Composite contactors and method of making thereof

Abstract

Methods for producing a laminate and a contactor by in-situ polymerization are disclosed. A contactor can be produced by in-situ polymerization or assembling a plurality of laminates. The contactor can be used in a sorptive separator for a sorptive gas separation process.

Description

[0001] COMPOSITE CONTACTORS AND METHOD OF MAKING THEREOF

[0002] FIELD

[0003] The present disclosure relates generally to structures and contactors with a solid active phase such as a solid sorbent or catalyst for use in sorptive gas separators and methods of manufacturing.

[0004] BACKGROUND

[0005] Sorptive gas separators are used in sorptive gas separation applications which include, but are not limited to, greenhouse gas reduction applications for separation of a target component, for example, an acid gas component, from a gaseous influent stream including, for example, the atmosphere or air, a combustion or flue gas stream, a biogas stream, or a process gas stream. Particular applications include carbon capture applications for separating carbon dioxide from the atmosphere or air, a combustion or flue gas stream, a biogas stream, or a process gas stream, thereby reducing the release of carbon dioxide (CO2) into the atmosphere.

[0006] For gas separation applications, it is desirable for sorptive separators to have contactors with a large surface area with an even distribution of a solid active phase across the large surface area to enable even, effective, and efficient reactions between the influent streams and the solid active phase. Even distribution of the solid active phase is affected by various factors, including the ability to control the morphology of the solid phase, which is not consistent in known examples of this technology.

[0007] Contactors may comprise sorbent structures, laminates, and / or substrates in the form of sheets or ribbons with thin cross-sections and large surface areas to accelerate reactions and heat-exchange, while offering the advantages of reducing the volume, weight, and / or heat capacity of the contactor. However, challenges of the thin cross-sections include the limited mechanical strength of the sheet or ribbon, which may result in lower manufacturing yields, reduced operating pressure or pressure differential thresholds, shortened lifetimes due to mechanical or chemical failure, and / or increased operating costs which can be due to the cost for replacing failed components. Fundamental sequence and steps of conventional methods for producing sorbent structures involve polymerization reactions for forming the solid active phase followed by shaping or forming the sorbent structure. For some sorbent structures, the solid active phase may be attached in and / or on a substrate where after the solid active phase is formed, the solid phase may be incorporated and / or attached on and / or in a substrate. Contactors may comprise a single sorbent structure, such as, an extruded monolith, or a plurality of sorbent structures, such as, substrates or laminates in the form of a sheet, where the plurality of sorbent structures or laminates can be assembled to form the contactor. Synthesis of the solid active phase can produce the polymer particles, beads or a slurry of polymer particles. After synthesis a powdering step may be desired which may include mechanical milling of the solid active phase to desirable sizes and size distributions suitable for slurry rheology requirements and facilitating penetration into the porous substrate. Production of the sorbent structure or laminate comprising sheets may include producing a slurry comprising the active phase, and coating on and in a porous substrate with the slurry. Some processes may include a step of activating the solid active phase through a temperature treatment process. Assembly of the sorbent structure may involve assembly of a plurality of the sorbent structures, laminates, or substrates with spacers to produce a contactor.

[0008] The conventional methods pose various challenges including a greater than desired number of manufacturing process steps which may result in a greater than desired amount of manufacturing equipment, personnel, and materials used.

[0009] Synthesis of the active phase, typically achieved by batch processing, may result in variable morphology and degree of aggregation between batches, which may often lead to further undesirable material variability for downstream manufacturing processes. The particle size of the polymer particles may be controlled by mechanical means such as milling of the particles which may diminish the performance of a sorbent. The use of dispersants and a binder for attaching the solid active phase to a substrate can add additional inert mass to the sorbent structure which may increase the energy intensity of the sorption process without contributing to the sorption process as well as may induce variability in the distribution of the solid active phase on and / or in the sorbent structure. The slurry coating process can be limited to simple geometries such as sheets and thin cross-sections as thicker sheets or substrates may result in non-homogeneous distribution of the active solid phase across the cross-section.

[0010] In situ polymerization reactions are used for preparation of monoliths with tailored pores for different applications. For example, affinity chromatography is prepared by in-situ polymerization reactions of glycidyl methacrylate with prior- conjugated peptide as disclosed in the publication titled, “Affinity Monoliths Generated by In Situ Polymerization of the Ligand”, R. Hahn, A. Podgornik, M. Merhar, E. Schallaun, and A. Jungbauer, Analytical Chemistry 2001 73 (21), 5126-5132, https: / / doi.org / 10.1021 / ac0103165.

