Modular Adsorbent Devices and Applications

Abstract

An adsorbent device includes adsorbent fibers laid along or wound around a center tube. In a specific example, the adsorbent fibers are porous solid amine adsorbent fibers. A module for purifying a raw fluid includes one or more adsorbent devices that can be installed in a vessel in series or in parallel. The module can be configured for axial or cross flow operation and can be employed to purify a gas containing a contaminant such as an acid gas. In some implementations, the module is provided with one or more heating elements that can be used to release adsorbed contaminant to regenerate the adsorbent fibers.

Claims

1. A fluid purification system, the system comprising: a vessel provided with an inlet for introducing a fluid to be purified and an outlet for collecting purified fluid; at least one adsorbent device within the vessel, the at least one adsorbent device comprising multiple adsorbent fibers; and an optional heating element at the exterior or in the interior of the vessel.

2. The fluid purification system of claim 1, wherein the adsorbent fibers are disposed along a length of or wound around a hollow center tube, forming a fiber arrangement, fluid communication between a shell side of the fiber arrangement and an interior space of the center tube being through one or more openings defined in the hollow center tube.

3. The fluid purification system of claim 1, further comprising one or more receptacles for engaging the at least one adsorbent device.

4. The fluid purification system of claim 1, wherein the vessel includes multiple adsorbent devices connected in series.

5. The fluid purification system of claim 1, wherein the vessel includes multiple adsorbent devices arranged in a parallel configuration.

6. The fluid purification system of claim 1, wherein the optional heating element is a heating jacket or a heat exchanger.

7. The fluid purification system of claim 1, wherein the fluid purification system is configured for axial flow or wherein the fluid purification system is configured for cross flow.

8. The fluid purification system of claim 1, wherein the fluid purification system is configured for shell side feeding, or wherein the fluid purification system is configured for bore side feeding.

9. The fluid purification system of claim 1, wherein the multiple adsorbent fibers form a fiber arrangement having an exterior surface.

10. The fluid purification system of claim 9, wherein the exterior surface of the fiber arrangement is partially wrapped by an impermeable stainless steel sheet, a copper sheet or a fiberglass sheet.

11. The fluid purification system of claim 9, wherein the exterior surface of the fiber arrangement is not covered or covered by a perforated plastic material.

12. The fluid purification system of claim 1, wherein the adsorbent fibers include a zeolite, activated carbon, MOF, COF or PAF material, or wherein the adsorbent fibers include linear polyethylenimine, branched polyethylenimine and polyvinylamine, or wherein the adsorbent fibers include a crosslinked linear polyethylenimine, crosslinked branched polyethylenimine and crosslinked polyvinylamine, or wherein the adsorbent fibers include a porous solid amine adsorbent in which an amine-containing polymer is embedded in a polymeric matrix.

13. A process for removing a contaminant from a fluid stream containing the contaminant, the process comprising: directing the fluid stream to a module containing at least one adsorbent device, wherein the adsorbent device includes adsorbent fibers; bringing the fluid stream in contact with the adsorbent fibers, whereby at least a portion of the contaminant is adsorbed by the adsorbent fibers to produce a purified fluid stream; and collecting the purified fluid stream from the module.

14. The process of claim 13, further comprising regenerating the adsorbent fibers.

15. The process of claim 13, further comprising desorbing the at least a portion of the contaminant from the adsorbent fibers by heat, reduced pressure, vacuum, or a combination of heat and reduced pressure or vacuum, thereby regenerating the adsorbent fibers.

16. The process of claim 13, wherein the adsorbent fibers are disposed along a length of or wound around a hollow center tube, forming an adsorbent arrangement, fluid communication between a shell side of the adsorbent arrangement and an interior space of the hollow center tube being through one or more openings defined in the center tube.

17. The process of claim 13, wherein the module includes multiple adsorbent devices arranged in series or wherein the module includes multiple adsorbent devices arranged in a parallel configuration.

18. The process of claim 13, wherein the process is configured for axial flow or wherein the process is configured for cross flow.

19. The process of claim 13, wherein the process is configured for shell side feeding or wherein the process is configured for bore side feeding.

20. The process of claim 13, wherein the fluid stream containing the contaminant is a flue gas, a biogas, hydrogen gas, natural gas or air, or wherein the contaminant is carbon dioxide, hydrogen sulfide or sulfur oxide.

21. The process of claim 13, wherein the adsorbent fibers include a material selected from the group consisting of zeolites, activated carbons MOFs, COFs and PAFs, or wherein the adsorbent fibers include linear polyethylenimine, branched polyethylenimine and polyvinylamine, or wherein the adsorbent fibers include a crosslinked linear polyethylenimine, crosslinked branched polyethylenimine and crosslinked polyvinylamine, or wherein the adsorbent fibers include a porous solid amine adsorbent in which an amine-containing polymer is embedded in a polymeric matrix.

22. A fluid purification device, the device comprising: a plurality of adsorbent fibers disposed along a length of a center tube or wound around the center tube, wherein: the center tube is hollow; and fluid communication between a shell side of the plurality of adsorbent fibers and an interior space of the center tube is through one or more openings defined in the center tube.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In the accompanying drawings, reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale; emphasis has instead been placed upon illustrating the principles of the invention. Of the drawings:

[0032] FIG. 1 is an illustration of a fiber adsorbent cartridge configured for axial flow, with adsorbent fibers layered around a center tube which has both ends equipped with o-rings;

[0033] FIG. 2 is an illustration of a fiber adsorbent cartridge configured for axial flow, with adsorbent fibers layered around a center tube having one end equipped with a receptacle and the other with an o-ring;

[0034] FIG. 3 is an illustration of a fiber adsorbent cartridge configured for axial flow, with adsorbent fibers layered around a center tube which has both ends equipped with o-rings;

