprior to the activation of the cartridge positioning system410. This activation comprises rotation of drive rods420and421in opposite directions. FIG.7Ddepicts the cartridge positioning system410activated to move platform412so as to position a third compartment312C, in this example the bottom compartment of cartridge310, in alignment with carrier mount430. FIGS.8A-8Gdepict an exemplary sequence of operations of the cartridge positioning system410for removing a carrier340from a cartridge310, according to the present disclosure. FIG.8Ais a plan view of a cut-away as indicated by section C-C inFIG.4, with certain elements omitted for clarity. A carrier340is position in a “seated” position within a compartment312between sidewalls322of a cartridge310. An actuator450is attached to structure414at a corner of the compartment312. The actuator450is vertically clear of the cartridge310such that the cartridge positioning system410can raise and lower the cartridge310without striking the actuator450. In this example sequence, the actuator450is shown in a “9 o'clock” position inFIG.8A. FIGS.8B-8Fare a portion of the view ofFIG.8A. FIG.8Bshows the configuration of cartridge positioning system410after counterclockwise rotation of the actuator450, as indicated by the arrow451, to an approximately “10 o'clock” position. The actuator450is configured to rotate about a center453and comprises a rotary engagement feature452and a tab454. In certain embodiments, the rotary engagement feature452comprises gear teeth. In certain embodiments, the rotary engagement feature452may comprise an alternate profile and material, for example a rubber drive wheel, while the linear engagement feature322may comprise a mating feature, for example a flat textured surface providing a non-slip surface for a rubber wheel. In certain embodiments, the gear teeth of the rotary engagement feature452are configured to mate with gear teeth of the linear engagement feature346. In certain embodiments, the gear teeth of the rotary engagement feature452have a pitch in the range of 2-20 teeth per inch, 3-10 teeth per inch, 4-8 teeth per inch, or 5-6 teeth per inch. InFIG.8B, the tab454of the actuator450is in contact with a surface of the notch344that is formed in the body of carrier340. FIG.8Cshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450, as indicated by the arrow451, to an approximately “8 o'clock” position. The carrier340has been moved toward the carrier mount (not shown inFIGS.8A-8G) by the motion of the actuator450and the rotary engagement feature452of the actuator450has engaged the linear actuation feature346of the carrier340. FIG.8Dshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “4 o'clock” position. The rotation of the actuator450, through the engagement of the rotary engagement feature452with the linear engagement feature352, has moved the carrier340further toward the carrier mount. FIG.8Eshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “2 o'clock” position, which has further moved carrier340toward the carrier mount. FIG.8Fshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “1 o'clock” position, which has further moved carrier340toward the carrier mount. The rotary engagement feature452has reached an end of the linear engagement feature346and the tab454extends beyond the “back” surface of the carrier340. FIG.8Gshows the configuration of cartridge positioning system410after further counterclockwise rotation of the actuator450to an approximately “8 o'clock” position, whereupon the tab454has been pushing on the back surface of the carrier340since passing approximately the “10 o'clock” position, which has further moved carrier340toward the carrier mount and, in the configuration shown inFIG.8G, into an “accepted” position of the carrier340in the carrier mount. The carrier mount is now able to move the carrier340into a viewing position of a system such as the slide examination system100shown inFIG.1. FIGS.9A-9Fdepict an exemplary sequence of operations of the cartridge positioning system410for inserting a carrier340into a cartridge310, according to the present disclosure. FIG.9Ashows the cartridge positioning system410in the initial configuration when carrier340is presented for unloading by the carrier mount (omitted inFIGS.9A-9Ffor clarity). The actuator450is shown in a “5 o'clock” position that positions the tab454clear of the carrier340. FIGS.9B-9Eare a portion of the view ofFIG.9A. FIG.9Bshows the configuration of cartridge positioning system410after clockwise rotation of the actuator450, as indicated by the arrow451A, to an approximately “8 o'clock” position wherein the tab454of the actuator450is in contact with a surface of the notch344A. FIG.9Cshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “10 o'clock” position. The rotary engagement feature452of the actuator450has engaged the linear actuation feature346of the carrier340. The carrier340has been moved into the compartment312of cartridge310(not shown for clarity) by the motion of the actuator450. FIG.9Dshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “1 o'clock” position. This rotation while the rotary engagement feature452is engaged with the linear engagement feature346of the slide carrier340has caused the slide carrier340to be moved further into the compartment312by the motion of the actuator450. FIG.9Eshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “6 o'clock” position. The carrier340has been moved further into the compartment312by the motion of the actuator450. The rotary engagement feature452has reached an end of the linear engagement feature346and the tab454extends beyond the “front” surface of the carrier340. FIG.9Fshows the configuration of cartridge positioning system410after further clockwise rotation of the actuator450to an approximately “10 o'clock” position, whereupon the tab454has been pushing on the front surface of the slide carrier340since passing approximately the “7 o'clock” position, which has further moved slide carrier340into the compartment312and, in the configuration shown inFIG.9F, into the “seated” position of the carrier340in the cartridge310. The cartridge positioning system410is now able to move the cartridge310into a new position such as shown inFIGS.7C-7D. FIG.10Ais a plan view of the top surface of an exemplary slide carrier1000, according to the present disclosure. Tabs1010are coupled to the body1020of the carrier1000and configured to removably couple to slides200, shown as slides200A and200B in the two slide mounting areas of the example carrier1000. Each tab1010comprises a gripper portion1014and a flexible portion1012. The carrier1000also comprises a retention hole1032that, in this example, has entry ramps1032. In certain embodiments, the retention hole1032is a circular through hole. The carrier1000also comprises a front-entry ramp1034and a back-entry ramp1035on the top surface of the body1020. FIGS.10B-10Care cross-section views of carrier1000ofFIG.10A. FIG.10Bdepicts the carrier1000in a first configuration that is representative of the carrier1000as first loaded into a carrier mount (most of which has been omitted for clarity). The slide200B is separately from the stops436of the carrier mount to allow movement of the carrier1000relative to the carrier mount. FIG.10Cdepicts the carrier1000in a second position wherein the slide200B has been vertically displaced to contact the stops436. This contact positions the slide in a known vertical position to enable a system, such as the slide positioning system ofFIG.1, to precisely position the slide200B. FIGS.11A-11Bdepict an exemplary actuation finger1050, according to the present disclosure.FIG.11Ashows the actuation finger1050as configured while the carrier1000is in the first configuration ofFIG.10B. In certain embodiments, this configuration of the actuator finger1050is determined by a first position of the finger-actuation slide434ofFIG.4(not shown inFIG.11A). FIG.11Bshows the actuation finger1050as configured while the carrier1000is in the second configuration ofFIG.10C. In certain embodiments, this configuration of the actuator finger1050is determined by a second position of the finger-actuation slide434. In certain embodiments, the tip of finger1050contacts the gripper1014and moves the gripper1014downward until slide200B contacts the stop436. In certain embodiments, the finger1050continues to apply a determined force to hold the slide200B against the stop436during operation of the slide positions system100. FIGS.12A-12Fdepict cut-away views of an exemplary carrier locking system1200, according to the present disclosure. FIG.12Adepicts an example system1200comprising a cartridge310having five compartments312with carriers1000disposed within four of the compartments312. In this view, the groove1036formed on the bottom surface of body1020of the carrier100is visible. The locking system1200comprises guide hole1210in top plate324, guide hole1214in bottom plate325, and guide holes1212in each of the separators330. In certain embodiments, the guide holes1210,1212, and1214are disposed on an axis1220. In certain embodiments, the axis1220is generally perpendicular to the plane of the compartments312. In general, the locking system1200is configured to allow separations between the spacers1230wherein the total of the separations is more than one and less than two times the remaining thickness of a slide carrier body1020after subtracting the depth of the groove1036. The effect of this limitation is that any slide carrier1000in a cartridge310can be with withdrawn but a second slide carrier1000cannot be displaced from its seated position while the first slide carrier1000is still partially inserted within the cartridge310. The guide system1200comprises a plurality of spacers1230(including spacers1230A and1230B) disposed generally within one or more of the guide holes1210,1212, and1214. In certain embodiments, the spacers1230(including top spacer1230A and bottom spacer1230B) are all identical and have a height. In certain embodiments, the spacers1230are approximately spheres having a height that is the same as the diameter of the sphere. In certain embodiments, the spacers1230comprise one of more of a metal, a ceramic, a plastic or other polymeric material, a glass, or any other solid material. In certain embodiments, the spacers1230comprise a coating or surface treatment, for example a friction-reducing material such as polytetrafluoroethylene (PTFE) or a wear-reducing treatment such as anodization. A portion of the spacers1230can move along axis1220. In certain embodiments, the bottom spacer1230B is fixed in guide hole1214. In certain embodiments, the height of spacer1230A and/or1230B are different from the spacers1230disposed between spacers1230A and1230B. In certain embodiments, the configuration of the spacers1230may differ within a locking system1200. A carrier1000that is disposed such that its retention hole1030is disposed on axis1220is in a “seated” position. With the four carriers1000in their respective seated positions as shown inFIG.12A, adjacent spacers1230are in contact with each other. In certain embodiments, guide hole1214is configured as a pocket having a depth that is less than the height of spacer1230B. In certain embodiments, guide hole1214has a depth that is approximately half the height of spacer1230B such that approximately half the spacer1230B protrudes in the lowest compartment. In certain embodiments, the thickness of a separator330and the height of a compartment312are in the range of 50%-150% of the height of a spacer1230. In certain embodiments, the thickness of a separator330and the height of a compartment312are in the range of 75%-125% of the height of a spacer1230. In certain embodiments, the thickness of a separator330and the height of a compartment312are in the range of 90%-110% of the height of a spacer1230. In certain embodiments, the thickness of a separator330and the height of a compartment312are approximately equal to the height of a spacer1230. FIG.12Bis a view from the “front” of the cartridge310, showing how the spacers1230ride within the groove1036. FIG.12Cdepicts the configuration of system1200while a carrier1000A is partially removed from a compartment312, i.e. the body1020is still interposed between adjacent spacers1230but the retention hole1030is not disposed on axis1220. Spacer1230D, disposed under the carrier1000A, rides in groove1036while spacer1230C, disposed above the carrier1000A, rides on the top surface of the body1020. The spacers1230that are above the carrier1000A are displaced upward by the thickness of the carrier above the groove1036. In certain embodiments, a spring (not shown inFIG.12Cfor clarity) applies a bias force F is provided in a downward direction to maintain the spacers1230in contact with the objects, carriers1000or other spacers1230, above and below them. In certain embodiments, this bias force F is partially provided by the weight of the spacers themselves. While the carrier locking system1200is configured as shown inFIG.12C, with a carrier1000partially removed from the compartment312, removal of other carriers1000from other compartments312is prevented by the displaced position of the spacers1230each substantially blocking a compartment312, for compartments above the partially removed carrier1000, and by the inability of the spacers1230of compartments312below the carrier1000to move at all. In certain embodiments, the displaced spacers1230are approximately centered in the height of the proximate compartments312. In certain embodiments, guide hole1210is configured as a pocket having a depth that is sufficient to allow spacer1230A to move upwards while a single carrier1000is partially removed but insufficient to allow two carriers to simultaneously be partially removed. In certain embodiments, this limitation on upward motion of the spacer1230A is provided by a travel limiting feature (not shown inFIG.12C) that is coupled to the top plate324. FIG.12Ddepicts the configuration of the carrier locking system1200after carrier1000A is “fully removed,” i.e. the body of carrier1000A is not interposed between spacers1230C and1230D. Spacer1230C and all the other spacers1230above1230C have moved downward such that spacers1230C and1203D are in direct contact. Now that the carrier1000A is fully removed, any other seated carrier1000can be removed, or a new carrier1000can be inserted into an open compartment312. FIG.12Edepicts the configuration of the carrier locking system1200when a locking feature1240that is movably coupled to the top plate324. The locking feature1240has an unlocked position that allows a carrier1000to be withdrawn from the cartridge310and a locked position that prevents any carrier1000from being withdrawn from any compartment312of the cartridge312.FIG.12Edepicts an example locking feature1240as a plate that has been moved to cover the guide hole1210, wherein the thickness of top plate324is such that the top spacer1230A must protrude above the top surface of the top plate324while a carrier1000is partially removed, as shown inFIG.12C. The position of locking feature1240inFIG.12Eis an exemplary locked position. Preventing the spacer1230A from protruding locks all the lower spacers1230in place and thereby prevents a carrier1000from being able to be removed. While the invention has been described with reference to particular aspects, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to a particular situation or material to the teachings of the invention without departing from the scope of the invention. Therefore, it is intended that the invention not be limited to the particular aspects disclosed but that the invention will include all aspects falling within the scope and spirit of the appended claims.
34,236
11857977
The correspondence between reference signs and component names inFIGS.1to3is as follows: 100—sub-clamp,110—upper plate body,111—first passage,120—lower plate body,121—second passage,130—upper pipeline connecting joint,140—lower pipeline connecting joint,150—input conduit,160—output conduit,170—sealing ring,180—connecting bolt,191—support spring,192—guide post,200—microfluidic chip,210—connecting port,310—male joint,320—female joint. DETAILED DESCRIPTION In order to make the purposes, technical schemes and advantages of this application clearer, the embodiments of this application will be described in detail below with reference to the drawings. It should be noted that the embodiments in the present application and the features in the embodiments can be arbitrarily combined with each other if there is no conflict. Many specific details are set forth in the following description in order to fully understand this application, but this application can be implemented in other ways different from those described here. Therefore, the protection scope of this application is not limited by the specific embodiments disclosed below. As shown inFIGS.1to3, a fixing clamp for a microfluidic chip provided by an embodiment of the present disclosure includes two sub-clamps100arranged to be spaced apart on left and right. Each of the sub-clamps100includes an upper plate body110having a first passage111, the first passage111having a first outer interface1111and a first chip docking port knot conveniently shown in the figures) located on a lower surface of the upper plate body110and at one end of the upper plate body110facing the other sub-clamp100; a lower plate body120having a second passage121, the second passage121having a second outer interface1211and a second chip docking port1212located on an upper surface of the lower plate body120and at one end of the lower plate body120facing the other sub-clamp100; and a spacing adjusting mechanism for connecting the upper plate body110and the lower plate body120together and adjusting a spacing between the upper plate body110and the lower plate body120. In the fixing clamp for a microfluidic chip, the first chip docking ports are located on the lower surfaces of the opposite ends of two upper plate bodies110, and the second chip docking ports1212are located on the upper surfaces of the opposite ends of two lower plate bodies120, so that when the microfluidic chip200is manufactured, a plurality of connecting ports210at the left end thereof are distributed on the upper and lower surfaces at the left end and a plurality of connecting ports210at the right end are distributed on the upper and lower surfaces at the right end. The connecting ports210on the upper surface and the connecting ports210on the lower surface are mutually unrestricted, and can be arranged more compactly, so that the area of the microfluidic chip200can be reduced and the experimental cost of the microfluidic chip is reduced. In an embodiment, as shown inFIG.1toFIG.3, the first chip docking port and the second chip docking port1212are located in the same row in a left-right direction, which reduces an arrangement space of the first chip docking port and the second chip docking port in a left-right direction, and reduces a length range occupied by the arrangement area of the connecting ports210on the microfluidic chip200in the left-right direction of the microfluidic chip200, thus effectively reducing the size of the microfluidic chip200in the left-right direction. Furthermore, as shown inFIG.1toFIG.3, the first chip docking port and the second chip docking port1212are arranged in a staggered manner in a front-rear direction, so that it is easier to correspondingly communicate with different channels in the microfluidic chip200, and the channels in the microfluidic chip200can be designed more compactly, thus reducing the occupied space and better reducing the area of the microfluidic chip200. Specifically, as shown inFIGS.1to3, the first passage111includes a plurality of mutually independent first passages and the second passage121includes a plurality of mutually independent second passages. A plurality of first chip docking ports and a plurality of second chip docking ports1212are located in the same row in the left-right direction and alternately arranged in the front-rear direction. When the connecting ports210of adjacent channels in the microfluidic chip200are arranged, the connecting ports210of one channel are configured to be arranged on the upper surface of the microfluidic chip200, and the connecting ports210of the other channel are arranged on the lower surface of the microfluidic chip200, thus eliminating the problem of the requirement of interval between the connecting ports210of the adjacent channels. At this time, the distances between two connecting ports210adjacent to each other in front and back on the upper surface and between two connecting ports210adjacent to each other in front and back on the lower surface meet the interval requirement (specifically, there is one connecting port210on the lower surface between two connecting ports210adjacent to each other in front and back on the upper surface, which can meet the requirement of “certain interval” in related technologies). The space occupied by the connecting ports210on the microfluidic chip200is relatively reduced, so that the size of the microfluidic chip200required by the fixing clamp in the front-rear direction and the left-right direction is smaller, which can reduce the experimental cost of the microfluidic chip200. In an embodiment, the first outer interface1111can be located on a side or top or other surface of the upper plate body110, and the second outer interface1211can be located on a side or bottom or other surface of the lower plate body120, both of which can achieve the purpose of the present application, do not deviate from the design concept of the present disclosure, which will not be described in detail here, and should be within the protection scope of the present application. Specifically, as shown inFIG.1toFIG.3, there are three first chip docking ports on the upper plate body110and two second chip docking ports1212on the lower plate body120. The first outer interface1111is located on the top surface of the upper plate body110, and the first passage111is configured as a vertical hole. The second outer interface1211is located on the side surface of the lower plate body120, and the second passage121is configured as a right-angle hole. The lower plate body120is directly placed on the table surface for supporting the whole fixing clamp. In addition, as shown inFIG.1toFIG.3, each sub-clamp100further includes an upper pipeline connecting joint130installed at the first outer interface1111; and a lower pipeline connecting joint140installed at the second outer interface1211. The upper pipeline connecting joint130and the lower pipeline connecting joint140are both configured as Luer joints. The female joint320of the Luer joint is screwed and fixed through an external thread, and the male joint310of the Luer joint is screwed into the female joint320of the Luer joint and connected with a conduit. The female joint320can be fixed on the upper plate body or the lower plate body first, and then the male joint310is installed on the female joint320. The conduit connected to the sub-clamp100at the left can be used as an input conduit150, and the conduit connected to the sub-clamp100at the right can be used as an output conduit160, which can be reasonably selected by a person skilled in the art according to actual needs. The number of these five sets of conduits (ten in total) used can be selected according to the experimental requirement, which can be all used or only a part used (such as only one, two, three or four sets). Specifically, as shown inFIG.1toFIG.3, one end of the upper pipeline connecting joint130is fixed to the first chip docking port from the first outer interface1111along the first passage111, and is in tight butting with the connecting port210on the upper surface of the microfluidic chip200through a sealing ring170, and the second chip docking port1212is in tight butting with the connecting port210on the lower surface of the microfluidic chip200through the sealing ring170, so as to ensure the tightness and prevent the problem of the liquid leakage during the experiment. In addition, the two ends of the microfluidic chip200are not in contact with the upper plate body110and the lower plate body120, thereby reducing the wear of the microfluidic chip200. The sealing ring170can be a silicone ring, a rubber ring or a fluorine ring and the like. By means of this fixing clamp, the microfluidic chip does not need to be installed repeatedly in repeated experiments of the same microfluidic chip, and the fluid enters the microfluidic chip by itself along the input conduit, so that the liquid inlet space is small (dead volume is small), and the microfluidic chip can withstand a certain pressure and speed of liquid. Moreover, most of the area of the microfluidic chip is unobstructed during the experiment, it can be applied to various modes such as a normally-placed microscope and an inversely-placed microscope, and is more conducive to the observation of the experiment. In an embodiment, as shown inFIGS.1and2, the spacing adjusting mechanism includes a connecting bolt180, the threaded end of which being passed through one of the upper plate body110and the lower plate body120and screwed on the other of the upper plate body110and the lower plate body120; and a support spring191, which is supported between the upper plate body110and the lower plate body120so that one of the upper plate body110and the lower plate body120abuts against a nut of the connecting bolt180. By screwing the connecting bolt180, the spacing between the upper plate body110and the lower plate body120can be adjusted, so that the upper plate body110and the lower plate body120can elastically clamp the ends of the microfluidic chip200and correspondingly are in sealed communication with an internal channels of the microfluidic chip200. Specifically, as shown inFIGS.1and2, the spacing adjusting mechanism further includes a guide post192which penetrates one of the upper plate body110and the lower plate body120and is fixedly connected with the other of the upper plate body110and the lower plate body120, and the support spring191is sleeved on the guide post192. There are a plurality of sets of the guide posts192and a plurality of sets of the support springs191, all of which are uniformly distributed on the front and back sides of the connecting bolt180, so that the upper plate body110and the lower plate body120are more evenly stressed in various positions and can better elastically clamp the microfluidic chip200. The upper plate body and the lower plate body can be made of stainless steel, glass or high molecular polymer and the like, and can be manufactured by lathe machining, laser cutting or injection molding and the like. In an embodiment, the first chip docking port and the second chip docking port are located in the same row in a left-right direction. In an embodiment, the first chip docking port and the second chip docking port are arranged in a staggered manner in a front-rear direction. In an embodiment, the first passage includes a plurality of mutually independent first passages and the second passage includes a plurality of mutually independent second passages, and a plurality of the first chip docking ports and a plurality of the second chip docking ports are located in the same row in the left-right direction and alternately arranged in the front-back direction. In an embodiment, the first outer interface is located on a side or top surface of the upper plate body, and the second outer interface is located on a side or bottom surface of the lower plate body. In an embodiment, each of the sub-clamps further includes an upper pipeline connecting joint installed at the first outer interface; and a lower pipeline connecting joint installed at the second outer interface. In an embodiment, one end of the upper pipeline connecting joint is fixed to the first chip docking port from the first outer interface along the first passage for tight butting with the connecting port on the upper surface of the microfluidic chip, and the second chip docking port is configured for tight butting with the connecting port on the lower surface of the microfluidic chip. In an embodiment, the upper pipeline connecting joint and the lower pipeline connecting joint are both Luer joints. In an embodiment, the spacing adjusting mechanism includes a connecting bolt, a threaded end of which being passed through one of the upper plate body and the lower plate body and screwed on the other of the upper plate body and the lower plate body; and a support spring supported between the upper plate body and the lower plate body so that one of the upper plate body and the lower plate body abuts against a nut of the connecting bolt. In an embodiment, the spacing adjusting mechanism further includes a guide post which penetrates one of the upper plate body and the lower plate body and is fixedly connected with the other of the upper plate body and the lower plate body, and the support spring is sleeved on the guide post. Compared with the prior art, in the fixing clamp for a microfluidic chip provided by embodiments of the present disclosure, the first chip docking ports are located on the lower surfaces of the opposite ends of the two upper plate bodies, and the second chip docking ports are located on the upper surfaces of the opposite ends of the two lower plate bodies, so that when the microfluidic chip is manufactured, a plurality of connecting ports at the left end are distributed on the upper and lower surfaces at the left end, and a plurality of connecting ports at the right end are distributed on the upper and lower surfaces at the right end, and the connecting ports on the upper surface and the connecting ports on the lower surface are mutually unrestricted and can be arranged more compactly. Therefore, the area of the microfluidic chip can be reduced, and the experimental cost of the microfluidic chip is reduced. To sum up, in the fixing clamp for a microfluidic chip provided by embodiments of the present disclosure, the first chip docking ports are located on the lower surfaces of the opposite ends of the two upper plate bodies, and the second chip docking ports are located on the upper surfaces of the opposite ends of the two lower plate bodies, so that when the microfluidic chip is manufactured, a plurality of connecting ports on the left end thereof are distributed on the upper and lower surfaces at the left end, and a plurality of connecting ports on the right end are distributed on the upper and lower surfaces at the right end, and the connecting ports on the upper surface and the connecting ports on the lower surface are mutually unrestricted and can be arranged more compactly. Therefore, the area of the microfluidic chip can be reduced, and the experimental cost of the microfluidic chip is reduced. In the description of the application, the terms “install”, “communicate”, “connect” and “fix” and the like should be understood in a broad sense. For example, “connect” can be a fixed connection, a detachable connection or an integrated connection; and it may mean a direct connection or an indirect connection through an intermediate medium. For a person ordinary skill in the art, the specific meanings of the above terms in this application can be understood according to specific situations. In the description of this specification, the descriptions of the terms “one embodiment”, “some embodiments”, “specific embodiments” and the like mean that specific features, structures, materials or characteristics described in connection with the embodiment(s) or example(s) are included in at least one embodiment or example herein. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. Although the embodiments disclosed herein are as above, they are embodiments adopted only for the convenience of understanding the application, and are not intended to limit this application. Without departing from the spirit and scope disclosed herein, any person skilled in the art to which the application pertains can make any modifications and changes in the implementation forms and details, but the scope of patent protection herein shall still be subject to the scope defined by the appended claims.