[0011] Novel structures and contactors for use in sorptive separators and their methods of manufacturing to improve their performance, quality and production throughputs while reducing manufacturing costs are thus highly desirable.

[0012] SUMMARY

[0013] In a first aspect, a method for producing a laminate comprises:

[0014] (a) forming a precursor mixture having a monomer, a crosslinker, and an initiator;

[0015] (b) incorporating the precursor mixture in and / or on a substrate;

[0016] (c) polymerizing the precursor mixture and forming a polymer in and / or on the substrate, and

[0017] (d) activating the polymer to produce the laminate.

[0018] In a second aspect, a method for producing a contactor comprises:

[0019] (a) forming a precursor mixture having a monomer, a crosslinker, and an initiator;

[0020] (b) incorporating the precursor mixture in and / or on a substrate;

[0021] (c) polymerizing the precursor mixture and forming a polymer in and / or on the substrate, and

[0022] (d) activating the polymer to produce a laminate, and

[0023] (e) assembling a plurality of laminates to produce the contactor. In a third aspect, a method for producing a contactor comprises:

[0024] (a) configuring at least one substrate to produce a substrate assembly;

[0025] (b) forming a precursor mixture of a monomer, a crosslinker, and an initiator;

[0026] (c) incorporating the precursor mixture in and / or on the substrate assembly;

[0027] (d) polymerizing the precursor mixture and forming a polymer in and / or on the substrate assembly, and

[0028] (e) activating the polymer to produce the contactor.

[0029] In another aspect, a contactor comprises:

[0030] (a) at least one substrate formed or assembled to produce a substrate assembly, the substrate assembly further comprising a plurality of passages, and

[0031] (b) a polymer in and / or on the at least one substrate, wherein the polymer sets and / or bonds the at least one substrate in a ridged structure or a self-supported structure.

[0032] BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1a is a photograph of a laminate or sorbent structure during an embodiment of an in-situ polymerization process before hydrolysis;

[0034] Figure 1 b is a photograph of a laminate or sorbent structure during an embodiment of an in-situ polymerization process after hydrolysis;

[0035] Figure 2a is a photograph of a contactor produced by the embodiment of an in-situ polymerization process of laminates or sorbent structures in sheet form prior to assembly as a contactor;

[0036] Figure 2b is a photograph of a contactor produced by the embodiment of an in-situ polymerization process of the contactor after laminates or sorbent structures were assembled into a form of the contactor;

[0037] Figure 3 is a graph with data from testing of a sorptive gas separation process of CO2 from air, with plots comparing the breakthrough curves of CO2 from different sorptive beds where a first sorptive bed (plot 51) was produced using the inventive methods of incorporating the polymer precursor on and / or in a substrate prior to polymerization reaction and the second and third sorptive beds (plots 52 and 53 respectively) were produced using the conventional method of incorporating the sorbent on and / or in a substrate from two different commercial sorbents;

[0038] Figure 4a is a column chart comparing the CO2 sorption capacity by weight of different laminates where a PNP2 laminate was produced using the inventive methods of incorporating the polymer precursor on and / or in a substrate prior to polymerization reaction and a laminate was produced using the conventional method of incorporating the sorbent on and / or in a substrate after polymerization reaction, at various temperatures and relative humidity levels (RH);

[0039] Figure 4b is a column chart comparing the water (H2O) sorption capacity by weight of different laminates where a PNP2 laminate was produced using the inventive methods of incorporating the polymer precursor on and / or in a substrate prior to polymerization reaction and a Sample 1 laminate was produced using the conventional method of incorporating the sorbent on and / or in a substrate after polymerization reaction, at various temperatures and relative humidity levels (RH), and Figure 5 is a column chart comparing the sorption capacities of laminates at an initial (dry) condition (columns shown as solid grey) versus after wet oxidation testing (columns shown with horizontal lines) for six different samples produced with PNP2. Laminates 1 , 2, and 3 were produced using the inventive methods of incorporating the polymer precursor on and / or in a substrate prior to polymerization reaction, while laminates 4, 5, and 6 were produced using the conventional method of incorporating the active phase layer on and / or in a substrate after polymerization reaction where a substrate was coated with the PNP after producing a PNP powder.