[0035] FIG. 4 is an illustration of a fiber adsorbent cartridge configured for axial flow, with adsorbent fibers helically wound around a center tube which has both ends equipped with o-rings;

[0036] FIG. 5 is an illustration of a fiber adsorbent cartridge configured for cross flow, with adsorbent fibers helically wound around a center tube which has both ends equipped with o-rings;

[0037] FIG. 6 is a diagram showing an axial fluid flow pattern for an axial flow fiber adsorbent cartridge;

[0038] FIG. 7 is a diagram showing a cross flow pattern for a cross flow fiber adsorbent cartridge;

[0039] FIG. 8 is an illustration of an adsorbent module in which a single adsorbent cartridge, configured as shown in FIG. 4, is installed in a vessel;

[0040] FIG. 9 is an illustration of a section of a center tube coupling connecting two adsorbent cartridges;

[0041] FIG. 10 is an illustration of a section of a center tube coupling connecting two adsorbent cartridges and including an optional centering support;

[0042] FIG. 11 is an illustration of an adsorbent module including five adsorbent cartridges installed in series in a long tubular housing;

[0043] FIG. 12 is an illustration of an adsorbent module in which multiple adsorbent cartridges are installed in a parallel configuration;

[0044] FIG. 13 is an illustration of an adsorbent module with parallel adsorbent cartridges arranged in rows;

[0045] FIG. 14 is an illustration of a module that contains a single adsorbent cartridge and is fitted with an external heating jacket;

[0046] FIG. 15 is an illustration of the multi-cartridge module of FIG. 11 fitted with an external heating jacket;

[0047] FIG. 16 is an illustration of a multi-cartridge adsorbent arrangement with one internal heat exchanger;

[0048] FIG. 17 is an illustration of a multi-cartridge adsorbent arrangement with two internal heat exchangers;

[0049] FIG. 18 is an illustration of an axial flow pattern in a module that includes five adsorbent cartridges installed in series, as shown in FIG. 11;

[0050] FIG. 19 is a cross sectional view of an adsorbent module with multiple cartridges installed in a parallel configuration and a heat exchanger;

[0051] FIG. 20 is a cross sectional view of another adsorbent module which includes multiple cartridges installed in a parallel configuration and multiple heat exchangers.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0052] The invention now will be described more fully hereinafter with reference to the accompanying drawings, in which illustrative embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0053] As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Also, all conjunctions used are to be understood in the most inclusive sense possible. Thus, the word “or” should be understood as having the definition of a logical “or” rather than that of a logical “exclusive or” unless the context clearly necessitates otherwise. Further, the singular forms and the articles “a”, “an” and “the” are intended to include the plural forms as well, unless expressly stated otherwise. It will be further understood that the terms: includes, comprises, including and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Further, it will be understood that when an element, including component or subsystem, is referred to and/or shown as being connected or coupled to another element, it can be directly connected or coupled to the other element or intervening elements may be present.

[0054] It will be understood that although terms such as “first” and “second” are used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Thus, an element discussed below could be termed a second element, and similarly, a second element may be termed a first element without departing from the teachings of the present invention.

[0055] 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 invention 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.

[0056] The invention generally relates to fluid purification equipment and techniques. The adsorption device (cartridge) described herein incorporates adsorbent fibers. One or more such devices can be assembled in a system (module). Further embodiments of the invention pertain to methods for preparing and/or using such adsorbent devices and/or modules.

[0057] Adsorbent devices that can be employed to prepare a module, for example, typically include multiple also referred to herein as a “plurality of” (i.e., at least two) adsorbent fibers disposed in various configurations (e.g., laid along to, typically in parallel, or wound around, e.g., helically) relative to a center tube.

[0058] In many cases, the adsorbent fibers form an arrangement also referred to herein as “bundle” or “fabric” around the center tube. The adsorbent fibers can be hollow adsorbent fibers. For many applications, however, non-hollow adsorbent fibers provide more adsorbing material for a given volume. In many embodiments, the fabric has a cylindrical shape. Its thickness may vary, depending on the type of cartridge, volume of gas treated or application. Typically, the fiber adsorbent arrangement has a thickness of at least about 1 inch, such as within a range of from about 1 inch to about 50 inches, preferably, from about 3 inches to about 20 inches.

[0059] The center tube can be a cylindrical hollow tube with openings (also referred to as holes, orifices or perforations) that allow fluid communication between an exterior (shell) surface of the fabric and the bore or lumen of the center (also referred to as “core”) tube. The center tube can be made from any nonimpermeable material that is compatible with the fluid streams being processed, e.g., metal, glass, wood, plastic, composite laminate, and the like. In an illustrative example, the center tube has a length within a range of from about 12 inches to about 100 inches and a diameter within a range of from about 0.5 inches to about 3 inches. The placement of the holes typically will depend on the kind of flow intended for the cartridge, as further described below.

[0060] Preparing an adsorbent fiber arrangement around the center tube often involves employing more than one fiber at the time, using, for instance, filaments of 4 to 32 fibers. Methods for laying or winding fibers in various configurations are known in the art, as described, for instance, in U.S. Pat. Nos. 5,837,033, 3,339,341 and 4,940,617, the contents of which are incorporated herein by this reference. Other approaches, e.g., those developed or refined in the future, also can be employed.

[0061] The fiber packing density can be controlled. With computerized winding techniques, for instance, the packing density can be precisely controlled using different winding parameters, such as winding angle, fiber spacing, phases, etc. This is described in U.S. Pat. No. 6,638,479, which is incorporated herein by this reference in its entirety.