16,871
11857978
DETAILED DESCRIPTION OF THE INVENTION Referring now to the figures of the drawings in detail and first, particularly toFIG.1thereof, there is shown schematically shows a fragmentation system1. The fragmentation system1has a housing2. The housing2is a metal housing. The housing2is constructed in the form of a silo. The housing2has an inlet3and a plurality of outlets4. Via the inlet3, which here is configured as a hole in the housing2, material5is introduced into the housing2. Fragmented material6is removed from the housing2via the outlets4. In each case different degrees of fragmentation of the fragmented material6are extracted via the plurality of outlets4. The fragmentation system1is connected to a material store7. The material store7is embodied as a bunker or as a silo. The material5can be stored in the material store7until fragmentation. The material5here is a coarse material, and contains blocks and stone-shaped elements. Here the material is concrete that is intended to be cleaned up and fragmented. The material store7is connected to the inlet3by means of a line in order to bring the material5from the material store into the housing2. A transport path8is provided in the housing2. The transport path8leads from the inlet3to the outlets4. The transport path8is embodied here in a rail-type fashion. The material5is transported along the transport path8in a transport direction9. The transport path8is embodied as a sequence of inclined planes sloping downward. In particular, the transport path8is embodied as a zigzag inclined plane sloping downward. The gradient of the transport path8and/or of sections of the transport path8is settable in a manner that is not illustrated. The slope angle of the transport path is preferably settable to be between 20 and 80 degrees relative to the horizontal. The conveying speed of the material along the transport path8is settable and/or variable by means of the setting of the slope angle of the transport path8. The transport path8has fractionation sections. In each case a first electrode10aand a second electrode10bare arranged in each of the fractionation sections; in this respect, see alsoFIGS.2and4. The electrodes10aand10bform a rail. In this case, the distance between the electrodes is less than a respective minimum diameter. The minimum diameters are different for the different fractionation sections, wherein the minimum diameter and/or the distance between the electrodes in the fractionation section decrease(s) over the course of the transport path8. The material5and/or fragments of the material can bear partly on the rails and/or the electrodes10aand10b. The material5and/or the fragments of the material can slide and/or be transported on the electrodes. The fragmentation system contains a plurality of high-voltage pulse sources11, wherein each of the high-voltage pulse sources11contains in each case one of the first electrodes10aand one of the second electrodes10b. The high-voltage pulse sources11are configured to generate a high-voltage discharge in a discharge chamber by means of the electrodes10aand10b. Material5which is situated on the transport path8and is situated between the electrodes10a,bor in the discharge chamber thereof is fragmented by means of the high-voltage pulse and/or the high-voltage discharge. The high-voltage discharge is effected, if material5is situated in the fractionation section, by the material5. A fragmentation of the material5corresponds to a comminution and especially a substance-specific comminution and/or cleaning up. The high-voltage pulse source11is configured to generate high-voltage discharges with a voltage of greater than 10 kilovolts. The fragmentation system1here contains six high-voltage pulse sources11and respectively six electrodes10aand10barranged at different locations along the transport path8. The high-voltage pulse sources11are operated with different operating parameters, in particular voltage, pulse length and/or power. The power and/or the voltage of the high-voltage pulse sources11decrease(s) over the course of the arrangement or in the transport direction9from inlet3to outlet4. This is owing to the fact, in particular, that a higher power is required for material5in the vicinity of the inlet3in order to fragment and/or separate the material, and lower operating parameters and powers are sufficient for material5and/or material fragments in the vicinity of the outlet4that have already been partly comminuted. In each case a sieving means12and a shaking belt13are arranged at the outlets4(here indicated symbolically at a distance from the latter). They serve to sort the fragments of the material, for example in such a way that small fragments are directly extracted and larger fragments are brought back into the housing2or remain in the housing2and undergo the further fragmentation. The fragmentation system1contains a conveying apparatus14. The conveying apparatus14contains a media tank15. A liquid medium16, here water, is arranged in the media tank15. The medium16is conveyed in a conveying direction by means of the conveying apparatus14. In this case, the medium16is fed for example in the region of the inlet3to the housing and/or to the transport path8and is collected at the outlet4. The collected medium16is filtered by means of a filter device and pumped back into the media tank15, such that the filtered medium16can be conveyed again. The conveying apparatus14, by means of conveying the medium16along the transport path8, serves to support the transport of the material5along the transport path8. By way of example, the transport speed of the material5along the transport path8is settable by means of a setting of the conveying rate of the medium16. The fragmented material6is collected and stored in a collecting container17. In particular, sieved fragmented material6is collected and stored in the collecting container17. The fragmented material6is a comminuted and preferably size- and/or type-purified and/or separated material5. FIG.2symbolically shows a segment of a transport path8, material5being transported in the transport direction9. The transport path8has a plurality of fractionation sections18. The transport path8and/or the fractionation sections18are/is embodied in a rail-type fashion, for example as top-hat rails. In each case a first electrode10aand a second electrode10bare arranged along the fractionation sections18. In this exemplary embodiment, the first electrode10aand the second electrode10bare arranged parallel to one another. The electrodes10aand10bdelimit the transport path8in terms of width. The electrodes10aand10beach have a longitudinal extent, wherein the longitudinal extent is in particular greater than 10 centimeters and is especially greater than 100 centimeters. The first electrode10apreferably forms a cathode, with the second electrode10bforming an anode. By means of the high-voltage pulse source11a high-voltage pulse19a,19band19cis able to generated as a high-voltage discharge (symbolized as an arrow). The electrodes10aand10bin the different fractionation sections18are operated in each case with different operating parameters of the high-voltage pulse source11. In this regard, the high-voltage pulse19ais a stronger pulse than the high-voltage pulse19b, with the high-voltage pulse19bbeing a stronger pulse than the high-voltage pulse19c. A stronger pulse means, in particular, that the voltage is greater and/or that the power is greater. While the material5before the beginning of the first fractionation section18has a first diameter, the partly fragmented material between the first fractionation section and the second fractionation section has a smaller diameter. Fragments which arise as a result of the first high-voltage pulse19a, and have a diameter smaller than the minimum diameter fall through spaces or gaps20between the rails and/or electrodes10aand10b(the selection means), such that they do not pass into the region of the second high-voltage pulse10b. The same applies analogously to fragments which arise as a result of the second high-voltage pulse19b. Fragmented material6having a diameter smaller than the minimum diameter is present after the last high-voltage pulse. FIG.3shows a further symbolic exemplary embodiment of a transport path8for material transport in the transport direction9. The transport path8is once again embodied in a rail-type fashion. The high-voltage pulse sources11once again have in each case a first electrode10aand a second electrode10b. In this exemplary embodiment, the electrodes10aand10bare arranged perpendicularly to the transport direction9. The electrodes10aand10bare embodied as rollers that are rotatable about their longitudinal axis. The roller-type electrodes10aand10bare configured for supporting the material transport. Between the electrodes10aand10b, in each case a high-voltage pulse19is able to be generated by means of the high-voltage pulse source11, wherein the high-voltage pulse19is directed in the same direction as the transport direction9. Between the electrodes10aand10b, material comminution is possible in each case by means of the high-voltage pulse19. FIG.4shows a further symbolic exemplary embodiment of a transport path8for material transport in the transport direction9. The high-voltage pulse sources11once again in each case have a first electrode10aand a second electrode10b. The electrodes10aand10bhere are arranged in the same direction as the transport direction9. However, the electrodes10aand10bof a high-voltage pulse source11are not arranged parallel to the transport path8, but rather form an angle with the transport direction9. The first electrode10aand the second electrode10bare each arranged in a v-shaped fashion. The distance between the first electrode10aand the second electrode10b, in particular in the constriction region, decreases in the course of the transport path8in the transport direction9. In this regard, the electrodes10aand10bcan form a transport retention at their constriction, such that in particular excessively large material fragments are retained. The high-voltage pulse19is perpendicular or angled with respect to the transport direction9in a manner similar toFIG.2. LIST OF REFERENCE SIGNS 1Fragmentation system2Housing3Feed4Outlet5Material6Material7Material store8Transport path9Transport direction10a,bElectrodes11High-voltage pulse sources12Sieving means13Shaking belt14Conveying apparatus15Media tank16Medium17Collecting container18Fractionation section19a-19cHigh-voltage pulse20Selection Means
10,587
11857979
DETAILED DESCRIPTION OF THE INVENTION Referring toFIGS.1to4, a highbanker10in accordance with the present invention comprises an upper hopper assembly12and a lower trough assembly14. The hopper assembly12is configured to accept placer deposit and water for feeding to the trough assembly14. The trough assembly14comprises first and second trough sections16,18that are removably detachable from each other. The first trough section16comprises a first surface20with first lateral edges22, while the second trough section18comprises a second surface24with second lateral edges26. Preferably, the first surface20and the second surface24are substantially co-planar with each other and generally define a substantially continuous surface on which one or more sluice mats27may be placed thereon. Alternatively, riffles may be formed on one or both of the first and second surfaces20,24so that the use of separate sluice mats27are not required. The sluice mats27separate heavier metals from the placer deposit and water as the placer deposit and water move along. The first trough section16comprises a pair of opposed first walls28a,28bextending from the first lateral edges22. The second trough section18comprises a pair of opposed second walls30a,30bextending from the second lateral edges26. Preferably, the first wall28aand the second wall30aare substantially continuous with each other, and the first wall28band the second wall30bare substantially continuous with each other. This acts to prevent material (e.g. placer deposit) from escaping between the first wall28aand the second wall30aand between the first wall28band the second wall30b. The highbanker10further comprises a plurality of legs32that are removably connected to the trough assembly14and are used to elevate the trough assembly14above the ground. In the embodiment shown inFIGS.1to4, four of the legs32are provided, with the legs32removably connected to the first trough section16. However, it is understood that a greater or fewer number of the legs32may be provided, and the legs32may be removably connected to one or both of the first and second trough sections16,18. Referring toFIGS.1and2, the legs32may be connected to first or second trough sections16,18using brackets34. For example, in the embodiment shown inFIGS.1to4, where the legs32are removably connected to the first trough section16, the first walls28a,28bcomprise attachment surfaces36that are configured to receive the legs32and the brackets34(best seen inFIG.5). The attachment surfaces36may be substantially planar and comprise one or more attachment surface openings38. The brackets34may comprise a central bracket portion40that is generally U-shaped, along with bracket flanges42extending from the central bracket portion40. The central bracket portion40is configured to engage with one of the legs32. The bracket flanges42comprise bracket openings44. The attachment surface openings38and the bracket openings44are configured to receive bracket fasteners46therethrough to secure one of the brackets34to one of the attachment surfaces36. In particular, when the bracket flanges42are secured to one of the attachment surfaces36, a portion of the leg32is held substantially flush against the attachment surface36. The central bracket portion40may comprise one or more central bracket openings48configured to accept leg fasteners50. The leg fasteners50may be screws that are threadedly engaged through the central bracket openings48and against the leg32in order to secure the leg32in place. The attachment surfaces36may be angled (with respect to a vertical plane) such that when the brackets34and the legs32are attached thereto, the legs32are splayed outwards. This acts to increase the stability and strength of the highbanker10when in use. Furthermore, depending on where along the legs32the brackets34engage, a height and an angle of the first trough section16(and consequently the first surface20) may be selected. In another embodiment, the bracket openings44may be elongated and forming an arc, such that the bracket34may be secured to the attachment surface36at different rotational angles. This also allows for the angle of the first trough section16to be differentially selected. As described earlier, the first surface20and the second surface24preferably define a substantially continuous surface. As such, if the first surface20is angled (i.e. with respect to the vertical or horizontal), the second surface24will be similarly angled. For example, when the highbanker10is in use, the first surface20(and consequently the second surface24) may be angled at an angle A with respect to the horizontal plane (as shown inFIG.3). This angling of the first surface20and the second surface24promotes the movement of placer deposit and water from the first trough section16to the second trough section18. The first trough section16comprises a first upper end52and a first lower end54. In the embodiment shown inFIGS.1to4, two of the legs32extend from the first trough section16proximate to the first upper end52, and two of the legs32extend from the first trough section16proximate to the first lower end54. Referring toFIGS.5to8, the hopper assembly12is pivotably connected to the trough assembly14, preferably proximate to the first upper end52. The highbanker10comprises a brace member56that extends between the trough assembly14and the hopper assembly12. The brace member56comprises a brace end58and two brace arms60extending from the brace end58. The brace end58is connected to the hopper assembly12, while the brace arms60are connected to the trough assembly14. The hopper assembly12comprises a hopper lower surface62. A series of ridges64is formed on the hopper lower surface62. The brace end58is configured to detachably engage with adjacent ones of the ridges64, as shown inFIGS.6and8. For example, the brace end58may be configured such that it is able to fit in between adjacent ones of the ridges64. By selecting the particular ones of the ridges64with which to engage the brace end58, a relative angle of the hopper assembly12with respect to the trough assembly14may be adjusted. For example,FIGS.5to8show two different possible angles (B, B′) for the hopper assembly12and the trough assembly14, depending on where along the ridges64the brace end58is engaged. Referring toFIGS.9to12, the second trough section18may be removably attached and detached from the first trough section16. The second trough section18comprises a second upper end66and a second lower end68. The second trough section18also comprises engagement portions70extending from each of the second walls30a,30bproximate to the second upper end66. The engagement portions70comprise outward-facing protrusions72. The second trough section18comprises a lip73extending from the second surface24. The lip73may be generally U-shaped, with the lip73extending along at least a portion of the second walls30a,30b. Because the lip73extends along a portion of the second walls30a,30b, a gap75is present between each of the engagement portions70and the lip73. Each of the first walls28a,28bcomprises a slot74proximate to the first lower end54. The slots74are configured to removably engage with the protrusions72when the second trough section18is connected to the first trough section16. Referring toFIGS.9and10, in order to connect the second trough section18to the first trough section, the second trough section18is first placed close to the first trough section16. The second trough section18may then be moved towards the first trough section16in direction C (as shown inFIG.10). The protrusions48will come into contact with a leading edge76on the first walls28a,28b. The protrusions72are preferably bevelled such that further movement of the second trough section18in the direction C will cause causing the engagement portions70to deflect inwards. Continual movement of the second trough section18in direction C will cause the protrusions72to slide along an inner surface78of the first walls28a,28b, with the engagement portions70still being deflected inwards. When the protrusions72reach the slots74, the protrusions72will engage into the slots74, and the engagement portions70will no longer be deflected inwards. The engagement of the protrusions72into the slots74secures the second trough section18in place with respect to the first trough section16(as shown inFIG.12). In addition, the lip73may engage the first surface20proximate to the first lower end54, thereby further helping to secure the second trough section18in place with respect to the first trough section16. In order to detach the second trough section18from the first trough section16, the engagement portions70are first pushed inwards in directions D (as shown inFIG.12). In order to facilitate this, the engagement portions70may comprise tabs80. The tabs80are sized such that they extend beyond the first walls28a,28bwhen the second trough section18is connected to the first trough section16. The tabs80provide a surface on which force may be applied to push the engagement portions70inwards. As the tabs80are pushed inwards, the protrusions72will begin to move out of the slots74. Once the protrusions72have cleared the slots74, the protrusions72may engage with the inner surface78of the first walls28a,28b. Movement of the second trough section18in direction E (as shown inFIG.12) will cause the protrusion72to move along the inner surface78(with the engagement portions70being deflected inwards) until the protrusions72reach the leading edge76. At that point, the engagement portions70will revert to their original orientation, and the second trough section18will be released from the first trough section16. Referring toFIG.10, the engagement portions70comprise a semicircular groove82configured to pivotably engage with the brace arms60. Furthermore, the first walls28a,28beach comprise a first wall opening84that is also configured to pivotably engage with the brace arms60. The first wall opening84is located proximate to the first lower end54, and preferably, in between the slot74and the first lower end54. The groove82and the first wall opening84are substantially aligned when the second trough section18is connected to the first trough section16. Each of the brace arms60comprises a wing86and a pin88extending from the wing86. When the second trough section18is connected to the first trough section16, the pin88is configured to engage with both the first wall opening84and the groove82, as shown inFIG.12. In particular, the pin88is preferably sized so that one portion fits within the first wall opening84while another portion rests on the groove82. For example, in one embodiment, the first wall opening84may have a diameter that is less than the diameter of the groove82. Accordingly, the pin88may comprise first and second pin portions90,92, with the first pin portion90having a smaller diameter than the second pin portion92. When the pin88is engaged with the first wall opening84and the groove82, the first pin portion90is sized to fit within the first wall opening84, while the second pin portion92is too large for the first wall opening84but is able to rest on the groove82. After the second trough section18has been connected to the first trough section16, the brace member56may be connected to the trough assembly14as follows. The brace arms60may be deflected inwards until the first pin portions90are able to be inserted through the first wall openings84on the first walls28a,28b. This will allow the brace arms60to partially revert back to their original orientation, until the first pin portions90have been fully inserted through the first wall openings84. However, the larger diameter of the second pin portion92will prevent the second pin portions92from passing through the first wall openings84. Instead, once the second pin portions92contact the first wall openings84, further outward movement of the brace arms60is prevented. The second pin portions92will rest on the grooves80of the second walls30a,30b. Because the brace arms60are still under some tension (from the previous inward deflection of the brace arms60), the brace arms60will tend to push outwards, resulting in the wings86exerting outward pressure on the second walls30a,30bproximate to the grooves80. This outward pressure by the brace arms60has the effect of securing the second trough section18in place to the first trough section16. The brace member56may be detached from the trough assembly14by deflecting the brace arms60inward so that the first pin portions90move through the first wall openings84. Once the first pin portions90have cleared the first wall openings84, the brace member56may be removed from the trough assembly14. Referring toFIGS.13and14, after the second trough section18has been detached from the first trough section16, the second trough section18may be nested within the first trough section16in order to reduce the overall length of the highbanker10for storage. To do so, the second trough section18may be rotated 180° laterally and placed within the first trough section16such that the second wall30aengages with the first wall28band the second wall30bengages with the first wall28a. In addition, the protrusion72on the engagement portion extending from the second wall30ais able to engage, at least partially, with the slot74on the first wall28b. Similarly, the protrusion72on the engagement portion extending from the second wall30bis able to engage, at least partially, with the slot74on the first wall28a. The engagement of the protrusions72, at least partially, with the slots74assist in securing the second trough section18within the first trough section16. The engagement of the protrusions72with the slots74may be effected by sliding the second trough section18down within the first trough section16in direction F (as shown inFIG.14). Furthermore, when the second trough section18has been nested within the first trough section16, the brace member56can be placed over the second trough section18. Referring toFIG.13, in one embodiment, after the brace member56has been placed on the second trough section18with the pins88proximate to the engagement portions70, the brace arms60may be deflected inwards until the pins88slide past the engagement portions70and into the gaps75. The brace arms60can be deflected inwards again until the first pin portions90are within the first wall openings84. The first pin portions90are then able to slide through the first wall openings84until the second pin portions92contact the first wall openings84, at which time further outward movement of the brace arms60is prevented. Because the brace arms60are still under some tension (from the previous inward deflection of the brace arms60), the brace arms60will tend to push outwards, resulting in the wings86exerting outward pressure on the second walls30a,30bproximate to the gaps75and on the engagement portions70and the lip73. This outward pressure by the brace arms60has the effect of securing the second trough section18in place within the first trough section16. For example, the brace arms60are normally splayed slightly outwardly (as best seen inFIG.4, an exploded view of the highbanker10). However, when the brace member56is attached to the first trough section16(using the first wall openings84), both when the second trough section18is connected to the first trough section16(as inFIG.11) and when the second trough section18is nested within the first trough section16(as inFIG.13), the brace arms60are substantially straight as they are still under some tension. Referring toFIGS.15to23, the hopper assembly12comprises a hopper96and a cover110that is removably attached to the hopper96. The hopper96comprises first and second hopper ends98,100and may be generally rectangular, although other shapes for the hopper96are also possible. The hopper96comprises an intake surface104located towards the first hopper end98and on which the placer deposit is loaded. The intake surface104is preferably elongated and may comprise a textured or contoured design. The hopper96further comprises a hopper periphery portion106that extends along a portion of the periphery of the hopper96. Preferably, the hopper periphery portion106may extend along a portion of the upper periphery of the hopper96. In one embodiment, the hopper periphery portion106extends for at least a length of the intake surface104, although it is also possible for the hopper periphery portion106to extend for greater or less than the length of the intake surface104. Referring toFIGS.15and16, the hopper periphery portion106may extend, at least partially, along three of the sides of the intake surface104. The hopper96further comprises a water intake108that is configured to attach to a water supply (such as a hose or the like) and to allow for the water to flow to the hopper periphery portion106. The water intake108is preferably located within the hopper periphery portion106proximate to the first hopper end98; however, it may be located at other locations along the hopper periphery portion106. The cover110is configured to fit over the hopper periphery portion106. The cover110comprises a cover surface112with a plurality of cover openings114formed on the cover surface112. The cover surface112preferably does not fit flush against the hopper periphery portion106; instead, the cover surface112and the hopper periphery portion106define, at least in part, a hollow116within which water from the water intake108can flow. Preferably, the hollow116extends for almost substantially an entirety of the hopper periphery portion106, although it may also extend for less than the entirety of the hopper periphery portion106. In order to define the hollow116, the cover surface112may be contoured such that at least a portion of the cover surface112does not contact the hopper periphery portion106when the cover110is fitted over the hopper periphery portion106(as seen inFIG.16). As water flows through the hollow116, water may escape from the hollow116through the cover openings114. The water escaping through the cover openings114may form streams of water that fall on the placer deposit on the intake surface104. In one embodiment, the cover110may comprise one or more cover standoffs118extending from the cover surface112. The cover standoffs118engage with corresponding hopper standoffs120extending from the hopper periphery portion106. The cover standoffs118and the hopper standoffs120may be configured to accept cover fasteners122for securing the cover110to the hopper periphery portion106. The cover standoffs118and the hopper standoffs120may also help to space the cover surface112apart from the hopper periphery portion106, thereby helping to define the hollow116. The hopper96comprises a window124located towards the second hopper end100. The window124is configured to allow the placer deposit and water to leave the hopper96through the window124and fall onto the first trough section16. When the highbanker10is in use, the hopper96may be angled (with respect to the horizontal) such that the first hopper end98is elevated with respect to the second hopper end100. As such, the placer deposit loaded onto the intake surface104, when contacted by the streams of water from the cover openings114, will tend to move along the intake surface104towards the window124. The textured or contoured design of the intake surface104may slow the movement of the placer deposit along the intake surface104, allowing more time to wash the placer deposit and to direct the placer deposit towards the hopper opening68. Referring toFIGS.20to23, the hopper assembly12may also comprise a screen126that is detachably placed over the window124. The screen126may comprise a plurality of screen openings128through which the placer deposit and water from the intake surface104may pass through into the first trough section16. Different ones of the screen126(each with different sizes for the screen openings128) may be interchanged to allow for different sizes and/or shapes of placer deposit to pass through the window124. Referring toFIG.21, the screen126may comprise one or more protruding fingers140that engage with corresponding sockets142on the hopper96to hold the screen126in place. Referring toFIGS.24to27, the hopper96is pivotably connected to the first trough section16. The hopper96comprises an elongated receiving portion130, while the first trough section16comprises opposed trough openings132. The hopper assembly12comprises a rod134that configured to pass across the receiving portion130and the trough openings132to allow for pivotable rotation of the hopper96with respect to the first trough section16from approximately 0° to approximately 90° (as shown inFIG.26). Referring toFIGS.25and27, the hopper96comprises one or more outward-extending tips136. The first trough section16may comprise one or more stops138that are configured to engage with the tips136when the hopper96has reached its maximum rotational angle with respect to the first trough section16. The engagement of the tips136with the stops138prevents excessive rotation of the hopper96with respect to the first trough section16, which could cause the hopper96to tip over. The rod134may be removably detached so as to separate the hopper assembly12from the trough assembly14. Referring toFIG.1, the hopper assembly12may further comprise a hopper fin144extending from the underside of the hopper96proximate to the window124. The hopper fin144comprises one or more notches146that are configured for attachment to a damper (not shown) for flattening or reducing the turbulence of the water (and placer deposit) exiting the window124. Referring toFIGS.28to31, the components of the highbanker10may be collapsed and nested from an assembled configuration (as shown, for example, inFIG.1) into a nested configuration shown inFIGS.28to31. The second trough section18may be nested within the first trough section16, as described above. In addition, the brace member56may be placed on top of the second trough section18, also as described above. The hopper assembly12may be pivoted towards the first trough section16until it is substantially resting on the first trough section16. The legs32may be detached from the first trough section16and stored within the (nested) second trough section18, as shown inFIG.28. In the nested configuration, the highbanker10is in a much more compact form for storage or transport. Assembly and disassembly of the highbanker10will now be described. In order to assemble the highbanker10into the assembled configuration shown inFIG.1, the legs32are attached to the first trough section16using the brackets34. The height and angle of the first surface20may be set by selecting where along the legs32the brackets34are used to secure the legs32to the attachment surfaces36. In addition, the angle of the first surface20may also be set by selecting the rotational angle of the brackets34. Once the legs32are secured to the first trough section16, the second trough section18may be connected to the first trough section16. The hopper assembly12may also be connected to the first trough section16by inserting the rod134through the hopper openings130and the trough openings132. The brace member56can then be attached to the trough assembly14by inserting the first pin portion90into the first wall openings84and by resting the second pin portion92on the grooves82. The angle of the hopper assembly12with respect to the trough assembly14can then be set by inserting the brace end58in between the appropriate adjacent ones of the ridges64. The highbanker10should be substantially in the configuration shown inFIG.1(i.e. the assembled configuration). An appropriate water supply can be connected to the water intake108. Sluice mats27, if needed, can then be placed on the first and second surfaces20,24. The highbanker10can now be used by introducing placer deposit onto the intake surface104. In order to disassemble the highbanker10from the assembled configuration shown inFIG.1to the nested configuration shown inFIG.28, the hopper assembly12may be lifted until the brace end58is no longer in between the ridges64. The brace arms60may be detached from the trough assembly14by deflecting the brace arms60inward until the first pin portions90have passed out of the first wall openings84. The second trough section18can then be detached from the first trough section16, rotated laterally 180°, and nested within the first trough section16. The brace member56can then be laid on top of the second trough section18and secured to the first trough section16. The hopper assembly12can be allowed to rest upon the nested second trough section18. The legs32may be removed from the first trough section16and placed within the second trough section18, resulting in the fully disassembled and nested configuration shown inFIG.28. Referring toFIGS.13and30, one or both of the first and second trough sections16,18may comprise ribs94. The ribs94may be formed on a side of one or both of the first surface20and the second surface24. For example,FIG.13shows the ribs94formed on an underside of the second surfaces24, whileFIG.30shows the ribs94formed on an underside of the first surface20. The ribs60provide additional strength and rigidity to the trough assembly14. One or more of the first and second trough sections16,18, the legs32, the brace member56, the hopper96, and the cover110may be formed from injection-moulded plastic. It will be appreciated by those skilled in the art that the preferred embodiment has been described in some detail but that certain modifications may be practiced without departing from the principles of the invention.
25,702
11857980
DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. EXAMPLES FIG.1shows an embodiment example of a magnetic separating section of the flocculation and magnetic separation device of the present invention. A magnetic drum1having magnets near the surface thereof and flocs4, containing a magnetic substance such as magnetite, on the flow8afrom the flocculation section, which is not shown in the figure, flow toward the drum1in the ascending direction opposite direction to the gravity direction99. A flow velocity distribution3ain a flow8ahas the highest flow velocity about or at the center and the slowest flow velocity on the wall of the flow channel. Therefore, the flocs collect in the portion of the flow where its velocity is high and its pressure is low in accordance with Bernoulli's equation. In order to prevent the fluid in front of the magnetic drum1from separating off from a bump-like protrusion5a, the direction of the flow is changed by about 180 degrees or so at the bump-like protrusion5ahaving a predetermined curvature. At that time, the flow in the vicinity of the bump-like protrusion5aflows along a curved wall6b, because the height of the bump-like protrusion5ais lower than the maximum height of a wall6athat forms one wall of the flow channel. The flock4rises and becomes a flock4acarried on a flow close to the surface of the liquid of the flow of the bump-like protrusion5a, and flows toward the magnetic drum1. Since the direction of rotation of the magnetic drum1is opposite to that of a fluid flow3b, fine eddies10are created, and the eddies10cancels out the velocity of the fluid, causing the floc4ato float on the surface of the water with almost zero velocity. The flocs4aon the surface of the water is attracted by the magnetic force of the magnet of the magnetic drum1, and move closer to the magnetic drum1, and sticks on the magnetic drum1by magnetic force. When the flocs4aon the water surface are attracted to the magnetic drum1by magnetic force and pulled up from the water surface, the forces acting on the flocs are surface tension and magnetic force. Since the surface tension is a weak force, the flocs4aare not broken. The magnetic drum1rotates in an opposite direction2to the flow direction of the flow3b, the flocs4bon the drum are, therefore, separated immediately from the fluid. Therefore, the area of the magnetic drum1required for the magnetic drum1to separate magnetically the flocs4ais small. Therefore, the magnetic drum1can be downsized because there is no need to take into account the travel time until the floc4adefies the fluid resistance and adheres to the magnetic drum1by magnetic force. The floc4bmoves with the rotation of the magnetic drum1and collides with a scraper9. Flocs4con the magnetic drum1are peeled off from the magnetic drum1by the scraper9pressed against the magnetic drum1, and a brush roller7rotating in a direction7bopposite to a rotating direction2. The scraper9is supported in slant from a higher position to a lower position. Therefore, flocs4dthat have moved from the magnetic drum1onto the scraper9move on the scraper9by gravity and are recovered in the free-falling as flocs4e. As shown with the flow3b, the treated water, from which flocs have been removed from the fluid, flow through the flow channel formed by the magnetic drum1and a wall6b, and then the direction of the flow is changed by 180 degrees or so at a bump-like protrusion5b. The treated water falls freely with a velocity distribution3cand is discharged as a flow8b. Further, the flocs4eare discharged as a flow8c. The flow velocity in the area between the bump-like protrusion5band the magnetic drum1is slow and close to zero. Therefore, even if flocs4that were not removed in the vicinity of the bump-like protrusion5aare present, they are attracted to the magnetic drum1in the vicinity of the bump-like protrusion5band are removed from the treated water. FIG.2shows an embodiment example of the separating section of a flocculation and magnetic separation device using a rotating drum11athat gives a flow velocity to the fluid and one magnetic drum11b. The non-magnetic rotating drum11arotates in a direction12asame as a flow18awhich includes flocs14and rotates at the rotation speed such that the peripheral speed thereof is at least equal to or higher than the average speed of a flow velocity. By forcibly increasing the flow velocity on the surface as in the Couette Flow, there is an effect that the portion of the flow having the highest flow velocity is brought closer to the vicinity of the rotating drum11a. The purpose of this is to increase the probability that the flocs will collect in a place where the flow velocity is high, that is, where the pressure is low, and that the flocs will be carried by a flow flowing to a magnetic drum12bthat is located at the subsequent stage and rotates in the opposite direction. From the flocculation area, which is not shown in the figure, the fluid including flocs flows toward the rotating drum11arotating in the direction18a, which is opposite to the direction of gravity99. As shown in a velocity distribution13ain the fluid, the velocity is fastest about in the center of the flow channel. The flocs14, therefore, collect in the center of the flow. The direction of the flow is changed by 180 degrees or so at a bump-like projection15ahaving a predetermined curvature. In a vicinity13bof the bump-like protrusion15a, the rotational force of the rotating drum11aincreases the speed of the flow. Therefore, the flow containing the flocs does not stay in the vicinity of the rotating drum11abut flows toward a wall16a. The high-velocity part of the flow13bin the flow channel formed by the rotating drum11aand the wall16ais closer to the rotating drum11athan when the drum11ais not rotating. This is attributable to the peripheral velocity of the rotating drum11a. Therefore, in a flow13din the vicinity of a bump-like protrusion15bwith curvature, the flow velocity is the highest at the part near the periphery. Flocs14ccollects in such a high flow velocity part and heads toward the magnetic drum11b. In the vicinity of the magnetic drum11b, there is a stagnant basin where the flow velocity is slowed down to almost zero by eddies20b. Due to this almost-zero velocity, flocs14bare attracted to the magnetic drum11arotating in the rotational direction12aand are moved then released from the magnetic drum11bby a slant-installed scraper19and a brush roller17awhich rotates in a rotational direction17bopposite to a rotational direction12b. The scraper19is supported in slant from a higher position to a lower position. Therefore, the flocs that have moved from the magnetic drum11bonto the scraper19move on the scraper19by gravity and are recovered by free-falling as flocs14e. The treated water from which the flocs have been removed flows around the magnetic drum11b, and the direction of flow is changed by about 180 degrees or so at a bump-like protrusion15cand is discharged by the gravity as a flow18bwith a velocity distribution13e. Flocs14eis also discharged as a flow18c. FIG.3shows an embodiment example of the present invention, which example is the magnetic separating section of the flocculation and magnetic separation device using two magnetic drums. The device of the present invention comprises a first magnetic drum21aand a second magnetic drum21barranged front and back each other. The first magnetic drum21arotates in a direction22aopposite to the direction of the flow that includes flocs and the second magnetic drum21brotates in a direction22bthe same as the flow that includes flocs. The flocculating section, though not shown in the figure, produces a flock-contained fluid by flocculating floating matters in a fluid together with magnetic substances such as magnetite. A flock-contained fluid flows out from the flocculation section, carried on a flow28a, of which flow direction is opposite to the gravity direction99, and heads toward the first magnetic drum21abeyond a bump-like protrusion25a. The flow28ahas the highest flow velocity about or at its center and the slow flow velocity in the vicinity of the wall26cof the flow channel. Therefore, the flocs collect in the portion of the flow where its velocity is high and its pressure is low according to Bernoulli's equation and the distribution of velocity forms as shown with a velocity distribution23a. In order to prevent the fluid from separating at a bump-like protrusion5aprovided at the front of the magnetic drum1, the direction of the flow is changed by about 180 degrees or so at that bump-like protrusion5ahaving a predetermined curvature. Like the velocity distribution23a, the velocity in the fluid is fastest in the center of the flow channel; the flocks24, therefore, collect in the center of the flow. At the time when the direction of the flow is changed largely by 180 degrees or so at the bump-like projection25ahaving a