[0040] DETAILED DESCRIPTION

[0041] Definitions:

[0042] Contactor: comprise at least one structure or laminate and at least one flow channel. The structure or laminate can form walls for defining at least a portion of a flow channel of a contactor. The walls can be porous. A contactor can comprise a solid active phase or compound such as, a sorbent, on and / or in the walls and a plurality of flow channels. The flow channels can be distributed substantially evenly or randomly within a contactor. The flow channels can be substantially parallel flow channels, such as, substantially parallel in relation to each other, and / or tortuous. The flow channels can be separated by the structure or laminate. A contactor can also comprise a honeycomb-like sorbent structure with walls comprising. The terms contactor, structure, structured sorbent bed, sorbent contactor, laminate, and bed may be used interchangeably herein. There may be one or more contactors in a sorptive separator.

[0043] Process fluid or process stream: a fluid or stream supplied to or admitted into a sorptive gas separator, for example, a feed stream, a regeneration stream, and / or a cooling stream. The phrase “process fluid” may be referred to and used interchangeably with the phrase “influent” herein.

[0044] Product fluid or product stream: a fluid stream recovered from a sorptive gas separator, for example, a first product stream, or a second product stream. The phrase “product fluid” may be referred to and used interchangeably with the phrase “effluent” herein.

[0045] Commercial resin-1 : a typical commercially available porous resin with a polystyrene-divinylbenzene skeleton and benzylamine functional groups used as a baseline for comparison with the inventive sorbents.

[0046] Commercial resin-2: another typical commercially available porous resin with a polystyrene-divinylbenzene skeleton with benzylamine functional groups used as a baseline for comparison with the inventive sorbents.

[0047] PNP2: a porous network polymer of divinylbenzene with ethylene-amine functional groups.

[0048] PNP2-HT: PNP2 polymer after thermal treatment at 160-180°C for about 16 h up to about 24 h.

[0049] Substrate: a physical support for a solid active phase such as a sorbent, preferably porous to enable a large surface area to volume ratio. Suitable examples include but are not limited to woven or non-woven carbon, glass, metal or polymer fiber material. The term “substrate” may be referred to and used interchangeably with the term “support” herein. Laminate: a laminate comprises a substrate with one or more solid active phase such as a sorbent in and / or on the substrate after polymerization. The term “laminate” may be used interchangeably with the terms “sorbent structure” or “sorptive structure”. Solid active phase: a sorbent or a catalyst in a solid phase, the term “solid active phase” may be referred to and used interchangeably with the term “sorbent” or “catalyst” herein.

[0050] Methods for producing a contactor to reduce challenges associated with the prior art methods of producing a contactor for a sorptive separator with a solid active phase, for example, a solid sorbent, for gas separation applications are disclosed. Conventional methods may involve the sequence and steps of polymerization reactions of the solid active phase, polymer particles, or polymer beads, followed by powdering, slurry formation, and incorporation, such as, coating and impregnating a substrate with the solid active phase. Novel in-situ polymerization methods disclosed herein can involve the sequence and steps of incorporating precursors of the polymers on and / or in a substrate followed by a polymerization reaction. The novel in-situ polymerization method may be conducted on one or more individual substrates prior to assembling the one or more individual polymerized laminates to form a contactor, or conducted after forming or assembling one or more substrates with precursors of the polymers into a contactor. In-situ polymerization of individual substrates or substrate components can involve conducting polymerizing reactions in individual substrates, followed by assembling a plurality of polymerized laminates components thereby producing a contactor. In-situ polymerization of an assembly of one or more substrates involves forming or assembling one or more substrates, producing an assembly of one or more substrates followed by polymerizing the assembly of one or more substrates thereby producing a contactor. Advantages of in-situ polymerization of an assembly of one or more substrates may include reducing the number of manufacturing steps relative to assembling a plurality of laminates orsubstrates, and forming a substantially unitary structure or laminate assembly thereby reducing or eliminating the need to add spacers between substrates or laminates and associated process steps.