[0062] The precision control of the fiber spacing offers the advantage of fast and uniform mass transfer. The pressure drop across a fiber adsorbent can be given as:

[00001]$\begin{array}{cc}\frac{\Delta p}{L}=\frac{150\mu }{d^2}{\left(\frac{1-\epsilon }{\epsilon }\right)}^2\left(\frac{v}{\epsilon }\right)+\frac{1.75\rho }{d}\left(\frac{1-\epsilon }{\epsilon }\right){\left(\frac{v}{\epsilon }\right)}^2& \left(1\right)\end{array}$

where L is the length, d is the cartridge diameter, ε is void fraction, and υ, μ are gas superficial velocity and viscosity, respectively. Equation 1 predicts that the pressure drop is a quadratic function of the interstitial velocity of the gas flow, and voidage.

[0063] The ends of the adsorbent fibers can be sealed with epoxy tube sheets. Techniques are described, for instance in U.S. Pat. Nos. 6,042,677, 6,290,756 and 6,709,494, which are incorporated herein in their entirety by this reference.

[0064] In some cases, e.g., if using computer controlled winding techniques to construct the device, threads can be used on one or both ends to hold the fiber tightly in place, as described, for example, in U.S. Pat. No. 6,638,479, which is incorporated herein in its entirety by this reference. Generally, these threads can provide a very effective seal for the fiber ends, rendering redundant epoxy sealing. Thus, in many implementations, the device uses epoxy sealing, or threads, or a combination of both.

[0065] In many embodiments of the invention, the complete device has a cylinder shape with the center tube extending outside the fiber arrangement. The ends of the center tube can be both in the same configuration or in a reciprocal configuration. In contrast to arrangements that employ hollow fiber membranes, contaminants such as acid gases are trapped or captured in the adsorbent material, which can be regenerated by cycling processes. Thus, the cartridge described herein does not need to provide for the extraction of a fluid fraction that is enriched with contaminant, as in the case of membrane separation devices.

[0066] The fiber arrangement can be covered (at least in part) with an impermeable wrap, with another type of covering or left uncovered. The choice depends, at least in part, on the flow configuration characterizing the cartridge.

[0067] Shown in FIG. 1 is cartridge 10 including center tube 12, provided with openings 14, and fiber arrangement (fabric) 16, which includes a plurality of adsorbent fibers 18, laid along, e.g., parallel, to the length of center tube 12.

[0068] Holes 14 are disposed at one end of the center tube and can include a single or, typically, two or more (e.g., 4, 50, 100, 200, etc., depending on the center tube diameter and treated gas flow volume) perforations.

[0069] In the embodiment of FIG. 1, fibers 18 are secured by epoxy tubesheets 20 and 22.

[0070] Wrap 24 partially encases fiber arrangement 16, being provided with wrap opening 26. Wrap 24 is made of an impermeable material, e.g., sheet plastic, metal, fiberglass, and so forth. In specific examples, the wrap material has a high thermal conductivity, such as, for instance, stainless steel sheet, copper sheet, etc. Materials characterized by high thermal conductivity can facilitate the heating of the adsorbents in systems in which a heat exchanger is placed outside of the cartridge.

[0071] As seen in FIG. 1, wrap 24 covers the section of the fiber arrangement 16 that is disposed over openings 14, while providing fluid communication between the exterior (at the shell side) and the fiber arrangement 16, through opening 26. This arrangement allows fluid to enter or exit the adsorbent fibers and generates an axial flow, as further described below.

[0072] Other implementations, for cross flow operations, for instance, do not employ a wrap or simply use a highly porous cover, e.g., for protecting (from impact, dirt, etc.) the fiber arrangement. Examples of highly porous covers that can be employed include perforated sheets made of plastics, metals, and/or fiber glasses, woven or non-woven porous materials made of plastics, metals, and/or fiber glasses and so forth.

[0073] Ends 28 and 30 of the center tube (also referred to as “extension pieces” 28 and 30) reach outwardly, beyond the epoxy tubesheets 20 and 22. One or both ends 28 and 30 can be constructed into a “nozzle” by machining one or more o-ring groove(s) into the circumference of the extension piece. When inserted into a corresponding receptacle, o-rings sitting in these grooves ensure the formation of a tight seal for the fluid flows. Other means can be employed for connecting, e.g., in leak-tight fashion, the center tube to conduits for directing a fluid stream into or out of the cartridge.

[0074] Ends 28 and 30 can be configured in various ways, presenting a high degree of flexibility in meeting the demands of any number of applications. For example, if only one cartridge is employed in the purification process, or for systems that include multiple cartridges installed in parallel, one of the ends 28 and 30 can be blocked off by a solid cap or can be inserted into a receptacle that is not communicating with any other conduit. On the other hand, systems that include cartridges connected in series can rely on both ends for passing a fluid stream from one cartridge to the next.

[0075] In the embodiment of FIG. 2, end 28 (which can be provided with an o-ring groove supporting an o-ring) is inserted into receptacle 36, configured to accept the nozzle at end 28; the nozzle at end 30 supports an o-ring, essentially as described above, and is shown without a corresponding receptacle. In the embodiment of FIG. 3, both ends 28 and 30 are shown as being inserted into receptacles 36 and 38, configured for connecting with the respective nozzles equipped with o-rings.

[0076] A receptacle can be open or closed to fluid communication. In the case of employing a single cartridge or a system in which multiple cartridges are installed in parallel, one of the ends 28 and 30 can be blocked off by a closed-off receptacle (or a solid cap). Receptacles designed to be open to fluid flow can be used when connecting cartridges that are installed in series.

[0077] Shown in FIG. 4 is cartridge 50 which includes center tube 12, provided with openings 14, disposed near end 30, and fiber arrangement 52, which is wound, e.g., helically, around the center tube. Winding techniques that can be employed are known in the art. See, for example, U.S. Pat. No. 5,837,033, which is incorporated herein in its entirety by this reference. Fiber arrangement 52 is partially encased by wrap 24 provided with opening 26, essentially as described above.