predetermined curvature, the flow velocity in the outer circumference reaches the fastest, therefore, the flocks24move to the flocs24acarried on a flow in the vicinity of the fluid surface, and the flocks24ahead the magnetic drum21a, carried on a flow flowing toward the magnetic drum21a. And further are attracted to the magnetic drum21aby the magnetic force of the magnet on the surface thereof. Flocs24b, which are attracted to the surface of the magnetic drum21aby magnetic force, attach on the magnetic drum21arotating in the rotation direction22a. Flocs24b, which are attracted to the surface of the magnetic drum21aby magnetic force, attach on the magnetic drum21arotating in the rotation direction22a. Then the flocs24bso attached to the magnetic drum21aare separated therefrom by a scraper29a, which is pressure-contacted to the magnetic drum21a, and by a brush27a. Being separated, the flocs24cmove on the scraper29aand recovered into a floc recovering section30. Since the direction of rotation of the magnetic drum21aand the fluid flowing in the flow channel between the magnetic drum21aand a curved wall26aof the flow channel are opposite in velocity direction, eddies are generated in the fluid. The eddies cause the flocs to adhere to the magnetic drum. In this instance, however, the rotation speed of the magnetic drum21aneeds to be low enough that the eddies do not break the flocs, and the rotation speed is controlled considering the flocculation state. The flow direction of the fluid is greatly changed by a bump-like protrusion25b, resulting in the movement of flogs toward the magnetic drum21b, and the magnetic force causes the flocs24dto attach to the magnetic drum21b. Since the flow direction of the fluid and the rotation direction of the magnetic drum21bis the same, there imposed no shearing or other force from the fluid, therefore the floc24don the surface of the magnetic drum21bwill not be separated by the fluid. The magnetic drum21brotates in the direction of rotation22b, and the floc24don the magnetic drum21bis scraped off by a scraper29bwhich is in pressure-contact and by a brush27b. The scraped flocs are then collected in the floc collection section30, as shown with the flocs24c. In the present invention, the floc collection section30can be integrated into one, so that the cost can be reduced. Instead of using the magnetic drum21b, a filter separation method, as shown inFIG.8, may be used. In the filter separation method, the same effect can be achieved by using a filter mesh of 47 microns or less so as to meet the removal standards for ballast water purification systems. FIG.4shows an embodiment example of the floc recovery section in the flocculation and magnetic separation device of the present invention. A recovery section34consists mainly of a magnetic drum31, a scraper37pressed against thereto, and a brush roller36used to peel off the flocs attracted by magnetic force on the surface of a magnetic drum31. The flocs moved from the magnetic drum31by the brush roller36onto the scraper37are moved further by gravity and collected in the floc recovery section34. Since the floc recovery section34is arranged in slant, the flocs move by gravity and are discharged from the end of the floc recovery section34. The floc recovery section34has a semi-cylindrical shape to collect the flocs, but a concave or inverted triangular cross-section is also acceptable. FIG.5shows an example of the embodiment configuration of the flocculation and magnetic separation device. In this configuration, a fluid59flows into a flocculation and magnetic separation device55, and the appropriate amount of flocculant from a flocculant storage tank40and the appropriate amount of magnetite from a magnetite solution storage tank41are fed into the device, which is then agitated by a stirrer43in a quick stirrer unit42to produce micro-flocs. Inorganic flocculant and magnetite can be fed in any order and may be fed at the same time. Then, an organic flocculant46such as a polymer is added and agitated by a stirrer45in a slow-speed stirrer44to produce flocs in a size of several hundred microns to several millimeters. The flocs enter the separating section, and the fluid including flocs, of which speed has been increased by the rotational force of a non-magnetic rotating drum49, head to a magnetic drum50. The floc attaching to the surface of the magnetic drum is scraped from the surface thereof by a scraper52and a brush roller51that are in press-contact with the surface of the magnetic drum. Plankton and micro-flocs in the fluid59are flocculated and become flocs, which are removed from the fluid by the magnetic drum50described above. A separation section may be the separation section shown in above-statedFIG.3. FIG.6shows an example of the slitting mechanism for breaking plastics floating in the ocean. When plastics drifting in the sea is taken in by a ballast pump together with ballast water, seawater63is sucked also into a pipe60by the ballast pump, which is not shown in the figure. A first slit section61is arranged at a predetermined angle611with respect to the fluid to be sucked. A second slit section62is arranged at the rear stage of the first slit section61at a predetermined angle622, which is different from the angle611, with respect to the fluid to be sucked. The reason that the angle611is an acute angle and the complementary angle of the angle622is an obtuse angle in relation to the sucking direction of seawater63is to prevent clogging between the slit61and the slit62caused by drifting plastics. The slits are placed at a predetermined angle with respect to the inflow direction so that the shearing force can work. FIG.7shows an embodiment example of the slit section of a slitting mechanism that breaks plastics floating in the ocean. A slit section61of a pipe60comprises plates61a,61b, and61ceach for forming slits thereon, as shown inFIG.6. A slit section62shown inFIG.6comprises plates62a,62b, and62ceach for forming slits thereon. The cross-section of the plates61a,61b,61c,62a,62b, and62care acute angles61xand65xwith respect to the inflow direction. The reason for being the acute angle is to break the inflowing plastic. The plates61a,61b,61c,62a,62b,62care arranged at equal intervals of65a.65b,65c, and65d. However, considering that the flow rate of the middle part is the maximum, spacings wider than the intervals65band65ccan be given to the plates65aand65d. With this, the effect for reducing the probability that the plastic waste may clog the slits will be produced. FIG.8shows an embodiment example of the broken plastic recovery mechanism of the present invention. A fluid73such as seawater that includes a plastic77broken by the slit mechanism mentioned before flows in through a pipe72. An endless belt filter70, consisting of a filter of predetermined mesh size, rotates continuously between the rollers71aand71b, and the fluid73containing the broken plastics77passes between the rollers71aand71b. While passing, the endless belt filter70holds and conveys the broken plastics77, which is then separated by a scraper75press-contacted on the endless belt filter70, and the separated broken plastics77are put in a floe recovery tank76. Further, the fluid73from which the broken plastics77has been removed flows into a pipe74. The fluid73contains fine floating matter such as microplastics and plankton. The fluid73is sent to the flocculation and magnetic separation device55described above and undergoes flocculation and magnetic separation to become the fluid59. In some cases, this recovery mechanism is installed at the rear stage of the magnetic separation mechanism to filter the objects that cannot be magnetically separated. FIG.9shows an embodiment example of the marine plastic, microplastic, and ballast water purification system of the present invention. The marine plastic, microplastic, and ballast water purification system100is a system that is equipped on a ship. The system comprises:a slitting mechanism101for breaking plastics,a pump102for supplying and draining seawater or freshwater,a recovering mechanism103for recovering large floating matters of tens of mm or more such as broken plastics,a recovery tank104for temporarily storing the recovered floating matters,a flocculation and magnetic separation mechanism105for recovering small floating matters of less than tens of mm, such as microplastics and plankton,a recovery tank106for temporally storing removed flocs that include microplastics or the like, anda control mechanism108. The flocculation and magnetic separation device105can be a composite mechanism that is a combination of a filter such as a ceramic filter and ozone or ultraviolet light. The treated water is temporarily stored in a ballast tank107. FIG.10shows an embodiment example of the operation method of the marine plastics, microplastics, and ballast water purification system. A course plan information center210is configured with:a means for acquiring marine traffic information202,a means for collecting marine plastic information203,a means for collecting geographic information204,a means for creating planned course295.a means for receiving planned course request201, anda means for providing planned course206. The means for acquiring marine traffic information202gathers the information of the automatic vessel identification system and other similar information collected from the base stations not illustrated in the figure. The means for collecting marine plastic information203collects information on the pollution caused by marine plastics in the sea area of which state is gathered by a satellite200. The means for acquiring geographic information202acquires the location of own ship, the port of destination, and the geographic information on the sea area between these two places included in the planned course request signal. A means for creating planned course205produces a planned course based on the information collected by the means for acquiring regional traffic information202mentioned above, the means for collecting marine plastics and other marine pollution information203, and the means for collecting geographic information204. When creating this planned course, the plan will take into account whether the ballast water is loaded, how much are the quantity of loaded ballast water when loaded, whether the removal work of ocean plastics and other marine pollution matters can be performed, and the urgency of the ocean plastics removal work. A ship220is equipped with a means for transmitting the planned course request221, a means for receiving the planned course222, and a steering means223that operates reflecting the received results. The results of the removal work for marine plastics and other marine pollution matters (removed marine area, amount of removed marine plastics, and other marine pollution matters) are transmitted to the course plan information center210. The course plan information center transmits this information to the International Maritime Organization (IMO) and other public organizations, and environmental protection groups. International organizations, such as the International Maritime Organization, and environmental protection groups will make this information available to the public and formulate strategies against marine pollution. As a result, if further removal of pollution is necessary, cooperation will be asked ships that are scheduled to sail near the area in question for taking measures against marine pollution. The collected marine plastics and other marine pollutants will be purchased by the government or municipality of the port of call as industrial waste. This means that the ships equipped with marine plastics, microplastics, and ballast water purification systems will take the charge of cleaning the ocean in addition to transporting oil and other valuable materials. FIG.11shows an embodiment example of the magnetic separating section of the flocculation and magnetic separation device of the present invention. A magnetic drum301having magnets near the surface thereof, and flocs304on a flow308afrom a flocculation section, which is not shown in the figure, containing magnetite and other magnetic substances flow in the direction opposite to the direction of gravity99toward the magnetic drum301. The velocity distribution303ain the flow308ahas the highest velocity almost at the middle and the low velocity at the wall of the flow channel. Therefore, the flocs gather in the center of the flow where the velocity is faster according to Bernoulli's law (Bernoulli's equation). In order to move the flocs304flowing in the middle of the fluid in the immediate front of the magnetic drum301to the fluid surface, the direction of flow is changed by about 180 degrees or so at a bump-like projection305ahaving a predetermined curvature, and the fluid flows along a concave305ahaving a predetermined curvature placed at the subsequent stage. This concave305band a bump-like protrusion305cconfigure a waterfall-basin-like structure, which produces eddies310a. Since the particle size of a floc304bis larger compared to that of a fluid molecule, this size difference produces fluid resistance, which causes the eddies310a. The eddies310amake the flocs304bfloat on the fluid surface. The flocs flow towards the magnetic drum301. Since the direction of rotation of the magnetic drum301is opposite to that of a fluid flow303b, this direction difference creates eddies310b, and the velocity of the fluid in the eddies310bcancels each other, resulting in a lower velocity of flocs4a. Flocs304aon the flow of low-velocity approach a magnetic drum1by the magnetic force and attracted thereon. Since the resistance acting on the flocs304ais mainly surface tension, the flocs304aare not easily broken. The magnetic drum301rotates in a direction302opposite to the flow303b, so that the floc304bon the drum is immediately separated from the water. Therefore, the contact area of the magnetic drum301required for separating magnetically the flocs304acan be reduced to an extent several mm above and below the fluid surface. The reason for this is that when the flocs304are attracted to the magnetic drum301, a new surface with no flocs attracted appears since the magnetic drum301is rotating. Therefore, the actual contact area on a magnetic drum301required for attracting flocs thereto by the magnetic force of the magnetic drum301is small. The magnetic drum1is not damaged by the fluid resistance. Furthermore, it is not necessary to consider the travel time of the flocks to adhere, by the magnetic force, to the magnetic drum1against the fluid resistance, as described in {Patent Literature 1}. Therefore, the magnetic drum301can be miniaturized. Flocs304con the magnetic drum301is separated therefrom by a scraper309pressed against the magnetic drum301and the brush roller307rotating in a rotation direction307aopposite to the rotation direction302, and the flocs304bmove onto the scraper309. The flocs304bare recovered by free fall due to gravity like flocs304d. Further, the treated water from which the flocs have been removed flows along the magnetic drum301as shown in the flow303b, and the direction of the flow is changed by about 180 degrees or so at the bump-like protrusion305c. The treated water flows with a flow velocity distribution303cand is discharged as a flow Sb. Further, the flocs4care discharged as a flow308c. INDUSTRIAL APPLICABILITY The International Maritime Organization (IMO) established the Convention for the Control and Management of Ships' Ballast Water and Sediments (hereinafter referred to as the Convention) in order to prevent the destruction of ecosystems caused by seawater substitution by ships' ballast water which includes species that did not originally exist in the sea area. However, the problem of ocean pollution by plastics and microplastics has arisen. The mainstream of ballast water treatment method is a sterilization method using ultraviolet rays, ozone, hypochlorous acid, or the like. This method can kill aquatic organisms in ballast water. However, the problem of marine pollution caused by the above-stated plastics and microplastics cannot be solved. Even a ship that collects marine plastics is built, it is still difficult to recover microplastics, though such a ship can recover large plastics. The present invention provides a method for simultaneous solving the problem of ecosystem destruction caused by ballast water and the problem of marine pollution caused by plastics and microplastics. {Reference Signs List}1, 11b, 22a, 22b,Magnetic drum31, 50, 3012, 12a, 12b, 22a,Direction of rotation22b, 78, 3023a, 3c, 13a, 13b,Flow velocity distribution23a, 23b, 303a, 303b3bDirection of flow4, 14, 304Flocs4a, 14a, 14c,Flocs flowing toward magnetic drum24a, 304a4b, 14d, 24b,Flocs attracted on magnetic drum24d, 304c4c, 14e, 14f, 24cRecovered flocs5a, 5b, 15a, 15b,Bump-like protrusion15c, 25a, 25b, 25c6a, 6b, 16a, 16bWall surface7, 17a, 17d, 27a,Brush roller27b, 51, 3077a, 17b, 17cBrash roller rotation direction7a, 17b, 17cFlow direction of fluid including flocs8b, 18b, 28bFlow direction of treated fluid8c, 18c, 18dFlow direction of recovered flocs9, 19a, 19b, 29a,Scraper29b, 37, 5211a, 49Rotating drum34Flocs recovery section40Flocculant storage tank41Magnetite storage tank42Slow stirring device44Quick stirrer43, 44Stirrer46Polymer storage tank59, 63, 73Fluid60, 72, 74Pipe61, 61a, 61b, 61c,Plate for forming slit62, 62a, 62b, 62c61x, 65xCross section of plate65a, 65b, 65c, 65dPlate spacing70Endless belt filter71a, 71bRoller76Flocs recovery tank100Marine plastics, microplastics and ballast waterpurification systems101Filtering mechanism102Pump103Recovering mechanism104, 106Recovery tank105Flocculation and magnetic separationmechanism107Ballast tank108Control console200Satellite210Course plan information center201Means for receiving planned course request202Means for collecting marine traffic information203Means for collecting information on marinepollution such as marine plastics204Means for collecting geographical information205Means for creating planned course206Means for providing planned course210Ships221Means for transmitting planned course request222Means for receiving planned course223Steering means305aConcave
27,368
11857981
DETAILED DESCRIPTION The invention can be implemented in numerous ways, including as a process; an apparatus; a system; a composition of matter; a computer program product embodied on a computer readable storage medium; and/or a processor, such as a processor configured to execute instructions stored on and/or provided by a memory coupled to the processor. In this specification, these implementations, or any other form that the invention may take, may be referred to as techniques. In general, the order of the steps of disclosed processes may be altered within the scope of the invention. Unless stated otherwise, a component such as a processor or a memory described as being configured to perform a task may be implemented as a general component that is temporarily configured to perform the task at a given time or a specific component that is manufactured to perform the task. As used herein, the term ‘processor’ refers to one or more devices, circuits, and/or processing cores configured to process data, such as computer program instructions. A detailed description of one or more embodiments of the invention is provided below along with accompanying figures that illustrate the principles of the invention. The invention is described in connection with such embodiments, but the invention is not limited to any embodiment. The scope of the invention is limited only by the claims and the invention encompasses numerous alternatives, modifications and equivalents. Numerous specific details are set forth in the following description in order to provide a thorough understanding of the invention. These details are provided for the purpose of example and the invention may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the invention has not been described in detail so that the invention is not unnecessarily obscured. Preparing consistent single cell gene expression libraries is labor intensive and requires extensive hands-on (i.e., manual) time. It would be beneficial if this could be automated, freeing lab personnel to perform other tasks. Automated techniques for the preparation of single cell gene expression libraries are disclosed in the present application. The techniques provided herein allow for the maximization of consistency in the libraries prepared and productivity of the personnel. The techniques improve quality and performance by 1) decreasing technical variability and generating reproducible results; 2) running pre-validated protocols for single cell assays; and 3) providing a robust workflow and ready-to-use solution. The techniques save time and resources by 1) reducing hands-on time in the lab; 2) eliminating the need for dedicated resources; and 3) requiring no specialized expertise. The techniques are integrated and validated. Single cell partitioning, barcoding, and library preparation are integrated together in one optimized instrument. As a result, less customization and optimization are needed, thereby improving productivity. FIG.1illustrates a front view of one embodiment of an automated single cell sequencing system100. The system includes an automated controller102on deck for single cell partitioning and barcoding. Reagents and consumables may be loaded onto the deck area104at the beginning of each run. Operations may be guided through an easy-to-use touchscreen computer106with Internet connectivity. System100includes a liquid handling gantry108that may perform pipetting steps throughout the entire single cell workflow. System100further includes one or more barcode scanners that enable lot and reagent tracking for reagents and consumables. FIG.2illustrates another view of one embodiment of an automated single cell sequencing system200. Automated single cell sequencing system200includes five carriers (202,204,206,208, and210) on the deck201. Some of the carriers are stationary and some of the carriers may slide in and out for loading and unloading items. Each of the carriers may be loaded with different types of labwares, modules, and consumables, such as a magnetic separator plate, a thermal cycler block, tips, reagent reservoirs, plates (e.g., polymerase chain reaction (PCR) plates and deep well plates), tubes, and the like. The terms labwares and modules may be used interchangeably in the present application. FIG.3illustrates yet another view of one embodiment of an automated single cell sequencing system300. Automated single cell sequencing system300includes five carriers (302,304,306,308, and310) and a disposal bin336on a deck301. As shown inFIG.2, an automated controller212for single cell partitioning and barcoding is located adjacent to the left most carrier202. The leftmost carrier202includes a magnetic separator plate214. An array of magnets218is located above magnetic separator plate214. Arrays of wells, tips or tubes may be placed above the array of magnets218. In some embodiments, a magnetic separator plate adapter217may be mounted on top of the magnetic separator plate214to keep the array of tips/tubes stable and sitting at the exact locations. The magnetic separator plate adapter217may rest above the magnetic separator plate214and the array of magnets218. The magnetic separator plate adapter217may be formed of plastic and include skirts. Magnetic separator plate adapter217may include a plurality of calibration posts216. Carrier202may further receive a cold plate reagent module220and other reagent modules222. In some embodiments, automated single cell sequencing system200may include a barcode reading system. A barcode reader is used to scan reagents and consumables. The barcode reading system enables experiment tracking and prevents reagent mix-ups. A barcode reader (not shown inFIG.2) may be placed above the five carriers (202,204,206,208, and210) on deck201. The barcode reader may be used to read the slots for holding the tips/tubes and the tips/tubes that go into the slots at different locations. The barcode reading system may include software logic to make sure that the right tubes (with reagents) are put at the right slots. The barcode reading system may also detect that the tubes are missing such that the system may inform the user about these errors. The system may check for color matching, lot numbers, and expiration dates. As shown inFIG.2, automated single cell sequencing system200may include a plurality of mirrors223to allow the barcode reader to read sideways and at more locations. In some embodiments, stickers with barcodes on the slots are covered by the tips/tubes if they are placed there. If the barcode reader reads the barcodes on the slots, then the slots are determined as being empty. If the barcode reader reads the barcodes on the tips/tubes, then the system may match the two barcodes. Carrier204(the second carrier from the left) includes an on-deck thermal cycler224(ODTC). A thermal cycler may be used to amplify segments of Deoxyribonucleic acid (DNA) via the polymerase chain reaction (PCR). Thermal cyclers may also be used to facilitate other temperature-sensitive reactions. In some embodiments, a thermal cycler has a thermal block with holes where tubes holding reaction mixtures may be inserted. The thermal cycler then raises and lowers the temperature of the block in discrete, pre-programmed steps. Carrier204further includes a rack226for storing disposable ODTC lids. Carrier206(the third carrier from the left) includes carrier spaces for receiving, storing, or loading tube strips, chips, gel beads, core or lifting paddles, ethanol reservoirs, primer, glycerol, and the like. Carrier208(the fourth carrier from the left) includes a sample index plate holder230. The carrier further includes a unit232for formulations and bead cleanups. Carrier208and carrier210(the fifth carrier from the left) may receive different consumables, such as pipette tips234. Automated single cell sequencing system200may further include a waste disposal bin236that is adjacent to carrier210. In some embodiments, a divider may be added to the waste disposal bin for separating the recycled tips and lids. With the added divider, one side of the disposal bin is used for storing the tips and the other side of the disposal bin is used for storing the lids. A gantry238may be programmed to drop the tips and the lids on different sides of the disposal bin. This prevents the lids from stacking up and toppling over, causing the system to malfunction. This allows the recycling of the lids while preventing contamination. The liquid handling gantry238in automated single cell sequencing system200may perform automated pipetting steps throughout the entire single cell workflow. Liquid handling gantry238is a movable liquid-handling pipetting device with precision positioning. A traditional manual pipette is a laboratory tool commonly used in chemistry, biology and medicine to transport a measured volume of liquid. A pipette can be used to aspire (or draw up) a liquid into a pipette tip and dispense the liquid. In manual pipetting, a piston is moved by a thumb using an operation knob. Accuracy and precision of pipetting depend on the expertise of the human operator. Automated pipetting has many advantages over manual pipetting. Automated pipetting enhances the throughput and the reproducibility of laboratory experiments. Automated pipetting takes the manual labor out of repeated pipetting, thereby shortening manual hands-on time. Reducing manual hands-on time frees up time and effort for other tasks, thereby greatly improving throughput. Furthermore, automated pipetting significantly reduces errors from manual pipetting, thereby enhancing reproducibility. The liquid handling gantry238in automated single cell sequencing system200includes a pipetting head, which is the mechanical component for liquid transfer. In some embodiments, the pipetting head is a multi-channel pipetting head for increased throughput. In some embodiments, the pipetting head may be an 8-channel pipetting head coupled to a pump system such that for each channel, a volume of liquid may be aspirated from a source container by creating suction and then dispensed into a destination container (e.g., a tube or a well). A disposable tip may be attached to each of the eight channels of the pipetting head, such that the liquid is not in direct contact with the pipetting head, preventing cross contamination. The liquid handling gantry238with the pipetting head may be programmed to move within a working area where liquid aspirating and dispensing take place. The working area may be the deck area201including the five carriers (202,204,206,208, and210) that may be loaded with different types of labwares, modules, or consumables, such as reagent reservoirs, plates (e.g., polymerase chain reaction (PCR) plates and deep well plates), tubes, and the like. For example, the pipetting head may be moved to the position of the reagent module240to dispense liquid into a row242of eight wells of the reagent module240. The position of the reagent module240and the position of the row of wells may each be specified by a set of offset distances in the x, y, and z axes from one or more reference points within deck area201. In some embodiments, the position of a certain module or labware may be recorded by single cell sequencing system200as a first set of offset values (in x, y, and z) from a reference point within deck area201, and the position of a row of wells within the module or labware may further be recorded by the system as another set of offset values from the position of the module or labware. In some embodiments, different positions within the working area are recorded by single cell sequencing system200as different sets of offset values from a single reference point within deck area201. In order to place the pipetting head into the appropriate source and destination containers, the liquid handling gantry238with the pipetting head may be moved by one or more actuators to different x and y positions in a plane substantially parallel to the floor of deck201. In addition, the pipetting head may be moved by one or more actuators in a direction substantially perpendicular to the plane, such that the pipetting head and the tips attached to the pipetting head may be inserted into or withdrawn from the source and destination containers. Magnetic separator plate214inFIG.2performs magnetic bead based cleanup. Magnetic beads are used for DNA purification and fragment size selection. Automated single cell sequencing system200uses the single-cell RNA-seq technology to analyze transcriptomes on a cell-by-cell basis through the use of microfluidic partitioning to capture single cells and prepare barcoded, next-generation sequencing (NGS) cDNA libraries. Specifically, single cells, reverse transcription (RT) reagents, gel beads containing barcoded oligonucleotides, and oil are combined on a microfluidic chip to form reaction vesicles called Gel Beads in Emulsion, or GEMs. After incubation, GEMs are broken and pooled fractions are recovered. Silane magnetic beads are used to purify the first-strand cDNA from the post GEM-RT reaction mixture, which includes leftover biochemical reagents and primers. In particular, consumables (e.g., test tubes or wells) containing the post GEM-RT reaction mixture and the magnetic beads may be loaded onto the magnetic separator plate214where the magnetic bead based cleanup is performed. Barcoded, full-length cDNA is then amplified via PCR to generate sufficient mass for library construction. FIG.4Aillustrates a top view of an embodiment of a magnetic separator plate402.FIG.4Billustrates a cross sectional view of the magnetic separator plate402.FIG.4Cillustrates another view of the magnetic separator plate402. As shown inFIG.4A, magnetic separator plate402is a magnet holder plate that holds an array of magnets404. Magnetic separator plate402is a 96-ring magnet plate, and the array of magnets404is an 8×12 array of magnets with eight magnets in a row and twelve magnets in a column. In some embodiments, each of the magnets404is a ring magnet. As shown inFIG.4B, a ring magnet may be a magnet with a shape of a hollow cylinder that is empty from inside and with differing internal and external radii. The hollow space of the cylinder allows a bottom end of a tube to be inserted therein. For example, a tube received by a ring magnet may be a finger-like length of glass or plastic tubing that is open at the top and closed at the bottom. FIG.5illustrates a plurality of strip tubes502that may be loaded onto the magnetic separator plate214or magnetic separator plate402where the magnetic bead based cleanup may be performed. As shown inFIG.5, each of the strip tubes502includes eight tubes504for storing the reaction mixture and the magnetic beads. FIG.6illustrates an exemplary consumable602that may be loaded onto the magnetic separator plate214or magnetic separator plate402where the magnetic bead based cleanup may be performed. In this example, consumable602is a 96-tube polymerase chain reaction (PCR) tube holder plate with an array of tubes604arranged as an 8×12 array of tubes with eight tubes in a row and twelve tubes in a column. FIG.7Aillustrates a top view of the 96-tube PCR plate602being loaded onto the magnetic separator plate402.FIG.7Billustrates a cross sectional view of the 96-tube PCR plate602being loaded onto the magnetic separator plate402.FIG.4Cillustrates a portion of a magnified cross-sectional view of the 96-tube PCR plate602being loaded onto the magnetic separator plate402. As shown inFIGS.7B and7C, the hollow space of a ring magnet (e.g.,404A or404B) allows the bottom end of a tube (e.g.,604A or604B) to be inserted therein. However, both the PCR plate602and the magnetic separator plate402are manufactured parts that have their respective sets of associated tolerances. All dimensions of a manufactured part have their associated tolerance, the amount that the particular dimension is allowed to vary. The tolerance is the difference between the maximum and minimum limits. Therefore, the length606A (the length from the center of the ring magnet404A to the center of the ring magnet404B) and the length606B (the length from the center of the ring magnet404B to the center of the ring magnet404C) may not be the same. Similarly, the length608A (the length from the center of the tube604A to the center of the tube604B) and the length608B (the length from the center of the tube608B to the center of the tube604C) may not be the same. These variations in dimensions may cause misalignments of the tubes and their corresponding ring magnets. As a result, some of the bottom ends of the tubes may no longer be inserted into the hollow spaces and resting within the hollow spaces of the ring magnets at the same depth, causing the PCR plate602to be tilted instead of leveled, and causing it to rest on the magnetic separator plate402at an angle, thereby degrading the performance of the magnetic bead based cleanup process. In the present application, an improved magnetic separator is disclosed. The magnetic separator comprises an array of magnets configured to interact with an array of tubes, wherein the array of tubes is attached to a plate. The magnetic separator further includes a magnetic separator plate adapter. In some embodiments, the adapter comprises a raised frame extending around a periphery of the array of magnets such that the raised frame is configured to support the plate, such that the array of tubes are suspended above the array of magnets. By suspending the array of tubes above the array of magnets, the bottom ends of the tubes are no longer resting within the hollow spaces of the ring magnets at different depths, thereby keeping the plate with the array of tubes leveled with respect to the array of magnets. The benefit is that the performance of the magnetic bead based cleanup process may be significantly improved. FIG.8Aillustrates a top view of a magnetic separator plate adapter802.FIG.8Billustrates a cross sectional view of the magnetic separator plate adapter802.FIG.8Cillustrates a bottom view of the magnetic separator plate adapter802.FIG.8Dillustrates another view of the top surface of the magnetic separator plate adapter802.FIG.8Eillustrates another view of the bottom surface of the magnetic separator plate adapter802. As shown inFIG.8A, magnetic separator plate adapter802includes four collars804at the four corners of the adapter. The collars804may be used to fix the location (the x and y location on the deck) of a consumable, such as a 96-tube PCR plate. For example, each of the collars804constrains the x location and the y location of the tube holder plate by having a tube inserted into the collar. The magnetic separator plate adapter802further includes four cylindrical feet806at the four corners of the adapter, such that the magnetic separator plate adapter802may be mounted on the magnetic separator plate402. In some embodiments, magnetic separator plate adapter802may be formed of plastic and includes skirts. Magnetic separator plate adapter802may include a plurality of calibration posts808. FIG.9Aillustrates a top view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402.FIG.9Billustrates a cross sectional view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402.FIG.9Cillustrates another cross sectional view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402.FIG.9Dillustrates a portion of a magnified cross sectional view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402. As shown inFIGS.9B,9C, and9D, a cylindrical foot806of the magnetic separator plate adapter802fits into a cylindrical hole on the magnetic separator plate402, thereby mounting the magnetic separator plate adapter802on the magnetic separator plate402and raising the magnetic separator plate adapter802above the magnetic separator plate402. FIG.10Aillustrates a view of the magnetic separator plate adapter802about to be loaded onto the magnetic separator plate402and the 96-tube PCR plate602about to be loaded onto the magnetic separator plate adapter802.FIG.10Billustrates another view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402and the 96-tube PCR plate602being loaded onto the magnetic separator plate adapter802. FIG.11Aillustrates a top view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402, and the 96-tube PCR plate602being loaded onto the magnetic separator plate adapter802.FIG.11Billustrates a cross-sectional view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402, and the 96-tube PCR plate602being loaded onto the magnetic separator plate adapter802.FIG.11Cillustrates another cross-sectional view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402, and the 96-tube PCR plate602being loaded onto the magnetic separator plate adapter802.FIG.11Dillustrates a portion of a magnified cross-sectional view of the magnetic separator plate adapter802being loaded onto the magnetic separator plate402, and the 96-tube PCR plate602being loaded onto the magnetic separator plate adapter802 The magnetic separator plate adapter802comprises a raised frame extending around the periphery of the magnetic separator plate402, such that the raised frame supports the 96-tube PCR plate602in such a way that the array of tubes604are suspended above the array of magnets404. As shown inFIG.11D, the array of tubes is suspended above the array of magnets404at a height such that the tubes604do not come in contact with their corresponding magnets404. By suspending the array of tubes604above the array of magnets404, the bottom ends of the tubes604are no longer resting within the hollow spaces of the ring magnets at different depths, thereby keeping the 96-tube PCR plate602with the array of tubes604leveled with respect to the array of magnets404. The benefit is that the performance of the magnetic bead based cleanup process may be significantly improved. Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed embodiments are illustrative and not restrictive.
22,657
11857982