[0051] The novel in-situ polymerization method of producing the contactor or sorbent structure may offer additional advantages including, enabling the laminates or sorbent structures to be configured with additional geometric shapes (other than a substantially planar sheet) and forms; the use of substrates with thicker cross-sections; novel sorbent compositions; reducing or eliminating the use of additives or binders, for example, used during a conventional slurry coating step, resulting in reducing the thermal capacity of the contactors thereby resulting in a further reduction in the energy intensity during operation; reducing the total number of manufacturing process steps such as elimination of the slurry coating step; improved uniformity in the distribution of a solid active phase in a substrate, and increased mechanical strength. Additionally, the novel method reduces challenges associated with batch-to-batch quality variations of solid polymer powder or beads during synthesis, and sorbent capacity losses associated with the resin milling of amine powder or beads or the amine resin formation and the variability in viscosity of the slurry coating for the prior art laminate coating process. These multiple sources of process variabilities may lead to increased costs and greater variability in process control during operation of the contactor.

[0052] In-situ polymerization of individual substrates or substrate components

[0053] In-situ polymerization of individual substrates with precursors of the polymers can involve growing amine-rich polymer precursors on and / or in a substrate, for example, a woven or non-woven carbon or glass fiber substrate, to form a laminate, which can be stacked or assembled to form a contactor.

[0054] In an embodiment, a method for producing a contactor can comprise the steps of: mixing a monomer, a crosslinker, and an initiator, for forming a precursor mixture; incorporating or impregnating the substrate with the precursor mixture; polymerizing the polymers, activating the polymers, for example, by hydrolysis, for forming the laminate; and assembling the contactor from a plurality of laminates.

[0055] In an embodiment, the method can further comprise at least one step of: mixing a pore-forming agent with the monomer, the crosslinker, and the initiator for forming the precursor mixture; adding a binder for forming the precursor mixture, conducting the polymerizing at an elevated temperature, such as increasing a temperature of the precursor mixture and / or substrate; after the activating step, functionalizing, for example, epoxidation or alkylation; after the activating step or the functionalizing step, washing the substrate or laminate; activating the binder; during the assembling step at least one of, adding spacers between at least a portion of the plurality of laminates, curing the spacers, adding a binder, activating the binder, cutting the laminates, and stacking the laminates.

[0056] This process can offer advantages than those already disclosed herein relative to conventional amine synthesis and contactor manufacturing processes methods by eliminating a milling step for milling polymers into fine particles and a slurry forming step. Instead, precursors of the polymers comprising a monomer mixture or a polymer precursor mixture can be incorporated in and / or on a porous substrate. This process may be especially desirable when attempting to reduce the amount of solvent used for a polymerization reaction. The amount of solvent used can be a function of the selected chemistry. A manufacturing process for a contactor may be categorized into two sub-processes, polymerizing individual substrates or substrate components, followed by assembling a plurality of polymerized individual laminates or laminate components, thereby producing a contactor.

[0057] Production of individual laminates

[0058] In an embodiment, a method for producing a laminate for a contactor, the method can comprise the steps of:

[0059] (a) forming a precursor mixture having a monomer, a crosslinker, and an initiator;

[0060] (b) incorporating the precursor mixture in and / or on a substrate;

[0061] (c) polymerizing the precursor mixture and forming a polymer in and / or on the substrate, and

[0062] (d) activating the polymer to produce the laminate.

[0063] In further embodiments of producing the laminate, the method can be further comprise at least one step of:

[0064] • during step (a), at least one of forming the precursor mixture having a pore-forming agent, and mixing a pore-forming agent with the monomer, the crosslinker, and the initiator;

[0065] • during step (b), incorporating the precursor mixture in and / or on the substrate can be by at least one of submerging the substrate at least partially in the precursor mixture, dipping the substrate in the precursor mixture, covering the substrate with the precursor mixture, coating the substrate with the precursor mixture, and spraying the precursor mixture on and / or in the substrate; • conducting the incorporating step in an environment which enables the polymerization of the precursor mixture, for example, a substantially inert environment, an environment with reduced levels of oxygen relative to the atmosphere or substantially void of oxygen;

[0066] • during step (c) conducting the polymerization or polymerizing the precursor mixture can be by increasing a temperature of the substrate and the precursor mixture to, and / or conducting the polymerization at a temperature in a temperature range of about 60°C to about 160°C, about 90°C to about 150°C, or about 100°C to about 140°C;

[0067] • during step (c) polymerizing the precursor mixture can be by exposing the precursor mixture to light;

[0068] • during step (c) polymerizing the precursor mixture can be at a pressure equal to or greater than about atmospheric pressure;

[0069] • during step (d) activating the polymer can be by converting amide into amine by any suitable techniques, such as, basic hydrolysis, acidic hydrolysis and thermal decomposition of amide;

[0070] • after step (d), functionalizing the polymer or an amine can be by epoxidation or alkylation;

[0071] • after step (d) removing contaminants, for example, unreacted monomers, crosslinkers, initiators, pore-forming agents, and / or by-products, from the laminate.