[0078] While the embodiments of FIGS. 1-4 are configured for axial or longitudinal flow (with a fluid stream passing through the fiber arrangement along the length of, e.g., parallel to, the center tube 12), cartridge 70 of FIG. 5 is configured for a transverse or cross-flow mode of operation. Cartridge 70 includes adsorbent fibers that are helically wound to form fiber arrangement 52 around center tube 12. Whereas in FIGS. 1-4 holes 14 are disposed at the end opposite wrap opening 26, in cartridge 70, holes 14 are disposed along the length of the center tube; the solid wrap of FIGS. 1-4 is replaced by porous cover 72, which is optional.

[0079] As discussed in relation to FIGS. 1-5, the cartridge can be designed to operate in an axial flow or a cross flow mode.

[0080] Shown in FIG. 6 is an axial flow pattern 80, in which a fluid stream to be purified, namely raw fluid stream 82, is fed from the shell (outer side) of the wound fiber adsorbent arrangement (fabric) 52. In more detail, the raw fluid enters the fiber arrangement through opening 26 of wrap 24 and travels through the fiber adsorbent fabric along (e.g., in a substantially parallel direction to) center tube 12, as indicated by the arrows. At least a portion of the contaminant present in the raw fluid stream 82 is removed by the adsorbent fibers resulting in a purified fluid stream, namely clean fluid stream 84, that exits the fiber adsorbent arrangement 52, passing through holes 14 (disposed in this embodiment near end 30) into the hollow space of center tube 12, to exit the cartridge at end 30 from the bore side of the center tube. The flow direction can be reversed (with raw fluid stream being fed from the bore side of the center tube and purified stream exiting the fiber arrangement 52 via wrap opening 26) without an adverse &Tea on the adsorption.

[0081] A cross flow pattern also can be employed in some cases. Shown in FIG. 7 is cross flow pattern 90 in which a raw fluid stream 82 is fed from the shell side of the fiber adsorbent arrangement (fabric) 52 (which in this embodiment is not covered or covered by a permeable covering), in a direction that is not parallel to the center tube but at an angle, typically substantially perpendicular, to center tube 12, e.g., as indicated by the arrows. As the raw fluid stream passes through the adsorbent fibers, at least a portion of the contaminant present in the stream becomes captured (adsorbed). A resulting purified stream, namely clean stream 84, exits the fiber arrangement through perforations 14 (which in this embodiment are disposed along the length of center tube 12), and leaves the cartridge from the bore side of the center tube. The flow direction can be reversed (by directing the raw fluid stream from the bore side of the center tube, through perforations 14, through fiber arrangement 52 and withdrawing a clean fluid stream from the shell side of the cartridge) without an adverse effect on the adsorption.

[0082] For many practical applications it is useful to assemble adsorbent devices such as those described with reference to FIGS. 1-5, for example, in a system (module). The module employs a vessel having an inlet for introducing a contaminated (raw) fluid and an outlet for collecting a purified (clean) fluid. The vessel can be made of any suitable material. Examples include aluminum, plastics, steel, stainless steel, fiber glasses, etc., depending on the intended applications. Vessel characteristics such as shape, dimensions, etc. can vary, depending on operation requirements, number of cartridges, cartridge dimensions, mode of assembling and/or operating them, the onsite space available for installing the module, fluid pressure, temperature, volume and so forth.

[0083] Shown in FIG. 8, for example, is module 11 in which vessel 13 encloses a single adsorbent cartridge, in this case adsorbent device 50 (of FIG. 4). Other adsorbent devices can be employed. Vessel 13 is provided with port 15, an inlet for feeding the fluid stream to be purified, and with receptacles 36 and 38 (described with reference to FIG. 3) and configured to receive, respectively, the nozzle at end 28 and at end 30 of a center tube.

[0084] In module 11, only one receptacle is configured for fluid communication. For example, receptacle 36 can provide a connecting port, specifically to an outlet for withdrawing a purified fluid from the vessel, while receptacle 38 lacks connection to an external port. In a different approach, end 30 is blocked, using a solid cap, for instance.

[0085] Optionally, one or more centering supports 25 (further described below) can be used to brace ends 28 and/or 30 during installation, to ensure, for instance, that the nozzle at the end of a cartridge properly engages with the corresponding receptacle.

[0086] Although a module containing a single adsorbent device can remove at least some contaminant is a fluid stream, such a module may not meet the demands of certain operations. For example, handling large volumes of raw fluid with a single adsorbent device in a module such as shown in FIG. 8 may turn out to be impractical or prohibitively expensive. Thus, many embodiments of the invention feature modules that include multiple (at least two) adsorbent devices, e.g., within a range of from about 5 to about 100 or more, such as within a range of from about 5 to about 25, from about 5 to about 50, from about 5 to about 75; or from about 25 to about 50, for about 25 to about 75, from about 25 to about 100; or from about 50 to about 75, from about 50 to about 100; or from about 75 to about 100 cartridges. Illustrative adsorbent modules can contain 3, 5, 8, 10, 20, 30, 50, 75, 100 or more adsorbent cartridges.

[0087] Vessels enclosing more than one cartridge can have any number of shapes or dimensions. Moreover, within a vessel, cartridges can be arranged in various configurations. Thus, designing a module may depend on the footprint available for the purification operation, flow volumes being handled, typical pressures encountered in a specific application, and/or other factors.

[0088] Some of the module designs can include vessel headers or manifolds for introducing and/or extracting fluids, for example. Others can use connecting elements (e.g., tubes, pipes, manifolds or other arrangements for directing fluids), supports (e.g., for bracing conduits or cartridges during installation or operation), spacers, and/or other components selected to provide improved mechanical stability, space optimization, synergies among module components, or other purposes.

