Large particle sorbent composites for swing adsorption processes

Abstract

Disclosed are articles, methods, and systems relating to an adsorbent composite. The adsorbent composite facilitates improved mass transfer in swing adsorption processes and applications thereof, such as gas separation. The adsorbent composite includes an adsorbent filler with a median particle size of greater than 100 µm. The adsorbent composite can be provided in the form of a sheet, where the sheet has a structure that facilitates parallel passage constriction of a fluid stream.

Description

Attorney Docket No. 450385.006706 2831WO01LARGE PARTICLE SORBENT COMPOSITES FOR SWING ADSORPTION PROCESSESCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of Provisional Application No. 63 / 692,771 , filed September 10, 2025, which is incorporated herein by reference in its entirety for all purposes.FIELD

[0002] The present disclosure relates generally to filtration materials, and more specifically, to a porous fibrillate polymer membrane that includes supported adsorbent particles durably enmeshed within the porous fibrillated polymer membrane that may be used for gas separation based on swing adsorption processes.BACKGROUND

[0003] Swing adsorption processes, including pressure swing adsorption and temperature swing adsorption among others, leverage cyclic variations in temperature and pressure fluctuations to separate gaseous components. Swing adsorption can be separated into phases, including an adsorption step, which involves capturing an adsorbate on an adsorbent material, and a desorption step, which involves removing the captured adsorbate from the adsorbent material, such as for collection. While the adsorption phase can occur at relatively low temperatures to condense and capture gas molecules, the desorption phase requires energy to heat the adsorbent material, thereby facilitating release of the captured compound. Such processes can be used to separate select substances from a gaseous mixture, such as a target compound from a fluid stream.

[0004] In one representative example, Pressure Swing Adsorption (PSA) fuel gas conditioning is used at natural gas gathering stations to remove impurities, like carbon dioxide (CO2), water vapor, and natural gas liquids (NGLs). NGLs include heavy hydrocarbon compounds such as ethane, propane, butane, iso-butane, and natural gasoline. Such conditioning is necessary to meet pipeline quality specifications, prevent condensation in pipelines, which can pose operational issues, and capture NGLs as1DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 valuable byproduct commodities. However, several challenges hamper efficient removal of NGLs from a natural gas stream, and burning unremoved NGLs in an engine can reduce engine power and cause damage. There is a need to improve aspects of the swing adsorption process, including the materials and methods thereof, to promote greater process efficiency.SUMMARY

[0005] According to one aspect, (“Aspect 1”), an adsorbent article for swing separation includes a porous fibrillated polymer membrane that includes supported adsorbent particles non-covalently immobilized within a node and fibril microstructure of the porous fibrillated polymer membrane, wherein the supported adsorbent particles have a particle size distribution defined by a D90 value of at least 200 microns, wherein the porous fibrillated polymer membrane includes the supported adsorbent particles in a range from about 30% to about 98%.

[0006] According to another aspect, (“Aspect 2”), the adsorbent article of Aspect 1 , wherein the supported adsorbent particles have a particle size distribution defined by a D10 value of at least 70 microns.

[0007] According to another aspect, (“Aspect 3”), the adsorbent article of any one of the preceding Aspects, wherein a mean particle size of the supported adsorbent particle is greater than or equal to 90 microns.

[0008] According to another aspect, (“Aspect 4”), the adsorbent article of any one of the preceding Aspects further includes a plurality of pleats, folds, ridges, embossed ridges, channels, and any combination thereof.

[0009] According to another aspect, (“Aspect 5”), the adsorbent article of any one of the preceding Aspects is in the form of a pleated sheet, folded sheet, rolled sheet.

[0010] According to another aspect, (“Aspect 6”), the adsorbent article of any one of the preceding Aspects, wherein the porous fibrillated polymer membrane has a porosity from about 20% to about 90%.

[0011] According to another aspect, (“Aspect 7”), the adsorbent article of any one of the preceding Aspects, wherein the porous fibrillated polymer membrane includes polytetrafluorethylene (PTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE),2DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 ultra-high molecular weight polyethylene (LIHMWPE), polyparaxylylene (PPX), polylactic acid (PLLA), and any combination or blend thereof.

[0012] According to another aspect, (“Aspect 8”), the adsorbent article of any one of the preceding Aspects, wherein the supported adsorbent particles have a particle population with a D50 value of 135 microns or more.

[0013] According to another aspect, (“Aspect 9”), the adsorbent article of any one of the preceding Aspects, wherein at least 40% of the porosity includes a pore size greater than 10 microns.

[0014] According to another aspect, (“Aspect 10”), the adsorbent article of any one of the preceding Aspects, wherein the adsorbent particles are configured with nanopores to selectively adsorb at least one target gas.

[0015] According to another aspect, (“Aspect 11”), the adsorbent article of any one of the preceding Aspects, wherein said at least one target gas includes ethane, propane, butane, or pentane.

[0016] According to another aspect, (“Aspect 12”), the adsorbent article of any one of the preceding Aspects, wherein the adsorbent article includes activated carbon, silica gel, alumina, metal-organic frameworks (MOFs), porous polymers, mesoporous silicas, graphene-based materials, a carbonaceous material derived from biomass, or a combination thereof.

[0017] According to another aspect, (“Aspect 13”), the adsorbent article of Aspect 1 , wherein the adsorbent article is in the form of a filter bag, a honeycomb, a monolith, a parallel passage contactor, a sheet, or any other suitable geometrically structured forms.

[0018] According to another aspect, (“Aspect 14”), the adsorbent article of Aspect 1 , wherein the supported adsorbent particle is located throughout a thickness of the fibrillated polymer membrane.

[0019] According to another aspect, (“Aspect 15”), the adsorbent article of any one of the preceding Aspects further including at least one additional porous support layer.

[0020] According to another aspect, (“Aspect 16”), the adsorbent article of Aspect 15 wherein the at least one additional porous support layer is a porous woven support, a porous non-woven support, a porous screen, a porous membrane, a porous fibrillated membrane, and any combination thereof.3DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01

[0021] According to another aspect, (“Aspect 17”), a gas separation adsorbent filter material including the adsorbent article of any one of Aspects 1-16.

[0022] According to another aspect, (“Aspect 18), a parallel passage contactor including the adsorbent article of any one Aspects 1-18.

[0023] According to another aspect, (“Aspect 19”), a gas separation system including the adsorbent article of any one of the preceding Aspects, the adsorbent filter material of Aspect 17, or the parallel passage contactor of Aspect 18.

[0024] According to another aspect, (“Aspect 20”), the gas separation system of Aspect 19, wherein the gas separation system includes a temperature swing adsorption system, a pressure swing adsorption system, or a combination thereof.