[0072] • after step (d), removing contaminants, for example, unreacted monomers, crosslinkers, initiators, pore-forming agents, and / or by-products, from the laminate, and drying the laminate, and

[0073] • prior to step (b), forming the substrate into a shape of the contactor, or assembling a plurality of the substrates to form a substrate assembly and / or a shape of the contactor.

[0074] In aspects of the method for producing the laminate, one or more of:

[0075] • the monomer can be at least one of N-vinylformamide, N-vinyl acetamide, N-vinyl phthalimide, N-vinylsuccinimide and any other suitable monomers, which will produce an ethylene amine structure during step (d); • the crosslinker can be a chemical having multiple double-bonds with at least two double-bonds, such as, divinylbenzene;

[0076] • the initiator can generate free radicals triggered by at least one of heat, an oxidative-reduction reaction, and light-induced decomposition;

[0077] • the initiators may include, for example, organic peroxides, azo compounds, or other suitable free radical producing initiators;

[0078] • the pore-forming agent can be at least one of a solvent, a suitable polymer which can be subsequently removed or washed out, a solid such as silica particles, sugar, and a salt;

[0079] • the laminate can comprise at least one active component, for example, a polymer or a sorbent, on and / or in the substrate;

[0080] • the polymer can be a polymeric compound;

[0081] • the polymer or the polymeric compound can be at least one of a porous polymeric amine sorbent, an amine sorbent, a PNP based sorbent, including but not limited to PNP2 or PNP2-HT;

[0082] • the sorbent can be a porous polymeric amine sorbent, an amine sorbent, a PNP based sorbent, including but not limited to PNP2 or PNP2-HT;

[0083] • the substrate can be at least one of an organic or inorganic porous substrate, carbon-fiber-based, glass fiber-based, metal-based, or polymer-based, and in embodiments, in the form of non-woven or woven material and can be configured in sheets, and

[0084] • the contactor can be for a sorptive separator for use in a sorptive gas separation process and / or application.

[0085] Production of a contactor from individual polymerized laminates

[0086] In an embodiment, a method for producing a contactor, the method can comprising the steps of:

[0087] (a) forming a precursor mixture of a monomer, a crosslinker, and an initiator;

[0088] (b) incorporating the precursor mixture in and / or on substrate; (c) polymerizing the precursor mixture and forming a polymer in and / or on the substrate;

[0089] (d) activating the polymer to produce a laminate, and

[0090] (e) assembling a plurality of laminates to produce the contactor.

[0091] In further embodiments, the method can further comprise at least one of:

[0092] • during step (a), at least one of forming the precursor mixture having a pore-forming agent, and mixing a pore-forming agent with the monomer, the crosslinker, and the initiator;

[0093] • in any one of steps (b), (c), (d), and (e) adding at least one spacer to the laminate and curing the at least one spacer;

[0094] • prior to step (e) cutting the laminate to a desired size;

[0095] • prior to or during step (e) adhering and / or sealing at least a portion of the outside perimeter of the plurality of laminates;

[0096] • prior to step (b), assembling a plurality of substrates for forming a substrate assembly;

[0097] • during step (b), incorporating the precursor mixture in and / or on the substrate can be by at least one of submerging the substrate at least partially in the precursor mixture, dipping the substrate in the precursor mixture, covering the substrate with the precursor mixture, coating the substrate with the precursor mixture, or spraying the precursor mixture in and / or on the substrate

[0098] • conducting the incorporating step in an environment which enables the polymerization of the precursor mixture, for example, a substantially inert environment, an environment with reduced levels of oxygen relative to the atmosphere or substantially void of oxygen;

[0099] • during step (c) conducting the polymerization or polymerizing the precursor mixture can be by increasing the temperature of the substrate and the precursor mixture to and / or conducting the polymerization at a temperature in a temperature range of about 60°C to about 160°C, about 90°C to about 150°C, or about 100°C to about 140°C; • during step (c) polymerizing the precursor mixture can be by exposing the precursor mixture to light;

[0100] • during step (c) polymerizing the precursor mixture can be at a pressure equal to or greater than about atmospheric pressure;

[0101] • during step (d) activating the polymer can be by converting amide into amine by any suitable techniques, such as, basic hydrolysis, acidic hydrolysis and thermal decomposition;

[0102] • after step (d), functionalizing the polymer or an amine can be by epoxidation or alkylation;

[0103] • after step (d) removing contaminants, for example, unreacted monomers, crosslinkers, initiators, pore-forming agents, and / or by-products, from the contactor, and

[0104] • after step (d) or during step (e) drying the laminate.