[0089] As an illustration, arrangement 21 of FIG. 9 includes tube coupling 23 connecting receptacle 36 (from a first device such as device 50 in FIG. 4) and receptacle 38 (from a second device such as another device 50 in FIG. 4). Tube coupling 23 can be made of steel, plastics, aluminum, fiber glasses, etc. and is dimensioned to accommodate a given arrangement of adsorbent devices.

[0090] Tube coupling 23 can be secured (inside the vessel) using at least one centering support 25, as illustrated in FIG. 10. An optional element, centering support 25 can be made of plastics, steel, aluminum, fiber glasses, etc. and can be dimensioned according to he interior vessel geometry.

[0091] As already noted, adsorbent devices within the module can be arranged in various configurations.

[0092] FIG. 11, for instance, shows module 41 in which vessel 43 houses five adsorbent cartridges, such as, for example, adsorbent devices 50 (FIG. 1). The devices are arranged in series and are labeled A through E. Vessel 43 can be a long tube made of steel, aluminum, fiber glasses, plastics or another suitable material and sized to accommodate the number and dimensions of the cartridges enclosed. In an illustrative example, the tube has a diameter within a range of from about 6 to about 30 inches, and a length within a range of 10 to 30 feet.

[0093] Port 15 can be connected to exterior piping and can be used for feeding the raw fluid stream into the vessel. Module ends 47 and 49 include receptacles that can engage, respectively, with the nozzles of the first and last adsorbent cartridge. In the embodiment of FIG. 11, there is no fluid communication at the receptacle at module end 47. Purified fluid is extracted at module end 49, where the receptacle is configured for fluid communication with external piping.

[0094] The cartridges are connected to one another using connecting elements such as described, for instance, with reference to FIG. 9. Optionally, the coupling tubes can be supported by centering supports, such as described with reference to FIG. 10. In more detail, cartridge end 30A is secured by optional centering support 25. Cartridge A is connected to cartridge B through tube coupling 23AB, optionally supported by one or more supports 25; cartridge B is connected to cartridge C via tube coupling 23BC, optionally secured by at least one centering support 25; and so on. In some cases, cartridge end 28E also can be supported by a centering support 25. Centering supports can be positioned at different locations within the module. Fewer, more or no centering supports can be employed.

[0095] Some situations render long tube configurations impractical, however. Thus, other adsorbent cartridge arrangements can be used to meet space limitations. Shown in FIG. 12, for example, is cartridge assembly 61 including multiple cartridges (e.g., cartridges 50 of FIG. 4) arranged to fit a vessel having a round cross-section.

[0096] For some large or extremely large flow applications (such as, for instance, the direct air CO.sub.2 capture or flue gas CO.sub.2 capture) the cartridges can be arranged in rows, to fit in a vessel or container with a rectangular (e.g., square) cross section. An example is presented in FIG. 13, showing cartridge assembly 81, which includes rows of adsorbent cartridges (e.g., cartridges 50 of FIG. 4).

[0097] Assemblies 61 and 81 illustrate adsorbent devices that are installed in a parallel configuration. Such configurations can be particularly well suited for situations in which the height or length of the available space is limited. Moreover, assemblies 61 or 81 can be fitted with common headers, manifolds and/or other piping arrangements for bringing in raw fluid to be distributed to each adsorbent cartridge. Clean fluid can be withdrawn from each cartridge and combined into a common output using manifolds, reservoirs and/or other suitable piping arrangements.

[0098] Cartridges and modules described herein can present additional options. Some relate to operations conducted to regenerate the adsorbent fibers that contain contaminant removed from the raw fluid.

[0099] Releasing the adsorbed contaminant, CO.sub.2, for instance, can be performed using heat, vacuum, reduced pressure, or any combination thereof. If the regeneration technique relies on heat, the desorption process can be a temperature swing adsorption (TSA) method, while many processes based on lowered pressures are known as pressure swing adsorptions (PSA). Another useful technique that can be employed to release adsorbed species, e.g., from the porous solid amine adsorbents further described below involves both heating and vacuum, the process being known as temperature-vacuum swing adsorption or TVSA. These techniques are well known in the art (see, e.g., U.S. Pat. Nos. 9,457,340, and 8,974,577, the entire contents of both being incorporated herein by this reference).

[0100] If TSA or TVSA techniques are employed, a module such as described in the present application can be provided with one or more heating element(s) that can be used to raise the temperature of the adsorbent fibers, thereby releasing the trapped contaminant and regenerating the fibers. Example of heating elements include but are not limited to heating tapes, heating coils, heating jackets, heat exchanging pipes, heat exchanging plates and so forth.

[0101] In some cases, the heating element is external to the vessel containing the adsorbent cartridge(s). Shown in FIG. 14, for example, is module 101 in which vessel 13, which encloses cartridge 50, essentially as described above, is fitted with heating/cooling jacket 103. The jacket is provided with ports 105 for introducing or withdrawing the heating/cooling fluid utilized in jacket 103. In module 121 of FIG. 15, tubular vessel 43, essentially as described with reference to FIG. 11, is provided with heating/cooling jacket 123, which has inlet/outlet ports 105 for the heating/cooling fluid being utilized. Other means of heating the exterior surface of the vessel can be employed.

[0102] One or more heating elements also can be installed in the interior of (within) the vessel containing the cartridges. For example, a heating jacket, heating coils, heating plates, heating tape, etc. can be installed at an interior surface the vessel. To speed up the heating/cooling operation, one or more heating elements can be installed in between, around, among, etc. cartridges present within the module. In some cases, a cartridge may be individually wrapped or contacted by a heating element. In others, some or all cartridges present can share a heating element.