[0025] According to another aspect, (“Aspect 21”), a method for separating at least one target gas from a gas stream mixture including contacting a gas stream mixture having a concentration of at least one target gas with the adsorbent article of any one of Aspects 1-15 or the gas separation adsorbent filter of Aspect 17, whereby the at least one target gas is selectively adsorbed from the gas stream mixture by the adsorbent article.

[0026] According to another aspect, (“Aspect 22”), the method of Aspect 21 further including collecting or concentrating said at least one target gas.

[0027] According to another aspect, (“Aspect 23”), the method of Aspect 21 or 22, wherein the gas stream has a BTU content of less than or equal to 1100 BTU / scf after the contacting step.BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments, and together with the description serve to explain the principles of the disclosure.

[0029] FIG. 1 is an SEM image of a comparative porous fibrillated composite containing 15 wt% PTFE and 85 wt% activated carbon adsorbent filler particles, where the filler particles have a relatively small average size (Sample 1).

[0030] FIG. 2 is an SEM image of a non-limiting embodiment of a porous fibrillated composite containing 15 wt% PTFE and 85 wt% activated carbon adsorbent filler particles, where the filler particles have a relatively large average size (Sample 2).4DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01

[0031] FIG. 3 is a graph showing the particle size of the adsorbent filler of the comparator composite Sample 1 and exemplary composite Sample 2.

[0032] FIG. 4 is a graph showing frequency response and phase lag of comparative composite Sample 1 and the non-limiting embodiment Sample 2 in a Volumetric Frequency Response (VFR) test.

[0033] FIG. 5 is a graph showing average pore size diameter of the comparator composite Sample 1 and the non-limiting embodiment Sample 2, as determined by mercury porosimetry.

[0034] FIG. 6 is an image of a sheet of a non-limiting embodiment of an adsorbent composite, as described herein.

[0035] FIG. 7 is an image of an additional non-limiting embodiment of an adsorbent composite described herein, where sheets of the adsorbent composite are spirally wound.

[0036] FIG. 8 is an image of an external view of non-limiting embodiment of spirally wound sheets containing adsorbent composite.DETAILED DESCRIPTION

[0037] Persons skilled in the art will readily appreciate that various aspects of the present disclosure can be realized by any number of methods and apparatus configured to perform the intended functions. It should also be noted that the accompanying figures referred to herein are not necessarily drawn to scale, but may be exaggerated to illustrate various aspects of the present disclosure, and in that regard, the drawing figures should not be construed as limiting.

[0038] Mass transfer plays a crucial role in the performance and efficiency of swing adsorption processes like pressure swing adsorption (PSA) or vacuum swing adsorption (VSA). It refers to the movement of adsorbate molecules (gases being adsorbed) from the bulk gas phase onto the porous adsorbent material and vice versa. The rate at which adsorbate molecules transfer from the gas phase onto the adsorbent particle surface determines the overall adsorption rate and kinetics. Efficient mass transfer ensures improved utilization of the adsorbent material's adsorption capacity by facilitating access of adsorbate molecules to the pore network and active sites within the adsorbent particles. The mass transfer characteristics of different adsorbent materials,5DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 which are determined in part by particle size and pore size play a crucial role in their selection for specific swing adsorption applications.

[0039] The present disclosure is directed to an adsorptive composite suitable for gas separation based on swing adsorption processes that includes or is formed of porous supported adsorbent particles durably enmeshed in a porous fibrillated polymer membrane. In some embodiments, the porous fibrillated polymer membrane comprises a volume fraction where at least 40% of the porosity includes a pore size greater than or about 9 microns, greater than or about 10 microns, greater than or about 11 microns, greater than or about 12 microns, greater than or about 13 microns, greater than or about 14 microns, or greater than or about 15 microns, as measured by mercury porosimetry. In some embodiments, the porous fibrillated polymer membrane comprises a volume fraction where at least 40% of the porosity includes a pore size of 5 to 55 microns 10 to 50 microns, 15 to 45 microns, 20 to 40 microns, or 25 to 35 microns, as measured by mercury porosimetry.

[0040] The supported adsorbent particles are designed to selective adsorb one or more target gases from a mixed gas / fluid stream. Non-limiting embodiments of target gases include carbon dioxide, sulfur oxides (SOx, such as SO2 and SO3), nitrogen oxides (NOx, such as NO and NO2), water vapor, natural gas liquids (NGLs), such as ethane, propane, normal butane, isobutane, natural gasoline (pentanes plus) or one or more combinations thereof.

[0041] NGLs are heavier hydrocarbon components that exist in the raw natural gas stream along with methane, the primary component of natural gas. Such compounds have higher boiling points compared to methane and can be separated from the gas stream using various extraction processes like absorption, cryogenic expansion, and fractionation. NGLs are valuable commodities that can be sold separately for various uses. For example, ethane can be used as feedstock in petrochemical plants for producing ethylene, propane and butanes may be used as fuel gases, petrochemical feedstocks, and refrigerants, and natural gasoline (pentanes plus) is a useful diluent for heavy crude oil transportation or a petrochemical feedstock.

[0042] In some embodiments, the porous fibrillated polymer membrane is perforated or otherwise contains mechanically formed holes therein. The adsorbent membrane composite may be used to separate one or more target gases from a fluid stream comprises a mixture of gases in swing adsorption applications to separate and6DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 optionally collect one or more target gases from a fluid stream comprising a mixture of gases. Additionally, the adsorbent article may be in the form of a filter bag, a honeycomb, a monolith or any other suitable geometrically structured forms.

[0043] The supported adsorbent particles include or are formed of at least one non-catalytic adsorbent material that is supported on and / or within a support substrate. Non-limiting examples of non-catalytic adsorbent particles suitable for incorporation onto the support substrate include activated carbon, carbon adsorbents, silica gel, alumina, metal-organic frameworks (MOFs), porous polymers, mesoporous silicas, graphene-based materials, carbonaceous materials derived from biomass, non-catalytic zeolites or a combination thereof. Exemplary sources of biomass from which non- catalytic adsorbent particles can be derived include wood, coconut shells, olive stones, bamboo, rice husk, grass, leaves, fruit peel, cellulose, lignin, tannins, glucose, sucrose, and starch.

[0044] Exemplary adsorbent particles have high surface areas and porosities that enable efficient adsorption of target molecules. They are typically non-catalytic, meaning they do not promote chemical reactions. In one example of catalytic material, zeolites, crystalline aluminosilicate materials with well-defined pore structures, can act as both adsorbents and catalysts due to their acidity and shape selectivity. Zeolites are commonly used in catalytic applications like fluid catalytic cracking (FCC) in refineries.