[0105] In aspects of the method for producing the contactor, at least one of:

[0106] • the monomer can be at least one of N-vinylformamide, N-vinyl acetamide, N-vinyl phthalimide, N-vinylsuccinimide and any other suitable monomers, which will produce an ethylene amine structure during step (d);

[0107] • the crosslinker can be a chemical having multiple double-bonds with at least two double-bonds, such as, divinylbenzene;

[0108] • the initiator can generate free radicals triggered by at least one of heat, an oxidative-reduction reaction, and light-induced decomposition;

[0109] • the initiators may include, for example, organic peroxides, azo compounds, or other suitable free radical producing initiators;

[0110] • the pore-forming agent can be at least one of a solvent, a suitable polymer which can be subsequently removed or washed out, a solid such as silica particles, sugar, and a salt;

[0111] • the polymer can be a polymeric compound, and in embodiments, the polymer or polymeric compound can be at least one of, a porous polymeric amine, a sorbent, an amine sorbent, a PNP based sorbent, including but not limited to PNP2 or PNP2-HT; • the laminate can comprise at least one active component, for example, a polymer or a sorbent, on and / or in the substrate;

[0112] • the polymer can be a polymeric compound;

[0113] • the polymer or the polymeric compound can be at least one of, a porous polymeric amine sorbent, an amine sorbent, a PNP based sorbent, including but not limited to PNP2 or PNP2-HT;

[0114] • the substrate can be at least one of an organic or inorganic porous substrate, carbon-fiber-based, glass fiber-based, metal-based, or polymer-based, in the form of non-woven or woven material and can be configured in a form of a sheet;

[0115] • the contactor and / or the substrate assembly can comprise at least one passage, and

[0116] • the contactor can be used in a sorptive separator in a sorptive gas separation process and / or application.

[0117] In-situ polymerization of a substrate assembly or a contactor

[0118] In an embodiment, a method for producing a contactor from polymerizing a substrate assembly can comprise the steps of: mixing a monomer, a crosslinker, and an initiator, for forming a precursor mixture; assembling a substrate assembly from a plurality of substrates in the form of sheets, impregnating the substrate assembly with the precursor mixture; polymerizing the polymers; activating the polymers, for example, by hydrolysis, and washing. The method can comprise an additional step of functionalizing, for example, epoxidation or alkylation, after the activating step. In one aspect, during the mixing step, a pore-forming agent can be mixed with the monomer, the crosslinker, and the initiator for forming the precursor mixture. The substrate assembly can be produced by assembling or forming one or more substrates with a strength component or feature for providing mechanical strength or supporting the substrate assembly during the in-situ polymerization process to a desired shape or configuration of a contactor. In embodiments, passages or gas flow channels of the contactor or substrate assembly may be supported and / or blocked with the strength component, a channel shaping component, and / or a channel blocking component made from an inert material, for example, glass. The substrate assembly can then be polymerized which may strengthen an individual substrate and / or bind two or more substrates to form a laminate assembly or a self-supported monolith structure.

[0119] The novel in-situ polymerization of a substrate assembly may desirably reduce the number of manufacturing process steps as well as reduce or eliminate the use of additives and / or binders used during a conventional slurry coating process. The novel process can also enable various geometries and forms, for example, other than substantially flat sheets, to be used for substrates as incorporating polymers on and / or in a substrate can be achieved on a variety of geometries and forms. For example, in- situ polymerization reactions may be achieved on pre-formed monoliths produced by extrusion, stacking or rolling of sheets or ribbons with or without embedded spacers, channel shapers, channel shaping components, strengthening components, and / or channel blocking components. In an embodiment, a precursor mixture may be incorporated on and / or in a substrate with or without removable spacers and / or channel shapers for creating flow channels by dipping the substrate into the precursor mixture or injecting the precursor mixture into the substrate before the polymerization reaction. After polymerization reactions, the removable channel shapers may be removed if sufficient mechanical support was created during the polymerization reaction step.