DETAILED DESCRIPTION OF THE INVENTION An apparatus according to a first embodiment of the invention is illustrated inFIGS.1to4. As shown inFIGS.1and2, the apparatus includes a support structure comprising a pair of end walls202,204connected together by a plurality of (for example, eight) threaded rods (not shown) which are secured to the end walls202,204by means of nuts either side of each wall. Mounted on the inwardly facing sides of the two end walls202,204are bearing assemblies250. The two ends of a tubular shaft216(referred to below as tube216) extend into the bearing assemblies and are rotatably mounted therein. The bearing assemblies typically comprise a cylindrical casing containing a plurality of bearings surrounding the ends of the tube216and in which the ends of the tube can rotate. The bearings can be of conventional type and thus, for example, can be taper bearings, roller bearings, needle bearings or an array of ball bearings. One or both bearing assemblies (and more usually the bearing assembly202) can be constructed so as to form a labyrinth seal as shown inFIG.3. Mounted on tube216is a cylindrical drum224. The drum224is fixed to the tube216such that the drum rotates with the tube216. The drum can be formed from a suitably tough plastics material or a corrosion resistant metal such as stainless steel, or a combination of plastics and metallic materials and, viewed from the exterior, is of generally cylindrical form. Tube216has two ends—a fluid supply end212and an outlet end214. At the fluid supply pipe end of the drum, the drum has a conical inner surface226. The conical inner surface226is shaped such that fluid entering the drum is diverted to the outermost regions of the drum where the centrifugal forces are the greatest. The conical inner surface provides this diversion without imparting substantial turbulence on the fluid stream. The conical inner surface may be an inner surface of the cylinder (in this case, whilst the outer wall of the cylinder is of constant width, the inside of the cylinder does not have a constant diameter). Alternatively, the conical inner surface may be a surface of a separate component which is placed within the cylinder to provide the same internal shape as described above. Where the conical inner surface is a surface of a separate component, the component may be formed from a material which is the same as or different from the material from which the drum is formed. For example, a separate component providing the conical inner surface may be formed from a corrosion resistant metal such as stainless steel or from a suitable tough plastics or composite material. The outer surfaces of the fluid supply pipe and the outlet pipe(s) can be sealed against the inner surfaces of the two ends of the tube216and optionally against the inner surface of collector outlet262by means of labyrinth seals, as shown inFIG.3. The labyrinth seals306have an inlet for receiving fluid feed pipe304and a circular recess for receiving an end of tubular shaft302(equivalent to tube216inFIG.1) of a drum224which is in fluid communication with the first chamber in the drum. Fluid enters the seal through fluid feed pipe304in direction F as shown inFIG.3. Whilst the fluid feed pipe304and labyrinth seal306do not rotate when the apparatus is in use, bearings within the labyrinth seal (not shown) allow the end of the tubular shaft302to rotate inside the labyrinth seal. The labyrinth seal contains tortuous paths308(typically less than 1 mm in width) which prevent leakage of the fluid from the seal. The use of labyrinth seals means that if the air feed pressure is greater than the fluid pressure being processed, then the fluid cannot push past the labyrinth seal and leak out. The labyrinth seal therefore provides a means for connecting a static, non-rotating fluid feed pipe to the rotating tubular shaft and drum, whilst preventing leaking of the fluid. The labyrinth seals can similarly be used to connect outlet pipes to the drum. The labyrinth seals306also comprise air inlets310which are in fluid communication with centre of the seal by means of the paths308. Air can be drawn into the labyrinth seal through the air inlets, either as a result of the pressure of the fluid passing through the seal, or by using an external pressured air source to inject pressured air into air inlet310. When the air pressure inside the labyrinth seal is sufficient, the drum shaft302will be suspended, taking the weight of the drum off the bearings in the seal. This means that the labyrinth seal is virtually friction free and therefore lasts longer compared to conventional seals, which easily degrade when the input fluid contains particulate matter, such as sand and/or grit. The tube216has two circumferential arrays of elongate, angled slots218,220and a plurality (in this embodiment three) of elongate longitudinal slots222located around the circumference of the tube. The function of the holes and slots is described below. The pipe bore is blocked by blocking elements217in the form of discs each having an annular sealing element set into its outer edge to form a seal against the inner wall of the pipe. The blocking elements or blanks prevent fluid from passing along the pipe bore. The interior of the drum is partitioned into a first chamber246and a second chamber248by disc assembly228. Holes in disc assembly228provide fluid communication between the first and second chambers. The intermediate disc assembly228, shown in more detail inFIG.4, comprises a disc228aof a transparent plastics material, although it could instead be formed from a non-transparent plastics material or a corrosion resistant metal such as stainless steel. The disc228ahas three circumferential arrays of holes. Seated in the outermost holes are bolts232. Bolts232serve to hold in place an annular sealing element234which is stretched around the bolts. The annular sealing element234of the intermediate disc assembly228sits tightly against the inner surface of the drum. The sealing element234is formed from a suitable elastomeric sealing material. Radially inwardly of the holes for bolts232is a circumferential array of six holes228cthrough which the threaded rods (not shown) pass, which secure disc assembly228to the drum. Radially inwardly of holes228care the holes228bof which, in this embodiment, there are six. Holes228ballow fluid communication through the disc228a. In addition to the central hole228eand three circumferential arrays of holes228b,228cand228d, the disc228ahas three passages228fextending from the radially outer edge of the disc to the central hole228e. Located within the three passages228fare three fastening bolts236. The inner ends of fastening bolts236extend through the slots222in the tube216and are anchored in a cylindrical sealing plug238. The sealing plug238is attached to a threaded actuator rod240which extends along the interior of the tube and out through a sealing gland associated with the pipe214. The end of the threaded actuator rod can be received in a rotatable actuator device, the rotation of which gives rise to longitudinal (axial) movement of the actuator rod and hence longitudinal movement of the sealing plug238along the tube. Thus, the actuator rod240can be used to move the sealing plug and, because the disc228is attached to the sealing plug238, movement of the sealing plug will also result in axial movement of the disc228. Movement of the sealing plug238and disc228enables the effective size of the opening defined by the slots252to be varied, for example by increasing the opening size to facilitate the passage therethrough of more viscous materials or larger particulates. By changing the size of the slots252, the separated fluid stream can be split at different points, to allow one separated material to pass through slot252and the other to continue to pass through the drum towards the outlet pipe214. Attached to the outer surface of the drum is an array of vanes (not shown). In this embodiment, the vanes are longitudinally oriented but they could instead be oriented at an angle, for example, of up to 45° (e.g. from about 15° up to 40°, or from about 20° up to 37°, or from about 25° up to 35°, or from about 30° to about 32°) with respect to the rotational axis of the tube216. In one embodiment, the vanes are formed in pairs, each pair being constituted by two sides of a strip of metal of channel section. The third (i.e. intermediate) side of the channel section strip is attached to the drum cylinder by means of rivets or other fastening elements. Between each vane, slots252are positioned to provide an opening into the interior of the drum. A static collector device254encircles the rotating drum but does not rotate with it. The collector device254comprises an annular channel-shaped structure, the open face of the channel shaped structure facing inwardly towards the rotating drum. The channel shaped structure has an interior circumferential channel enclosing the vanes on the outer surface of the rotating drum. There is a small clearance between the inner edges of the channel-shaped structure and the outer surface of the rotating drum. The collector device254does not rotate with the rotating drum but is fixed to the support structure202,204. The vanes on the outer surface of the drum form a fan seal which reduces the air pressure within the circumferential channel and hence draws air through the gap between the outer surface of the drum and the collector device. This serves to prevent leakage of materials through the gap between the collector device and drum. Means (not shown) may be provided for adjusting the gap between the outer surface of the drum and the collector device should this be considered necessary or desirable to assist the prevention of leakage between the drum and the collector device. At its lower end (the term “lower” referring to its orientation in use), the channel-shaped structure has a circular or oval opening262which defines an outlet for the collector. The opening262is connected to a tube for carrying away materials passing through the opening. The rotation of the rotating drum is driven by a drive belt266which engages with a drive wheel264. The drive belt is linked to a hydraulic powered turbine, a high-pressure air powered turbine or a motor (not shown). In one particular embodiment, the apparatus can be used to separate an oil-water sludge into a predominantly water-containing component and a predominantly oil-containing component. Thus, an oil-water sludge is pumped through an inlet pipe (seeFIG.3) in direction D and thence into the tube216which under the influence of the drive belt266. The passage of oil-water sludge along the interior of the tube is blocked by blocking element217and therefore it passes into the centrifugal chamber246through the slots218in the wall of the tube. The movement of the sludge into the chamber is assisted by the centrifugal force imparted by the rotating tube. Inside the chamber246, the conical inner surface226guides the fluid stream to the outermost region of the drum, in a way to minimise turbulence. The centrifugal force created by the rotation of the drum causes separation of the oil and the water in the sludge. Since water is denser than oil, the water moves preferentially to the outer region of the drum and passes out though the holes252into the collector device254, from where it is directed to a collection vessel (not shown) through opening262. The remainder of the fluid, which by this time contains much less water, passes through the holes228bin plate228and back into the interior of the tube216through slots220. From there, the oil passes out through the pipe214and is collected. The position of plate228can be altered to vary the amount of fluid passing through slots252. In the embodiment shown, plate228can be moved to partially block holes252, however in other embodiments, the plate can be moved to completely block holes252. An apparatus substantially as shown inFIGS.1to4has been used to separate a 50:50 water:oil mixture. The separated water component has a residual oil content of 18.51 ppm (0.001851%) and the separated oil component had a residual water content of 0.25%. Alternatively, when the fluid stream comprises heavy particles, the sealing plug238can be positioned such that it completely blocks holes252. When holes252are blocked any heavy particles, for example metals particles, are trapped in the drum with the remaining fluid passing through plate228and out through the longitudinal tube's outlet end214. Then with the fluid supply pump shut off but with the drum still rotating the sealing plug238can be positioned to open holes252to recover any heavy material that has been trapped in the drum. It has been found that, using the apparatus as described above, good separation of oil from water can be achieved. In order to maximise the separation of water and oil, the speed of rotation of the drum can be varied by simple trial and error until an optimal speed is found. An apparatus substantially as shown inFIGS.1to4has also been used to separate sand and grit from water. A slurry of sand in water (approximately 13.4% sand) was subjected to a series of separations carried out at different rotational speeds. Separated sand was collected in the collector254whereas water from which sand particles had been removed was collected through outlet214. At a rotational speed of 1500 rpm, the water collected through outlet214contained 59 mg/ml (0.0059%) residual sand. At a rotational speed of 1772 rpm, the water collected through outlet214contained 46 mg/ml (0.0046%) residual sand. At a rotational speed of 2250 rpm, the water collected through outlet214contained 19 mg/ml (0.0019%) residual sand. On the basis of the above results, it is envisaged that removal of substantially all of the sand from the water would be achieved at a rotational speed of about 3500 rpm. The results set out above demonstrate that the apparatus of the invention provides an effective means of separating the components of a fluid stream. An apparatus according to a second embodiment of the invention is illustrated inFIGS.5to9. As shown inFIGS.5and6, the apparatus includes a support structure base402and three upstanding support pillars404,406,408. Mounted on the inwardly facing sides of two of the upstanding support pillars404,406are bearing assemblies, which are of conventional construction. A drum410formed from stainless steel extends between the two bearing assemblies. The drum has a cylindrical central section412and two conical end portions414. The drum is formed from two parts. The first part comprises one conical end portion and the majority of the cylindrical section with the second part comprises the other conical end portion and a cylindrical axially extending wall, which forms part of the central cylindrical section when assembled. Each of the two parts comprise a flange at the end of their cylindrical sections and are sealed together by means of one or more sealing clamps416. At the apexes of each of the two conical end portions is a hollow shaft418which engages with the bearing assemblies in the upstanding support pillars404,406,408. The two shaft ends extend into the bearings and are rotatable therein. One end of the hollow shaft is connected to a fluid supply pipe. The outer surfaces of the fluid supply pipe are sealed against the inner surfaces of the hollow shaft. One of the conical end sections of the drum is provided with a hole through which a fluid to be separated enters the drum (the drum inlet). The other conical end section of the drum is provided with outlets through which a separated or purified fluids exits the drum (the drum outlet). The drum inlet is connected to a pressurised source of fluid to be separated or purified. Inside the drum inlet there is a spider diverter420, shown inFIG.9. The spider diverter420takes the form of a tube420awith a number (in this case three) radially extending walls420b. The tube is blocked and serves to prevent fluid from passing through the hollow shaft418. As the inside of the tube is blocked, fluid entering through the fluid inlet passes between the radially extending walls and are then diverted outwardly by the outer surface of the skin, through the annular channel between the drum wall and the inner wall. The cylindrical and conical sections of the drum both have a double-skinned arrangement formed by the inner surface422of the drum and the outer surface of an inner wall424. There is therefore an annular channel426between the outer surface of the inner wall and the inner surface of the drum wall. The double-skinned arrangement means that the fluid is subjected to maximum centrifugal forces towards the radially outer region of the drum. The drum and inner wall are shaped so that the cross-sectional area along the length of the drum is constant. Therefore, the distance between the inner surface of the drum and the inner wall decreases along the conical section of the drum, as the diameter of the cross-section increases. This means that the fluid can travel through the drum with no change in velocity. The inner surface of the drum and the outer surface of the skin are both formed from stainless steel and are polished to reduce turbulence being imparted on the separating fluid. On entering the system, the fluid mix is moved via the spider diverter420and the conical inner wall424towards the outer diameter of the main separation drum. The angles of the conical sections encourage fluid to the radially outer parts of the drum where centrifugal forces are highest in a low turbulence manner. A pump moves the mix through the separation drum and the centrifugal force causes heavier particles to migrate towards the outer wall422, leaving lighter particles towards the inner wall. At the outlet end of the drum there is a diverter cone430. The diverter cone divides the fluid flow into two. The less dense component of the fluid passes one side (the radially inner side) of the diverter and through the drum outlet. The denser component of the fluid passes the other side (the radially outer side) of the diverter and through a separate outlet positioned perpendicular to the drum outlet. The diverter cone430can be actuated back and forth on the rotational axis of the system to change the division point in the cross section of the flow. The diverter cone430is formed from a blade of stainless steel and is connected to a tubular shaft. The stainless steel blade is polished to minimise turbulence and promote laminar flow of the fluid through the apparatus. The tubular shaft partitions the outlet end of the tube into an inner outflow432and an outer outflow434. The denser component of the fluid stream, having passed the diverter cone on its radially outer side, then passes through outer outflow434. The less dense component, having passes on the radially inner side of the diverter cone, then passes through inner outflow432. Both outflows may be directed back to the central area where an arrangement of lip seals and O-ring seals channel the outflows to their respective outlet pipes. Alternatively, the outer outflow434directs the denser component of the fluid to an outlet pipe which is angled at approximately perpendicularly to the axis of rotation of the drum and the inner outflow432directs the less dense component to another outlet pipe, aligned with the hollow shaft418. The drum is mounted on roller bearings (not shown) at each end. Rotation of the drum is driven by a drive belt which engages a pulley that is fastened through the drum fabrication and into the spider diverter420. The drive belt is linked to an electric motor. Alternatively, the drive belt can be linked to a hydraulic powered turbine or a high-pressure air powered turbine. In use, a mixture of fluids to be separated (for example, a mixture of oil and water) is pumped into the input, ideally using a low turbulence type of pump (such as a wobble plate piston pump). The drum is then spun at high rotational speed (circa 3,000 rpm) via the belt drive. The spider diverter420maintains mechanical continuity through the central tube418of the system while permitting fluid entry into the annular channel426. The degree of separation and/or purity of the fluids separated by any of the embodiments described herein can be determined by measuring the transparency or optical absorbance of the separated fluids. Based on the determined degree of separation and/or purity of the separated fluids, the separation apparatus can be tuned to maximise separation. The measurement of the degree of separation works on the principle of the clearer the fluid the greater light will pass through a fluid therefore providing a higher reading to a measuring light meter (e.g. a device containing a light dependent resistor which provides a reading based on the amount of light detected). To ensure a consistent light source, LED light sources are used. A schematic diagram of a system to determine the degree of separation of the separated fluids is shown inFIG.10. Apparatus602is provided with inlet604for receiving a fluid stream comprising two fluid components, first outlet606and second outlet608. Fluid exiting apparatus602through first outlet606contains a greater proportion of a first fluid than the inlet fluid. Similarly, fluid exiting the apparatus through second outlet608contains a greater proportion of a second fluid than the inlet fluid. Each of the first and second outlets are connected to separate light boxes610. The light box contains a light source, e.g. a light emitting diode612and a light detector, which may be or comprise a light dependent resistor614. The fluids pass in between the light sources and the light detector. The light box then provides a reading based on the light detected by the light detector. In order to determine the composition of the separated components of the fluid stream materials, the absorbance of samples with known ratios of the two fluids to be separated can be determined. Then, once the relationship between the absorbance and the ratio of the two fluids is known, the ratio of components the separated fluids can be determined by measuring their absorbance. FIGS.11and12show a vortex separation device according to an embodiment of the invention. The vortex separation device may be used either alone or in combination with a further separation device (for example, a centrifugal separation apparatus such as the apparatuses shown inFIGS.1to9). The vortex separation device comprises a separation tube (802) disposed between an upstream T-connector (804) and a downstream T-connector (806). Each T-connector (804,806) has a pair of coaxial longitudinally aligned end openings and a perpendicular (with respect to the longitudinal openings) lateral opening. These openings serve as the connector inlets or outlets. The three openings of the T-connectors (804,806) are internally threaded to allow connection with other components of the vortex separation device The lateral opening (804a) on the upstream T-connector is connected by means of its internal thread to an externally threaded end of a tubular member (808) which in turn is connected to a pressurised fluid source. The lateral opening (804a) on the upstream T-connector therefore serves as a fluid inlet. A first end opening (804b) of the upstream T-connector (804) serves as an outlet for the T-connector. The outlet is internally threaded for connection with an externally threaded first double-ended tubular spigot (810). Fluid passes from the outlet of the upstream T-connector through the first double-ended tubular spigot (810) and then onward to a circular vortex-inducing plate (812). The first double-ended tubular spigot (810) has a central portion and two externally threaded end portions. One of the externally threaded end portions engages with the outlet of the upstream T-connector (804b), whilst the other engages with a threaded bore of the circular vortex-inducing plate (812). A fluid to be separated enters the vortex separation device via the upstream T-connector (804) and passes through a series of parallel channels. Within the first double-ended tubular spigot there are a number of guide walls (814) which define the parallel channels. The guide walls (814) may be made from a metal or plastics material, which is sufficiently rigid so as not to deform as the fluid stream passes through the double-ended spigot (810). In example of the arrangement of the guide walls (814) within the upstream T-connector (804) is shown inFIG.13A. The guide walls (814) have a substantially U-shaped cross-section and have a base portion (814b) and two substantially perpendicular arms or side walls (814a) at each side of the base portion. One of the arms (814a) of each guide wall is bent to provide clearance for the rotating drive shaft (820). The two arms or side walls (814a) and the base (814b) define a channel with an open side, which faces away from the interior wall of the first double-ended spigot (810). The guide walls are attached (for example, by means of screws/rivets (814c)) to the interior wall of first double-ended spigot (810) equidistantly around its inner circumference. An alternative arrangement of the guide walls (814) is shown inFIG.13B. In this arrangement, the guide walls (814) have a substantially U-shaped cross-section and have a base portion (814b) and two converging arms or side walls (814a) at each side of the base portion. The two arms (814a) and the base (814b) define a channel with an open side, which faces the centre of the first double-ended spigot (810). The guide walls are attached (for example, by means of screws/rivets (814c)) to the interior wall of first double-ended spigot (810) equidistantly around its inner circumference. InFIGS.13A and13B, screws/rivets (814c) are used to secure the guide walls to the interior of the first double-ended spigot (810). However, it will be appreciated that in practice, the screws/rivets may be countersunk into the first double-ended spigot (810) in order to further reduce the turbulence of the fluid stream passing through the first double-ended spigot (810). Alternatively, the guide walls can be fixed to the interior wall of the double-ended spigot using other fastenings/adhesives. When a drive shaft (820) is present, the guide walls (814) are arranged to provide a central space through which the drive shaft can pass (as shown inFIGS.13A and13B). The guide walls (814) collimate the fluid before it passes through a vortex-inducing plate or fan. The vortex inducing plate which causes rotation of the fluid to form a vortex. Due to the centrifugal forces operating on the components of the fluid, as the fluid passes through the separator tube (802), the denser component(s) of the fluid are forced to the outer regions of the separator tube, whilst the less dense components accumulate at or close to the longitudinal axis of the separator tube. The denser component then passes through a radially outer annular collector channel (838) and is directed out of the vortex separator via a lateral opening on the downstream T-collector (806a). The less dense component passes through the radially inner central inner collector tube (836). As shown inFIG.14A, on one side, the vortex-inducing plate (812) has a circular, internally threaded bore for connection with the first double-ended spigot (810). As shown inFIG.14B, on its other side, the vortex-inducing plate (812) is provided with several (e.g. six) angled conduits (816) spaced equally around the plate and positioned such that fluid passing through the channels is formed into a vortex. The conduits extend through the plate and through the base of the bore. The vortex-inducing plate (812) also has a central opening, which is fitted with a bearing (818) through which a drive shaft (820) can pass and freely rotate. As the fluid passes through the angled conduits in the vortex-inducing plate (812), the fluid stream is rotated to form a vortex. The use of the vortex-inducing plate (812) is particularly useful when the fluid stream to be separated comprises a mixture of oil and water. A second longitudinal opening (804c) of the upstream T-connector (which is positioned opposite the first longitudinal opening) is sealed with a first plug (822). The first plug comprises an externally threaded spigot and a cap having a diameter at least as large as the externally threaded spigot. The first plug also has a central hole, fitted with a bearing (824), through which the threaded drive shaft (820) passes. The drive shaft (820) is able to rotate within the first plug (822). The drive shaft (820) passes from the outside of the upstream T-connector, through the first plug (822) and upstream T-connector (804) and into the separator tube (802). At the end of the shaft located inside the separator tube (802), an impeller (826) is non-rotatably mounted onto the drive shaft. The impeller (826) has a central hub with a plurality (e.g. six) blades radiating outwardly from the hub. The hub also has a threaded central hole to allow the impeller (826) to be threaded onto the drive shaft (820). At an end of the shaft which protrudes from the first plug (822), a pulley wheel (828) is non-rotatably mounted on the shaft. The pulley wheel (828) has a circumferential groove about which a drive belt (830) can be located. The drive belt (830) is connected to an electric motor (832) and the motor can thereby drive rotation of the drive shaft (820) and the impeller (826). The fluid, which has already passed through the vortex-inducing plate (812), is therefore further rotated by the impeller (826) to increase the rotational velocity of the fluid. As the fluid travels down the separator tube (802), due to its rotation and the centrifugal forces acting upon it, separation of the fluid takes place. The denser component(s) of the fluid stream accumulate at the outer regions of the separator tube (802) whilst the less denser component(s) accumulate at the inner regions of the separator tube (802). The downstream end of the separator tube (802) is connected to one of the longitudinal openings of the downstream T-connector (806b) by a second double ended-spigot (838). The second double ended spigot (838) is tubular and has a central portion and two end portions. The end portions may be threaded or ribbed to so that a water-tight connection may be made with the tubular pipe (802) and the downstream T-connector (806). The other longitudinal opening of the downstream T-connector (806c) is sealed with a second plug (840). The second plug (840) comprises an externally threaded spigot and a cap having a diameter at least as large as the externally threaded spigot. The second plug (840) has a central hole through which a central inner collector tube (836) can pass. The inner collector tube (836) extends from the interior of the separation tube (802), through the downstream T-connector (806) and out through the second plug (840). This inner collector tube serves as a first outlet, i.e. an outlet for the denser component of the fluid stream. Around the inner collector tube (836) there is an annular channel (838) which serves as an outlet for the denser component of the fluid stream. The annular channel (838) is in fluid communication with an outlet pipe (842) in lateral opening (806a) on the downstream T-connector, which serves as a second outlet, i.e. an outlet for the less dense component. The outlet pipe (842) and inner collector tube (836) may be provided with valves (not shown) which can be opened or closed to control release of the separated fluid components from the vortex separation device. The vortex separation device described above is particularly useful for separating a fluid stream comprising oil and water. In another embodiment, in the vortex separation device described above, the vortex-inducing plate may be replaced with a bladed impeller. This embodiment is particularly useful for separating a fluid stream comprising water and sand. As the difference if density between water and sand is greater than for water and oil, the impeller, drive shaft and motor may not be required for efficient separation and may therefore be omitted from the device. A shaft may still be present and be non-rotatably fixed to the device. The bladed impeller may be non-rotatably mounted on or attached to the shaft. In yet a further embodiment, in the vortex separation device described above, the vortex-inducing plate is removed and instead the ends of the guide walls are bent at an angle of 45°. The guide walls themselves serve to introduce a vortex to the fluid stream. Again, this embodiment is particularly useful for separating a fluid stream comprising water and sand. As the difference if density between water and sand is greater than for water and oil, the impeller, drive shaft and motor may not be required for efficient separation and may therefore be omitted from the device. Using the vortex separation device of this embodiment (having the bent guide walls and without the impeller, drive shaft or motor). A mixture of 2.61% by weight of fine white sand (grain size of <200 μm) and water was passed through the vortex separation device described above. The motor was set to drive the impeller at 1600 rpm. The water obtained from output (806) of the vortex separation device contained sand at a level of 6 ppm. The vortex separation device can be used in combination with the centrifugal separation devices described herein (for example, those substantially as shown inFIGS.1to9). As shown above, an apparatus substantially as shown inFIGS.1to4can be used to provide water having a sand content of 19 ppm to 59 ppm. This water stream can then be passed through the vortex separation device substantially shown inFIGS.11to12to further reduce the sand content down to 6 ppm. Similarly, the vortex separation device can be used to further separate an oil and water mix that has been at least partially separated by a centrifugal separation device substantially as shown inFIGS.1to9. The embodiments described above and illustrated in the accompanying figures and tables are merely illustrative of the invention and are not intended to have any limiting effect. It will readily be apparent that numerous modifications and alterations may be made to the specific embodiments shown without departing from the principles underlying the invention. All such modifications and alterations are intended to be embraced by this application.
34,709
11857983
DETAILED DESCRIPTION OF THE INVENTION With reference toFIGS.1-9, the present invention provides a shower head that can be prevented from falling off, comprising a shower head1and a fixing seat2which the shower head1is magnetically attached to, and also comprising a first magnetic assembly3and a second magnetic assembly4to achieve magnetic attachment between the shower head1and the fixing seat2. One of the first magnetic assembly3and the second magnetic assembly4is mounted on a back side of the shower head1, and another one of the first magnetic assembly3and the second magnetic assembly4is mounted on the fixing seat2. The first magnetic assembly3comprises a first mounting seat31, a first magnetic piece32, and a fastener33; the first mounting seat31is recessed from an end surface thereof to form an annular groove311; the first magnetic piece32is mounted in a space enclosed by an inner side wall of the annular groove311; the fastener33is installed in the first mounting seat31and is movable along a radial direction of the annular groove311so as to be movable in and out of the annular groove311; the fastener33is also provided with a fastener groove331which is in communication with the annular groove311; one side of an opening of the fastener groove331is provided with a position limiting flange332. The second magnetic assembly4comprises a second mounting seat41and a second magnetic piece42; an insertion cylinder411is projected from the second mounting seat41; a periphery of a free end of the insertion cylinder411is provided with a position limiting ring412; the second magnetic piece42is mounted inside the insertion cylinder411. During use, the insertion cylinder411is inserted into the annular groove311, so that the second magnetic piece42and the first magnetic piece32are magnetically attached to each other, and the fastener33is driven to move into the annular groove311along a radial direction of the annular groove311so that the position limiting ring412is prevented from moving along an axial direction of the annular groove311by the position limiting flange332of the fastener33. A specific embodiment of the present invention is illustrated below. The first magnetic assembly3and the second magnetic assembly4arranged on the shower head1and the fixing seat2achieve both the functions of male-female connection and magnetic connection without affecting the original functions of the shower head1and the fixing seat2. Therefore, the first magnetic assembly3and the second magnetic assembly4can be freely disposed anywhere on the shower head1and the fixing seat2. In this embodiment, the first magnetic assembly3is mounted on a back side of the shower head1, and the second magnetic assembly4is mounted on a front side of the fixing seat2. In other words, in some other embodiments, the first magnetic assembly3may be mounted on the front side of the fixing seat2, and the second magnetic assembly4may be mounted on the back side of the shower head1. Further, the first mounting seat31and the second mounting seat41are connected to the shower head1and the fixing seat2by screw connection so that the first mounting seat31and the second mounting seat41can be removably connected for easier assembly and disassembly. The first magnetic assembly3or the second magnetic assembly4is mounted on the back side of the shower head1, and specifically on a back side of a shell of the shower head1, and more specifically on a back side of the shower head1which is opposite to a front disc of the shower head1where water comes out. According to this mounting position, there will be sufficiently large space provided for the designs of the first magnetic assembly3or the second magnetic assembly4. Of course, according to some other embodiments, the first magnetic assembly3or the second magnetic assembly4may be mounted on a handle of the shower head1. Further, the shower head1and the fixing seat2are provided with a first mounting groove11and a second mounting groove21respectively so as to mount the first magnetic assembly3and the second magnetic assembly4. With reference toFIG.5, one side of the fastener groove331is a first inclined surface333. The first inclined surface333is positioned on a side of the fastener groove331which is more proximal to a center of the annular groove311along a radial direction of the annular groove311. When the first magnetic piece32and the second magnetic piece42are magnetically attached to each other, a portion of the insertion cylinder411is also inserted into the fastener groove331and abuts against the first inclined surface333, and due to abutment against the first inclined surface333, an end of the portion of the insertion cylinder411inserted into the fastener groove331will drive the fastener33to move into the annular groove311along a radial direction of the annular groove311. Therefore, the second mounting seat41can drive the fastener33to move by means of the first inclined surface333. In other words, the magnetic force between the first magnetic piece32and the second magnetic piece42is translated into a radial force of the fastener33through the first inclined surface333so that the fastener33is driven to move into the annular groove along radial direction of the annular groove. With reference toFIG.5, an outer side of the position limiting flange332facing away from the fastener groove and an inner side of the position limiting flange332facing towards the fastener groove are provided with a second inclined surface334and a third inclined surface335respectively. The second inclined surface334and the third inclined surface335achieve a similar function like the first inclined surface333in that they are also used for translating external force to radial force of the fastener33. Specifically, when said end of the portion of the insertion cylinder411is in contact with the second inclined surface334during insertion of the insertion cylinder411into the annular groove311, the fastener33is being pushed away from the annular groove311along a radial direction of the annular groove311so that the position limiting ring412can pass the position limiting flange332and thus allowing the insertion cylinder411to be inserted into the insertion groove331. When user needs to take out the shower head1, pull the shower head1along an axial direction of the insertion cylinder411so that the position limiting ring412will first be in contact with the third inclined surface335; similarly, by continue pulling the shower head1, the fastener33will also be pushed away from the annular groove311along a radial direction of the annular groove311so that the position limiting ring412can pass the position limiting flange332to allow the insertion cylinder411to be disengaged from the annular groove331. The annular groove311is positioned on a front side of the first mounting seat31; a back side of the first mounting seat31is provided with a fastener mounting groove312extending into the annular groove311along a radial direction of the annular groove311so that the fastener mounting groove312is in communication with the annular groove311through an outer side wall of the annular groove311. The fastener33is movably fitted in the fastener mounting groove312so as to be moved along a radial direction of the annular groove311as driven by the insertion cylinder411. Further, with reference toFIG.4, two sides of the fastener mounting groove312are each provided with the a guiding platform313; two sides of the fastener33are each provided with a guiding flange336slidably fitted with a corresponding guiding platform313. Slidable fitting between each guiding platform313and a corresponding guiding flange336guides a moving direction of the fastener33, and also limits the fastener33from being disengaged from the fastener mounting groove312and hence prevents the fastener33from falling off the first mounting seat31. The first mounting seat31is provided with a first mounting hole314in which the first magnetic piece32is mounted; the second mounting seat41is provided with a second mounting hole413in which the second magnetic piece42is mounted. In this embodiment, the first mounting hole314and the second mounting hole413are positioned at a center of the annular groove311corresponding to the space enclosed by the inner side wall of the annular groove311and a center of the insertion cylinder411respectively. Further, a first shell34is fitted and axially limited in the first mounting hole314, and a second shell43is fitted and axially limited in the second mounting hole413. The first shell34and the second shell43house the first magnetic piece32and the second magnetic piece42respectively so that the first magnetic piece32and the second magnetic piece42will not easily fall off. Also, the first shell34and the second shell43protect surfaces of the first magnetic piece32and the second magnetic piece42and achieve waterproof and anti-corrosion functions. Besides, the shower head1and the fixing seat2are provided with a first column12and a second column22respectively. In accordance with the mounting positions of the first magnetic assembly3and the second magnetic assembly4, the first column12and the second column22are inserted into the first shell34and the second shell43respectively and also abut against the first magnetic piece32and the second magnetic piece42respectively so as to fix the first magnetic piece32and the second magnetic piece43. In other words, except for the first mounting seat31and the second mounting seat41, all other components do not require additional connective means. After the first mounting seat31and the second mounting seat41are fixed, all other components are fixed in position relative to one another by their structural relationships. Accordingly, assembly is more convenient. The second magnetic assembly4also comprises a friction ring44disposed circumferentially around the insertion cylinder411. The friction ring44can be made of materials like polyoxymethylene so as to contain good physical; mechanical and chemical properties, and particularly good resistance against frictions. Accordingly, the friction ring44can have a long service life and prevent friction loss of the first mounting seat31and the second mounting seat41, and can also reduce the squeaking sounds produced by frictions when the first mounting seat31and the second mounting seat41are in contact with each other. The friction ring44can be removably mounted to the second mounting seat41by, for example, fastening. The first magnetic piece32is made of stainless steel; the second magnetic piece42is a neodymium magnet. In this embodiment, since the first magnetic assembly3is mounted on the shower head1and the second magnetic assembly4is mounted on the fixing seat2, the stainless steel first magnetic piece32is mounted on the shower head1and can be magnetically attracted by the magnet on the fixing seat2to achieve magnetic connection between the shower head1and the fixing seat2. Since the shower head1itself is not magnetic, use of the shower head1will not be affected. The fixing seat2can be a socket installed on a wall, or can be a three-way connector according to this embodiment. A water inlet end of the three-way connector is connected to a water supply; a water outlet end of the three-way connector is in communication with the water inlet end, and is connected to at least one water outlet device such as a water hose of the shower head and/or an overhead shower head; the shower head1is directly attached magnetically to a third end of the three-way connector. By use of this three-way connector, number of parts during installation can be reduced, and the structure resulted can be more clean and neat. With reference toFIG.8andFIG.9the present invention has the following operating principles: When the shower head1is placed near to the fixing seat2, the first magnetic piece32and the second magnetic piece42are guided to be magnetically attracted to each other; when the insertion cylinder411is inserted into the annular groove311, an end of a portion of the insertion cylinder411inserted into the annular groove311will abut against the second inclined surface334so that the fastener33will be driven to move away from the annular groove311along a radial direction of the annular groove311and thereby allowing the insertion cylinder411to continue its insertion. When the shower head1is continued to be placed nearer to the fixing seat2, the end of the portion of the insertion cylinder411abut against the first inclined surface333so that the fastener33is driven to move reversely into the annular groove311along the radial direction of the annular groove311, so that the position limiting flange332locks the position limiting ring412, Accordingly, the shower head1is locked in position along an axial direction of the annular groove311/the insertion cylinder411. Therefore, the present invention can lock the shower head1in case when user accidentally displaces the shower head1due to various external forces, thereby protecting the shower head1from falling off. Specifically, when the shower head1is accidentally displaced in a tilted condition with respect to the fixing seat2as shown inFIG.9, the position limiting ring412can act vertically onto the third inclined surface335so that the fastener33cannot move and so the locking state of the shower head1is still being maintained. Only when the shower head1is positioned parallel to the fixing seat2as shown inFIG.8can the shower head1be pulled to disengage from the fixing seat2. According to the above technical solutions, the present invention provides a fastener33in the first magnetic assembly3, wherein the fastener33is movable along a radial direction; specifically, after the insertion cylinder411is inserted into the annular groove311, an end of a portion of the insertion cylinder411abutting against the fastener33will drive the fastener33to move into the annular groove311along a radial direction of the annular groove311, so that the position limiting flange332of the fastener33limits the position limiting ring412of the insertion cylinder411from moving along an axial direction of the annular groove311/insertion cylinder411, thereby preventing the shower head1from falling off. The annular groove311and the insertion cylinder411are both in a circular shape so that the shower head1can be fixed with the fixing seat2no matter how the showerhead1is rotated on a plane parallel to the fixing seat2before it is fixed with the fixing seat2. Use of the present invention is facilitated since the shower head1can be fixed with the fixing seat2at more than one position at any angle rotated with respect to the fixing seat2on the plane parallel to the fixing seat2. The first magnetic piece32and the second magnetic piece42achieve the basic magnetic connection, and provide a magnetic driving force which is translated to a radial force of the fastener33during insertion of the insertion cylinder411into the annular groove311. The greater the magnetic force, the more stable will be the position limiting effect between the position limiting flange332and the position limiting ring412. The embodiment described above and the accompanying drawings are not intended to limit the types and forms of the present invention. Any non-inventive changes or modifications of the embodiment described above by a skilled person in the art should fall within the scope of present invention.