[0045] The supported adsorbent particles may be porous, non-porous or substantially non-porous. As used herein, “porous” is meant to denote a porosity of at least 10%, or at least 20%, and preferably at least 30%. As used herein, the term “substantially non-porous” is meant to denote that there is a measurable amount of porosity, but not exceeding 5%.

[0046] The support substrate can include a porous woven support, a porous nonwoven support, a porous screen, a porous membrane, a porous fibrillated membrane, or a combination thereof. Exemplary porous woven support substrates can include stainless steel felt batts or scrims, or ceramic fiber woven mats. Exemplary porous nonwoven support substrates can contain glass, ceramic, or polymers. Non-limiting examples of porous membranes and screens can include metallic screens, meshes made of stainless steel or other alloys, polymeric membranes with controlled pore sizes, ceramic membranes, or like alumina or cordierite monoliths. In another representative example, a fibrillated membrane including polytetrafluoroethylene (PTFE) can serve as7DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 a porous fibril lated membrane. Any of the various support substrates can have parallel channels.

[0047] In some embodiments, the adsorbent particles are durably enmeshed in an expanded polymer matrix. As used herein, the phrase “durably enmeshed” is meant to describe an adsorbent particle that is non-covalently immobilized within the fibri Hated microstructure of the polymer membrane. No separate binder is present to fix the adsorbent particles in the membrane. Additionally, the adsorbent particle is located throughout the thickness of the fibrillated polymer membrane.

[0048] The supported adsorbent particles may be on and / or in the porous fibrillated membrane in an amount greater than about 30 wt%, greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, or greater than about 90 wt% where the wt% is based on the total weight of the fibrillated membrane with the supported adsorbent particles. In addition, the supported adsorbent particles may be on and / or in the porous fibrillated membrane in a range from about 30 wt% to about 98 wt%, from about 30 wt% to about 90 wt%, from about 30 wt% to about 85 wt%, from about 30 wt% to about 80 wt%, from about 30 wt% to about 75 wt%, from about 30 wt% to about 70 wt% , from about 30 wt% to about 65 wt%, or from about 30 wt% to about 60 wt% of the fibrillated polymer membrane with the supported adsorbent particles.

[0049] In addition, the porous fibrillated polymer membrane has a total porosity from about 20% to about 90%, from about 30% to about 90%, from about 40% to about 90%, from about 50% to about 90%, from about 60% to about 90%, from about 70% to about 90%, or from about 80% to about 90%.

[0050] The polymer forming the fibrillated polymer membrane includes or is formed of the immobilize adsorbent particles is selected to be inert or resistant to degradation by components present within the fluid stream of intended use. In one embodiment, the polymer forming the fibrillated polymer membrane is inert or resistance to degradation by the materials within the mixed fluid (e.g. gas) stream comprising one or more target gases. In particular, the polymer may be both insoluble and inert to the fluid stream in which it is used. In some embodiments, the fibrillated polymer membrane may be perforated. As used herein, the term “perforated” refers to perforations (e.g., holes) spaced throughout some or all of the membrane.8DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01

[0051] The fibrillated polymer membrane may include or be formed of polytetrafluoroethylene (PTFE), expanded polytetrafluoroethylene (ePTFE), poly(ethylene-co-tetrafluoroethylene) (ETFE), ultrahigh molecular weight polyethylene (LIHMWPE), polyethylene, polyparaxylylene (PPX), polylactic acid (PLLA), polyethylene (PE), expanded polyethylene (ePE), and any combination or blend thereof. It is to be understood that throughout this disclosure, the term “PTFE” is meant to include not only polytetrafluoroethylene, but also expanded PTFE, modified PTFE, expanded modified PTFE, and expanded copolymers of PTFE, such as, for example, described in U.S. Patent No. 5,708,044 to Branca, U.S. Patent No. 6,541 ,589 to Baillie, U.S. Patent No. 7,531 ,611 to Sabol et al., U.S. Patent No. 8,637,144 to Ford, and U.S. Patent No. 9,139,669 to Xu et al. The porous fibrillated polymer membrane may also be formed of one or more monomers of tetrafluoroethylene, ethylene, p-xylene, and lactic acid. In at least one embodiment, the porous fibrillated polymer membrane includes or is formed of solvent inert sub-micron fibers of an expanded fluoropolymer.

[0052] In some embodiments, the fibrillated polymer membrane is a polytetrafluoroethylene (PTFE) membrane or an expanded polytetrafluoroethylene (ePTFE) membrane having a node and fibril microstructure. The fibrils of the PTFE particles interconnect with other PTFE fibrils and / or to nodes to form a net within and around the supported adsorbent particles, effectively immobilizing them. Therefore, in one non-limiting embodiment, the fibrillated polymer membrane may be formed of a network of PTFE fibrils immobilizing and enmeshing the supported adsorbent particles within the fibrillated microstructure.

[0053] The porous fibrillated polymer membrane may be formed by blending fibril lating polymer particles with the supported adsorbent particles in a manner such as is generally taught in United States Patent No. 7,710,877 to Zhong, et al., United States Publication No. 2010 / 0119699 to Zhong, et al., U.S. Patent No. 5,849,235 to Sassa, et al., U.S. Patent No. 6,218,000 to Rudolf, et al., or U.S. Patent No. 4,985,296 to Mortimer, Jr. to induce sufficient fibrillation of the polymeric binder. The resulting adsorbent composite (typically in the form a sheet, tube, etc.) may be subjected to further mechanical manipulation such as calendaring, folding, crimping, perforation, compaction, embossing, expansion, and any combination thereof. If subjected to expansion, the expansion may be uniaxial, biaxial, radial or combinations thereof. As used herein, the term “fibrillating” refers to the ability of the fibrillati ng polymer to form a9DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 node and fibril micro structure. The mixing may be accomplished, for example, by wet or dry mixing, by dispersion, or by coagulation. Time and temperatures at which the mixing occurs varies with particle size, material used, and the amount of particles being comixed and can be determined by those of skill in the art. The uniaxial or biaxial expansion may be in a continuous or batch processes known in those of skill in the art and as generally described in U.S. Patent No. 3,953,566 to Gore and U.S. Patent No. 4,478,665 to Hubis.Adsorbent Particles

[0054] In some embodiments, the supported adsorbent particles have a particle distribution based, at least in part, on a D90 value greater than 60 microns. D90 represents the particle diameter at which 90% of the sample's mass or volume is comprised of smaller particles. For example, if the D90 value is 100 pm, 90% of the particles by mass have a diameter of less than 100 pm, while the remaining 10% are larger than 100 pm.