[0120] In an embodiment, a method for producing a contactor for a sorptive separator can comprise the steps of:

[0121] (a) configuring at least one substrate to produce a substrate assembly;

[0122] (b) forming a precursor mixture of a monomer, a crosslinker, and an initiator;

[0123] (c) incorporating the precursor mixture in and / or on the substrate assembly;

[0124] (d) polymerizing the precursor mixture and forming a polymer in and / or on the substrate assembly, and

[0125] (e) activating the polymer to produce the contactor.

[0126] In further embodiments, the method can further comprise at least one of: • during step (a), at least one of forming the precursor mixture having a pore-forming agent, and mixing a pore-forming agent with the monomer, the crosslinker, and the initiator;

[0127] • adding at least one spacer to the substrate assembly and curing the at least one spacer;

[0128] • during step (c), incorporating the precursor mixture in and / or on the substrate assembly can be by at least one of submerging the substrate assembly at least partially in the precursor mixture, dipping the substrate assembly at least partially in the precursor mixture, covering the substrate assembly at least partially with the precursor mixture, coating the substrate assembly at least partially with the precursor mixture, and spraying the precursor mixture in and / or on the substrate assembly;

[0129] • incorporating the precursor mixture in and / or on the substrate assembly can be in an environment which enables the polymerization of the precursor mixture, for example, a substantially inert environment, an environment with reduced levels of oxygen relative to the atmosphere or substantially void of oxygen;

[0130] • during step (d) conducting the polymerization or polymerizing the precursor mixture can be by increasing the temperature of the substrate and the precursor mixture to and / or conducting the polymerization at a temperature in a temperature range of about 60°C to about 160°C, about 90°C to about 150°C, or about 100°C to about 140°C;

[0131] • during step (d) polymerizing the precursor mixture can be by exposing the precursor mixture to light;

[0132] • during step (d) polymerizing the precursor mixture can be at a pressure equal to or greater than about atmospheric pressure;

[0133] • during step (e) activating the polymer can be by converting amide into amine by any suitable techniques, such as, basic hydrolysis, acidic hydrolysis and thermal decomposition;

[0134] • after step (e), functionalizing the polymer or an amine can be by epoxidation or alkylation; • after step (e), removing contaminants, for example, unreacted monomers, crosslinkers, initiators, pore-forming agents, and / or by-products, from the contactor, and

[0135] • after step (e), drying the contactor.

[0136] In further aspects, at least one of:

[0137] • the monomer can be at least one of N-vinylformamide, N-vinyl acetamide, N-vinyl phthalimide, N-vinylsuccinimide and any other suitable monomers, which will produce an ethylene amine structure during step (e);

[0138] • the crosslinker can be a chemical having multiple double-bonds with at least two double-bonds, such as, divinylbenzene;

[0139] • the initiator can generate free radicals triggered by at least one of heat, an oxidative-reduction reaction, and light-induced decomposition;

[0140] • the initiators may include, for example, organic peroxides, azo compounds, or other suitable free radical producing initiators;

[0141] • the pore-forming agent can be at least one of a solvent, a suitable polymer which can be subsequently removed or washed out, a solid such as silica particles, sugar, and a salt;

[0142] • the contactor can comprise at least one active component, for example, a polymer or a sorbent, on and / or in the substrate assembly;

[0143] • the polymer can be a polymeric compound;

[0144] • the polymer or polymeric compound can be at least one of, a porous polymeric amine, an amine sorbent, a PNP based sorbent, including but not limited to PNP2 or PNP2-HT;

[0145] • the substrate can be at least one of an organic or inorganic porous substrate, carbon-fiber-based, glass fiber-based, metal-based, or polymer-based, in the form of non-woven or woven material and can be configured in a form of a sheet;

[0146] • the contactor and / or the substrate assembly can comprise at least one passage;

[0147] • performing step (a) and step (b) can be concurrently or performing step (b) can be after step (a), and • the contactor can be used in a sorptive separator in a sorptive gas separation process and / or application.

[0148] In an embodiment, the inventive process utilizes a precursor mixture with a small fraction of or substantially no solids which may advantageously minimize the change in viscosity between different batches. If it is desirable to increase the viscosity of the precursor mixture, soluble polymers may be added to the precursor mixture and then removed post polymerization reaction via a washing process or step. Alternatively, a small fraction, for example, less than about 20% by volume, of the product polymer may be formed and milled in a separate process and added to the precursor mixture as a thickening agent.