[0103] Shown in FIG. 16, for instance, is cartridge assembly 141 in which single heat exchanger 143 is located among cartridges arranged in an assembly similar to that described with reference to FIG. 12. FIG. 17 illustrates a section of a cartridge assembly that is similar to that of FIG. 13, e.g., is formed of parallel cartridges arranged in rows. Cartridges are heated or cooled by more than one heat exchanger (two heat exchangers 143A and 143B being shown in the figure). The module described herein can employ finned tube heat exchangers with longitudinal or transverse fins, or other suitable types of heat exchangers, as known in the art.

[0104] Heat exchanger fluid can enter or exit the heat exchanger via ports 145 (FIG. 16) or ports 145A and 145B in FIG. 17). A header, manifold and/or other piping (separate from the means for introducing or collecting fluid being purified in the module) can be dedicated to supplying or extracting the heat exchanger fluid.

[0105] In some embodiments, steam (which is widely available and can represent an inexpensive source of heat) is directed into the module to recover the adsorbed contaminant, CO.sub.2, for instance.

[0106] Temperatures, pressures and/or other parameters relevant to the adsorption or desorption stage can be monitored or controlled using techniques and devices known in the art. Adjustments can be made by an operator, for example. In automated processes, conditions and parameters can be computer controlled.

[0107] The module embodiments described herein offer wide operational flexibility. Raw fluid, for example, can be ted at the shell or at the bore side of the cartridges. The fluid flow in the module can be configured for an axial or cross flow pattern. Series or parallel assemblies can address specific needs.

[0108] As one example, FIG. 18 illustrates axial flow configuration 161, with raw fluid 163 being fed from the shell side of cartridges A through E, connected in series as described with reference to FIG. 11. In more detail, raw fluid enters vessel 43 at inlet 15, near module end 47, and becomes distributed, preferably distributed evenly, among cartridges A though E (as indicated by arrows a, b, c, d, and e). From the shell side of each cartridge, the raw fluid enters each adsorbent fabric through wrap opening 26 (FIG. 4) and passes through the fabric along (e.g., in parallel to) each center tube (as indicated by the dotted line arrows). Purified fluid leaves each fabric adsorbent and enters the lumen of each cartridge via holes 14 (FIG. 4). With the cartridges connected to one another as described with reference to FIG. 11, purified fluids in the lumen of individual cartridges become combined and exit vessel 43 as a common purified stream 165 at module end 49.

[0109] If desired, a reversed configuration with bore side feeding and shell side collection can be implemented as well, without a negative on the adsorption. It is also possible to operate a module with cartridges linked in series in cross flow mode. For example, cartridges 50 in FIG. 18 can be replaced with cartridges 70, as described with reference to FIGS. 5 and 7.

[0110] Shown in FIG. 19 is module 201 in which multiple adsorbent cartridges 50 (designed for axial flow, as already described) are arranged in parallel in vessel 203, which has a round transverse cross section. In illustrative examples, vessel 203 has an inner diameter (ID) within a range of from about 30 inches to about 1000 inches. Centrally installed relative to cartridges 50 is heat exchanger 143, essentially as described above. Heat exchanger fluid is supplied through inlet conduit 205 and leaves the vessel via outlet conduit 207. In some implementations, the heat exchanger is absent, as are the connections and ports for the heat exchange fluid.

[0111] During operation, the raw fluid enters vessel 203 through inlet port 15 and is distributed to the shell side of cartridges 50 through wrap opening 26. With end 28 of each cartridge being closed, e.g., using cap 209, the fluid travels through the adsorbent fabric along (e.g., parallel to) the center tube. At least a portion of the contaminant becomes trapped by the adsorbent fibers and a purified (clean) fluid passes from the adsorbent fabric into the interior of each center tube via holes 14 (FIGS. 4 and 6). Individual clean streams exit each cartridge at ends 30, pass into receiving component 213, which can be a piping arrangement, a manifold, a reservoir, etc., to be combined into a common purified output which leaves the module via outlet conduit 215. In another approach, individual clean streams exit the vessel through individual ports and can be combined as desired outside the vessel.

[0112] Module 201 can be operated in a reverse manner, with bore side feeding and shell side collection without an adverse effect on the adsorption.

[0113] In FIG. 20, module 301 includes rows of cartridges 50 (see FIG. 13, for instance) enclosed in vessel 303 which has a rectangular, e.g., square, cross section. Vessel 303 can have a length within a range of from about 5 to about 50 feet and a height within a range of from 40 to 100 inches. Rows of cartridges can be accommodated using other vessel shapes and/or dimensions.

[0114] A group of adsorbent devices 50 is heated by heat exchangers 43. Heat exchanger fluid enters the module via inlet conduit 305, is distributed to heat exchangers 43 via header 307 and exits vessel 303 via outlet conduit 309.

[0115] Raw fluid is introduced to vessel 303 via inlet conduit 15 and enters each cartridge 50, from the shell side, via wrap opening 26. With end 28 capped (using cap 209, for example), raw fluid proceeds through the adsorbent fabrics along the center tubes, in an axial flow pattern essentially as described above. Clean fluid exits the fabrics, passes to the lumen of the center tubes via holes 14 (FIGS. 4 and 6) and exits each cartridge at end 30. Individual clean streams can be collected and combined using manifold 313 or another suitable collection arrangement. A common clean output stream leaves vessel 303 through outlet conduit 315.

[0116] In a different approach, individual output streams from ends 30 of cartridges 50 exit the module through individual ports and can be combined outside the vessel. A reversed input-output configuration, with raw fluid being fed from the bore side of each individual cartridge, and purified fluid being collected at the shell side of the cartridges can be implemented without a detrimental effect on the adsorption.