[0055] In some embodiments, the supported adsorbent particles may have a D90 value greater than 180 microns (pm), greater than 190 microns, greater than 200 microns, or greater than 210 microns. Additionally, the supported adsorbent particles may have an upper value of 300 to 500 microns. In some embodiments, the supported adsorbent particles have a particle population with a D50 value of greater than 120 microns, greater than 130 microns, greater than 140 microns, or greater than 150 microns. In some embodiments, the supported adsorbent particles have a D20 value of greater than 70 microns, greater than 80 microns, greater than 90 microns, or greater than 100 microns. In some embodiments, the supported adsorbent particles may have a D10 value greater than 50 microns (pm), greater than 60 microns, greater than 70 microns, or greater than 80 microns. In addition, the mean particle size of the supported adsorbent particle is greater than or equal to ( / .e. at least) 80 microns, 90 microns, 100 microns, 110 microns, or 120 microns.

[0056] In some embodiments, the supported adsorbent particles may have a D10 to D90 range of about 50 to 260 microns, 60 to 250 microns, 70 to 240 microns, 80 to 230 microns, or 90 to 220 microns. In some embodiments, the supported adsorbent particles may have a D10 to D50 range of about 50 to 170 microns, 60 to 160 microns, 70 to 150 microns, 80 to 140 microns, or 90 to 130 microns. In some embodiments, the supported adsorbent particles may have a D50 to D90 range of about 130 to 26010DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 microns, 140 to 250 microns, 150 240 microns, 160 to 230 microns, or 170 to 220 microns.

[0057] In some embodiments, the supported adsorbent particles may have a 090 to D10 ratio of at least 2, at least 2.5, at least 3, or at least 3.5. In some embodiments, the supported adsorbent particles may have a D90 to D10 ratio of less than 5, less than 4, or less than 3. In some embodiments, the supported adsorbent particles may have a D90 to D10 ratio of about 1 to 4, 2 to 4, 2.5 to 3.5, 2 to 3, or 3 to 4.

[0058] In some embodiments, the adsorbent composite has a bulk density of less than about 1 .0 g / cc, 0.9 g / cc, 0.8 g / cc, 0.7 g / cc 0.6 g / cc, 0.55 g / cc, 0.5 g / cc, 0.45 g / cc, 0.4 g / cc, 0.35 g / cc, 0.30 g / cc, 0.25 g / cc, or 0.2 g / cc. The adsorbent composite may have a bulk density ranging from about 0.1 to 0.6 g / cc, 0.2 to 0.5 g / cc, 0.3 to 0.4 g / cc, 0.3 to 0.35 g / cc, 0.35 g / cc to 0.45 g / cc, or 0.4 g / cc to 0.45 g / cc.

[0059] In some embodiments, the porous fibrillated polymer membrane comprises a volume fraction where at least 30%, 40%, 50%, 60%, or 70% of the porosity includes a pore size greater than or about 1 micron, greater than or about 2 microns, greater than or about 3 microns, greater than or about 4 microns, greater than or about 5 microns, greater than or about 6 microns, greater than or about 7 microns, greater than or about 8 microns, greater than or about 9 microns, greater than or about 10 microns, greater than or about 11 microns, greater than or about 12 microns, greater than or about 13 microns, greater than or about 14 microns, or greater than or about 15 microns (as measured by mercury porosimetry).

[0060] By way of non-limiting example, disclosed adsorbent composites can be manufactured in the shape of a sheet, a pleated sheet, a tube or tubular shape, a jelly roll, a hyperbolic (e.g., a hot dog bun), or a furled cylindrical configuration, or any configuration that facilitates parallel passage contraction through which a gas stream can flow. Exemplary parallel passage structures include a plurality of ridges opposed by a flat surface, including sheets having the same structure arranged in multiple overlapping layers. Various orientations may be contemplated from the provided structure, including, e.g., stacked sheets, such as arranged ridge-to-ridge, flat surface- to-flat surface, ridge-to-flat surface, or a combination thereof, and sheets spirally wound in a circular shape, with the ridge peaks facing the inner center of the circle, the outer edges of the circle, or a combination thereof.11DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01

[0061] In some embodiments, the adsorbent sheets are arranged in multiple, overlapping layers. In some embodiments, the multiple, overlapping layers are spaced by the substantially parallel ridges to allow gas flow between the layers. In some embodiments, the ridges may be created by embossing, carving, molding or stamping. In some embodiments, the adsorbent composite may include a parallel passage contactor structure. The adsorbent composite may include one or more self-supported adsorbent sheets. Self-supported means that the sheets do not require a supportive layer or a backing. In some embodiments, the adsorbent composite may include substantially parallel ridges disposed on one or more self-supported adsorbent sheets. Swing Adsorption Applications

[0062] Adsorbent composites with improved mass transfer capabilities, such as the adsorbent composites, methods, and systems of the present disclosure, are highly beneficial for swing adsorption processes like temperature swing adsorption (TSA) and pressure swing adsorption (PSA). These processes rely on efficient adsorption and desorption cycles, where rapid mass transfer is crucial for achieving high productivity and separation performance. Current understanding in the art supports use of adsorbents having a smaller particle size, e.g., to decrease intraparticle diffusion path length, thereby enhancing mass transfer rates. In contrast, disclosed composites, which contain comparatively larger particles, have unexpectedly advantageous properties for applications involving mass transfer, e.g., gas separation processes.

[0063] Aside from swing adsorption processes, the adsorbent composites of the disclosure may be included in additional applications. For example, adsorbent composites of the disclosure can be used in water treatment processes, e.g., removing organic and inorganic contaminants like dyes, heavy metals, antibiotics, and other pollutants from wastewater. The properties of the adsorbent composite may facilitate greater adsorption efficiency and increased treatment capacities. Another potential application includes air purification. Disclosed adsorbents may be used to capture volatile organic compounds (VOCs), odors, and other gaseous pollutants from indoor air or industrial emissions.

[0064] In other representative examples, adsorbent composites of the disclosure can be used for gas storage, such as for charging and discharging gases like hydrogen, methane, or carbon dioxide, or as a stationary phase in a liquid or gas chromatography column. Although particles having catalytic capabilities are excluded from the disclosed12DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 adsorbent composites, various embodiments of systems including such adsorbent composites can incorporate a catalytically active material, such as upstream, downstream, or on either side of a disclosed adsorbent composite. Such an arrangement could create a bifunctional system to facilitate catalytic reactions and product separation.

[0065] Adsorbent composites of the disclosure may capture and separate contributors to air pollution, e.g., greenhouse gas emissions, from point and mobile sources through adsorption-based separation processes. Representative examples of point sources include power plants, refineries, and industrial facilities, which are stationary and emit large quantities of CO2 and other pollutants. Exemplary mobile sources include on-road vehicles, such as cars and trucks, and non-road sources, such as aircraft, ships, and construction equipment. Various embodiments of disclosed composites can be utilized in mobile emission control systems, such as automotive catalytic converters or exhaust gas recirculation (EGR) systems, to adsorb and remove pollutants like NOx, CO2, and particulate matter.