15,453
11857984
It should be noticed that the figures are drawn schematically and not to scale. In particular, certain dimensions may be exaggerated to a higher or lesser extent in order to improve the overall intelligibility. Corresponding parts are denoted by a same reference sign throughout the drawing A first embodiment of a spray nozzle unit1and a cross section of the spray nozzle that is applied in said unit is shown inFIGS.1and2. The spray nozzle and spray nozzle unit are intended for a spray device for spraying at least one fluidic microjet2at an inclined angle α relative to a centre line of a nozzle orifice. The spray nozzle comprises a substantially planar support body11made from silicon, glass, plastic or photosensitive polymer with a thickness of between 50 and 675 micrometer having at least one cavity5with a diameter w of typically 10-100 micrometer extending from a first main (downstream) surface7to a second main (upstream) surface6thereof. A thin membrane layer4made typically from a thin film ceramic material like (poly) silicon, silicon nitride, silicon oxide or silicon carbide forms a nozzle membrane that is suspended over the cavity5and that has at least one nozzle orifice9with diameter typically between 0.5 and 20 micrometer in fluid communication with said cavity. The cavity5and said nozzle orifice9form a geometrically defined asymmetric fluid flow resistance as said nozzle orifice9is positioned near an edge wall10, i.e perimeter, of said cavity, in particular at a distance (d) less than one to three times the diameter of the nozzle orifice. This causes the microjet (2) to emit at an inclined angle (α) with respect to the substantial planar membrane layer (4). A centre of the cavity may be understood as a centre seen in the lateral direction, i.e. in a direction parallel to the downstream surface of the membrane layer. The orifice9is a-centrally positioned, i.e. it is positioned with an offset in respect of the centre of the cavity5, seen along the downstream surface. The flow path towards said orifice also has an a-centrical, i.e. asymmetrical flow profile in terms of flow resistance. This results in a microjet2emanating from said orifice under an angle of deflection α relative to a centre line of said orifice.FIG.3depicts the dependence of the inclination angle α with respect to the distance d between the edge wall10and the edge of a nozzle9with a diameter of 4 micron in a cavity5having a diameter w of 40 micron (seeFIG.2). Shifting the nozzle more than 3 micron from the edge already gives a steep decrease of the inclination angle, from 8° to less than 2°. InFIG.4an embodiment of a spray nozzle with an array of cavities5each with a diameter of typically between 10 and 100 micrometer and a distance between adjacent cavities of 5 to 200 micrometer is shown enabling different inclination angles α of the microjets2that are dependent on the distance d of the orifices with respect to the edge walls10of the fluid cavities5. Each orifice is provided with a different offset in respect of the corresponding cavity. As the offsets differ, the angles of ejection of the microjets also differ. Membrane layers for spraying can be made with known micro machining techniques. A mono crystalline silicon wafer with thickness of typically between 100 and 675 micron is provided to form a membrane layer support body. Using Low Pressure Chemical Vapour Deposition a layer of low stress silicon nitride with a thickness of 0.5-1.5 micron is grown on said support body to form a membrane layer. With a suitable mask a photo lacquer pattern with 4.5 micron, typically between 0.5 and 20 micron, orifices at the front side of the wafer and a pattern with 40 micron, typically between 10 and 100 micron, diameter openings at the back side, that register i.e. correspond with said at least one opening at said front side, is being exposed and developed. With the aid of anisotropic reactive ion etching at least one opening with a diameter of 4.5 micron, typically between 0.5 and 20 micron, and a length of 1 micron, typically between 0.5 and 1.5 micron, is etched in the silicon nitride layer to create at least one nozzle orifice. With the use of deep reactive ion etching a cavity with a diameter of 40 micron, typically between 10 and 100 micron, and a length of 200 micron, typically between 100 and 675 micron, is made in the silicon wafer, forming the support body. The membrane layer extending over the cavity and comprising said at least one orifice forms a nozzle membrane that is suspended over the cavity. A freely suspended, hanging nozzle membrane having a circular cross section with a diameter of 40 micron and being made of a 1 micron thick silicon rich silicon nitride layer, can easily withstand spray pressures of 100-150 bar. InFIG.5another embodiment of a spray nozzle with a nozzle orifice9having a direct boundary28with the edge wall10in a cylindrical cavity5with a diameter of 40 micron. The observed inclination angle is found to be dependent on the size of the nozzle orifice9as presented inFIG.6. An inclination angle larger than 5° is found when the diameter of the nozzle orifice9is larger than 10% of the cavity diameter w. An inclination angle larger than 10° is found when the diameter of the nozzle orifice9is larger than 25% of the cavity diameter w. InFIG.7a fluid simulation is presented of a cylindrical cavity with a round membrane layer having a diameter of 40 micron and a thickness of 1 micron. In the membrane layer a number of nozzle orifices with a diameter of 4 micron have been placed showing different spray inclination angles depending on the offset and the distance to the edge wall and also depending on the relative position of adjacent nozzle orifices. InFIG.7a (virtual lateral and parallel to the membrane layer) channel with a height comparable with the diameter of the nozzle orifice can be discerned, enabling a lateral impulse contribution of the fluid that is passing through the nozzle orifice. When the fluid is flowing parallel to the nozzle membrane just before it is jetted via the nozzle it will have a specific lateral impulse (mass density times lateral velocity) upon flowing through the nozzle orifice. When the fluid passes the nozzle it will also acquire a vertical impulse (mass density times vertical velocity) with respect to the membrane layer. When the membrane layer is relatively thin a major part of the lateral impulse will also be transferred to the jet emanating from the nozzle. The jet inclination angle will then be determined by the ratio of the transferred lateral and vertical impulse, typically the ratio should be larger than 0.1 and preferably larger than 0.2. The closer the orifice is positioned near the edge wall of the cavity the larger the residual lateral impulse of the microjet, and the more oblique is the angle of inclination. The lateral impulse is defined as the mean lateral impulse of the fluid near the nozzle exit, and to be more precise the lateral impulse as averaged over a virtual lateral channel with a channel height equal to the diameter of the nozzle orifice and having a boundary with the nozzle membrane, for cases in which the total height of the lateral channel is much larger than the diameter of the nozzle orifice. It will be clear that with a single membrane layer membrane many different layouts are possible for the placement of the nozzle orifices on the nozzle membrane. With preference in a round membrane the orifices are angularly distributed and can comprise a first set of angular distributed nozzles adjacent to the cavity wall, a second set of angular distributed nozzles with a distance to the cavity wall of approximately two times the nozzle orifice diameter, and a further set of angular distributed nozzles more inwards to the membrane. In optional cases when a large amount of nozzle orifices are needed, e.g. more than ten or twenty it is likewise possible to make more than one free hanging membrane in the nozzle support body (see alsoFIG.4). Such free hanging membranes themselves can then be angularly distributed on the membrane layer, and the location of the orifices on each of the membranes can be chosen that a maximum amount of diverging jets can be obtained. Also in optional cases the cavity of the support body is ring shaped, and also the nozzle membrane that is suspended over the cavity is ring shaped. This is advantageous when a large number of orifices is needed for high throughput spraying at a large pressure. The pressure strength of the ring shaped membrane is strongly determined by the inner width of the ring, which can be chosen to be e.g. 40 micron whereas the total outer diameter of the ring can be several hundreds of microns. InFIG.8another embodiment of a spray nozzle is depicted comprising a fluidic channel32directly underneath and parallel to the nozzle membrane (44) with a mean diameter between 0.3 to 3 times the mean diameter of the orifice and a length between 0.5 to 5 times the mean diameter of the orifice. The fluidic channel32enables a lateral impulse contribution of the fluid that is passing through the nozzle orifice. The entrance of the fluidic channel32has preferably a very sharp, well-defined edge of 70-100 degrees. InFIG.9a fluid simulation is presented clearly showing that a large angle of inclination of the emanating jet is attainable with this measure according to the invention. Many embodiments are possible, such as choosing a cavity edge wall10that is positively tapering towards the nozzle orifice9. It will be clear that many measures to increase the lateral impulse in combination with a thin nozzle membrane are possible to yield large inclination angles. Very large inclination angles (α>10-20°) can thus be obtained when the lateral channel over a specific length beneath the nozzle membrane has a height comparable or smaller than the nozzle orifice diameter. With preference the width of the lateral fluidic channel32is also chosen small and comparable to the nozzle orifice diameter, seeFIG.10. The smaller the lateral channel and the smaller the nozzle orifice length the larger the inclination angle is observed. For example a jet inclination angle of 37° has been obtained with a spray device having a nozzle orifice with a diameter of 4 micron, a length of 0.7 micron connected to a lateral fluidic channel with a height of 1 micron, a length of 8 micron and a width of 5 micron (FIG.10). A number of angular distributed nozzle orifices9with such fluidic channels32is depicted inFIG.11. The effect of a possible bending of the nozzle membrane is depicted inFIG.12. As can be noticed bending over an angle β adds to the inclination angle α of the jet to give a total deflection over an angle of α+β. In some cases it may be desirable to construct a nozzle orifice having a cross section plane at the second main surface substantially offset from the substantially flat membrane layer, especially in cases when a number of different angles of inclination are needed in one spray nozzle unit. Some nozzles can then be constructed according to one of the above said embodiments, and some according to the latter mentioned substantially offset condition. An embodiment (seeFIG.13) is characterized in that the nozzle orifice9extends over the support body11, while the support body11is locally etched beneath said extension37of said nozzle orifice9to a depth between 0.3 to 3 times the mean diameter of the orifice creating an orifice for spraying at least one fluidic microjet2at an inclined angle. In a further embodiment (seeFIG.14) of the nozzle according to the invention the membrane layer comprises a multilayer sandwich of a first silicon nitride layer40with a thickness of typically 0.5-1.5 micrometer, a silicon oxide layer42with a thickness of typically 0.5-5 micrometer and a second silicon nitride layer43with a thickness of typically 0.5-5 micrometer. The membrane layer is provided with an orifice9that extends partly over the support body11and partly within the cavity5that is provided in said support body. The orifice9comprises a cavity39that is formed in said multilayer membrane layer with the first silicon nitride layer40having an extension41over the cavity39with diameter 10-100 micrometer and a length of 100-675 micrometer and with the cavity39extending through the first silicon nitride layer (40) with an opening diameter that is smaller than or equal to the cavity39diameter and the silicon oxide layer42and with a second silicon nitride layer43, in which the orifice9with diameter of 0.5-20 micrometer is etched through extending in the silicon oxide layer42. Another embodiment of a spray nozzle membrane forming itself a significant contribution to the lateral impulse of the emanating jet is depicted inFIG.15. Here a geometrically asymmetric fluid flow resistance inside the nozzle membrane itself is created, such that the liquid flowing through the orifice near the edge wall of said cavity has a lower velocity than the liquid through the same orifice near the middle of the nozzle membrane, which enables to emit at a specific inclination angle with respect to the membrane layer. With preference a cross section of said nozzle orifice is oval, tear, moon, V or U shaped. Also is depicted inFIG.15a nozzle membrane that has one symmetrically shaped orifice in the middle of the nozzle membrane to allow jetting without any inclination. Another embodiment is shown inFIG.16, adjacent to a nozzle orifice one or more protrusions or rim shaped barriers50are provided. The barrier typically has a rim height of between 1 and 10 micrometer, a rim length of typically the nozzle diameter and a width of typically 0.2-5 micrometer. Such a barriers appears to influence the flow profile and significantly change the impulse direction and deflection angle of the emanating jet. A single rectangular protrusion or rim shaped barrier may be present on one side of the nozzle orifice, as shown inFIG.17, but more than one barrier may also be present at more sides adjacent the nozzle orifice. Examples of such embodiments are shown inFIG.18. The barrier50may be rectangular but also shapes such as semi-circular that closely fits around a orifice9are possible (FIG.18). The length and the height of these protrusions or rim shaped barriers will influence the deflection angle of the jet. Some results showing the relation between the declination angle and these properties of the barrier, such as the shape and height, are shown inFIG.28for a nozzle membrane with a diameter of 50 μm, an orifice having a diameter 4.5 μm, and a rim shaped barrier with a varying shape and height placed at about 0.75 μm from the edge of the orifice. The fluid is water at a pressure of 7 bar with a flow rate of 1.33 ml/hr and the membrane has a thickness of 850 nanometer. The deflection angle is proportional to the barrier height and levels of when the height becomes equal to the orifice diameter of, in this embodiment, 4.5 micron (cf.FIG.28). Both the straight barrier and the semi-circular (180°) barrier are placed as closely as possible near or around the orifice edge. The deflection of a straight wall barrier is about half the deflection of a semi-circular barrier, if both barriers have equal height. The optimum barrier height is between 10% and 100% of the orifice diameter, in particular between 50% and 80% of the orifice diameter. The deflection angle appears also proportional to the size of the circular arc of the barrier, as shown inFIG.29. The height of the circular arc barrier is 4 μm and the barrier is placed at the edge of an orifice with a diameter of 4.5 μm. The deflection angle is optimum in a circular arc range of 120°-330°, or more particular between 180° and 260°. The deflection angle decreases with increasing distance between the semi-circular barrier and the round shaped orifice, as shown inFIG.30. For larger orifices the deflection angle decreases slower with increasing distance between the barrier and the orifice (with similar flow speeds). Preferably the distance between the orifice and the semi-circular barrier is less than 25% the orifice diameter, in particular less than 10% of the orifice diameter. Another preferred embodiment is shown inFIG.19, where the cavity5with a typical diameter of 10-90 micrometer is smaller than the nozzle membrane44with a typical diameter of 30-100 micrometer, leaving a recessed area55with a typical height ranging of 0.5-10 micrometer and a typical length of 0.5-20 micrometer at which the nozzle orifice9with a diameter 0.5-15 micrometer is placed at a position between the edge of the cavity5and the edge of the nozzle membrane and rim shaped barriers (50) are created at the recessed area55around the nozzle orifice to direct the liquid from the cavity and resulting in an inclined jet emanating from the nozzle orifice. Rim shaped barriers may be fixed at the nozzle membrane as in the embodiment shown inFIGS.16and21, leaving a gap60typically varying between 50 nanometre and 1.5 micron between the barrier50and nozzle support body11. Such a barrier50may also be fixed at the support body11as shown inFIG.20. The gap60decouples the nozzle membrane44from the support body11and greatly reduces stress points near these rim shaped barriers50to the nozzle membrane44resulting in a very high pressure strength of the nozzle membrane44such that the membrane typically can withstand pressures of 150-200 bars for a silicon nitride membrane with a diameter of 50 micron. In any case it is preferential to have a void free and obstacle free membrane edge that is circular shaped. A preferred embodiment of a spray nozzle unit with rim shaped barriers may lead to jet deflection angles that are much larger than without the rim shaped barrier. Moreover the presence of rim shaped barriers leads to less pressure losses in the spray nozzle unit than for embodiments without rim shaped barriers for a given deflection angle. Another embodiment of a spray nozzle membrane is shown inFIG.22where a non-circular orifice is placed closely to the wall of the cavity. The long elongated orifice with a length at least twice the width of the orifice has a more asymmetrical flow pattern than a circular orifice with the same orifice surface area in case the orifices are placed with the same distance between the nozzle membrane edge and nozzle orifice edge, which is typically less than 3 times a diameter of the nozzle orifice, and thus the jet emanating from the elongated orifice has more inclination than the circular pore. A further advantage of long elongated orifices in a nozzle membrane is the fact that the local bending of the membrane is deviating from the normal bending curve of a membrane giving the emanating jet additional inclination, as shown inFIG.23. Another preferred embodiment of a spray nozzle membrane is shown inFIG.24, where one or more nozzle orifices9are placed in between two adjacent corrugation zones48,49. The corrugation zones have a width of typically 2.5-5 micrometer and a height of typically 1-5 micrometer. The outer corrugation zone is placed on or near the edge10of the membrane44at a distance of typically 0-10 micrometer. A special embodiment of a nozzle according to the invention is shown inFIG.25. In this embodiment two or more deflecting nozzle orifices9are positioned in such a way that two or more deflecting jets2will collide above the nozzle membrane44in a point or spot of intersection. If the velocity and kinetic energy of the jets is sufficiently high the collision of the jets will create droplets that are much smaller than the diameter of the nozzle orifice9. This means that relatively large nozzle orifices9are allowed to generate a spray with a specific droplet size and size distribution. Larger nozzle orifices are less sensitive for clogging than smaller orifices. Two or more deflecting jets that collide can also be obtained with two or more orifices in the same membrane through use of barriers as depicted inFIG.16. It is also conceivable within the scope of the invention that two or more different liquids collide above the nozzle body. To that end the present embodiment may be provided with two or more separate cavities with separate means for supply of the subject liquids. This collision technology has many applications, especially in the field of collision of liquids with low stress materials, such as liquids containing bio-active material like peptides, vesicles and cells. Because the orifices can be made relatively large, whereas its depth relatively small, the passage of the vulnerable liquids are under mild low shear conditions. Applications are in fast 3D printing techniques, tissue engineering and similar applications. FIG.26shows a preferred embodiment of the nozzle according to the invention having two or more deflecting nozzle orifices9that are positioned in such a way that they will release two or more deflecting jets2under a deflected angle such that they will collide above the nozzle membrane44in a point or spot of intersection. This embodiment further comprises a central nozzle orifice9that emanates a microjet2without deflection from a centre line of said orifice such that also this microjet2will cross the point or spot of intersection of the other microjets2. This central microjet delivers a momentum at the point of intersection that is directed away from the main surface of the membrane thereby dragging the droplets with it. This counteracts droplets from being cast towards the membrane surface. Another embodiment is characterized in that a first zone of said second main surface of said membrane layer which surrounds said nozzle orifice is at least partly hydrophobic. This nozzle orifice is self-cleaning. Another embodiment is characterized in that the spray nozzle unit comprises at a main surface of said membrane layer an air diffusor, capable in reducing the vertical velocity of the jet exiting the nozzle orifice, wherein the air diffusor is conically or trumpet shaped with at least one air inlet opening at a height near the membrane layer. Another embodiment is characterized in that the spray nozzle unit comprises at least one nozzle orifice with a perimeter slightly elevated above the surrounding surface of the membrane that enables jetting, in which said perimeter particularly has a height between 10% and 50% of a diameter of the nozzle orifice. Another embodiment is characterized in that the spray nozzle unit is provided with filtration means which comprise a filtration plate which is in fluid communication with said cavity at said first main surface side of said membrane layer support body. Although the invention has been described hereinbefore with reference to a number of certain embodiments, it will be understood that the invention is by no means restricted to these embodiments. Instead numerous embodiments and variations are feasible for a skilled person without departing from the scope and spirit of the invention. Particularly the skilled person will appreciate that the following special embodiments emerge from the scope and spirit of the present invention: Particular Embodiments of the Invention 1. A spray device, for spraying a fluidic microjet spray, comprising a spray nozzle unit, said spray nozzle unit comprising at least one spray nozzle having a chamber for receiving a pressurized fluid therein and having a perforated nozzle wall for releasing a microjet spray of said fluid, characterized in that said spray nozzle is formed by a nozzle body, comprising a support body with at least one cavity that opens at a main surface of said support body, said support body being covered by a membrane layer at said main surface and said membrane layer being provided with at least one nozzle orifice throughout a thickness of said membrane layer at an area of said cavity to form a nozzle membrane at each of said at least one cavity that is in fluid communication with the respective cavity, in that said at least one nozzle orifice comprises at least one deflecting nozzle orifice, releasing said microjet under a deflected angle that is directed away from an imaginary centre line of said orifice, and in that said at least one deflecting nozzle orifice is in open communication with a fluidic flow channel that has a lateral asymmetrical flowprofile in terms of a fluid flow resistance from said cavity towards said nozzle orifice. 2. Spray device according to embodiment 1, characterized in that said nozzle membrane comprises a central region at the area of said cavity and a peripheral region between said central region and an edge of said cavity, and in that at least one deflecting nozzle orifice is located within said peripheral region. 3. Spray device according to embodiment 1 or 2, characterized in that at least one deflecting nozzle orifice is positioned near a peripheral wall of said cavity, in particular at a distance between a centre of said deflecting nozzle orifice and said peripheral wall that is less titan three times a diameter of said nozzle orifice, and preferably less than said diameter of said nozzle orifice. 4. Spray device according to embodiment 1, 2 or 3, characterized in that said at least one deflecting nozzle orifice has a diameter larger than 10% of a diameter of said cavity and particularly has a diameter larger than 25% of the diameter of said cavity. 5. Spray device according to any of the preceding embodiments, characterized in that said cavity is configured to impose a lateral impulse on said fluid in said fluidic flow channel that is conveyed to the liquid while forming the microjet. 6. Spray device according to embodiment 5, characterized in that said said cavity comprises at least one relatively shallow lateral extension at said main surface, said membrane comprising at least one deflecting orifice at the area of said extension. 7. Spray device according to embodiment 6, characterized in that said extension generally has a width between 0.3 and 3 times a diameter of said deflecting orifice and a length between 0.5 and 5 times a diameter of said orifice. 8. Spray device according to embodiment 6 or 7, characterized in that said extension generally has a depth that is between 0.3 to 3 times a diameter of said orifice. 9. Spray device according to anyone of embodiment 6, 7 or 8, characterized in that said support body has been locally etched to form said at least one lateral extension of said cavity. 10. Spray device according to embodiment 6, 7 or 8, characterized in that said a least one lateral extension of said cavity comprises a substantially ring-shaped extension along a periphery of said cavity in fluid communication with a plurality of angularly distributed deflecting nozzle orifices. 11. Spray device according to embodiment 6, 7 or 8, characterized in that said a least one lateral extension of said cavity comprises a plurality of angularly distributed local extensions of said cavity, each being in fluid communication with at least one deflecting nozzle orifice. 12. A spray device according to any of the preceding embodiments, characterized in that said at least one deflecting orifice has a non-axi symmetrical shape having a wider part and a narrower part, particularly an oval, tear, moon, V or U shape, and in that said wider part of said nozzle orifice faces away from an edge wall of said cavity. 13. Spray device according to anyone of the preceding embodiments characterized by comprising at least one fluid barrier near said at least one deflecting orifice that is at least partly positioned in said fluidic flow channel towards said nozzle orifice, said at least one barrier being provided assymetrically with respect to said nozzle orifice. 14. Spray device according to embodiment 13, characterized in that said barrier comprises at least one rim that extends from said membrane to inside said flow channel. 15. Spray device according to embodiment 13 or 14, characterized in that said at least one barrier leaves a gap for fluidic passage of between 50 nanometer and 5 micrometer. 16. Spray device according to embodiment 13, 14 or 15, characterized in that said at least barrier is provide along a lineair, multi-linear or curvalinar contour around said deflecting nozzle, said contour being open at a side of said orifice that is directed to a centre of said cavity. 17. Spray device according to anyone of the preceding embodiments, characterized in that said cavity is generally ring-shaped, and in that said at least one deflecting nozzle orifice comprises groups of orifices that are distributed along an outer periphery of said generally ring-shaped cavity. 18. Spray device according to anyone of the preceding embodiments, characterized in that said spray nozzle is provided with filtration means which comprise a filtration plate that is in fluid communication with said cavity and that is provided onto an upstream surface of said support body. 19. Spray device according to anyone of the preceding embodiments, characterized in that said at least one deflecting nozzle orifice has a diameter of between 0.4 and 20 micron. 20. Spray device according to anyone of the preceding embodiments, characterized in that air difussor means are provided downstream of said nozzle, said air diffusor means being onfigured to reduce a velocity of the fluidic microjet that emanates from said nozzle, wherein said air diffusor means are conically or trumpet shaped and comprise at least one air inlet opening. 21. Spray device according to anyone of the preceding embodiments, wherein the liquid is a cosmetic liquid or a wafer cleaning liquid, characterized in that said spray nozzle has a microjet divergence angle greater than 10°. 22. Spray device according to any of the preceding embodiments, characterized in that said cavity has a generally circular or polygonal cross-section at said main surface and in that said at least one deflecting nozzle orifice comprises a set of a number of deflecting nozzle orifices that are angularly distributed along at least a part of a peripheral edge of said cavity, in particular at a distance from said edge that is less than a diameter of an orific. 23. Spray device according to embodiment 22, characterized in that at least one further set of deflecting spray nozzele orifices is angularly distributed along at least a part of said peripheral edge of said cavity, particularly at a distance from said edge that is between one and three times said diameter of an orific. 24. Spray according to anyone of the preceding embodiments, characterized in that said nozzle membrane is configured to bend during operation from a substantially flat initial state to an at least partly curved profile under pressure while releasing said microjet spray, and in that said at least one nozzle orifice is located near a point of inflection in said curved profile of said nozzle membrane. 25. Spray device according to embodiment 24, characterized in that said nozzle membrane is configured to bend in that said membrane is corrugated, comprising at least one corrugation along a periphery of said cavity. 26. Spray device according to embodiment 25, characterized in that said membrane comprises at least two laterally spaced corrugations along the periphery of said cavity and in that said at least one deflecting orifice is positioned in between adjacent corrugations. 27. Spray device according to embodiment 24, characterized in that said nozzle membrane is configured to bend in that said membrane is provided with at least one deflecting nozzle orifice that is elongated and allows said membrane to deflect along an edge of said elongated nozzle orifice. 28. Spray device according to anyone of the preceding embodiments, characterized in that a bare surface of said spray nozzle is hydrophobic at least at an area adjacent said at least one nozzle orifice. 29. Spray device according to anyone of the preceding embodiments, characterized in that said support body comprises a plurality of cavities that are distributed at said main surface, particularly distributed angularly at said surface, each one of said cavities being spanned by a nozzle membrane having at least one deflecting nozzle orifice. 30. Spray device according to anyone of the preceding embodiments, characterized in that said support body comprises a semiconductor body, preferably a silicon body. 31. Spray device according to anyone of the preceding embodiments, characterized in that said membrane layer comprises a ceramic layer, particularly of a thickness that is generally less than 2 microns, more particularly a silicon nitride layer. 32. Spray device according to anyone of the preceding embodiments, characterized in that said deflecting orifice extends partly beyond an edge of said cavity and partly over said cavity. 33. Spray device according to anyone of the preceding embodiments, characterized by further comprising a liquid supply system for supplying a pressurized liquid to said cavity of at least one spray nozzle. 34. Spray device according to anyone of the preceding embodiments, characterized in that said membrane has a thickness less that 50% of a diameter of said orifice, particularly less that 25% of said diameter. 35. Spray device according to embodiment 16, characterized in that said at least one barrier surrounds said orifice substantially along a semi-circular arc that subscribes an angle of between 120 and 330 degrees, particularly of between 180 and 260 degrees, around said orifice. 36. Spray device according to embodiment 16, characterized in that said barrier is spaced from said orifice over a distance that is less than 25% a diameter of said orifice, particularly less than 10% of said diameter of said orifice. 37. Spray device according to anyone of the preceding embodiments, characterized in that the spray nozzle unit comprises at least one nozzle orifice with a perimeter slightly elevated above the surrounding surface of the membrane that enables jetting, in which said perimeter particularly has a height between 10% and 50% of a diameter of the nozzle orifice. 38. Spray device according to anyone of the preceding embodiments, characterized in that said membrane comprises at least two deflecting nozzle orifices, releasing said microjet under a deflected angle along a jet line that is directed away from an imaginary centre line of the respective orifice, and in that the jet lines of said at least two nozzle orifices intersect one another to cause said emanating microjets to collide during operation. 39. Spray device according to embodiment 38, characterized in that said membrane comprises at least one third nozzle orifice, releasing said microjet under a substantially non-deflected angle along a jet line that is directed along an imaginary centre line of said third orifice, and in that the jet lines of said at least two nozzle orifices intersect with said jet line of said third orifice to cause said emanating microjets to collide during operation. 40. Spray device according to any of the preceding embodiments, characterized in that micro-valve means are present upstream of said defelcting nozzle orifice, said valve means comprising a micro-valve disc in close proximity of a micro-valve seat, said micro-valve disc resting on said micro-valve seat in a normally closed state and lifting from said seat once an upstream pressure threshold is exceeded to open a fluid passage between said micro-valve disc and said micro-valve seat towards said fluidic flow channel. 41. Spray device according to embodiment 40, characterized in that said nozzle membrane constitutes one of said micro-valve seat and said micro-valve disc. 42. Spray device according to anyone of the preceding embodiments, characterized in that said membrane comprises at least two deflecting nozzle orifices, releasing said microjet under a deflected angle along a jet line that is directed away from an imaginary centre line of the respective orifice, and in that said at least two nozzle orifices have a mutually different lateral cross section. 43. Spray device according to embodiment 42, characterized in that said membrane comprises at least two groups of deflecting nozzle orifices, releasing said microjet under a common deflected angle along a jet line that is directed away from an imaginary centre line of the respective orifice, and in that the orifices within each of said at least two groups of nozzle orifices feature a substantially identical lateral cross section that is distinct from a lateral cross section of the orifices in the other of said at least two groups of deflecting nozzle orifices. 44. Spray device according to anyone of the preceding embodiments, characterized in that at least one of said deflecting orifices has a triangular lateral cross-section. 45. Spray nozzle body of the type as applied in the spray device according to anyone of the preceding embodiments.
37,040
11857985