[0117] For cross flow operation, cartridges 50 in module 201 or 301 can be replaced with cartridges designed for cross flow, as described with reference to FIGS. 5 and 7, for example. In this approach, the raw fluid stream can be fed from the shell side of the fiber adsorbent cartridges and travels through the adsorbent fabric in a direction substantially perpendicular to the center tube. From the adsorbent fabric, purified fluid passes into the lumen of the center tubes 12 (through holes 14 disposed, e.g., as shown in FIG. 5) and exits each cartridge from the bore side of the center tube. Individual purified streams obtained from individual cartridges can be combined in a common purified output within or externally to the vessel. The flow direction can be reversed (with raw fluid being fed from the bore side and clean fluid withdrawn from the shell side) without an adverse effect on the adsorption process.

[0118] More than one module can be employed, to meet the requirements of a specific application, for instance.

[0119] In contrast to modular arrangements that employ hollow fiber membranes, contaminants such as acid gases are trapped or captured in the adsorbent material, which can be regenerated by cycling processes. Thus, the module designs described herein do not need to provide for the extraction of a fluid fraction that is enriched with contaminant, as in the case of membrane separation systems.

[0120] The adsorbent fibers employed in the modules described herein can be formed using any suitable adsorbent material. Examples include zeolites, MOFs, COFs, PAFs active carbon and others. In some cases, the adsorbing material is dispersed in a porous polymer matrix, as described, for instance, in U.S. Pat. Nos. 10,525,399 and 10,525,400; and U.S. Patent Application Publication Nos. 20210008523 and 20210031168. The contents of these documents are incorporated herein by reference in their entirety.

[0121] In an illustrative implementation, the adsorption device and/or the module include(s) a porous solid amine adsorbent that is particularly well suited for the removal of an acid gas from contaminated fluid streams. Such an adsorbent is described in U.S. Provisional Application Nos. 63/220,734 and 63/220,745, both filed on Jul. 12, 2021, in U.S. Non-Provisional Patent Application filed concurrently herewith, under Attorney Docket No. 0413.0004US1, and the International Patent Application, filed concurrently herewith under Attorney Docket No. 0413.0004WO1, the entire contents of these documents being incorporated herein by this reference. As seen in these documents, porous solid amine adsorbents, typically robust and self-supporting, can be prepared by contacting a first solution with a second solution.

[0122] Among the constituents of the first solution is an amine-containing compound (a substance that includes functional groups such as —NH.sub.2, —RNH, or —RR′N), and another polymer.

[0123] In specific embodiment, the amine-containing compound is a water-soluble amine-containing polymer. As used herein, the term “amine-containing polymer” or “amine polymer” refers to polymers that contain —NH.sub.2, —RNH, or —RR′N functional groups attached to/separated by —CH.sub.2CH.sub.2—, —CH.sub.2CH.sub.2CH.sub.2—, or —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—. The R and R′ groups can be methyl, ethyl, propyl, etc. groups and can be the same or different.

[0124] The water-soluble amine polymer can be provided in a wide range of molecular weights, from about 400 to about 10,000,000, for example. Some implementations utilize a water-soluble amine polymer within a range of from about 1,000 to about 1,000,000.

[0125] In one example, the water-soluble amine compound (e.g., polymer) includes a unit skeletal structure represented by Formula 1:

—[(CH.sub.2).sub.x—NR].sub.y—  (1)

[0126] In the unit skeletal structure, R may be hydrogen or a branched chain; x is an integer of 1 to 4, and y is an integer of 2 to 1,000,000. In specific implementations, the amine compound is a linear or branched polyethylenimine (for x=2) or a linear or branched polypropylenimine (for x=3).

[0127] In another example, the water-soluble amine compound (e.g., polymer) includes a structure represented by Formula 2:

—[(CH.sub.2).sub.x—CH(NH.sub.2)].sub.y—  (2)

[0128] where x is an integer of 1 to 4 and y is an integer of 2 to 1,000,000. In specific implementations, the amine compound represented by Formula 2 is a polyvinylamine (in the case of x=1).

[0129] The amount of the water-soluble amine compound can be within a range of from about 5 to about 50% based on the total weight of the first (e.g., dope) solution.

[0130] The first solution also includes another constituent, typically a water insoluble polymer. The water insoluble polymer forms a porous polymeric structure upon contact with a solvent such as water, providing a mechanical support for the porous solid amines formed from the reaction with a multifunctional acid. In the absence of a water insoluble polymer, the porous solid amine adsorbent will be sticky and difficult to shape into a desired configuration.

[0131] Water insoluble polymers that can be utilized to prepare the first solution can be natural or synthetic. Examples of natural polymers include lignin, cellulose, cellulose derivatives, (such as cellulose acetates, for instance), and others. Examples of synthetic polymers include polyacrylonitrile, poly(methyl methacrylate), polystyrene, polyethylene terephthalate), aromatic polyamides, aliphatic polyamides, polyesters, polyetherketones, polyethersulfones, polyetheresters, polysulfones, polyvinyl fluoride, polybenzimidazoles, polybenzoxazoles, polyazoaraomatics, poly(2,6-dimethylphenylene oxide), polyphenylene oxides, polyureas, polyurethanes, polyhydrazides, polyazomethines, polyacetals, polyquinoxaline, polyamideesters, polyacetylenes, polymer with intrinsic porosities (PIMs), polyesters, any combinations (blends) or copolymers thereof.

[0132] Many embodiments of the invention utilize water insoluble polymers that exhibit a glass transition temperature or a melting point above 100° C. Advantageously, such polymers are expected to withstand temperatures employed during the thermal regeneration of the adsorbent, without a significant pore collapse.