[0066] The disclosed adsorbent composites can be used to separate NGLs from a natural gas stream. In embodiments, the adsorbent composites can be used in methods to produce natural gas streams with less than 1100 BTU / scf (BTUs per standard cubic foot), less than 1000 BTU / scf, or less than 900 BTU / scf A level of 1100 BTU / scf is generally desirable for pipeline quality specifications. Several natural gas pipelines have strict requirements for the heating value of the gas being transported, typically in the range of 950-1100 BTU / scf. Gas having a BTU content above this range can cause operational issues. Additionally, higher BTU content indicates a higher concentration of heavier hydrocarbons like ethane, propane, butanes etc. These NGLs can condense into liquids in the pipeline at typical operating temperatures and pressures, leading to operational problems. Lowering the BTU content below 1100 BTU / scf ensures maximum NGL extraction.

[0067] FIG. 1 depicts a comparative adsorbent composite 100 composed of activated carbon adsorbent particles 110 enmeshed and immobilized within a PTFE matrix 120. Relative to the comparative composite of FIG. 1 , FIG. 2 depicts a nonlimiting embodiment of an adsorbent composite 200 composed of larger activated carbon adsorbent particles 210 enmeshed and immobilized within a PTFE matrix 220.13DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01The larger particle size of the adsorbent particles results in the formation of voids 230 that contribute to the collective void volume of the composite 200.

[0068] In one embodiment, the adsorbent composite 200 has a D10 value of about 60 to 80 microns, 60 to 70 microns, or 70 to 80 microns. In one embodiment, the adsorbent composite 200 has a D50 value of about 140 to 160 microns, 140 to 150 microns, or 150 to 160 microns. In one embodiment, the adsorbent composite 200 has a D90 value of about 220 to 250 microns, 230 to 250 microns, or 225 to 240 microns. In one embodiment, the adsorbent composite 200 has a D90 to D10 ratio of about 3 to 4, 3 to 3.5, or 3.5 to 4.

[0069] In one embodiment, the adsorbent composite 200 can be formed into a sheet. FIG. 6 depicts an exemplary adsorbent sheet 600 containing adsorbent composite 200 of FIG 2. In one embodiment, the adsorbent sheet containing the adsorbent composite can be modified (for example, embossed) to include raised features / ridges (also referred to herein as embossed ridges). The raised features / ridges can be continuous (extending across the entire surface of adsorbent sheet without breaks in ridges) or discontinuous and / or alternating ridges as shown in FIG 6. In one embodiment, the adsorbent sheet 600 can be modified to include raised features / ridges, including intact portions 610 and raised features / ridges 620. In one embodiment, the raised features / ridges 620 are spaced throughout the adsorbent sheet 600. In other embodiments, the raised features / ridges 620 are located only in portions of the adsorbent sheet 600.

[0070] In one embodiment, the raised features / ridges 620 have a length 630 of at least about 0.1 mm. In another embodiment, the raised features / ridges620 have a length 630 of less than about 1000 mm. In some embodiments, the raised features / ridges620 have a length 630 of 0.1 to 500 mm, 0.1 to 250 mm, 0.1 to 100 mm, 0.1 to 50 mm, 0.1 to 40 mm, 0.1 to 30 mm, 0.1 to 20 mm, 0.1 to 10 mm, 1 to 45 mm, 1 to 35 mm, 1 to 25 mm, 1 to 15 mm, or 1 to 5 mm.

[0071] In one embodiment, the raised features / ridges 620 have a width 640 of at least about 0.1 pm. In another embodiment, the raised features / ridges 620 have a width 640 of less than about 50 mm. In some embodiments, the raised features / ridges 620 have a width 640 of 0.1 pm to 50 mm, 0.1 pm to 40 mm, 0.1 pm to 30 mm, 0.1 pm to 20 mm, 0.1 pm to 10 mm, 0.1 pm to 1 mm, 1 pm to 45 mm, 1 pm to 35 mm, 1 pm to 25 mm, 1 pm to 15 mm, 1 pm to 10 mm, or 1 pm to 5 mm.14DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01

[0072] In various embodiments, the raised features / ridges 620 have a spacing 650 from an adjacent raised feature / ridge that has a length of about 0.1 pm. In another embodiment, the raised features / ridges 620 have a spacing 650 from an adjacent raised feature / ridge with a length of less than about 50 mm. In some embodiments, the spacing 650 has a length of 640 of 0.1 pm to 50 mm, 0.1 pm to 40 mm, 0.1 pm to 30 mm, 0.1 pm to 20 mm, 0.1 pm to 10 mm, 0.1 pm to 1 mm, 1 pm to 45 mm, 1 pm to 35 mm, 1 pm to 25 mm, 1 pm to 15 mm, 1 pm to 10 mm, or 1 pm to 5 mm.

[0073] In various embodiments, the raised features / ridges 620 are formed in a pattern in the adsorbent sheet 600. Larger raised features / ridges correspond to larger spacing between adjacent raised features / ridges, and smaller raised features / ridges correspond to closer spacing between adjacent raised features / ribs. The raised feature / ridges pattern may be designed so that airflow through the raised features / ridges is consistent across the adsorbent sheet 600. Some suitable patterns include square patterns, triangular patterns, amorphous patterns, or any other comparable pattern that generally complies with a minimum raised features / ridges density.

[0074] FIG. 7 depicts a top down view of a nonlimiting embodiment of an adsorbent sheet arranged in a spirally wound orientation 700. The overlapping layers 710 are spaced by hollowed repeating quadrilateral units 720, such as providing voids 730 resulting in a parallel passage contactor structure, which allows gas flow through the plurality of voids 730 and between the layers 710.

[0075] FIG. 8 depicts a top down view of a nonlimiting embodiment of an adsorbent sheet arranged in a spirally wound orientation 800. Sheet raised features / ridges 810 are visible from the exterior of the spirally wound sheets.

[0076] Additional materials having a variety of adsorbent, heat exchanging, or catalytic properties can be included in a system involving any of the preceding embodiments. Such additional adsorbents can be positioned either upstream or downstream of the adsorbent composite 200 and can contain a distinct adsorbent or group of adsorbents in order to provide the adsorbent composite material 200 with the ability to separate / collect one or more target gases from a fluid / gas stream mixture. The choice of upstream and downstream materials depends on factors such as the specific application, operating conditions, and the desired performance characteristics, e.g., adsorption capacity, selectivity, pressure drop, and energy efficiency.15DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01

[0077] Materials suitable as a pre-filter or guard bed can be included up stream of the adsorbent composite. Pre-filters, guard beds, and the like are used to remove particulates, moisture, or other contaminants from a feed stream before it reaches the main adsorbent, serving to protect the adsorbent composite and improve its lifespan Non-limiting examples of upstream materials include activated carbon, zeolites, or metal-organic frameworks (MOFs).