Like reference numerals have been used in the figures to identify like components. DETAILED DESCRIPTION OF THE INVENTION An airpot beverage dispenser10for holding drinkable liquids. The dispenser10has an operating state for dispensing a liquid contained in the dispenser, and a leak-proof locked state in which the liquid cannot be dispensed and will not leak from the dispenser if not in an upright position or when being transported. The dispenser10is shown fully assembled in the operating state inFIGS.1,2and4-6, and in the locked state inFIG.18. The dispenser10includes a substantially cylindrical container body12and a lid14having a lower lid portion16and an upper lid portion18. As best seen inFIGS.4-6, the container body12has an upper end portion20with an aperture22, and a sidewall portion24extending downwardly from the upper portion20and closed at the lower end of the sidewall portion by a bottom wall26to define an interior beverage cavity28for holding hot or cold drinkable liquids therein. The exterior of a lower end portion30of the lower lid portion16has threads17and the interior of the upper portion20of the container body12has corresponding threads20A for threadably attaching the lid14to the container body12, but other means for removably coupling the lid to the container body may be used. A seal19extends about the lower lid portion16to provide a fluid-tight seal between the lower lid portion and the container body12. A bail handle32is rotatably attached to a collar34attached to the upper end portion20of the body12for carrying the dispenser10. As best shown inFIGS.7-8, the lower lid portion16includes a transversely extending upper wall16A and a lower lid compartment16B positioned below the upper wall16A. The lower lid portion16has vertically oriented first and second through passageways16C and16D, respectively, extending fully through the upper wall16A and the lower lid compartment16B. The second through passageway16D is in longitudinal alignment with a longitudinal axis38of the lid14, and has a lower end in fluid communication with the beverage cavity28. The first through passageway16C is radially, outwardly offset from the second through passageway, and also has a lower end in fluid communication with the beverage cavity28. The upper lid portion18is rotatably coupled to the lower lid portion16by a hinge36for rotation of the upper lid portion relative to the lower lid portion about an axis of rotation transverse to the longitudinal axis38of the lid14and container body12. The lower lid portion16has a lower lid hinge member36A, and the upper lid portion18has an upper lid hinge member36B rotatably connected together by a hinge pin36C. The lid14is rotatively movable between a closed position as shown inFIGS.1,2,4-9, and18where the upper lid portion18is rotated downward relative to the lower lid portion16and is position adjacent thereto, and an opened position as shown inFIG.15where the upper lid portion is rotated upward relative to the lower lid portion. When in the lid14is in the closed position, the upper lid portion18may be secured to the lower lid portion16in the closed position by two latches40, as shown inFIGS.1,2and18. The upper lid portion18may be unlatched from the lower lid portion16when it is desired to rotate the lid14to the opened position as shown inFIG.15, such as for putting a drinkable liquid in the beverage cavity28for dispensing from the dispenser10, for cleaning of the dispenser or putting the dispenser in the locked state, as will be described in greater detail below. When the lid14is in the closed position with each of the two latches40latched, a lower end of a lower latch portion40A is rotatably connected to the lower lid portion16, an upper end of the lower latch portion is hinged to a lower end of an upper latch portion40B, and the upper end of the upper latch portion extends or is hooked over an outward edge18A of a depression18B in an outer sidewall18C of the upper lid portion18(best seen inFIG.15showing the lid in the opened position). As shown inFIGS.4-9, the dispenser10includes a spout42supported by the lower lid portion16for dispensing or discharge of liquid from within the beverage cavity28. The spout42is movable between a dispensing position shown inFIGS.4-6and7-9, and a stored position shown inFIG.17.FIG.18shows the exterior of the dispenser10when the spout42is in the stored position within the lid14and not visible. The spout42has a spout head portion43with a downturned, discharge outer end spout portion44located outward of the container body12and the lower lid portion16, and a vertically oriented, inward end spout portion46positioned in the vertically oriented first through passageway16C of the lower lid portion, with a laterally extending middle spout portion47extending between the outer end spout portion44and the inward end spout portion46. An internal fluid conducting spout channel50extends through the outer end spout portion44, the middle spout portion47and the inward end spout portion46. An inward end portion of the spout channel50of the inward end spout portion46has an enlarged opening52sized to removably receive therein in fluid tight sealing engagement, an upper end portion54of a spout conduit portion, referred to herein as a feed tube or straw56. As shown inFIGS.4-6, the straw56has an internal fluid conducting straw channel58extending between an upper straw end portion54and a lower straw end portion60. The straw channel58is in fluid communication with the inward end portion of the spout channel50and has a lower end straw opening61positioned adjacent to the bottom wall26of the body container12for conducting liquids in the beverage cavity28upwards through the straw channel58to and through the spout channel50, for discharge from the outer end spout portion44for deposit in a drink container (not shown) for drinking. When the spout42is in the dispensing position, the straw56enables a user to draw liquid from within the beverage cavity28without having to tip the dispenser10for pouring, as will be described in greater detail below. In the illustrated embodiment, the spout head portion43is not removable from the straw56. A seal62is positioned between the inward end spout portion46and the inner wall of the first through passageway16C of the lower lid portion16to provide a fluid-tight seal therebetween, while allowing the inward end spout portion to rotate within the first through passageway and be moved upward and downward in the first through passageway as needed when the user is moving the spout42between the dispensing position and the stored position. It is noted that while the spout42is removable from the lower lid portion16, the spout need not be removed to move the spout between the dispensing position and the stored position. The spout channel50includes an upright first channel portion50A extending within the outer end spout portion44, an upright second channel portion50B extending within the inward end spout portion46, and a laterally extending third channel portion50C extending within a laterally extending middle spout portion47. The spout head portion43has an aperture66in the wall of the spout channel50at the inward end of the middle spout portion47of the spout channel50, sized to removably receive a plug68therein (just above the upper end of the second channel portion50B). The aperture66is in straight alignment with the third channel portion50C to provide easy access the third channel portion50C for cleaning of the third channel portion, which is positioned between two right angle bends in the spout channel50. To dispense the liquid from within the beverage cavity28through the spout42, the dispenser10has a bellows70positioned at least partially within an upwardly open chamber72within the upper lid portion18in longitudinal alignment with the longitudinal axis38of the lid14(seeFIGS.4-10,26B and27B). The bellows70has an upper bellows end wall74with an upper bellows end aperture74A and a lower bellows end wall76with a lower bellows end aperture76A. The upper and lower bellows end apertures74A and76A are centrally located in alignment with the longitudinal axis38of the lid14. A tubular bellows collar75has an upper end and a lower end, with a fluid channel extending therebetween. The upper end of the bellows collar75is attached to the lower bellows end wall76with the upper end of the fluid channel of the bellows collar in fluid communication with the lower bellows end aperture76A. A bellows spring78has a cylindrical upper spring end portion78A and a conical lower spring end portion78B. The lower spring end portion78B is positioned within the bellows70, and the upper spring end portion78A extends through the upper bellows end aperture74A and has an upper end78C terminating above the upper bellows end wall74. As will be described below, the bellows70may be compressed/collapsed in the process of dispensing the liquid from within the beverage cavity28. The bellows70of the illustrated embodiment has a sufficiently resilient corrugated outer wall70A that after being collapsed, the outer wall acts as in integral spring that moves the upper bellows end wall74upward and expands the bellows once the downward force being applied by a user is removed. However, in an alternative embodiment, a lower portion78D of the upper spring end portion78A may be in driving engagement with the interior side of the upper bellows end wall74to supply additional upward return force to assist in moving the upper bellows end wall upward to expand the bellows70after being collapsed. A lower portion78E of the lower spring end portion78B is in contact with the interior side of the lower bellows end wall76. The chamber72within which the bellows70is positioned has a circumferentially extending, cylindrical chamber sidewall80, an open upper chamber end81, and a transversely extending chamber bottom wall82located below the lower bellows end wall76and within the upper lid portion18. The chamber bottom wall82has a chamber bottom wall aperture84centrally located in alignment with the longitudinal axis38of the lid14, as best shown inFIGS.7-9. As shown inFIGS.7-14, a valve assembly86has a valve support member88and a valve90. The valve support member88includes an annular flange portion92with a central flange aperture93and a circumferentially extending sidewall portion94projecting downward from the flange portion and extending circumferentially about the central flange aperture. The flange portion92is attached to the lower bellows end wall76and the central flange aperture93is in alignment with the longitudinal axis38of the lid14and the lower bellows end aperture76A. The sidewall portion94extends through the chamber bottom wall aperture84for downward and upward axial movement of the valve support member88relative to the chamber bottom wall82, as the bellows is compressed/collapsed and expanded, respectively. A lower end portion of the sidewall portion94has an inwardly projecting circumferentially extending valve retainer ridge96. The valve90has a tubular downwardly extending valve base portion98, a duckbill valve portion100, and a skirt valve portion102. The duckbill valve portion100and the skirt valve portion102are coaxially arranged and extend downward from the valve base portion98. The valve base portion98is positioned within the sidewall portion94of the valve support member88and has a longitudinally extending fluid channel in alignment with the longitudinal axis38of the lid14. The bellows collar75extends downward from the lower bellows end wall76through the central flange aperture93and into the interior of the valve base portion98within the fluid channel of the valve base portion. The valve base portion98has an exterior circumferentially extending groove104, which when the valve base portion is positioned within the sidewall portion94of the valve support member88, receives the retainer ridge96of the sidewall portion therein to securely hold the valve90in place during operation of the valve assembly86. The duckbill valve portion100of the valve90has an upper end portion106attached to the lower end of the valve base portion98and a lower end portion108with two opposing sidewalls110and112. The lower ends of the opposing sidewalls110and112have a normally closed exit aperture or slit114extending between them. The duckbill valve portion100is a one-way valve only permitting downward air flow out of the lower bellows end aperture76A when the duckbill valve portion is opened. The skirt valve portion102of the valve90has a skirt wall116extending fully around the duckbill valve portion100. An upper end portion118of the skirt wall116is attached to the upper end portion106of the duckbill valve portion100, and a lower end portion120of the skirt wall defines a central aperture122. The skirt wall116is convex in curvature in vertical profile (a mid-portion116A having a larger diameter or transverse wall separation dimension than either one of the upper and lower end portions118and120, seeFIGS.11-11C), and at least one of the lower end portion and mid-portion, and preferably both are flexible enough to flex under a sufficiently high pressure within the beverage cavity28of the container body12(e.g., 50 psi), to act as a blow off or relief valve, as will be explained in more detail below. A coil return spring124is positioned between the flange portion92of the valve support member88(and hence the lower bellows end wall76) and the chamber bottom wall82of the chamber72, with the sidewall portion94of the valve support member positioned within the coils of the return spring. The chamber bottom wall82has an upwardly opening spring retainer groove126extending about the chamber bottom wall aperture84for receiving a lower end of the return spring124. An upper end of the return spring124is in engagement with the flange portion92of a valve assembly86. The return spring124assists in upward return movement of the valve assembly86after having been moved downward, as will be described below. An actuator or push button128is used to manually move the upper bellows end wall74downward to cause discharge of liquid from within the beverage cavity28when the dispenser10is in the operating state. The push button128has a button top wall130positioned above the upper bellows end wall74and spanning across the upper bellows end wall, and a circumferentially extending, cylindrical button sidewall132extending downward from the button top wall (in the general shape of an inverted cup) and terminating in a button sidewall lower end128A positioned within the chamber72of the upper lid portion18for reciprocal movement within the chamber along the longitudinal axis38of the lid14. The button top wall130is positioned above a chamber sidewall upper end80A of the chamber sidewall80, and the button sidewall132extends downward sufficiently that the button sidewall lower end128A is below and inward of the chamber sidewall upper end80A, and as the push button128is depressed by a user and the bellows70is vertically compressed or collapsed (see movement sequence inFIGS.4-6and inFIGS.7-9showing downward movement of the pushbutton), the extent of the button sidewall132within the chamber sidewall increases. The upper end78C of the upper spring end portion78A of the bellows spring78engages the underside of the button top wall130. A best seen inFIGS.7-9, a button valve134is attached to the underside of the button top wall130in coaxial alignment with the longitudinal axis38of the lid14and upper bellows end aperture74A. The button valve134includes an annular seal134A and centrally located, downwardly projecting alignment members134B that project into the upper bellows end aperture74A and around the upper spring end portion78A to help maintain proper coaxial alignment of the button valve with the upper bellows end aperture and capture the upper spring end portion therebetween. An annular valve seat74B is attached to the upper bellows end wall74and positioned within and extends about the upper bellows end aperture74A in coaxially arrangement with the upper bellows end aperture. When the push button128is in a raised position (i.e., a fully upward position), as shown inFIGS.1,2,4and7, that is, it has not been pressed downward by a user and hence the bellows70are not vertically collapsed the seal134A of the button valve134is positioned above and spaced apart from the valve seat74B (see gap135inFIGS.4and7) and the upper bellows end aperture74A is open. It is to be understood that the button valve may be constructed with the seal134A attached to the upper bellows end wall74and the valve seat74B attached to the underside of the button top wall130. When the dispenser10is in the operating state, as the user begins to press the push button128downward to start the liquid dispensing process, the bellows spring78begins to collapse downward and the seal134A moves downward with the downward movement of the push button. With sufficient downward movement of the push button128, the gap135closes and the seal134A moves into fluid tight sealing engagement with the valve seat74B, and thereby closes the upper bellows end aperture74A (seeFIGS.5and8). Since the duckbill valve portion100is closed, this traps the air within the bellows70so that the air can be compressed under the continued downward force applied by the user to the push button128for application of that pressure to the air space above the liquid within the beverage cavity28. It is noted that in this position the skirt valve portion102may be in contact with but likely not in fluid tight sealing engagement with an annular valve seat portion136of the upper wall16A of the lower lid portion16(seeFIGS.5,8and13). As the user continues to press the push button128downward, the bellows70moves farther downward and the pressure of the air trapped within the bellows70progressively increases. When the downward force applied by the user on the push button128exceeds the spring force of the return spring124positioned between the flange portion92of the valve support member88and the chamber bottom wall82of the chamber72, the lower bellows end wall76and the valve assembly86attached thereto move downward toward the upper wall16A of the lower lid portion16. This moves the lower end portion120of the skirt wall116of the skirt valve portion102downward into fluid tight sealing engagement with the annular valve seat portion136of the upper wall16A of the lower lid portion16(seeFIGS.6,9and14). In this position, the mid-portion of the flexible skirt wall116of the skirt valve portion102is more outwardly deformed (i.e., the mid-portion116A bulging more radially outward beyond the upper and lower end portions118and120) than in the previously described positions of the skirt wall. As the lower end portion120of the skirt wall116of the skirt valve portion102is moved downward after the initial contact with the annular valve seat portion102, the shape of the skirt wall116tends to deflect or deform with the mid-portion116A of the flexible skirt wall progressively bowing outward farther with a smoothly curved shape without any sharp bends. Continued downward force applied by the user to the push button128and the resulting further compressing of the bellows70causes the air pressure trapped within the bellows70to eventually reach a pressure level sufficient to force open the duckbill valve portion100(i.e., the two opposing sidewalls110and112at the lower end portion108of the duckbill valve portion separate at the slit114). This forms an air passageway for the pressurized air in the bellows70to flow downward through the tubular bellows collar75, then through the fluid channel of the valve base portion98, then through the opened slit114of the duckbill valve portion100, through the interior sealed space defined by the skirt wall116of the skirt valve portion102, then into the second through passageway16D of the lower lid portion16, and finally, into the interior of the beverage cavity28above the liquid within the beverage cavity. Continued downward force applied by the user to the push button128will further compress the bellows70and force additional pressurized air through the air passageway and into the beverage cavity28. The stiffness of the lower end portion108of the duckbill valve portion100determines how easy it is to open the duckbill valve portion and hence how much downward force must be applied by the user to the push button128to pump the bellows70up to the pressure needed to cause the two opposing sidewalls110and112at the lower end portion108of the duckbill valve portion to separate at the slit114and complete the air passageway to the beverage cavity28. As soon as the duckbill valve portion100is open and sufficient pressurized air enters the beverage cavity28as described above, the liquid within the beverage cavity28will begin to be forced upward through the straw channel58into the spout channel50and out of the outward end of the first channel portion50A of the discharge outer end spout portion44for dispensing to a beverage container (not illustrated) positioned therebelow. This results in reduction of the air pressure within the bellows70and the closure of the slit114of the duckbill valve portion100. After liquid begins to flow from the spout42, and before accomplishing a full depression of the push button128, should the user decide to stop the flow of liquid out of the spout, the user simply needs to stop depressing the push button, but to prevent any residual pressure in the beverage cavity28above atmosphere from continuing to force more than the desired amount of liquid out of the spout, the user may remove the downward force being applied to the push button and allow the push button to move upward. As will be described below, this almost immediately vents the residual pressure out of the beverage cavity28, thus eliminating the residual pressure that was pushing the liquid out of the spout42and avoiding the possibility of auto-pumping. If a single depression of the push button128does not result in the desired amount of the liquid within the beverage cavity28being dispensed out through the spout42, one or more additional depressions or downward strokes of the push button128will be required. To accomplish another depression of the push button128, the user simply removes the downward force being applied to the push button, which results in the return spring124moving the lower bellows end wall76and the valve assembly86attached thereto upward, in the corrugated outer wall70A of the bellows70acting as an integral spring moving the upper bellows end wall74upward, and in the bellows spring78moving the push button128upward, which causes the bellows to expand vertically upward from its collapsed state and return the upper bellows end wall74to its fully raised position, and the push button128to move upward at the same time. While the bellows70is expanding, air is being drawn into the bellows through the upper bellows end aperture74A since the user is no longer applying the downward force on the push button128necessary to keep the button valve134closed. It is noted that in the illustrated embodiment while the bellows is expanding upward, the bellows spring78actively lifts the push button128to reduce the effective downward load on the upper bellows end wall74since the spring force of the corrugated outer wall70A of the bellows70is not particularly high. When the upper bellows end wall74reaches its fully raised position, the push button128is still not in its fully raised initial position. However, the bellows spring78will continue to move the push button128upward until the gap135between the seal134A of the button valve134and the valve seat74B again exists. The bellows spring78is sized such that when the upper bellows end wall74reaches its fully raised position, the upper spring end portion78A extending through the upper bellows end aperture74A will not have fully expanded and will continue to move the push button128upward to separate the button top wall130of the push button from the upper bellows end wall74sufficiently to again establish the gap135. The beverage container10is then ready for the user to again depress the push button128for a full length stroke. It is noted that the user need not wait until the upper bellows end wall74reaches its fully raised position to again apply the needed downward force to the push button128, but the result will be a lesser pressure being achieved for the trapped air in the bellows70. Whether after a full downward depression of the push button or at any point after the downward movement of the push button causes the pressurized air within the bellows70to open the duckbill valve portion100and flow into the beverage cavity28, the user may remove the downward force being applied to the push button128and allow the push button to move slightly upward. The upward movement of the valve assembly86breaks the seal between the lower end portion120of the skirt wall116of the skirt valve portion102and annular valve seat portion136of the upper wall16A of the lower lid portion16, which results in any pressure above atmosphere remaining in the air space above the liquid within the beverage cavity28being exhausted to atmosphere via air passageways138within the lower lid portion. This immediately eliminates the air pressure forcing the discharge of the liquid and thereby stops the flow of the liquid out of the spout42, and preventing any auto or self-pumping from occurring. The dispenser10may be placed in its leak-proof locked state in which the liquid within the beverage cavity28will not be dispensed, and will not leak from the dispenser if the dispenser should not be in an upright position or if the dispenser is tilted or shaken while being transported. To change the dispenser10from the operating state to the locked state, the push button128is allowed to move to the raised position shown inFIGS.1,2,4,7and12, and when in the raised position, the two latches40, which are latched when the lid14is in the closed position, are unlatched. After unlatching both of the two latches40, the user may rotate the upper lid portion18about the hinge36, to raise the upper lid portion sufficiently (preferably enough to place the lid14in the fully opened position shown inFIG.15) to allow the user to move the spout42from the dispensing position shown inFIG.16to the stored position shown inFIG.17. When the dispenser10is in the operating state and the lid14is in the closed position, the middle spout portion47extends laterally through an upwardly open, perimeter wall recess16E in a top perimeter wall portion16F of the lower lid portion16, and is captured therein by the chamber bottom wall82of the upper lid portion18positioned immediately thereabove. A lower side of the chamber bottom wall82has a downwardly extending protrusion82D, which extends down to within a circular retainer wall42A attached to and extending upwardly from the middle spout portion47to maintain the position of the spout in the perimeter wall recess16E. The perimeter wall portion16F projects upwardly beyond the upper wall16A of the lower lid portion and terminates below the chamber bottom wall82. To move the spout42from the dispensing position to the stored position, with the lid14in the opened position or at least a partially opened position, the spout is pulled upward to move the middle spout portion47upward and out of the perimeter wall recess16E. The spout42is then rotated clockwise (when view from above) until positioned above an upwardly opening, upper wall storage recess16G in the upper wall16A of the lower lid portion16. The upper wall recess16G is sized and shaped to receive the outward end portion of the middle spout portion47therein. An upwardly projecting plug144is positioned within a recess16H within the upper wall recess16G at a location corresponding to the location of the first channel portion50A when the middle spout portion47is within the upper wall recess, such that when the middle spout portion is moved over the upper wall recess and push downward into the upper wall recess to place the spout42in the stored position, the plug144enters the first channel portion50A and is in fluid tight sealing engagement with the outer end spout portion44. This seals the first channel portion50A against liquid passing out of the first channel portion while the spout42remains in the stored position. It is noted that when pulling the spout42upward to move the middle spout portion47out of the perimeter wall recess16E, the straw56moves upward with the spout and remains in fluid tight sealing engagement with the spout. In an alternative embodiment described below, the straw56may be maintained in its position and the spout42disconnected from fluid communication with the straw when the spout is pulled upward to move the middle spout portion47out of the perimeter wall recess16E. After the spout42is moved to the stored position shown inFIG.17, the lid14is moved to the closed position by rotating the upper lid portion18downward, and then latching the upper lid portion to the lower lid portion16using the latches40. The push button128is next depressed and moved downward to the fully depressed position shown inFIG.18. When in the fully depressed position, the push button128is rotated clockwise (when view from above) to a locked push button position. It is noted that an alternative sequence is to move the push button128downward to the fully downward position and then rotate the push button into the locked push button position while the lid is in the opened position before moving the lid14to the closed position, and thereafter move the upper lid portion18downward to the lid closed position and then latching it to the lower lid portion16. In the alternative embodiment mentioned above, the straw56may be maintained in its position and the spout42disconnected from fluid communication with the straw56when the spout is pulled upward to move the middle spout portion47out of the perimeter wall recess16E. In this alternative approach, the upper straw end portion54carries an O-ring (not shown) which maintains a fluid tight sealing engagement with the spout42when in the dispensing position. When the spout42is pulled upward and rotated to move the spout to the stored position, the O-ring on the upper straw end portion54is disconnected from fluid tight sealing engagement with the spout, but the upper straw end portion remains within a downwardly opening recess (not shown) in the underside of the spout, and the seal62remains positioned between the inward end spout portion46and the inner wall of the first through passageway16C of the lower lid portion16to provide a fluid-tight seal therebetween. As such, any liquid passing out of the upper straw end portion54while the spout42remains in the stored position flows into the downwardly open recess in the underside of the spout42and drains back down into the beverage cavity28. This alternative embodiment eliminates the need for the plug144in the recess16H to seal the first channel portion50A of the spout42while in the stored position. To guide the up and down reciprocal movement of the push button128within the chamber72and provide its proper alignment in the chamber, and also to hold the push button in the locked push button position when the push button is in its fully depressed position, the button sidewall lower end128A has a outwardly extending arm128B and five radially outward extending tabs128C (best shown inFIGS.19and20), and the chamber sidewall80has six vertically extending open channels or grooves80B (best shown inFIG.21), within which the arm and tabs may be movably disposed for upward and downward movement as the push button128moves upward and downward. One of the vertical grooves80B is sized and shaped to receive the outwardly extending arm128B and the other five grooves are sized and shaped to each receive one of the five tabs128C. The outwardly extending arm128B and the five tabs128C are shown inFIG.22rotated into vertical alignment with the vertical grooves80B for upward and downward movement within the vertical grooves. When the push button128is moved downward into its it fully depressed position, the push button may be rotated clockwise when view from above (counterclockwise when viewed from below as inFIGS.22and23) from the position shown inFIG.22with the outwardly extending arm128B and the five tabs128C in vertical alignment with the vertical grooves80B, until each is rotated into engagement with one of six elongated, vertically extending stops80C, as shown inFIG.23(see alsoFIG.27A), whereat the push button is in the locked push button position.FIG.26Ashows the position of the outwardly extending arm128B and the five tabs128C rotated to mid-way between the vertical grooves80B and the stops80C. To permit this rotation of the outwardly extending arm128B and the five tabs128C between the vertical grooves80B and the stops80C, the lower end portion of the chamber sidewall80has six horizontal open channels or grooves80D (seeFIG.21) extending around the inward perimeter of the chamber sidewall, each permitting one of the outwardly extending arm128B and the five tabs128C to be rotated between the one of the vertical grooves80B and one of the stops80C, while preventing upward movement of the outwardly extending arm and the tabs during that rotation. However, to hold the push button128securely in the locked push button position and prevent unintended rotational movement of the outwardly extending arm128B and the five tabs128C back toward the vertical grooves80B, an upwardly extending lock recess80E is provided adjacent to each stop80C sized to receive the one of the outwardly extending arm or tab in engagement with the stop. When the push button128is released by the user after the push button has been rotated into the locked push button position, there is a slight upward movement of the push button provided by the bellows spring78that moves the arm128B and the five tabs128C upward into its corresponding lock recess80E. In addition to holding the push button128in the locked push button position, it secures the dispenser10in the locked state and the bellows70in its collapsed state. It is noted that when the dispenser10is in the locked position, any downward movement of the push button128, including the movement just described, will not cause additional air to enter the bellows70and hence not pump out any liquid in the beverage cavity28, since the bellows is sealed on both ends by the seal134A of the button valve134at the upper end and by the duckbill valve portion100of the valve90at the lower end. If the push button128were pumped when in the locked push button position, it would just slightly deform the bellows, but not moving any air through the bellows to the beverage cavity28. When the user desires to change the dispenser10from the locked state back to the operating state, the user sufficiently depresses the push button128downward to move the outwardly extending arm128B and the five tabs128C downward and out of the lock recesses80E and into the horizontal grooves80D, and rotates the push button counterclockwise when view from above (clockwise when viewed from below as inFIGS.22and23) until the arm and the tabs are again each in vertical alignment with one of the vertical grooves80B. The user then need only release the push button128to remove any downward being applied to the push button, and allow the push button and the bellows end wall74to rise upward under the force applied by the bellows spring78to their fully raised positions. Each of the stops80C is located adjacent to one of the vertical grooves80B, such that when the push button128is being rotated from the locked push button to the position with the outwardly extending arm128B and the five tabs128C in vertical alignment with the vertical grooves80B, the stops will prevent further rotation of the arm and the tabs beyond their position in vertical alignment with the vertical grooves. The latches40are then unlatched, the upper lid portion18is rotated upward sufficient to allow the user to move the spout from its stored position in the upper wall recess16G back to its dispensing position, and then the upper lid portion is closed and latched back to the lower lid portion16. This places the dispenser10back into the operating state. When the spout42is in the stored position and the push button128is rotated into the locked push button position, the push button will have been sufficiently depressed to move the lower end portion120of the skirt wall116of the skirt valve portion102into fluid tight sealing engagement with the annular valve seat portion136of the upper wall16A of the lower lid portion16(and the duckbill valve portion100will be closed). In this situation, the skirt valve portion102is designed to serve as a pressure relief valve and release a portion of the pressure within the beverage cavity28if that pressure increases, such as through fermentation over time of the liquid remaining in the beverage cavity, to a level approaching an internal pressure which might cause damage to the dispenser. In operation, when the pressure within the beverage cavity28reaches a release pressure, the pressure within the beverage cavity28will cause at least a momentary separation between at least a portion of the skirt wall116and the annular valve seat portion136through which the excess pressure is relieved (i.e., the skirt wall will “burp” gas as shown inFIG.28), and then the skirt wall116will once again come fully into fluid tight sealing engagement with the annular valve seat portion136. The release pressure at which the skirt valve portion102releases the excess pressure depends on the flexibility of the material selected for skirt wall116and the shape of the skirt wall, which can be selected to provide a desired pressure at which the skirt valve portion will prevent being exceeded. It is noted that if the lid14is in the closed position, with the push button128in the raised position, and the spout42is in the dispensing position, when the push button is moved into the fully depressed position it cannot then be rotated into the locked push button position. This is because clockwise rotation of the push button128will cause the arm128B at the button sidewall lower end128A to engage a stop member42B attached to and extending upwardly from the middle spout portion47, which limits clockwise rotational movement of the push button when the spout42is in the dispensing position (seeFIGS.24and25). The stop member42B extends upward from the spout through an aperture82E in the chamber bottom wall82with its upper end positioned in the path of rotational movement of the arm128B. Rotational movement of the arm128B resulting from rotation of the push button128toward the locked push button position is not prevented when the spout42has been moved to the stored position, sitting in the upper wall recess16G. This is because when in the upper wall recess16G, the spout42and the top of the stop member42B are positioned sufficiently below the vertical position of the arm128B that the arm128B will pass over them and be unimpeded by the stop member as the push button128is rotated into, or out of, the locked push button position. It is noted that if the push button128could be placed in the locked push button position without moving the spout42to the stored position, and hence the spout remained in the dispensing position, sufficient agitation of the liquid in the beverage cavity28might result in self-pumping of the liquid out of the spout. It is further noted that the upper end of the stop member42B is positioned immediately below a lower end80F of the chamber sidewall80such that when the dispenser10is in the operating state and the lid14is in the closed position, and the middle spout portion47extends laterally through the perimeter wall recess16E in a top perimeter wall portion16F of the lower lid portion16, the middle spout portion is captured therein by the lower end of the chamber sidewall being82D positioned immediately thereabove. As described above, the removable plug68is provided to aid in cleaning the third channel portion50C of the spout channel50of the spout42. Additionally, the spout42is removable from the first through passageway16C of the lower lid portion16and the straw56may be disconnected from the inward end spout portion46to facilitate cleaning of the spout and straw. As shown inFIGS.7-9and as described above, the lower lid portion16includes the upper wall16A and the lower lid compartment16B positioned below the upper wall16A. The upper wall16A is in fluid tight sealing engagement with the lower lid compartment16B positioned therebelow to define a dry internal, lower lid portion chamber150therebetween. A lower wall146of the lower lid compartment16B has two apertures146A and146B, and the upper wall16A has two apertures148A and148B. As shown inFIGS.29-32, a first conduit152is vertically positioned within the lower lid portion chamber150and defines the first through passageway16C of the lower lid portion16, and has upper and lower open ends. The lower end of the first conduit152is in alignment with the aperture146A of the lower wall146and in fluid tight sealing engagement with the lower wall, and the upper end of the first conduit is in alignment with the aperture148A of the upper wall16A and in fluid tight sealing engagement with the upper wall. Similarly, a second conduit154is vertically positioned within the lower lid portion chamber150and defines the second through passageway16D of the lower lid portion16, and has upper and lower open ends. The lower end of the second conduit154is in alignment with the aperture146B of the lower wall146and in fluid tight sealing engagement with the lower wall146, and the upper end of the second conduit is in alignment with the aperture148B of the upper wall16A and in fluid tight sealing engagement with the upper wall. A Styrofoam insulation puck or block156is positioned within the lower lid portion chamber150, with a vertically oriented, first block through passageway156A through which the first conduit152fully extends and a vertically oriented, second block through passageways156B through which the second conduit154fully extends. The first and second block passageways156A and156B are cylindrical in shape and have a cross-sectional size to receive the first and second conduits152and154, respectively, snuggly therein with their sidewalls in engagement with the block15. The outer perimeter of the block15is sized to fit snuggly within the lower lid portion chamber150with the outer sidewall of the block in engagement with the inner sidewall of the lower lid compartment16B. The block15is positioned within the lower lid portion chamber150before the upper wall16A and the lower lid compartment16B are sealed together. The insulation block156provides the lower lid portion16of the lid14with improved thermal properties. Other insulating material may be used other than air. The first conduit152receives the inward end spout portion46, the seal62and the upper end straw portion54therein, and the second conduit154is an air passageway to the beverage cavity28through which the pressurized air produced by the compression of the bellows70passes. As best seen ifFIG.1, the bail handle32includes a first handle support portion158and a second handle support portion160, and a grippable handle portion162. A first end portion158A of the first handle support portion158is rotatably attached to the collar34, which is attached to the upper end portion20of the container body12, and a first end portion160A of the second handle support portion160is rotatably attached to the collar, on a side of the container body opposite the attachment of the first handle support portion. A second end portion158B of the first handle support portion158is fixedly attached to one end of the grippable handle portion162, and a second end portion160B of the second handle support portion160is fixedly attached to the opposite end of the grippable handle portion. A third handle portions158C of the first handle support portion158, located between the first and second end portions158A and1586, has an inward portion164and an outward portion166defining a pass-through attachment opening168therebetween, which is fully encircled by the inward and outward portions164and166. A third handle portions160C of the second handle support portion160, located between the first and second end portions160A and160B, has an inward portion170and an outward portion172defining a pass-through attachment opening174therebetween, which is fully encircled by the inward and outward portions170and172. The attachment openings168and174each have a transverse are each sized to permit a rope, clip or other attachment member to extend therethrough to facilitate securing the dispenser10to a support, such as a fence, car, boat or other vehicle, to support the weight of the dispenser and the liquid in the internal container cavity28, or to facilitate securing an item to the dispenser, such as a package of drink additive, a spoon or a sugar container. While shown with two attachment openings168and174, it is to be understood that alternatively the dispenser10may have only a single attachment opening. The foregoing described embodiments depict different components contained within, or connected with, different other components. It is to be understood that such depicted architectures are merely exemplary, and that in fact many other architectures can be implemented which achieve the same functionality. In a conceptual sense, any arrangement of components to achieve the same functionality is effectively “associated” such that the desired functionality is achieved. Hence, any two components herein combined to achieve a particular functionality can be seen as “associated with” each other such that the desired functionality is achieved, irrespective of architectures or intermedial components. Likewise, any two components so associated can also be viewed as being “operably connected,” or “operably coupled,” to each other to achieve the desired functionality. While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that, based upon the teachings herein, changes and modifications may be made without departing from this invention and its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of this invention. Furthermore, it is to be understood that the invention is solely defined by the appended claims. It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases shouldnot be construedto imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to inventions containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations, or two or more recitations). Accordingly, the invention is not limited except as by the appended claims.