[0133] The amount of water-insoluble polymer in the first solution can be within a range of from about 5 to about 50 weight %.

[0134] The first solution can be prepared by combining the water insoluble polymer and the water-soluble amine polymer in a polar solvent. In many implementations, the polar solvent is an organic liquid that is miscible with water. It can dissolve the amine polymer as well as the water-insoluble polymer. Examples include but are not limited to ethanol, propanol, n-butanol, tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMAc or DMA), dimethylsulfoxide (DMSO), N-methyl pyrrolidone (NMP), or mixtures thereof. Other polar solvents can be employed.

[0135] The polar solvent can be present in the first solution in an amount within a range of from about 50 to about 90 wt %.

[0136] The first solution can be a homogeneous solution in which all three components, namely the water-insoluble polymer, the water-soluble amine polymer and the polar solvent, are miscible.

[0137] The first solution can include other ingredients such as, for instance, a non-solvent component and/or a particulate material.

[0138] In one typical implementation, the second solution is an aqueous solution containing a multivalent (multifunctional) acid, i.e., an acid having two or more acid functional groups. In another typical implementation, the second solution is an aqueous solution containing a multivalent metal ion, such as Ca.sup.2+, Cu.sup.2+, Zn.sup.2+, and Me.sup.2+.

[0139] The aqueous solution can include water in an amount of at least 80% based on the total weight of the aqueous solution, preferably in an amount that is equal or greater than 95 wt %.

[0140] The multifunctional acid can be an inorganic acid, such as sulfuric acid or phosphoric acid, or an organic acid. Examples of suitable multifunctional organic acids (having two or more —COOH groups) include oxalic acid, citric acid, malic acid, tartaric acid, humic acid, dithiodipropionic acid, succinic acid, sulfosuccinic acid, phytic acid, trans aconitic acid, polyacrylic acid and its copolymers, polyvinylphosphonic acid and its copolymers, polystyrene sulfonic acid and its copolymers, polystyrene phosphonic acid and its copolymers, polystyrene carboxylic acid and its copolymers, and the like, or any mixtures thereof.

[0141] In one example, the acid concentration in the aqueous solution is in the range of 0.01% to 30%, preferably in the range of 0.1% to 10% relative to the total weight of the aqueous solution.

[0142] In some cases, the second solution is simply an acid-water solution. In others, the second solution further includes one or more additive(s).

[0143] Porous solid amine adsorbents are prepared by bringing together the two solutions. In many cases the product is formed rapidly, e.g., in a matter of seconds.

[0144] Porous solid amine adsorbents also can be prepared by contacting a first (dope) solution such as described above with a second solution that contains a metal ion (Cu.sup.2+, for instance) that can form a multiligand metal complex. The metal ion can be a component in a multifunctional metal salt. Procedures are described in U.S. Provisional Application No. 63/220,745, filed on Jul. 12, 2021, U.S. Non-Provisional Patent Application filed concurrently herewith, under Attorney Docket No. 0413.0004US1, and International Patent Application, filed concurrently herewith under Attorney Docket No. 0413.0004WO1, the entire contents of these documents being incorporated herein by this reference.

[0145] Without wishing to be bound by any particular theory or interpretation, it is believed that once the first solution (e.g., dope) is brought into contact with the aqueous solution containing a multifunctional chemical agent (e.g., a multifunctional acid or metal salt), the water insoluble polymer chain is frozen into solid state by a non-solvent induced phase inversion, while the water soluble amine compound is frozen into solid state by a rapid crosslinking reaction between at least some of the amine functional groups and the multifunctional chemical agent. It is further believed that without the multifunctional chemical agent, the water-soluble amine compound would become rapidly diffused into the water solvent precluding the formation of a functional adsorbent.

[0146] The porous solid amine adsorbent can be fabricated in various forms including fibers, hollow fibers and others. To form a (non-hollow) porous solid fiber, for example, the first (dope) solution (containing a water insoluble polymer and a water soluble amine polymer) can be extruded through a needle, passed through air, then brought into contact with the second solution (namely the aqueous solution containing a multifunctional acid). Techniques that can be followed or adapted are described, for example, in U.S. Pat. No. 5,181,940, except that no bore fluid is utilized.

[0147] In illustrative examples, the porous solid amine adsorbents are fabricated in fibers (which can be hollow or non-hollow fibers) having any desired outer diameters, e.g., within a range of from about 5 mil to about 50 mil. Other properties characterizing the fibers prepared as described herein (such as, for instance, a surface porosity that can be in the range of 1% to 60% by area) can be obtained by selecting or adjusting the equipment design, the process conditions or other factors.

[0148] The porous solid amine adsorbents, e.g., in the shape of fibers, can be further processed. In an optional step, for example, the porous solid amine adsorbents can be washed with water, alcohol or another suitable washing medium, e.g., to remove the solvent as completely as possible.

[0149] The porous solid adsorbent obtained by contacting the first and second solution, optionally washed, can be dried under ambient conditions or in an oven, e.g., at temperatures such as from 50° C. to 100° C. In some cases, heat treatment (in a suitable oven, for instance) can be undertaken, e.g., to impart desired mechanical properties to the product adsorbent.

[0150] In some embodiments, the adsorption device or the module is employed to remove an acid gas contaminant (CO.sub.2, H.sub.2S, SO.sub.2, for instance) from a fluid stream such as flue gases, biogas, hydrogen gas, natural gas or air. The acid gas released from the adsorbent fibers can be stored or used in other applications. For example, the carbon dioxide desorbed from the fibers employed in the cartridge can be utilized for enhanced oil recovery, to prepare synthetic fuels, such as methanol, methane, jet fuels, etc. In some embodiments, the carbon dioxide is injected for storage.

[0151] While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.