[0078] Materials with heat exchanging properties may also be included, upstream or downstream, in a system involving the adsorbent composite. In one illustrative example, materials with high thermal conductivity, such as aluminum or stainless steel, can be placed upstream of the adsorbent composite to preheat or precool the feed stream to facilitate improved the efficiency of the adsorption / desorption cycle in TSA processes. Condensers or coolers made of materials like stainless steel or copper can be used downstream to cool the desorbed gas stream, allowing for the recovery of the desorbed component (e.g., CO2, water vapor) in a condensed phase.

[0079] Exemplary systems involving a disclosed adsorbent composite include fibrous materials. Non-limiting examples of fibrous materials include felt batts or scrims, which may be composed of stainless steel or ceramic fibers. The fibrous material can act as a support structure, preventing the adsorbent composite from fluidizing or being carried away by the gas flow. The fibrous materials may also be arranged downstream of an adsorbent composite.

[0080] In one embodiment, an additional porous fi bri Hated polymer membrane(s), as well as further intermediate felt batts and / or scrims may be provided upstream and downstream, respectively, of each porous fibrillated polymer membrane may be included to separate the porous fibrillated polymer membranes and provide room for circulation between the porous fibrillated polymer membranes.

[0081] In the embodiments described above, the porous fibrillated polymer membrane effectively distributes the adsorbent particles throughout the membrane, in both the length and thickness directions. In addition, the porous nature of the fibrillated polymer membrane allows for efficient and reliable transport of fluid through the adsorbent surface. Adsorbent loss is minimized because the supported adsorbent particles are durably enmeshed within the fibrils of the porous fibrillated polymer membrane.16DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01TEST METHODSParticle Size / Shape Distribution Assay

[0082] Particle size distribution measurements were carried out on a Microtrac Series 5000-3L Sync particle size and shape analysis system which combines laser diffraction with dynamic image analysis (Microtrac MRB, York PA, USA). The instrument is controlled using the Microtrac FLEX 12 software (Microtrac) using default setting supplied by the manufacturer unless otherwise noted. This instrument uses a combination of two techniques into a single instrument. Laser diffraction analysis is carried out using the scattered light from multiple lasers through a stream of suspended particles. Dynamic image analysis is also performed on the particle stream using a highspeed, high-resolution camera.

[0083] The sample is prepared as follows: Approximately 0.5 grams of sample powder were placed into a vial and dispersed using several milliliters of reagent grade isopropyl alcohol, I PA, (Sigma Aldrich, St Louis MO, USA). The use of an ultrasonic horn was used to aid in breaking up any agglomerates of particles in the sample (Qsonica, Newtown CT, USA). If the suspension remains stable to precipitation, it can be used for analysis as is. Otherwise, the addition of a small amount of appropriate surfactant may be needed.

[0084] The testing procedure is generalized as follows: (1) after filling the Sync instrument with fresh I PA, the Sync transducer was zero’ed using the SetZero procedure; (2) once zero’ed, the “Sample loading” procedure was initiated and the sample suspension was added dropwise to the instrument reservoir until the light transmission measured by the Sync was within the acceptable range, typically 88-90% T; (3) optical parameters for the particle and solvent (refractive indices, etc.) were input for subsequent calculations; and (4) the data collection was then initiated using the FLEX software.

[0085] The particle size analysis is performed by the software once it collects and averages the scattered light. Particle size distributions are calculated using Mie scattering theory and tabulated on a volume basis. Various ways to analyze the data are provided including the usual particle size distribution plot, cumulative distribution plot, percentiles, and other moments of the distribution.

[0086] Particle shape analysis is performed over many images (typically on the order of 100,000). In addition to the raw images, there are approximately 20 descriptors17DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 that are used to quantify the distribution of shapes for the 2D projections. These include parameters that describe the circularity, form, roughness, and geometry classes and are tabulated on a number basis.Volumetric Frequency Response Assay

[0087] The mass transfer kinetics of adsorption and desorption can be controlled by several mechanisms including micropore diffusion, macropore diffusion, and macropore advection. Frequency response methods have been shown to be some of the best techniques for investigating these rate-limiting mechanisms. These methods typically take a system that has been degassed and is initially in equilibrium and then subject it to a continuous perturbation in the form of a sinusoidal function of one physical variable such as pressure, volume, or concentration. The system then produces a periodic response with the same frequency of the perturbed variable but with a different amplitude and phase lag that reflects the unique thermodynamics and kinetics of the system.

[0088] A volumetric frequency response (VFR) system was developed for studying the mass transfer characteristics of gases in microporous adsorbents at the University of South Carolina. The VFR system and the method of data analysis are described in Hossain, M.l. et al., “Mass Transfer Mechanisms and Rates of CO and N2 in 13X Zeolite from Volumetric Frequency Response", Ind. Eng. Chem. Res., (2019) 58: 21679-21690 and Hossain, M. I. et al., “110th Anniversary: New volumetric frequency response system for determining mass transfer mechanisms in microporous adsorbents”, Ind. Eng. Chem. Res. (2019), 58:17462-17474). Essentially, the differential pressure response to a small cyclic perturbation in volume was measured in a closed system after equilibrium was established at a constant temperature and pressure. The frequency of the volumetric perturbation can be varied between 10'5Hz to 100 Hz.

[0089] The analysis developed for this VFR system typically uses the amplitude ratio and phase lag between the input (volume) and output (pressure) variables. There are two features from plots of these variables that are worth noting. Firstly, larger intensities are indicative of more adsorption and desorption taking place. Secondly, the position of the maxima in the phase lag data indicate different transport resistances. The ones at lower frequencies are typically associated with heat transfer resistance, while the ones at higher frequencies are associated with mass transfer resistances. The18DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 maxima in frequency for these phase lag curves provide a crude estimate of the time constants associated with these resistances. Typically, materials that exhibit a peak at higher frequencies in the phase lag curves also exhibit faster mass transfer kinetics.