48,701
11857986
DETAILED DESCRIPTION OF THE INVENTION As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to particular modes of practice, and it is to be appreciated that all changes, equivalents, and substitutes that do not depart from the spirit and technical scope of the present invention are encompassed by the present invention. In the description of the present invention, certain detailed explanations of the related art are omitted if it is deemed that they may unnecessarily obscure the essence of the invention. The terms used in the present specification are merely used to describe particular embodiments and are not intended to limit the present invention. An expression used in the singular encompasses the expression of the plural, unless it has a clearly different meaning in the context. In the present specification, it is to be understood that terms such as “including” or “having,” etc., are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof disclosed in the specification and are not intended to preclude the possibility that one or more other features, numbers, steps, actions, components, parts, or combinations thereof may exist or may be added. While such terms as “first” and “second,” etc., can be used to describe various components, such components are not to be limited by the above terms. The above terms are used only to distinguish one component from another. Certain embodiments of the present invention will be described below in more detail with reference to the accompanying drawings. Those components that are the same or are in correspondence are rendered the same reference numeral, and redundant descriptions are omitted. FIG.1is a perspective view of a tubeless dispenser container1000according to an embodiment of the invention with the overcap10separated,FIG.2is a cross-sectional view of the tubeless dispenser container1000illustrated inFIG.1across line A-A′, andFIG.3is an exploded perspective view of the tubeless dispenser container1000illustrated inFIG.1. Referring toFIGS.1to3, a tubeless dispenser container1000according to an embodiment of the invention can be a container for dispensing a content (not shown) held within a filling space905and can mainly include a bottle part950, a connector part750, and a pump part450. The bottle part950can have the filling space905formed in its interior and can have a supply hole945, for permitting the flow of the content, and air holes965, for permitting the inflow of air, formed in its upper surface. A channel part980can also be formed on the inner wall on one side of the bottle part950, where the channel part980can have a hollow space within to form a bottle channel985. One end of the bottle channel985can be formed at a lower portion of the filling space905, while the other end of the bottle channel985can be formed at an upper portion of the filling space905to be connected with the supply hole945. When there is a content (not shown) filled in the filling space905, the air holes965can be positioned above the surface of the content (not shown), whereas the one end of the bottle channel985can be positioned below the surface of the content (not shown), with respect to the surface of the liquid phase or gel phase content (not shown). The connector part750can be coupled to an upper portion of the bottle part950and can serve to provide a space for placing the pump part450and designate the position of the pump part450while at the same time spatially separating the supply hole945and the air holes965of the bottle part950. The pump part450can be secured to the designated position of the connector part750to suction and dispense the content (not shown) supplied through the supply hole945. That is, after removing the overcap10, when the user presses the nozzle100, the pump guide500may move down to open the pump inflow holes540, allowing the content within the pump space650to enter the pump inflow holes540, pass through the guide passage550, valve space250, nozzle space150, and nozzle passage140, and ultimately be dispensed through the dispensing hole130. With a tubeless dispenser container1000according to an embodiment of the invention, the bottle part950itself can provide a supply channel, obviating the need for a plastic tube as in the prior art. This can resolve the problem of the dispenser container1000having a lowered aesthetic due to the crude plastic tube of the interior being visible, even when the bottle part950is fabricated from a transparent material. In a dispenser container that utilizes a pump, suctioning the content requires that the air pressure inside the filling space905be kept at a certain level and the pressure at the pump side be kept lower than the air pressure inside the filling space905. In cases where a plastic tube is connected directly to the pump as in the prior art, such negative pressure can be easily formed simply by increasing the airtightness of the pump itself. However, in cases where the supply channel is formed by coupling several components together as in an embodiment of the invention, it is very important to provide an airtight seal between the portions requiring a negative pressure and the portions kept at a normal pressure. A more detailed description of an embodiment of the invention is provided below with reference toFIG.3. A tubeless dispenser container1000according to an embodiment of the invention can include the pump part450, connector part750, and bottle part950, as well as an overcap10that may be detachably coupled onto the upper portion. Here, the pump part450can include a nozzle100, a valve200, an elastic element260, a housing cover300, a piston400, a guide500, a disk530, and a housing600; the connector part750can include a pump cap700and an inner cap800; and the bottle part950can include a bottle body900and a base990. The nozzle100can correspond to the portion that may be pressed by the user and may dispense the content correspondingly. The nozzle100can be open at the bottom and can have the dispensing hole130formed in one side. The nozzle100can have a space formed therein, defined by an outer edge110, and can have a connecting boss120formed on an inner side of the outer edge110. The connecting boss120can have a cylindrical shape with an open bottom and can form a nozzle space150therein. A nozzle passage140can be formed in an upper portion of the nozzle100, where the nozzle passage140can have one end connecting to the nozzle space150and the other end continuing to the dispensing hole130. The connecting boss120of the nozzle100can be inserted into a connecting part230of the valve200to be coupled and secured onto the valve200. When the nozzle100is moved up and down together with the valve200, the outer edge110of the nozzle100can move along the inner perimeter of the inner mounting part720of the pump cap700. The valve200can be coupled to the nozzle100and the guide500and can manipulate the piston400and guide500by way of the force applied by the user and the restoring force of the elastic element260. The valve200can have a hollow cylindrical shape overall and can include a head part210, a connecting part230, and a cylinder part240. The head part210can protrude outwardly from the upper end of the valve200and extend downward so as to form a connection groove220. An upper portion270of the elastic element260can be inserted in and secured to the connection groove220. The nozzle100and the valve200can be coupled to each other, as the connecting boss120of the nozzle100is inserted into the connecting part230. As shown in the drawings, a curb can be formed on each of the connecting boss120and the connecting part230, and the curbs can be configured to contact each other, so that when the nozzle100is pressed down, the valve200can be pressed downward by the nozzle100, and when the valve200is moved up, the nozzle100can be pressed upward by the valve200. It would be possible to couple the connecting boss120and the connecting part230more securely by forming a protrusion and an indentation configured to mate with each other on the outer perimeter of the connecting boss120and the inner perimeter of the connecting part230. When the connecting boss120is inserted into the connecting part230, the valve space250of the valve200can connect with the nozzle space150of the nozzle100. The cylinder part240can be configured in the shape of a hollow cylinder. A stem520of the guide500can be inserted into the interior space of the cylinder part240, and as such, the interior space of the cylinder part240can have an inner diameter corresponding to the outer diameter of the stem520. However, at a lower portion of the interior space of the cylinder part240, an inner contact part430of the piston400can also be inserted, and the interior space of the cylinder part240can have a larger inner diameter at the lower portion correspondingly. It would be possible to couple the valve200and the guide500more securely by forming a coupling protrusion245on the inner perimeter of the cylinder part240and a corresponding indentation in the outer perimeter of the stem520. The elastic element260can be coupled between the valve200and the housing cover300or housing600and can serve to return the nozzle100, valve200, and guide500to their original positions by way of an elastic force when the external force applied by the user is removed. An elastic element260based on an embodiment of the invention can be made from a material capable of elastic deformation and can be shaped as a hollow tube overall. The upper portion270of the elastic element260can be coupled to the valve200, for example by being inserted into the connection groove220of the head part210, etc., and a lower portion290of the elastic element260can be coupled to the housing cover300or housing600by a similar method. The drawings illustrate an example in which a portion of the housing cover300is inserted to the inner side of the lower portion290of the elastic element260. A reinforcement rib280can be formed in the middle of the elastic element260. The reinforcement rib280, which may be a portion that is formed with a greater thickness to limit the elastic deformation, can enable the elastic element260to provide a restoring force more effectively by preventing folding, buckling, etc., in a portion of the elastic element260. The housing cover300can be coupled to an upper portion of the housing600to increase airtightness between the valve200and the housing600. The housing cover300can include a head part310that is located at the top and a contact part330that extends to a particular length along the vertical direction. The head part310of the housing cover300can protrude outwardly from the upper end of the housing cover300and extend downward so as to form a connection groove320. An upper portion of the housing600can be inserted in and secured to the connection groove320of the housing cover300. The cylinder part240of the valve200can be configured to move up and down within the housing600, where the cylinder part240can be inserted through the center hole of the contact part330. The tight contact between the valve200and the housing cover300, provided in the form of surface contact over the vertical length of the contact part330, can provide a high level of airtightness for maintaining separated pressure environments in the interior of the housing600and in the pump space650. The piston400can be mounted onto the stem520of the guide500and can include an outer contact part410, a bridge420, and an inner contact part430. The outer contact part410can be configured to tightly contact the inner perimeter of the housing600, and the inner contact part430can be configured to contact the stem520of the guide500. The bridge420can connect the outer contact part410and the inner contact part430with each other. When the nozzle100is not pressed, the piston400can be arranged at a position that closes the pump inflow holes540formed in the guide500. The guide500can be coupled to the valve200and can be configured to move up and down within the housing600according to the force applied by the user. The guide500can include a head part510and a stem520. The head part510can be positioned within the pump space650of the housing600and can have a larger diameter than that of the piston400, thereby forming a curb below the piston400. The stem520can be elongated and can have the shape of a hollow cylinder through which a guide passage550may be formed, where one or more pump inflow holes540formed in the stem520can connect the guide passage550with the outside of the guide500. The disk530can be arranged at a lower portion of the housing600and can include multiple holes, so that even when the guide500is moved down as far as possible, the housing inflow hole630in the bottom of the housing600remains unclosed. The housing600can form a pump space650, into which the content can be suctioned and in which the piston400and guide500may move up and down. The housing600can include a flange610and a body620. The body620of the housing600can be inserted into the holding space850of the inner cap800, and the pump space650can be formed inside the body620. One or more housing inflow hole630can be formed in a designated position in a lower portion of the body620. The flange610can protrude outward from an upper portion of the housing600and can facilitate the coupling of the housing600onto the connector part750. When the user presses the nozzle100, the nozzle100as well as the valve200and guide500coupled to the nozzle100may move down together, whereas the piston400may not move down immediately, due to the friction caused by the tight contact with the housing600. As the piston400does not move down but the guide500does move down, the pump inflow holes540of the guide500can be opened. After the guide500has moved down by a particular distance, the lower end of the valve200can press the bridge420of the piston400and cause the piston400to move down together, but at this time, the pump inflow holes540of the guide500can maintain opened states. As the guide500moves downward, the volume of the pump space650can be decreased, and the resulting increase in pressure can suction the content (not shown), which was previously drawn into the pump space650, through the opened pump inflow holes540. The content that enters the pump inflow holes540can pass through the guide passage550, valve space250, nozzle space150, and nozzle passage140and be dispensed through the dispensing hole130. When the user stops pressing on the nozzle100, the nozzle100as well as the valve200and guide500coupled to the nozzle100may be moved up together by the restoring force of the elastic element260, but once again, the piston400may not move up immediately, due to the friction caused by the tight contact with the housing600. As the piston400does not move up but the guide500does move up, the pump inflow holes540of the guide500can be closed. After the guide500has moved up by a particular distance, the head part510of the guide500can press the piston400and cause the piston400to move up together, but at this time, the pump inflow holes540of the guide500can maintain closed states. As the guide500moves upward, the volume of the pump space650can be increased, and the resulting decrease in pressure can draw the content (not shown) of the filling space905through the supply channel into the pump space650. Some of the components of the pump part450can be combined into a single integrated body as long as such integration does not inhibit the operations described above. The following provides a more detailed description of the bottle part950of a tubeless dispenser container1000according to an embodiment of the invention. FIG.4andFIG.5are perspective views of the bottle body900of the tubeless dispenser container1000according to an embodiment of the invention as seen from above and below, respectively. Referring toFIGS.2to5, the bottle part950can include a bottle body900and a base990. The bottle body900can have the shape of a hollow cylinder overall, with the filling space905formed therein and with an open bottom. The base990can be coupled to the open bottom of the bottle body900. The bottle body900may correspond to the main portion of the bottle part950and can form the filling space905on the inside. The bottle body900can have a supply hole945, for permitting the flow of the content, and air holes965, for permitting the inflow of air, formed in the upper surface. A channel part980can be formed on the inner wall on one side within the bottle body900, where the channel part980can have a hollow interior to form a bottle channel985. The channel part980can have one end opening to a lower portion of the filling space905and can have the other end opening to the upper surface of the bottle body900by way of the supply hole945. Thus, the bottle channel985can be formed such that one end connects to a lower portion of the filling space905and the other end connects with the supply hole945at an upper portion of the bottle part950. As mentioned above, while there is content (not shown) filled within the filling space905, the air holes965can be positioned above the surface of the content (not shown), and the one end of the bottle channel985can be positioned below the surface of the content (not shown), with respect to the surface of the liquid phase or gel phase content (not shown). Thus, until the content (not shown) is used up, the flow path for the content and the flow path for air can be spatially separated by the content itself, allowing the two different flow paths to have different pressure conditions. The base990can be coupled to the open bottom of the bottle body900. Depending on the embodiment, the base990can be detachably coupled or fixedly coupled by thermal fusion, etc., or can be configured to be rotatable even after being coupled. When the base990is coupled to the bottom of the bottle body900, a certain gap can be formed between a lower portion of the channel part980and the lower surface of the base990, so that the lower end of the bottle channel985can be open towards the filling space905. When the content of the filling space905is to be drawn into the pump space650, the content in the filling space905can be drawn into the bottle channel985through the opening in the lower portion of the channel part980, moved up through the channel part980by the negative pressure, drawn through the supply hole945and into the recessed part970, and finally drawn through the housing inflow hole630and into the pump space650. Referring toFIG.4andFIG.5, the bottle body900can include a perimeter part910, a ledge920, a mounting rim930, an upper surface940, airduct protrusions960, a recessed part970, and a channel part980. The perimeter part910of the bottle body900can correspond to the side portion of the bottle body900and can form the filling space905on its inside. The channel part980formed on the inner surface of the perimeter part910can, together with the inner surface of the perimeter part910, form the bottle channel985. While the drawings illustrate an example in which the perimeter part910has a cylindrical shape with a constant outer diameter and constant inner diameter, the invention is not limited thus, and the perimeter part910can employ any of a variety of shapes that allows the bottle channel985to maintain a particular cross-sectional area. In one embodiment of the invention, the perimeter part910can be formed from a completely transparent or semi-transparent material. The perimeter part910can have a blocked top, which may thus form the upper surface940, and a mounting rim930can be formed on the upper surface940. The ledge920of the bottle body900may be the portion formed on the outside of the mounting rim930. The ledge920can have the same height as the upper surface940or can have a different height. When the pump cap700and the overcap10are coupled to the bottle body900, the lower ends of the pump cap700and overcap10can contact the ledge920of the bottle body900. The mounting rim930can have an annular shape and can protrude by a particular length from the upper surface940of the bottle body900. The mounting rim930can be placed in tight contact with the connector part750in order to seal the supply channel as well as to couple the connector part750onto the bottle part950. The outer perimeter of the mounting rim930can be provided with a protrusion935for coupling and sealing the connector part750. The upper surface940of the bottle body900can correspond to the block top of the perimeter part910. The upper surface940can have the same height as the ledge920or can have a different height. The supply hole945formed in the upper surface940can connect with the open top of the channel part980. The air holes965can also be formed in the upper surface940, where the air holes965can connect directly with the filling space905below the upper surface940to allow an inflow of air. The airduct protrusions960and the recessed part970can also be provided on the upper surface940of the bottle body900. The airduct protrusions960can protrude upward to a particular length from the upper surface940of the bottle body900. The airduct protrusions960can be formed in the shape of a hollow cylinder, where the passages inside the airduct protrusions960can connect with the air holes965. That is, the passage inside an airduct protrusion960can be regarded as an extension of an air hole965. A recessed part970can be formed in the upper surface940of the bottle body900. The recessed part970can be formed in correspondence to the position of the pump part450so as to hold portions of the pump part450and the connector part750. Of course, in certain embodiments, the recessed part970can be omitted or implemented as another structure. Within the bottle body900, a channel part980can be formed on one side. The channel part980can form a bottle channel985therein, where the channel part980can be open only at the lower end and upper end so as to separate the bottle channel985from the filling space905. The channel part980can be structured such that a lower entrance of channel part980can be opened even when the base990is couple to the bottom of the bottle body900. To this end, the channel part980can extend to a length that leaves a gap between the lower entrance of the channel part980and the lower surface of the base990. For example, the lower end of the channel part980can be positioned slightly higher than the lower end of the bottle body900, or the lower end of the channel part980can be positioned at the same height as the lower end of the bottle body900but with the side surface of the base990coupling to the bottom of the bottle body900at a higher position than the lower surface of the base990. In certain embodiments, the lower entrance of the channel part980can be formed in a side surface of the channel part980instead of the bottom surface of the channel part980. When the content of the filling space905is to be drawn into the pump space650, the negative pressure formed in the pump space650can suction the content in the filling space905through the bottle channel985of the channel part980, and the content can be moved up along the channel part980, drawn through the supply hole945and into the recessed part970, and drawn through the housing inflow hole630and into the pump space650. Although the drawings illustrate an example in which just one channel part980is formed in the bottle body900, it is possible to form a multiple number of channel parts980and a multiple number of bottle channels985in the bottle body900. For example, for a bottle body900that has two air holes965formed in the upper surface940as in the illustrated drawings, it would be possible to form two supply holes945, in positions staggered by 90 degrees from the air holes965with respect to the center of the upper surface940, and form two channel parts980that connect to the two supply holes945. Coupling the base990to the open bottom of the bottle body900can complete the bottle part950. As the base990is coupled to the bottom of the bottle body900, there is no need to form an opening for filling the content in an upper portion of the bottle body900. This can eliminate the possibility of air infiltrating through paths around an opening, which would otherwise be required. The paths of air infiltration at the bottom of the bottle body900can basically be blocked by the content itself, and a level of airtightness that does not result in any leakage of the content would be sufficient. FIG.6is a perspective view illustrating the base992of a tubeless dispenser container1000according to a second disclosed embodiment of the invention. The base992illustrated inFIG.6can be rotatably coupled to the bottle body900. That is, the base992can be configured such that, even after the base992is coupled to the bottom of the bottle body900, the base992is able to rotate in relation to the bottle body900without being detached from the bottle body900or allowing any leakage of the content. In this type of base992, a protruding curb997can be formed along the edge of the inside lower surface, and one or more inflow indentations995can be formed in designated positions of the protruding curb997. The protruding curb997can be implemented in a form protruding to a particular height above the inside lower surface of the base992, and the inflow indentation995can correspond to a gap where the protruding curb997does not protrude from the inside lower surface of the base992. According to this embodiment, the channel part980can be structured such that the lower entrance is open downwards, and the protruding curb997can protrude to a height corresponding to the lower entrance of the channel part980. When a user uses a tubeless dispenser container1000having a base992according to this embodiment, the user can rotate the base992of the bottle part950, and depending on the rotated angle of the base992, either the protruding curb997or the inflow indentation995can be positioned at the lower entrance of the channel part980. If the protruding curb997is positioned at the lower entrance of the channel part980, the protruding curb997can close the lower entrance and prevent the content from entering the pump space650. However, if the inflow indentation995is positioned at the lower entrance of the channel part980, the inflow indentation995can keep the lower entrance of the channel part980open, thereby permitting the content to enter the pump space650as the dispenser container1000is used. FIG.7is a cross-sectional view illustrating a tubeless dispenser container according to a third disclosed embodiment of the invention. The base993illustrated inFIG.7can be fixedly secured to the bottle body900and can be configured such that the lower surface994is inclined. That is, in cases where the channel part980is formed on just one side of the bottle body900as inFIG.7, the inside lower surface994of the base993can have a downward incline towards the side where the channel part980is provided. As mentioned above, it is necessary to separate the supply channel for the content (not shown) from the path of inflow for air into the filling space905, and inside the filling space905, the content (not shown) itself may serve to separate the supply channel from the path of air inflow. As one end of the bottle channel985is positioned below the surface of the content (not shown), air cannot enter the supply channel of the content (not shown). However, as the tubeless dispenser container1000is used more and more, the surface of the content will gradually be lowered, and when the content within the filling space905is almost exhausted after an extended period of use, it may occur that the lower entrance of the channel part980becomes exposed above the surface of the content. In this case, the vacuum within the supply channel would be broken, and the pump part450would no longer be able to operate properly. In this embodiment, the inside lower surface994of the base993can be made to incline downwards toward the lower entrance of the channel part980, so that the content within the filling space905may be directed towards the bottle channel985. Compared to a base990,992having the inside lower surface formed in a horizontally flat shape, the base993having the inside lower surface994inclined downward towards the lower entrance of the channel part980can delay the exposure of the lower entrance of the channel part980above the surface of the content, even when there is smaller amount of content remaining in the filling space905, thereby helping the user to completely use up the content. FIG.7assumes an example in which there is only one channel part980formed in the bottle body900and thus illustrates the lower surface994of the base993as having a downward incline in one direction only. However, in cases where there are two channel parts980formed in the bottle body900, for example, the base993can be formed such that the lower surface994has a downward incline towards the position of each of the channel parts980. A tubeless dispenser container1000according to an embodiment of the invention may have the container itself provide the supply channel instead of using a plastic tube, and therefore a high level of airtightness between the flow path of the content and the flow path of the air is required throughout the structure of the tubeless dispenser container1000. The following provides a more detailed description of the structure of the connector part750, which allows a tubeless dispenser container1000according to an embodiment of the invention to maintain a high level of airtightness. FIG.8AandFIG.8Bare perspective views of the inner cap800of a tubeless dispenser container1000according to an embodiment of the invention, andFIG.9AandFIG.9Bare perspective views of the pump cap700of a tubeless dispenser container1000according to an embodiment of the invention. Referring toFIGS.8A and8B, the inner cap800of a tubeless dispenser container1000based on an embodiment of the invention can mainly include a flat part830that is shaped as a circular plate, a contact rim820that extends upward from the edge of the flat part830, a flange810that extends outward from an upper portion of the contact rim820, insertion parts840and protrusion parts860that protrude upward from the flat part830, and holding parts870,880that protrude upward and downward from the middle of the flat part830. The flat part830can be implemented in the shape of a circular plate and can be implemented in a size corresponding to the area of the upper surface of the bottle body900inside the mounting rim930. The contact rim820can extend upward from the edge of the flat part830, and the flange810can be formed extending outward from the end portion of the contact rim820. The outer diameter of the contact rim820can be formed in a size corresponding to the inner diameter of the mounting rim930of the bottle body900. Thus, the inner cap800can be coupled to an upper portion of the bottle body900by way of force-fitting into the inside of the mounting rim930, as a result of which the outer perimeter of the contact rim820can tightly contact the inner perimeter of the mounting rim930. To provide increased airtightness, one or more sealing protrusions825can be formed on the outer perimeter of the contact rim820. The extending length of the contact rim820can be made slightly shorter than the extending length of the mounting rim930. Thus, when the inner cap800is mounted on the bottle body900, the flange810of the inner cap800can be caught on an upper portion of the mounting rim930, and the flat part830may not tightly contact the upper surface of the bottle body900. The resulting gap between the flat part830and the upper surface of the bottle body900can form a portion of the supply channel between the supply hole945and the recessed part970. An insertion part840can protrude upward from the flat part830and can have the shape of a hollow cylinder, forming an insertion cavity845therein that opens downward. A protrusion part860having the shape of a hollow cylinder can be formed at an upper portion of the insertion part840, where the passage865of the protrusion part860can connect with the insertion cavity845. However, the insertion cavity845can be formed with an inner diameter that is greater than the inner diameter of the passage865of the protrusion part860. When the inner cap800is mounted on the bottle body900, the airduct protrusions960of the bottle body900can be force-fitted into the insertion cavities845, and the outer perimeters of the airduct protrusions960can be placed in tight contact with the inner perimeters of the insertion parts840. In this state, the passages of the airduct protrusions960(i.e., the air holes965) can connect with the passages865of the protrusion parts860. Thus, the protrusion parts860can be regarded as extensions of the airduct protrusions960. The inner diameters of the insertion parts840can correspond to the outer diameters of the airduct protrusions960, and the inner diameters of the protrusion parts860can correspond to the inner diameters of the airduct protrusions960. In a structure requiring airtightness, one of the positions where undesired air infiltration is most likely to occur is at the boundaries between components. Since a tubeless dispenser container1000according to an embodiment of the invention requires airflow at the air holes965connecting to the filling space905but requires a thorough blocking of airflow at other portions, airtight sealing around the airduct protrusions960of the bottle body900is especially important. By having the airduct protrusions960extend a particular length and be force-fitted into the insertion cavities845of a particular depth, the boundary between the inner cap800and the bottle body900formed around the airduct protrusions960can be increased in length. Thus, the potential paths for air infiltration at the boundary between the inner cap800and the bottle body900can be blocked by surface contact over a large distance, thus effectively blocking any undesired air infiltration. The holding parts870,880can protrude upward and downward with respect to the flat part830and can have a hollow inside to thereby form a holding space850therein. The holding part870formed above the flat part830can be open in an upward direction, while the holding part880formed below the flat part830can be open in a downward direction. The pump part450can be inserted and installed within the holding space850. To facilitate the securing of and sealing around the pump part450, one or more sealing protrusions855can be formed in the holding space850. The content that has been drawn from the filling space905and through the bottle channel985to arrive at the supply hole945can then move to recessed part970adjacent to the supply hole945, pass through the space between the inner perimeter of the recessed part970and the outer perimeter of the holding part880, and move through the housing inflow hole630that is exposed through the open bottom of the holding part880, to subsequently move into the pump space650. Since a tubeless dispenser container1000according to an embodiment of the invention is structured such that the base990is coupled to the bottom of the bottle body900, the content can be filled in the filling space905through the open bottom of the bottle body900, and there is no need for a separate opening in the recessed part970for holding the pump part450. The lower surface of the flat part830of the inner cap800may form a part of the supply path for the content (not shown), and insertion cavities845forming the flow path for air may be formed in the lower surface of the flat part830. However, since the air holes965connecting to the filling space905continue to the upper portions of the airduct protrusions960, the air holes965may not be exposed at the lower surface of the flat part830. That is, at the boundary from the exit of an air hole965to the lower surface of the flat part830, the potential path of airflow may be blocked by surface contact over a length corresponding to the depth of the insertion cavity845, whereby a high level of airtightness can be obtained, and the flow paths for the content and the air can be separated spatially. Referring toFIGS.9A and9B, the pump cap700of a tubeless dispenser container1000based on an embodiment of the invention can mainly include an outer mounting part710and an inner mounting part720. The outer mounting part710can include a part formed in an annular shape and a part extending inward from the annularly shaped part. The outer mounting part710can be placed in tight contact with and be coupled to the outside of the mounting rim930of the bottle body900. One or more protrusions717can be provided on the inner perimeter of the outer mounting part710to facilitate the coupling and sealing with respect to the mounting rim930of the bottle body900. Also, one or more detent protrusions715can be provided on the outer perimeter of the outer mounting part710to allow a detachable coupling of the overcap10. The inner mounting part720can be formed extending with an incline in a frustoconical shape, and the nozzle100can be exposed at the open top. The inner mounting part720can provide a space for housing the pump part450and can secure the housing cover300and the nozzle100. On the inside of the inner mounting part720, there can be formed a ledge part740, which may protrude inward to provide a curb, as well as a securing part760, which may protrude downward from the inner side of the ledge part740. The securing part760can have the shape of a hollow cylinder and can form a through-hole755therein. As illustrated inFIGS.9A and9B, insertion parts770can also be formed on a lower portion of the ledge part740, where the insertion parts770can have the shape of a hollow cylinder to form insertion cavities775therein. Cavities can be formed in designated locations of the ledge part740, and the air holes725can be formed inside such cavities. When the pump cap700and the inner cap800are coupled to each other, the protrusion part860of the inner cap800can be force-fitted into the insertion cavity775of the pump cap700, and the outer perimeter of the protrusion part860can tightly contact the inner perimeter of the insertion part770. In this state, the passages865of the protrusion parts860can be connected with the air holes725of the ledge part740. Thus, the air holes965formed in the upper portion of the filling space905can be connected with the outside by way of the air holes965in the airduct protrusions960of the inner bottle900, the passages865in the protrusion parts860of the inner cap800, and the air holes725in the pump cap700. When the pump part450is coupled to the pump cap700, the pump part450can be inserted through the through-hole755of the inner mounting part720and can be disposed within the recessed part970of the inner bottle900and the holding space850of the inner cap800. When the pump part450is pressed and inserted with a sufficient force, the head part310of the housing cover300can be forced under the securing protrusion730of the ledge part740, and the head part310can be secured between the ledge part740and the securing protrusion730. Of course, in certain embodiments, the structure can be modified such that the head part310of the housing cover300is positioned between the pump cap700and the inner cap800. However, the structure of the embodiment illustrated in the drawings can simplify the assembly process to thereby provide advantages in time and cost reduction. Some of the components of the connector part750, i.e., the pump cap700and inner cap800, can be combined into a single integrated body as long as such integration does not inhibit the operations described above. However, these can also be fabricated separately and assembled together for easier manufacture and assembly. A more detailed description is provided below, with reference toFIG.10andFIG.11, of the flow paths of the content and the air within a tubeless dispenser container1000.FIG.10andFIG.11are cross-sectional views of a portion of the tubeless dispenser container1000illustrated inFIG.1across line A-A′ and line B-B′, respectively. First, referring toFIG.2andFIG.10, when the user presses the nozzle100from the state shown inFIG.10and subsequently stops pressing on the nozzle100so that a negative pressure is created within the pump space650, the content (not shown) in the filling space905may move from the lower portion of the filling space905and through the bottle channel985inside the channel part980to arrive at the upper portion of the bottle body900and the supply hole945and may then enter the recessed part970and move through the housing inflow hole630to be supplied to the pump space650. Later, when the nozzle100is pressed again, the content within the pump space650can pass through the pump part450to be dispensed through the dispensing hole130of the nozzle100. Referring toFIG.11, the airduct protrusions960of the bottle body900may be inserted in the insertion cavities845of the inner cap800, and the protrusion parts860of the inner cap800may be inserted in the insertion cavities775of the pump cap700. As a result, the air holes965formed in the upper surface of the bottle body900can be connected, by way of the protrusion parts860of the inner cap800and the insertion parts770of the pump cap700, with the air holes725in the inner mounting part720of the pump cap700. As presented above, a tubeless dispenser container1000according to an embodiment of the invention can provide a supply channel for the content using the structure of the container itself without using a separate plastic tube. Unlike conventional containers that use a separate plastic tube, a tubeless dispenser container1000according to an embodiment of the invention requires high airtightness at each component of the dispenser container and requires an effective prevention of air infiltration particularly at the contact boundaries between different components, as these are particularly vulnerable to air infiltration. A tubeless dispenser container1000according to an embodiment of the invention includes a small number of components to begin with, some of which may be integrated into a single body to provide an even smaller number of components. As the container includes a small number of components, the boundaries between components can be decreased, and the risk of air infiltration can be greatly reduced. Also, as illustrated inFIGS.10and11, a tubeless dispenser container1000according to an embodiment of the invention has the portions vulnerable to air infiltration blocked by surface contact over a particular length at the boundaries between the bottle body900, inner cap800, and pump cap700. That is, members such as the mounting rim930, protrusion parts860, holding parts870,880, airduct protrusions960, etc., extend beyond a particular length and provide surface contact over the entire extending length. Such a structure can greatly enhance the airtightness at the contact boundaries between components, which can be particularly vulnerable to undesired air infiltration, thereby allowing the tubeless dispenser container1000to smoothly perform a dispensing function using the structure itself and without using a separate plastic tube. In the embodiments illustrated in the drawings, the structure described above can be omitted at certain portions, such as at the coupling portion between the bottle body900and the base990, where airtightness can be easily obtained using other methods. While the foregoing provides a description with reference to certain embodiments of the present invention, it should be appreciated that a person having ordinary skill in the relevant field of art would be able to make various modifications and alterations to the present invention without departing from the spirit and scope of the present invention set forth in the scope of claims below.
44,244
11857987
DETAILED DESCRIPTION OF THE INVENTION FIG.1illustrates a block diagram showing a system environment100in which various embodiments may be implemented. The system environment100may include an unmanned aerial vehicle102, a vehicle104, a user computing device106, wearable glasses108worn by a user, and a network110. The unmanned aerial vehicle102may include one or more cameras112, one or more sensors114, one or more software modules116, lidar118, structured light emitters120, and light-emitting diodes (LEDs)122. Various components in the system environment100may be interconnected over the network110. Hereinafter, the unmanned aerial vehicle102may be referred to as a drone. The drone102may be used to paint buildings, walls, houses, and other targets. In one embodiment, the drone102may be used for scanning and replicating murals in an urban area. In another embodiment, the drone102may be used for cleaning the area. In another embodiment, the drone102is remotely controlled by a painter to paint a house. In another embodiment, the drone102may be used for security. The drone102is preferably used for roller-based, spray-based, paintbrush, and other types of painting. The drone102may include the one or more cameras112for capturing images while performing the operations such as painting and cleaning. The images may correspond to high resolution photographs and/or panoramic images. In one case, when the drone102is used for cleaning purposes, it may capture images before and after cleaning to ensure that the cleaning achieves the desired results without damage. It should be noted that the one or more cameras112may be light field cameras (i.e., plenoptic cameras), tracking cameras, wide-angle cameras, and/or 360-degree cameras. In one case, the drone102may use a thermal camera (not shown) as well, without departing from the scope of the disclosure. The drone102may include the one or more sensors114to sense data related to the various operations, such as painting and cleaning, performed by the drone102. In one embodiment, the data corresponds to images indicating the roughness of a surface, such as that of a building, wall, or house. The one or more sensors114include infrared (IR) sensors124, ultraviolet (UV) sensors126, speed and distance sensors128, image sensors130, bump map sensors132, chemical sensors134, and spectroscopic sensors136. The IR sensors124may be used by the drone102to determine how “wet” the paint is. Further, the IR sensors124may be used for search and surveillance operations. The UV sensors126may be used to detect how dry the paint is and other aspects of the image captured by the one or more cameras112. The speed and distance sensors128may be used to detect the speed of the drone102and measure the distance between the drone102and another object, without actual physical contact with the object. The image sensors130may be used to detect and convey information about what constitutes an image. The image sensors130may be used along with the one or more cameras112to create digital images. The bump map sensors132may be used to determine texture, roughness and curvature of a surface, such as that of a building, wall, or house. Further, the bump map sensors132may identify surfaces that should be sanded. In one embodiment, the drone102may sand automatically based on the identification of the surface. The chemical sensors134may be used to sense chemical composition. In one embodiment, the chemical sensors134may be used to detect chemicals present in environmental, industrial and emergency response situations. The spectroscopic sensors136may be used to more deeply analyze paint composition and application. A spectrographic image includes information in non-visible spectra, including IR and UV. A spectrographic image of the painting target can reveal information that is not visible in a normal photograph, such as dirt, damage, paint defects, uneven application, et al. The drone102may use its spectroscopic sensors136to record a spectroscopic image of the target before and/or after painting for any of a number of purposes, including, but not limited to, detecting dirt or damage, verifying paint application and consistency, and measuring paint mixture and curing properties. Further, the drone102may include the one or more software modules116for processing the data captured by the one or more cameras112and the one or more sensors114. The one or more software modules116may include physics-based software138for modeling of light interactions. Further, the one or more software modules116may include a visual software module140for determining whether recorded images look correct. Further, the one or more software modules116may include a machine learning module142for finding objects and/or regions to paint. Further, the one or more software modules116may include various other software to determine one or more things. The one or more things may include, but are not limited to, paint colors that are suited for the surface, what color the paint will have when cured, how long the paint has been drying, creation of a three-dimensional (3D) map, and whether coverage is correct or another coat is needed. Further, the one or more software modules116may include software to separate various layers of painting and create an additive layered painting plan, to make layers when a set of spot paints are used, or to predict a mixture of two thin colors and a result of the mixture of the two colors. In one case, the spot paints may be of specific colors. As an example, the color may be specified using the CMYK color model. Further, the one or more software modules116include software for remotely controlling painting apparatus with the user computing device106and artificial intelligence (AI). Further, the one or more software modules116include software to monitor the usage of equipment, such as paintbrush, roller, and/or sprayer. Further, the one or more software modules116may include software to alert a rental facility in case of a fault. Further, the one or more software modules116include software to order delivery of paint refills if the user runs out, and to support the user who is using more than one drone102to quickly paint the target. It will be apparent to one skilled in the art that the above-mentioned software has been provided only for illustration purposes. In one embodiment, the drone102may be integrated with some other software as well, without departing from the scope of the disclosure. In one embodiment, the drone102may be integrated with the lidar118to test surface anomalies detected by the one or more sensors114. In one case, the bump map sensors132may detect roughness of the surface, and then the lidar118may test the surface anomalies. Further, the drone102may be integrated with the structured light emitters120to test surface deformities. Further, the drone102may be integrated with LEDs122of various frequencies to test whether the painting was executed correctly. In one case, the LEDs122may correspond to localized LEDs for consistently preserving the color. In one embodiment, localized, focused light may be used to view an area being worked on without variation by ambient light or darkness. In one embodiment, the drone102is integrated with backup spray nozzles (not shown). The backup spray nozzles are used when the drone102detects clogging in the nozzle. Further, the drone102may integrated with one or more physical rollers to detect surface anomalies. In one embodiment, the drone102may be integrated with a liquid collection system (not shown). The liquid collection system may have a vacuum hose and a filter at the end of the hose. The liquid collection system may be used for storing fluid that is being supplied through the hose to the drone102for various operations, such as cleaning and washing the area or dust debris created by the sanding. In one embodiment, the drone102may be integrated with a paint supply system (not shown) for supplying paints to the drone102. The paint supply system may include one or more containers being filled with different types of paint. The different types of paint may include, but are not limited to, latex-based paint, water-based paint, stucco paint, and oil-based paint. Thereafter, the drone102may receive the paint through the paint supply system for painting the target. In one embodiment, the drone102may be integrated with a sanding attachment. In one embodiment, the system100may use six degrees of freedom (6DoF) for capturing data such as images in free space. It should be noted that a mechanical and an actuation method may be used to fully control the drone102with six or more degrees of freedom. In one embodiment, a full directional authority may be enabled on each individual thrust vector by introducing two additional degrees of freedom (twist and tilt) to each rotor. Further, a resulting system may possess omnidirectional thrust-vectoring capabilities, fully decouple the position and attitude dynamics, and minimize wasted thrust over its entire configuration space. Such features may allow the drone102to assume any arbitrary body orientation and thus to angle itself with respect to a work surface for the purpose of physical interaction, without departing from the scope of the disclosure. In one embodiment, the drone102may be integrated with Sound Navigation and Ranging (SONAR)144that uses