[0090] A Volumetric Frequency Response (VFR) test was used to determine the mass transfer characteristics of the adsorbent composites of Example 1 and Example 2 upon exposure to gases using the methodology described in Hussein, M.l. et al., supra. Briefly, the adsorbent composite test samples were placed into the sample chamber and activated under vacuum (1 .5e-5torr (-0.002 Pa)) at 150 °C for 40 hours. After cooling back to room temperature (~ 22 °C), the test gas (CO2) was used to pressurize the sample chamber to a target pressure of 100 torr in a jacketed beaker at 25 °C. Once the system was equilibrated, the volume of the sample chamber was subjected to modulation at a series of predefined frequencies from 3e-4Hz to 100 Hz. Ten cycles were run at each frequency to ensure sinusoidal periodic behavior. Data analysis was performed using the procedure described in the published reference (see Hossain, M.l. et al., supra). The volumetric response, i.e. the change in adsorbed gas volume within the adsorbent pores, was measured as a function of the oscillation frequency. At low frequencies, the adsorbent can equilibrate with the gas, resulting in a large volumetric response. At high frequencies, there is insufficient time for equilibration, leading to a smaller response.Mercury Porosimetry Testing

[0091] Porosity measurements were performed on a Micromeritics AutoPore V mercury porosimeter (Micromeritics, Norcross, Ga., USA), using Micromeritics MicroActive software version 2.0. Quadruple Distilled Virgin Mercury - 99.9995% purity (Bethlehem Apparatus, Bethlehem, PA) was used as received for tests. Tests used a solid type penetrometer with a bulb volume of 5 cm3and a stem volume of 0.392 cm3(SN: 07-0979). Pieces of the composite samples were cut into 1 cm X 2 cm strips and enough of these strips were weighed on an analytical balance to provide a total mass of approximately 0.25 g. After noting the mass, the sample pieces were placed in the penetrometer.

[0092] The test parameters were as follows: (1) the penetrometer was placed into the low pressure port on the AutoPore and evacuated to 50 microns Hg, followed by 5 min unrestricted evacuation; (2) the penetrometer was then filled with mercury at 0.519DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 psia (-3.5 kPa) and equilibrated for 10 seconds; pressure was subsequently applied to the capillary using nitrogen in steps up to 30 psia (-0.21 MPa), equilibrating for 10 seconds at each step prior to determining the intrusion volume via the standard capacitance measurement with the penetrometer capillary; (3) the penetrometer was removed from the low pressure port after returning to atmospheric pressure and then weighed to determine the amount of mercury added; (4) the penetrometer was subsequently placed into the high pressure port on the AutoPore and the pressure was again increased in a series of steps up to approximately 60,000 psia (~ 413.7 MPa) allowing 10 sec at each step to equilibrate prior to intrusion volume measurements.

[0093] The intrusion volume V at any pressure is determined through a capacitance measurement using the pre-calibrated capillary (f.e., a cylindrical capacitor where the outer contact is the metallized coating on the external surface of the glass capillary, the inner contact is the liquid mercury, and the dielectric is the glass capillary). The total intrusion volume divided by the sample mass gives the specific intrusion volume (in mL / g).

[0094] The volume occupied by the sample was calculated at the two extreme target pressures, namely, 0.5 psia (-3.5 kPa) and 60,000 psia (~ 413.7 MPa). Since the penetrometer has a known calibrated volume, the difference between this volume and the mercury volume (determined from the mass increase after mercury addition at low pressure and the density of mercury) yields the volume of the sample including any pores. Dividing the mass of the sample by the volume at this low pressure provides the bulk density of the sample. At high pressure, where mercury has been pushed into the pores by an amount given by the intrusion volume, the skeletal density can be approximated by dividing the sample mass by the adjusted sample volume (e.g., low pressure volume minus total intrusion volume).

[0095] Pore Size Distribution

[0096] The diameter of the pores being filled at a given pressure is calculated using the Washburn equation:

[0098] where Di = pore diameter at the 1thpressure point, = surface tension, 0= contact angle and Pi - pressure. The most basic plot from mercury intrusion porosimetry is pore diameter (microns) on a logarithmic scale vs. the corresponding specific cumulative intrusion volume (cc / g). More typically, the compression effect resulting from 20DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 the use of a log scale is compensated by dividing the difference in volume by the difference in the logarithm of diameters as follows:

[0099] MogD = logVDij++11~-lVoigDi[000100] This mathematical formula is favored since it causes equal peak areas on a plotted semilog curve to represent equal pore volumes.[000101]Total Pore Area[000102] The total pore area was determined through a series of intermediate calculations. First, the diameter of the pores being filled at a given pressure was calculated using the Washburn equation:—4ycos6[000103] where Di = pore diameter at the ith pressure point, y = surface tension, 0 = contact angle and Pi = pressure. The mean diameter for the ith point is then taken to be:Dmi = (Di +Di-i) 12[000104] The incremental specific intrusion volume for the ith point was calculated from the total intrusion volume taken at each point (li): lii = h - h-i[000105] Finally, the incremental specific pore area for the ith point was calculated from the incremental intrusion volume and the mean diameter from:Aii = (4 X lii) / Dmi[000106] The total (i . e. , cumulative) specific pore area for the ith point was then calculated as:Ai = Aii + Aii-i + ... +Ai i .Bulk Density[000107] The bulk density of the sample is the density of the solid including all open pores and internal void volume. The bulk density was calculated by dividing the sample mass by the low pressure mercury intrusion volume. Sample mass was determined by weighing on an analytical balance of + / - 0.01 mg sensitivity.Bulk Density = M / (VL ow Pressure)Skeletal Density21DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01[000108] The skeletal density is the density of a solid calculated by excluding all open pores and internal void volume. The skeletal density was calculated by dividing the sample mass by the adjusted sample volume (low pressure volume minus total intrusion volume). The sample mass was determined by weighing on an analytical balance of + / - 0.01 mg sensitivity.Skeletal Density = M / ((VL ow Pressure) — (VHigh Pressure)) where VLOWPressure is volume of the sample at 0.5 psia (~3.5 kPa) and VHigh Pressure is total intrusion volume at 60,000 psia (~ 413.7 MPa).Total Porosity[000109] The total porosity within the substrate is simply the void volume of the sample divided by the total volume of the sample. This can be calculated as:%Porosity = 100 * (total intrusion volume at 60,000 psia (~ 413.7 MPa)) / (volume of the sample at 0.5 psia (~3.5 kPa)).Thickness[000110] Membrane thickness was measured by placing the membrane between the two plates of a Kafer FZ1000 / 30 thickness snap gauge (Kafer Messuhrenfabrik GmbH, Villingen-Schwenningen, Germany). The average of the three measurements was used.[000111] EXAMPLES[000112] EXAMPLE 1[000113] Preparation of Adsorbent Composite “Sample 1 ” Comprising Adsorbent Filler Particles Having Smaller Average Size and Distribution[000114] A composite blend of 15 wt% polytetrafluoroethylene (PTFE) fine powder (The Chemours Company, Wilmington, DE) and 85 wt% OXPLIRE™ 410-A activated carbon adsorbent (Puragen Activated Carbons, Palm Beach Gardens, FL, United States) was blended in a manner generally taught in United States Patent Application Publication No. 2005 / 0057888 to Mitchell, et al. and subsequently embossed to create a composite tape with ridges ( “Fabrication and Testing of Expanded PTFE Structured Adsorbents with Parallel Channels”, Adegunju et al., Annual Meeting of the American Institute of Chemical Engineers (AICHe), November, 2021. FIG. 1 shows an SEM image of the resulting porous fibrillated PTFE composite 100 (“Sample 1”) including adsorbent particles 110 enmeshed and immobilized within the PTFE matrix 120. FIG. 3 shows the22DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO01 particle size distribution of the adsorbent particles 110. The corresponding particle size distribution by quantile is provided in Table 2. The porous fibrillated PTFE composite has a thickness of approximately 40 mil (-1020 pm) and a density of -0.556 g / cm2. Subsequently this material was tested in a Volumetric Frequency Response (VFR) test fixture (Hossain, M.l. et al., supra) and found to have a peak phase lag (degrees) at a frequency of 11.3 Hz (Table 1). The average pore size diameter was measured using mercury porosimetry (FIG. 5).[000115] EXAMPLE 2[000116] Preparation of Adsorbent Composite “Sample 2” Comprising Adsorbent Filler Particles Larger Average Size and Distribution[000117] A composite blend of 15 wt% PTFE fine powder (The Chemours Company, Wilmington, DE) and 85 wt% OXPURE™ 410-A activated carbon adsorbent (Puragen, Florida, United States) was blended in a manner generally taught in United States Patent Application Publication No. 2005 / 0057888 to Mitchell, et al. and subsequently embossed to create a composite tape with ridges (Adegunju et al., supra). FIG. 2 shows an SEM image of the resulting porous fibrillated PTFE composite 200 (“Sample 2”) including adsorbent particles 210 enmeshed and immobilized within the fibrillated PTFE matrix 220 and including empty spaces, or voids 230, that contribute to the void volume of the composite. FIG. 3 shows the particle size distribution of the adsorbent particles 210, which are comparatively larger than Sample 1 100 and the adsorbent particles therein 110. The corresponding particle size distribution by quantile is provided in Table 2. The porous fibrillated PTFE composite has a thickness of 60 mil (-1520 pm) and a density of approximately 0.451 g / cm2. Subsequently this material was tested in a Volumetric Frequency Response (VFR) test fixture (Hossain, M.l. et al., supra)and found to have a peak phase lag (degrees) at a frequency of 33.1 Hz (FIG. 4). The average pore size diameter was measured using mercury porosimetry (FIG. 5).Table 1.23DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO011= 25 °C @ 100 torr (-13.33 kPa)Table 2.24DMS US.366231104.1