sound propagation to navigate, communicate, and/or detect objects. Further, the SONAR144may be used to aid in an indoor “altitude hold” mode and/or for checking distance from a wall. Further, the drone102may be integrated with Global Positioning System (GPS)146and triangulation devices148. The GPS146may be used for tracking the location of the drone102. Further, the triangulation devices148may be used to capture data related to one or more activities of the drone102. It will be apparent to one skilled in the art that the above-mentioned components of the drone102have been provided only for illustration purposes. In one embodiment, the drone102may be integrated with laser as well, without departing from the scope of the disclosure. The drone102may be, but is not limited to, a flying quadcopter tethered to a hose and a rolling floor system, a quadcopter tethered to van, a drone with feet, a robotic arm coming out of a vehicle, or a robotic arm coming out of a ground rolling system, where the robotic arm is connected to a painting system. It should be noted that some other types of drone may be used for painting, scanning, and replicating murals in an urban area, without departing from the scope of the disclosure. The vehicle104may be used for cleaning an urban area. It should be noted that the vehicle104may correspond to an autonomous vehicle. In one embodiment, the vehicle104may capture images of the urban area. In one case, the images may correspond to dirt and garbage images. Successively, the vehicle104may catalog the images. Successively, the vehicle104may send the captured images to a remote station (not shown) where they are compared with stored images. Based at least on the comparison, the vehicle104may receive a command for cleaning the area. In one case, the command may be received from the remote station or from the user. Thereafter, the vehicle104may apply the paint in order to preserve and maintain the aesthetics of the urban area. In one case, the vehicle104may be a street sweeper. In another case, the vehicle104may be a three-wheeler or four-wheeler, without departing from the scope of the disclosure. The user computing device106is preferably used by the user for remotely controlling and guiding the drone102. In one case, the user may correspond to a painter. In one embodiment, the user may zoom in to an area using the user computing device106. For example, the user may identify an area where the paint needs to be done using a sprayer. Based at least on the identification, the user may give precise directions to the drone102. In one case, the directions may include slowly painting with the sprayer, roller, or paintbrush. In another case, the directions may include cleaning and sanding areas. In one embodiment, a mobile application running on the user computing device106may allow the user to order more paint if needed. Such functioning of the drone102eliminates the need of the user to mask to avoid overspray. The user computing device106may be realized through a variety of computing devices, such as a desktop, a computer server, a laptop, a mobile phone, a personal digital assistant (PDA), or a tablet computer. In one embodiment, the user may wear the wearable glasses108to monitor the area painted by the drone102. Further, the user wearing the wearable glasses108may look and see previews of how the house will look with different colors and patterns. Further, the use of the wearable glasses108may allow the user to see an overlay aligned with the target showing areas that need to be sanded or masked. Further, the user may remotely view, zoomed in, what is being painting and may operate the drone102for areas that are hard to reach. In one embodiment, a virtual reality (VR) device may be used by the remote painter to do the motions of painting the house, the motions of the painter turning into paint strokes. The network110corresponds to a medium through which content and data flow between various components of the system environment100(i.e., the unmanned aerial vehicle102, the vehicle104, the user computing device106, and the wearable glasses108worn by the user). Examples of the network110may include, but are not limited to, a Wi-Fi network, a Bluetooth mesh network, a wide area network (WAN), a local area network (LAN), or a metropolitan area network (MAN). Various devices in the system environment100may connect to the network110in accordance with various wired and wireless communication protocols, such as Transmission Control Protocol over Internet Protocol (TCP/IP), User Datagram Protocol (UDP), and 2G, 3G, or 4G communication protocols. In some embodiments, the network110may be a cloud network or cloud-based network. FIG.2is a block diagram illustrating a system200, in accordance with at least one embodiment. The system200may be considered as the drone102and/or the vehicle104. For the purpose of ongoing description, the system200has been considered to be the drone102. The drone102includes a microprocessor202, an input device204, a memory206, a machine learning unit208, a tensor processing unit (TPU)210, a transceiver212, a comparator214, and an image capturing device216. The microprocessor202is coupled to the input device204, the memory206, the machine learning unit208, the TPU210, the transceiver212, the comparator214, and the image capture device216. The transceiver212may connect to the network110through the input terminal218and the output terminal220. The microprocessor202includes suitable logic, circuitry, and/or interfaces that are operable to execute one or more instructions stored in the memory206to perform predetermined operations such as painting and cleaning. The microprocessor202may be implemented using one or more microprocessor technologies known in the art. Examples of the microprocessor202include, but are not limited to, an x86 microprocessor, an ARM microprocessor, a reduced instruction set computer (RISC) microprocessor, a complex instruction set computer (CISC) microprocessor, an application-specific integrated circuit (ASIC), or any other microprocessor. The input device204may comprise suitable logic, circuitry, interfaces, and/or code that may be operable to receive an input from the user. The input may correspond to one or more commands of the user. The commands may include, but are not limited to, painting a particular building using oil paint, latex paint, and/or performing spray-painting on a particular area of the building. The input device204may be operable to communicate with the microprocessor202. It will be apparent to a person skilled in the art that the input device204may be a part of the vehicle104. In such a scenario, the input device204may receive a command such as cleaning the area and applying paint. Examples of the input device204may include, but are not limited to, a touch screen, a keyboard, a mouse, a joystick, a microphone, a camera, a motion sensor, a light sensor, and/or a docking station. The memory206stores a set of instructions and data. Some of the commonly known memory implementations include, but are not limited to, a random access memory (RAM), a read-only memory (ROM), a hard disk drive (HDD), and a secure digital (SD) card. Further, the memory206includes the one or more instructions that are executable by the microprocessor202to perform specific operations. It will be apparent to a person with ordinary skill in the art that the one or more instructions stored in the memory206enable the hardware of the system200to perform the predetermined operations. The machine learning unit208may be used to find regions to paint. In one example, the drone102may utilize the machine learning unit208to find and paint the edges of a wall. The machine learning unit208may use any number of machine learning or artificial intelligence technologies to achieve its purposes, including, but not limited to, neural networks, convolutional neural networks, supervised learning, unsupervised learning, reinforcement learning, and deep learning. Further, the TPU210may be an artificial intelligence (AI) accelerator application-specific integrated circuit (ASIC). The TPU210may be used for neural network machine learning. The transceiver212transmits and receives messages and data to or from various components of the system environment100(e.g., the vehicle104and the user computing device106) over the network110. In some embodiments, the transceiver212is coupled to the input terminal218and the output terminal220through which the transceiver212may receive and transmit data/messages, respectively. Examples of the input terminal218and the output terminal220include, but are not limited to, an antenna, an Ethernet port, a USB port, or any other port that can be configured to receive and transmit data. The transceiver212transmits and receives data/messages in accordance with the various communication protocols—such as TCP/IP, UDP, and 2G, 3G, or 4G communication protocols—through the input terminal218and the output terminal220. The comparator214may be configured to compare the images taken before and after the cleaning to ensure that cleaning achieves the desired results without damage. Further, the comparator214may be configured to detect the difference between dirt and the image itself through a particle detection or obstacle detection technique. In one embodiment, the comparator214may be realized through either software technologies or hardware technologies known in the art. Though the comparator214is shown outside the microprocessor202inFIG.2, a person skilled in the art would appreciate that the comparator214may be implemented inside the microprocessor202without departing from the scope of the disclosure. The image capture device216may be configured to capture the images of the operations performed by the drone102. It should be noted that the images may be captured before and after the painting operations. In some embodiments, the image capture device216may include a camera (not shown) that may be integrated into the drone102. It will be apparent to a person skilled in the art that the image capture device216may be a part of the vehicle104. In such a scenario, the image capture device216may capture images before and after cleaning to preserve and maintain the aesthetics of the urban area. The image capture device216may be implemented using one or more image sensing technologies known in the art, such as, but not limited to, a charge-coupled device (CCD) image sensor and a complementary metal oxide semiconductor (CMOS) image sensor. FIG.3illustrates a drone302with an onboard painting system304, in accordance with at least one embodiment. The drone302may be equipped with the onboard painting system304for rendering a visual image on a structure (not shown). The structure may include, but is not limited to, a wall, building, or house. The onboard painting system304may include one or more paint containers306for storing the paint of different colors and types. The one or more paint containers306may receive paints of different colors from a reservoir308via a hose310. Further, the reservoir308may be placed on the ground. It should be noted that only one hose310is shown inFIG.3. In one embodiment, more than one hose310connected to the reservoir308for different colors may be used as well, without departing from the scope of the disclosure. The drone302includes one or more spray nozzles312connected to the onboard painting system304. In one embodiment, the one or more spray nozzles312may be connected to the one or more paint containers306. Further, the one or more spray nozzles312may be actuated electronically to spray a desired color of paint on the target. It should be noted that the one or more spray nozzles312may be chosen or configured to spray and apply paint on the target at a desired granularity based at least on the commands of the user. For example, the granularity may be a droplet diameter and a flow rate. In another embodiment, the drone302may automatically select the one or more spray nozzles312for applying the desired paint. In one embodiment, the one or more spray nozzles312may be chosen commensurate with the size of the target, a thickness of the paint, a distance of the UAV to the target structure when applying paint, and the pattern or image to be painted. It should be noted that only three spray nozzles312are depicted inFIG.3. In one embodiment, more than three spray nozzles312may be used as well, without departing from the scope of the disclosure. The drone302may include a plurality of blades314so that the drone302may fly. Further, the drone302may include backup spray nozzles316that are used when the spray nozzle312gets clogged. It should be noted that the drone302may automatically detect the clogging of the spray nozzle312and switch to the backup spray nozzles316. Further, the drone302may be connected to a power source318for powering the drone302via an electrical connection320. The power source318may include one or more batteries. Further, the drone302may be used for roller-based, spray-based, paintbrush, and other types of painting. In one embodiment, the drone302may include one or more power take-off engines (not shown) and electronic fuel injection system engines (not shown) for powering the drone302for flight, which may include power generators onboard for controlling the speed of motors within the craft. Further, the drone302may include a communication module for receiving control and navigation information. In one embodiment, the drone302may receive commands from the user. The commands may describe actions such as slowly painting with the sprayer, roller, or paintbrush. In an alternate embodiment, the drone302may include a flight controller/processor, a navigation system, an altimeter, and a vision-tracking device. For example, a drone navigation subsystem may include a radio and amplifiers suitable for drone system communications in radio frequency bands such as ultrahigh frequency (UHF), very high frequency (VHF), and/or Wi-Fi, for real-time communication with the user computing device106. In one embodiment, the drone302may include a memory storage device that receives and stores programmed flight path control information including instructions to navigate the drone302along a predetermined path, as well as control information and commands to configure the onboard painting system304for painting the structure. It will be apparent to one skilled in the art that the drone302may be integrated with the one or more cameras112, the one or more sensors114, the one or more software modules116, the lidar118, the structured light emitters120, and the LEDs122, described above. It should be noted that the drone302may include some other modules and components as well, without departing from the scope of the disclosure. FIG.4Aillustrates a perspective view of an alternate embodiment of a drone402, in accordance with at least one embodiment. The drone402may include a plurality of rotor arms404having a plurality of rotors406, each at an end portion of a boom408. In one case, the drone402may incorporate propellers into the body of the drone402. Further, the drone402may include a landing system410. In one case, the landing system410may correspond to legs, skids, and/or skis. Further, the drone402may be connected to a ground station412using a tether414. The tether414may be connected at a tether connection portion416. The tether connection portion416may be a permanent or removable connection. Further, the tether connection portion416may be configured to provide data, power, and fluid connections to or from the drone402. In one case, the tether414may include a liquid transportation channel418and an electrical connection420. The electrical connection420may supply power to the drone402using a power source422. In one embodiment, the drone402may have a built-in battery for supplying power to the drone402. Further, the drone402may receive paint from a reservoir424via the tether414. It should be noted that the tether414may be of a length appropriate for performing a task or may be longer than needed and may contain another tether management device. In one embodiment, the tether414may be used to exchange data and information between the ground station412and the drone402. In one embodiment, more than one tether414connected to the reservoir424for different colors may be used as well, without departing from the scope of the disclosure. In one embodiment, the reservoir424may contain one or more paint containers (not shown) for supplying different types of paint. The one or more paint containers may include solar paints. In one case, the one or more paint containers may be integrated with one or more batteries for supplying power. Further, the drone402may include one or more spray nozzles426for applying paint or another sprayable material. The one or more spray nozzles426may be connected to the one or more paint containers for receiving different types of paint. Further, the one or more spray nozzles426of different tips may be used. For example, the tips may correspond to a sprayer, a roller, or a paintbrush. Further, the one or more spray nozzles426may be configured to optimally apply paint when positioned normal to the surface being painted. In one case, the position may be determined based on various other parameters such as wind speed, spray material viscosity, or a thickness of the applied material. It should be noted that only three spray nozzles426are depicted inFIG.4. In one embodiment, more than three spray nozzles426may be used as well, without departing from the scope of the disclosure. In one embodiment, the one or more spray nozzles426are equipped with one or more sensors, such as pressure sensors, to aid in precisely identifying the location of walls. Further, the one or more spray nozzles426may be actuated using motors or actuators controllable by a command and control system428to adjust the orientation and/or position of the one or more spray nozzles426. Such movement of the one or more spray nozzles426may be used to reach or point in directions that are inaccessible. Further, the drone402may include backup spray nozzles426that are used when one of the spray nozzles426gets clogged. It should be noted that the drone302may automatically detect the clogging of the spray nozzle426and switch to the backup spray nozzles. Further, the command and control system428may receive inputs from sensors430to determine the positioning of the drone402relative to the surroundings. In one case, the sensors430may be omnidirectional sensors. Further, the command and control system428may control the plurality of rotors406to pilot the drone402, to control altitude and attitude, pitch, yaw, and angular orientation of the drone402. In one embodiment, the command and control system428may receive instructions from the user to fly to a designated area and perform a task. In one case, the task may correspond to painting a wall, cutting in portions of the wall, and/or painting an image on the wall. In one embodiment, the cameras and the one or more sensors may be used to detect “skips.” Based on the detection, the command and control system426may cause the drone402to repaint such deficient areas. Such instructions may be received from the user via the user computing device106. It should be noted that the drone402may operate autonomously after receiving the instructions. Further, the drone402may be supported by a mechanical component, such as a supporting device432for stabilizing the drone402. It should be noted that the drone402may be integrated with the camera112, the one or more sensors114, the one or more software modules116, LIDAR118, the structured light emitters120, and LED122, described above, without departing from the scope of the disclosure. In an alternate embodiment, the drone402may include an integrated paint supply unit434for supplying the paint or other sprayable material, as shown inFIG.4B. It should be noted that the paint supply unit434may include one or more paint containers for supplying different types of paint. Further, the paint supply unit434may be detachable from the drone402. For example, when the drone402is instructed to change the paint supply unit434, the drone402may fly down to a base station (not shown) and change the paint supply unit434with another paint supply unit. In one embodiment, the paint supply unit434may rotate in all directions to paint the target while the drone402is standing still. In one embodiment, the drone402may be integrated with a power supply unit436for supplying power to the drone402. Further, the power supply unit436may be detachable from the drone402. For example, when the drone402is instructed to change the power supply unit, the drone402may fly down to the base station (not shown) to change the power supply unit434with another power supply unit. In one case, the power supply unit436may be a rechargeable battery. In one embodiment, the drone402may be configured for cleaning purposes, as shown inFIG.4C. The drone402may include a cleaning device438for cleaning the target. The cleaning device438may include one or more water containers (not shown). Further, the cleaning device438may use Dilute Sulfuric Peroxide (DSP) to clean the house. Such features of the drone402may be beneficial for performing different tasks, such as cleaning and painting. As shown inFIG.5A, the drone402, tethered with the reservoir424, may be used to paint (shown as506) a wall502of the house504. The drone402may receive the paint supply from the reservoir424. As discussed above, the reservoir424may contain one or more paint containers (not shown) for supplying different types of paint. At first, the drone402may capture images of the wall502. The images may be panoramic images. It should be noted that the images may be captured using one or more cameras. In one case, the drone402may automatically scan the wall502. The scanning of the wall502may correspond to a three-dimensional (3D) scan. In one embodiment, the drone402may detect the edges of the wall502. Successively, the drone402may create a high-resolution picture using the images. Further, the drone402may use a bump map (i.e., surface distance map), such as one acquired using lidar, to correct the image, and use localized light to consistently preserve the color. Successively, the drone402may perform cleaning of the wall502. In one case, the drone402may act as a cleaning drone. Further, the drone402may take pictures after the cleaning to ensure that the cleaning does not affect the image. Successively, the drone402may detect a difference between dirt and the picture itself through a particle detection technique or an obstacle detection technique. Thereafter, the drone402may use the one or more spray nozzles426for applying paint or another sprayable material on the wall502. Further, the one or more spray nozzles426may be configured to optimally apply paint when positioned normal to the surface being painted. In one case, the position may be determined automatically by the drone402based on various other parameters, such as wind speed, spray material viscosity, or a thickness of the applied material. In another case, the position may be determined automatically by the sensors430to position the drone402in one or more positions and orientations to carry out the desired task. It should be noted that the drone402may be integrated with artificial intelligence (AI) technology and/or edge-finding algorithms. Further, the drone402may have a database that is configured to store details related to good and bad edge-painting techniques. In one embodiment, the drone402may use one or more tools, such as a sprayer, a paintbrush, and/or a roller, to perform different types of painting. It will be apparent to one skilled in the art that the above-mentioned drone402for painting the wall502has been described only for illustration purposes. In the case of murals, the drone402may automatically scan the wall502. Based at least on the scanning, the drone402may replicate murals by accurately scanning a mural and painting a scaled replica of the mural in one or more other locations. In one embodiment, the drone402may design advertisements in mural form, without departing from the scope of the disclosure. As shown inFIG.5B, the single drone402may perform tasks including, but not limited to, cleaning the house504, taping the house504, painting the house504with a sprayer508, painting the house504with a roller510, and/or painting the house504with a paintbrush512. For example, in a first scenario (shown as514), the drone402may perform taping of the house504. The taping may protect sections of the house504from paint overspray. In a second scenario (shown as516), the drone402may paint the house with the sprayer508. In a third scenario (shown as518), the drone402may paint the house504with the roller510. In a fourth scenario (shown as520), the drone402may paint the house with the paintbrush512. In one embodiment, the drone402may deploy ultraviolet (UV) protection coating to protect the underlying material from the harmful effects of radiation. It should be noted that all these tasks may be performed one after another by the single drone402. Such modular drones may be efficient, reliable, and cost-effective. As shown inFIG.5C, multiple drones402a,402b,402c, and402dmay perform different tasks. The multiple drones402a,402b,402c, and402dmay work in tandem. For example, the drone402amay perform taping of the house504. In one case, the taping may be performed using liquid mask. The liquid mask may correspond to spray that is applied to those surfaces not requiring painting. Similarly, the drone402bmay paint the house504with the sprayer508. On the other hand, the drone402cmay paint the house504with the roller510. Similarly, the drone402dmay paint the house504with the paintbrush512. Such scenarios wherein the multiple drones402a,402b,402c, and402dperforming different tasks simultaneously may make the process more time-efficient. It should be noted that while four drones are depicted inFIG.5C, any number of drones may be used in tandem without departing from the scope of the disclosure. FIGS.6A,6B, and6Cillustrate remote-control painting of a house602by a painter604steering the drone302, in accordance with at least one embodiment. Hereinafter, the drone302explained inFIG.3may be used as a reference for explanation purposes. As shown inFIG.6A, the painter604may prepare a plan for painting the house602. For purposes of illustration, the plan may include, but is not limited to, painting a wall606of the house602using a roller or a sprayer, painting the edges of the wall606using a paintbrush, and cleaning the windows608of the house602. It should be noted that the pre-planning may be performed based at least on scanning of the house602performed by the drone302. In one embodiment, the painter604may wear wearable glasses610to do the planning of painting the house602. The wearable glasses610may allow the painter604to see how the house602will look after painting. The detailed description of the wearable glasses610is provided below in conjunction withFIG.7. Successively, the painter604may embed the plan for painting the house602in the drone302. It should be noted that the drone302may be preprogrammed with a flight path to paint the house602in a similar manner as prepared by the painter604. As shown inFIG.6B, the drone302may start painting the wall606by moving from one direction to another i.e., from left to right. Further, the drone302may pick up a roller612for painting the wall606of the house602. Further, the drone302may contain algorithms which determine, on-the-fly, the appropriate actions to take in order to paint the wall606of the house602. Further, the drone302may figure out which tool to use near edges. In an example, the drone302may use a paintbrush614on the edges and/or a sprayer616on the entire surface of the wall606. Further, the drone302may receive the paint supply from a reservoir618. The reservoir618may contain one or more paint containers620of different colors. The drone302may automatically fill the onboard painting system304from the reservoir618and perform the painting of the house602. In one embodiment, the drone302may receive the paint supply from the reservoir618via a tether (not shown). It should be noted that video cameras and/or other sensors attached to the drone302may monitor the paint application and adjust the paint flow or paint pressure. In one embodiment, the drone302may complete an additional pass over the area with another spray for optimal paint application and coverage. As shown inFIG.6C, the painter604may wear the wearable glasses610. Using the wearable glasses610, the painter604may monitor the functioning of the drone302in real time. The painter604may zoom in on live video or images to see an area where the drone302is painting. Further, the painter604may give one or more commands to the drone302. The one or more commands may include, but are not limited to, using the paintbrush614on the edges and/or the sprayer616on the entire surface of the wall606. Such use of the wearable glasses610for guiding and controlling the drone302may be efficient and effective. FIG.7illustrates the wearable glasses610, in accordance with at least one embodiment. The wearable glasses610may be worn by the painter604(shown inFIG.6) in preparing a plan to paint the house. The wearable glasses610may be integrated with AR technology, light field technology, and/or VR positioning technology. It should be noted that the wearable glasses610may include some other technologies as well, without departing from the scope of the disclosure. The wearable glasses610may include a frame702and one or more lenses704. The one or more lenses704may be detachably mounted in the frame702. The frame702may be made up of a material such as a plastic or metal. The wearable glasses610may allow the painter604to define one or more actions for painting the house. Further, the wearable glasses610may include one or more cameras706for capturing images. Further, the wearable glasses610may have an integrated battery and a central processing unit (CPU), in accordance with at least one embodiment. The battery may be disposed within the frame702of the wearable glasses610. It should be noted that the battery may be disposed at various positions on the frame702. For example, the battery may be disposed at an end of the frame702of the wearable glasses610. In one case, the battery may be a rechargeable battery. It will be apparent to one skilled in the art that the above-mentioned components of the wearable glasses610have been provided only for illustration purposes. In one embodiment, the wearable glasses610may include a separate display device, a sound output unit, a plurality of cameras, an elastic band, or any number of other accoutrements without departing from the scope of the disclosure. FIG.8illustrates a user802controlling the drone302in real time, in accordance with at least one embodiment. At first, the drone302may perform 3D scanning of a house804. Successively, the drone302may capture images of the house804. Thereafter, the drone302may perform painting of the house804based at least on one or more commands received from the user802. The user802may pilot the drone302to the designated area and cause the drone302to perform the task by sending a series of commands (i.e., remote control operation). It should be noted that the user802may use a tablet806to guide the drone302. The user802may zoom in on live video or images captured by the drone302on the tablet806. In one case, the user802may easily select portions of the house804to paint by first taking an image or a series of images of the house804via onboard cameras within the tablet806. In one embodiment, the user802, using the tablet806, may analyze the image in real time. Based at least on the analysis, the user802may select an area for painting or performing some other task. In one embodiment, the house804may be scanned and a report may be prepared. For example, the report may specify that windows need cleaning whereas other windows do not. In another example, a specific section of the house804may need painting whereas another section may only need spot treatments and another section may not need any coating or paint. In one embodiment, the user802may view a bump map of a surface on the tablet806. The bump map may correspond to a surface the drone302is painting. Thereafter, the user802may give the one or more commands to the drone302. In one example, a command may be to paint a desired portion of a wall by flying in a raster pattern and spraying paint on the wall while flying. The one or more commands may include, but are not limited to, using a paintbrush at edges, using a sprayer for painting the walls of the house, and/or using a roller for a particular design on the walls of the house. Based on the one or more commands of the user702, the drone302may perform the painting of the house804. The drone302may receive the paint supply from a reservoir618. The reservoir618may include the one or more paint containers620for supplying paint to the drone302. The drone302may automatically fill the onboard painting system304from the reservoir618and perform the painting of the house804. It should be noted that the drone302may paint the house804after receiving the commands from the user802in real time. It will be apparent to one skilled in the art that the drone302may receive the paint supply from the reservoir618via a tether (not shown), without departing from the scope of the disclosure. In one embodiment, the user802may paint the house804using paint that is only visible to the user802while wearing the infrared (IR) glasses. It should be noted that such paint is not visible to the user802without the IR glasses. After painting by the user802, the drone302may start painting the house in a similar manner by detecting the location of the IR-visible paint. Such scenarios may allow the user802to get the house802painted in the desired manner using the invisible paint. In one embodiment, the user802may use a laser scanner (not shown) and a projector system (not shown) to assist in painting the house804. It should be noted that a standing laser may be used, without departing from the scope of the disclosure. FIGS.9A and9Billustrate a drone902with feet904, painting a house906, in accordance with at least one embodiment. As shown inFIG.9A, the drone902may be hung with wires908to paint the house906. The wires908may be rotated through a plurality of rollers910. It should be noted that the plurality of rollers910may be a part of the drone902. Further, the drone902may include a spray nozzle912for spraying the paint. It should be noted that the drone902may receive the paint supply from a reservoir914. The reservoir914may include one or more containers916of the paint. Such a drone902may be used to perform various types of painting such as spray painting using a sprayer918, roller-based painting using a roller920, and/or fine-grained painting using a paintbrush922. As shown inFIG.9B, a user924may use a tablet926in real time to check the painting done by the drone902. In one case, the user924may zoom in to see a particular section of the house906. Based at least on the scanning, the user924may give an instruction to the drone902. The instruction may include, but is not limited to, using the paintbrush922to do the painting at a particular section of the house906. In one example, the user924may give a command such as to use the roller920while painting the wall of the house906. Such monitoring may allow the user924to identify errors in the painting in real time and correct them by giving instructions to the drone902. In an alternate embodiment, the reservoir914may be placed on a roof928of the house906, as shown inFIG.9C. Further, the drone902may receive the paint supply from the reservoir914. As discussed above, the reservoir914may include the one or more containers916of the paint. It should be noted that the drone902may receive the paint supply via a tether930. Further, the drone902may be integrated with a motor932that allows movement of the drone902. It should be noted that the movement may be adjusted using the wires908. Such movement may help the drone902in painting the house906. Further, the drone902may paint the house906by moving from one direction to another—e.g., from left to right. While painting the house906, the drone902may utilize the feet904for holding a position on a wall strongly in order to apply the paint. In one embodiment, other components, such as the sprayer918and the roller920, may be placed on the roof928. In another embodiment, the motor932may be placed on the roof928along with the reservoir914, shown inFIG.9D. The motor932(i.e., a stationary motor) may control the drone902while painting the house906. Such a scenario may be helpful in painting large buildings. FIGS.10A and10Billustrate a vehicle (autonomous)1000for cleaning and painting an area1002, in accordance with at least one embodiment. The vehicle1000may include one or more cameras1004, a vacuum cleaner1006, and a spray nozzle1008. At first, the vehicle1000may drive to various places for cleaning. Successively, the vehicle1000may automatically detect garbage1010in the area1002. Successively, the vehicle1000may capture images of the area1002. The images may correspond to the garbage1010present in the area1002. It should be noted that the images may be captured using the one or more cameras1004. In one embodiment, the images may be stored in a memory (not shown). Successively, the vehicle1000may send the captured images to a remote station (not shown). It should be noted that the remote station may compare the captured images with historical data corresponding to the area1002. Successively, the vehicle1000may receive a command from the user for cleaning the area1002. Thereafter, the vehicle1000may perform cleaning of the area1002using the vacuum cleaner1006. After cleaning the area1002, the vehicle1000may perform painting on a portion of the area1002. The vehicle1000may use the spray nozzle1008for spraying the paint, as shown inFIG.10B. It should be noted that the paint may be supplied from the vehicle1000. In one case, if the spray nozzle1008gets clogged, the vehicle1000may change the spray nozzle1008with the backup spray nozzles1008automatically. Such operation of the vehicle1000may be performed automatically for maintaining and preserving the aesthetics of the area1002. It should be noted that the vehicle1000may include more than one spray nozzle1008as well, without departing from the scope of the disclosure. FIG.11illustrates a vehicle1100for deploying a drone1102to paint a house1104, in accordance with at least one embodiment. The vehicle1100may correspond to a rentable self-service painting vehicle. Further, the vehicle1100may include a box1106that is used for storing the drone1102. When the vehicle1100is used for painting the house1104, the vehicle1100may drive to a home and deploy the drone1102automatically. In one case, the drone1102may correspond to a mobile rolling drone. Further, the drone1102may receive the paint from the vehicle1100via a tether (not shown) and may be powered by the vehicle1100. In one embodiment, the vehicle1100may utilize the drone1102for detecting theft. It should be noted that the drone1102may include various components, such as a plurality of sensors, one or more cameras, a spray nozzle, and/or backup spray nozzles, as discussed above, without departing from the scope of the disclosure. FIG.12illustrates a flowchart1200showing a method for painting the house, in accordance with at least one embodiment. The flowchart1200is described in conjunction withFIGS.1to11. At step1202, an analysis of a house may be performed. The analysis may include capturing images of the house and/or three-dimensional (3D) measurements. In one embodiment, the analysis may be performed by the drone. In another embodiment, the analysis may be performed by the user (i.e., painter). At step1204, one or more beacons and Infrared (IR) paint may be laid. In one embodiment, the one or more beacons may be laid by the drone. In another embodiment, the IR paint may be laid by the painter. At step1206, one or more commands may be received. The one or more commands may be provided by the painter to the drone. The one or more commands may include, but are not limited to, performing painting using oil or latex paint, performing painting using different colors, and/or performing spray painting on a particular area of the house. In one embodiment, the painter may prepare a design on a computer and thereafter may provide the one or more commands to the drone. At step1208, taping and/or boundary spray may be performed. It should be noted that step1208may be performed by the drone. At step1210, three-dimensional (3D) printing may be performed. The 3D printing may include, but is not limited to, hole filling. Further, the drone may perform sanding to make the surface smooth. In one embodiment, the drone may deploy 3D scanning as well, without departing from the scope of the disclosure. At step1212, painting of the house may be performed. It should be noted that the drone may perform painting of the house. At step1214, an analysis of the painted house may be performed. The analysis may be performed by the user to determine how well the painting was executed. In one case, the user may give commands to the drone to do the painting using different brushes—e.g., using the paintbrush at the edges, etc. At step1216, a protective coating may be applied. In one case, the protective coating may correspond to ultraviolet (UV) protection coating. At step1218, tape and/or boundary spray may be removed. At step1220, a final verification of the house may be performed by the user. At step1222, the one or more beacons may be removed. It should be noted that the drone may remove the one or more beacons automatically after painting the house. FIG.13illustrates a flowchart1300showing a method for painting a target and improving results using machine learning, in accordance with at least one embodiment. The flowchart1300is described in conjunction withFIGS.1to11. “Machine learning” here may comprise any number of machine learning or artificial intelligence technologies necessary to achieve the objectives of the invention, including, but not limited to, neural networks, convolutional neural networks, supervised learning, unsupervised learning, reinforcement learning, and deep learning. At step1302, a first set of images may be captured from a number of painted and unpainted targets. The first set of images may depict targets in a variety of conditions varying from poor to acceptable. Further, the first set of images may be taken under a variety of conditions such as rain, night, and/or day. Further, the first set of images may be captured at varying angles and distances. The first set of images may be stored for subsequent reference using some means such as, but not limited to, a database or other electronic data storage. Each image in the first set of images may be assigned a set of labels or tags indicating its characteristics. Such labels or tags may include such characteristics as “good,” “poor,” “incomplete,” “old,” “unpainted,” etc., indicating the qualities of the paint applied. At step1304, a set of machine learning algorithms may be applied to the first set of images to train a first classifier that can be used to estimate the characteristics of a new image not included in the first set. Such use of machine learning would be well known to one skilled in the art. At step1306, a second set of images corresponding to the current target may be captured. The second set of images may be taken under a variety of conditions such as rain, night, and/or day. Further, the second set of images may be captured at varying angles and distances. The second set of images may be added to the first set of images for storage and subsequent reference. At step1308, the first classifier may be applied to the second set of images to estimate the current condition of the target with respect to painting. The estimated condition may be used to adjust the behavior of the drone in painting the target. At step1310, painting of the house may be performed by the drone. At step1312, a third set of images corresponding to the current target may be captured. The third set of images may be taken under a variety of conditions such as rain, night, and/or day. Further, the third set of images may be captured at varying angles and distances. The third set of images may be added to the first set of images for storage and subsequent reference. At step1314, an observer's input may be used to adjust the behavior of the drone using reinforcement learning. The observer may indicate whether the paint job was acceptable or unacceptable, possibly using a series of values on a gradient scale between the two. The observer's feedback may be indicated to the drone's control mechanism using an input channel such as a computer or mobile device. The drone's control mechanism may use the observer's feedback to adjust its control algorithm to do a better job of receiving positive observer feedback in subsequent painting, and thus to produce better execution of paint jobs. At step1316, the improved drone control algorithm may be transferred to all other drone systems and thus may be used for painting the house. At step1318, a set of machine learning algorithms may be applied to the first set of images, which may now include the second set of images and the third set of images, to train an improved second classifier that can be used to estimate the characteristics of a new image not included in the first set. At step1320, the improved second classifier may be transferred to all other drone systems and used for subsequent evaluation of targets before and after painting. The disclosed embodiments encompass numerous advantages. Various embodiments of methods and systems for performing painting using drones have been disclosed. The disclosure provides the user with flexibility to remotely control the drone. Such operation may solve a problem of paint-matching a house by having all necessary paints and dyes in the system. Further, the disclosure discloses a rentable self-service painting vehicle that may drive to a home and paint a house by deploying a mobile rolling drone out of the vehicle that is powered by and supplied paint by the vehicle itself. Such a rentable self-service painting vehicle may solve a problem of a rentable automatic drone painting system for consumers that may be loaded into a vehicle. Also, such a rentable self-service painting vehicle may solve the problem of cleaning the rentable drone by the rental facility. In one embodiment, the drone may be used for replicating murals by providing accurate scanning of the murals and producing scaled replicas of the murals in other locations. Further, the drone may put advertisements in mural form. Further, the disclosure discloses an autonomous vehicle that is used for cleaning an area and thereby preserving and maintaining aesthetics of the area. Further, the disclosure discloses that the autonomous vehicle may install one or more drones for detecting theft. Such a method and system for performing operations using the drones may reduce manpower, increasing efficiency and reliability. The disclosed methods and systems, as illustrated in the foregoing description or any of its components, may be embodied in the form of a computer system. Typical examples of a computer system include a general-purpose computer, a programmed microprocessor, a microcontroller, a peripheral integrated circuit element, and other devices, or arrangements of devices that are capable of implementing the steps that constitute the method of the disclosure. The computer system may comprise a computer, an input device, a display unit, and the internet. The computer may further comprise a microprocessor. The microprocessor may be connected to a communication bus. The computer may also include a memory. The memory may be random-access memory or read-only memory. The computer system may further comprise a storage device, which may be a hard disk drive or a removable storage device such as a floppy disk drive, an optical disk drive, an SD card, flash storage, or the like. The storage device may also be a means for loading computer programs or other instructions into the computer system. The computer system may also include a communication unit. The communication unit may allow the computer to connect to other computer systems and the Internet through an input/output (I/O) interface, allowing the transfer and reception of data to and from other systems. The communication unit may include a modem, an Ethernet card, or similar devices that enable the computer system to connect to networks such as LANs, MANs, WANs, and the Internet. The computer system facilitates input from a user through input devices accessible to the system through the I/O interface. To process input data, the computer system may execute a set of instructions stored in one or more storage elements. The storage element(s) may also hold other data or information, as desired. Each storage element may be in the form of an information source or a physical memory element present in or connected to the processing machine. The programmable or computer-readable instructions may include various commands that instruct the processing machine to perform specific tasks, such as steps that constitute the method of the disclosure. The systems and methods described can also be implemented using software alone, hardware alone, or a varying combination of the two. The disclosure is independent of the programming language and the operating system used by the computers. The instructions for the disclosure may be written in any programming language, including, but not limited to, assembly language or machine instructions, C, C++, Objective-C, Java, Swift, Python, and JavaScript. Further, software may be in the form of a collection of separate programs, a program module containing a larger program, or a portion of a program module, as discussed in the foregoing description. The software may also include modular programming in the form of object-oriented programming. The processing of input data by the processing machine may be in response to user commands, the results of previous processing, or a request made by another processing machine. The methods and systems of the disclosure may also be implemented using various operating systems and platforms, including, but not limited to, Unix, Linux, BSD, DOS, Windows, Android, iOS, Symbian, a real-time operating system, and a purpose-built operating system. The methods and systems of the disclosure may be implemented using no operating system as well. The programmable instructions may be stored and transmitted on a computer-readable medium. The disclosure may also be embodied in a computer program product comprising a computer-readable medium with any product capable of implementing the above methods and systems or the numerous possible variations thereof. Various embodiments of the methods and systems for performing painting using drones and autonomous vehicle have been disclosed. However, it should be apparent to those skilled in the art that modifications in addition to those described are possible without departing from the inventive concepts herein. The embodiments, therefore, are not restrictive, except in the spirit of the disclosure. Moreover, in interpreting the disclosure, all terms should be understood in the broadest possible manner consistent with the context. In particular, the terms “comprises,” “comprising,” “including,” and “id est” should be interpreted as referring to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, used, or combined with other elements, components, or steps that are not expressly referenced. A person with ordinary skill in the art will appreciate that the systems, modules, and submodules have been illustrated and explained to serve as examples and should not be considered limiting in any manner. It will be further appreciated that the variants of the above disclosed system elements, modules, and other features and functions, or alternatives thereof, may be combined to create other, different systems or applications. From the foregoing it is believed that those skilled in the pertinent art will recognize the meritorious advancement of this invention and will readily understand that while the present invention has been described in association with a preferred embodiment thereof, and other embodiments illustrated in the accompanying drawings, numerous changes modification and substitutions of equivalents may be made therein without departing from the spirit and scope of this invention which is intended to be unlimited by the foregoing except as may appear in the following appended claim. Therefore, the embodiments of the invention in which an exclusive property or privilege is claimed are defined in the following appended claims.
62,887