Claims

Attorney Docket No. 450385.006706 2831WO01WHAT IS CLAIMED IS:1 . An adsorbent article for swing separation comprising: a porous fibril lated polymer membrane that includes supported adsorbent particles non- covalently immobilized within a node and fibril microstructure of the porous fibrillated polymer membrane, wherein the supported adsorbent particles have a particle size distribution defined by a D90 value of at least 200 microns, wherein the porous fibrillated polymer membrane includes the supported adsorbent particles in a range from about 30% to about 98%.

2. The adsorbent article of claim 1 , wherein the supported adsorbent particles have a particle size distribution defined by a D10 value of at least 70 microns.

3. The adsorbent article of any one of the preceding claims, wherein a mean particle size of the supported adsorbent particle is greater than or equal to 90 microns.

4. The adsorbent article of any one of the preceding claims, further comprising a plurality of pleats, folds, ridges, embossed ridges, channels, and any combination thereof.

5. The adsorbent article of any one of the preceding claims in the form of a pleated sheet, folded sheet, rolled sheet.

6. The adsorbent article of any one of the preceding claims, wherein the porous fibrillated polymer membrane has a porosity from about 20% to about 90%.

7. The adsorbent article of any one of the preceding claims, wherein the porous fibrillated polymer membrane comprises polytetrafluorethylene (PTFE), poly(ethylene- co-tetrafluoroethylene) (ETFE), ultra-high molecular weight polyethylene (LIHMWPE), polyparaxylylene (PPX), polylactic acid (PLLA), and any combination or blend thereof.

8. The adsorbent article of any one of the preceding claims, wherein the supported adsorbent particles have a particle population with a D50 value of 135 microns or more.25DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO019. The adsorbent article of any one of the preceding claims, wherein at least 40% of the porosity comprises a pore size greater than 10 microns.

10. The adsorbent article of any one of the preceding claims, wherein the adsorbent particles are configured with nanopores to selectively adsorb at least one target gas.11 . The adsorbent article of any one of the preceding claims, wherein said at least one target gas comprises ethane, propane, butane, or pentane.

12. The adsorbent article of any one of the preceding claims, wherein the adsorbent article comprises activated carbon, silica gel, alumina, metal-organic frameworks (MOFs), porous polymers, mesoporous silicas, graphene-based materials, a carbonaceous material derived from biomass, or a combination thereof.

13. The adsorbent article of claim 1 , wherein the adsorbent article is in the form of a filter bag, a honeycomb, a monolith, a parallel passage contactor, a sheet, or any other suitable geometrically structured forms.

14. The adsorbent article of claim 1 , wherein the supported adsorbent particle is located throughout a thickness of the fibril lated polymer membrane.

15. The adsorbent article of any one of the preceding claims further comprising at least one additional porous support layer.

16. The adsorbent article of claim 15, wherein the at least one additional porous support layer is a porous woven support, a porous non-woven support, a porous screen, a porous membrane, a porous fibrillated membrane, and any combination thereof.

17. A gas separation adsorbent filter material comprising the adsorbent article of any one of claims 1-16.

18. A parallel passage contactor comprising the adsorbent article of any one claims 1-18.26DMS US.366231104.1Attorney Docket No. 450385.006706 2831WO0119. A gas separation system comprising the adsorbent article of any one of the preceding claims, the adsorbent filter material of claim 17, or the parallel passage contactor of claim 18.

20. The gas separation system of claim 19, wherein the gas separation system comprises a temperature swing adsorption system, a pressure swing adsorption system, or a combination thereof.21 . A method for separating at least one target gas from a gas stream mixture comprising contacting a gas stream mixture having a concentration of at least one target gas with the adsorbent article of any one of claims 1 -15 or the gas separation adsorbent filter of claim 17, whereby the at least one target gas is selectively adsorbed from the gas stream mixture by the adsorbent article.

22. The method of claim 21 , further comprising collecting or concentrating said at least one target gas.

23. The method of claim 21 or 22, wherein the gas stream has a BTU content of less than or equal to 1100 BTU / scf after the contacting step.27DMS US.366231104.1

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