[0149] In an embodiment, a method for producing a laminate or a contactor for a sorptive separator can comprise the steps of:

[0150] (a) mixing a vinyl amine monomer precursor or a cyclic amine precursor, a divinyl monomer cross linker, a solvent, and a polymerization initiator for forming a precursor mixture;

[0151] (b) incorporating the precursor mixture in and / or on a substrate;

[0152] (c) polymerizing the precursor mixture in and / or on the substrate for forming a polymer in and / or on the substrate, and

[0153] (d) activating the polymer.

[0154] In embodiments of the method, at least one of:

[0155] • during step (c) polymerizing the precursor mixture can be by increasing the temperature of the substrate and the precursor mixture to and / or conducting the polymerization at a temperature in a temperature range of about 60°C to about 160°C, about 90°C to about 150°C, or about 100°C to about 140°C;

[0156] • during step (c) polymerizing the precursor mixture can be by exposing the precursor mixture to light;

[0157] • conducting a ring-opening polymerization on the vinyl amine monomer precursor or the cyclic amine precursor;

[0158] • during step (d) activating the polymer is by hydrolyzing the polymer;

[0159] • during step (d) activating the amine groups; • after step (d) removing solvent and / or unreacted reactants;

[0160] • forming polymer particles in and / or on the substrate;

[0161] • interlocking the polymer particles and the substrate, and

[0162] • interlocking the polymer particles and a plurality of substrates.

[0163] In aspects of the method at least one of: the solvent can promote the formation of a porous network in the polymer; the substrate can be porous; the substrate can have a pore volume of equal to or greater than 80% of a volume of the substrate, and the substrate can have an average pore diameter of equal to or greater than 1 micron.

[0164] Contactor

[0165] In an embodiment, a contactor can comprise:

[0166] (a) at least one substrate formed or assembled to produce a substrate assembly, the substrate assembly further comprising a plurality of passages, and

[0167] (b) a polymer in and / or on the at least one substrate, wherein the polymer sets and / or bonds the at least one substrate in a ridged structure or a self-supported structure.

[0168] In further embodiments, the contactor can comprise one or more of:

[0169] • a unitary structure;

[0170] • the polymer can be a polymeric compound;

[0171] • the polymer or polymeric compound can be at least one of a sorbent, a porous polymeric amine sorbent, an amine sorbent, a PNP based sorbent, including but not limited to PNP2 or PNP2-HT.

[0172] • the at least one substrate can be a plurality of substrates and assembled to produce the substrate assembly;

[0173] • a substrate on the outside perimeter of two or more sides of the contactor for providing mechanical support for the contactor;

[0174] • the at least one substrate can be at least one of an organic or inorganic porous substrate, carbon-fiber-based, glass fiber-based, metal-based, or polymer-based, in the form of non-woven or woven material and can be configured in sheets, and • one or more spacers between the one or more substrates.

[0175] In one aspect, the contactor can be for use in a sorptive separator in a sorptive gas separation process and / or application.

[0176] In an embodiment, a contactor can comprise:

[0177] (a) an amine polymer, and

[0178] (b) at least one substrate configured in the shape of a sheet, a ribbon, a tube, a honeycomb monolith, or a rolled monolith, with a thickness of the at least one substrate between 0.1 mm to 2 mm and a length of equal to or greater than 100 mm.

[0179] In embodiments of the contactor, at least one of: the substrate can have a pore volume of equal to or greater than 80% of a volume of the substrate; the amine polymer can occupy equal to or greater than 40% of the pore volume; the substrate can have an average pore size greater than 1 mm; the amine polymer can be from reacting a vinyl amine or a cyclic amine and a divinyl monomer with a cross-linker having at least 6 carbon atoms; the amine polymer can comprise a heat capacity, the contactor can comprise a heat capacity, wherein the heat capacity of the amine polymer is equal to or greater than 50% of the heat capacity of the contactor; the substrate can be porous; the substrate can be an organic porous substrate; the substrate can be an inorganic porous substrate; the amine polymer is a porous polymeric amine; the porous polymeric amine can have a surface area measured by Brunauer-Emmett-Teller (BET) at liquid nitrogen temperature of equal to or greater than 1 m2 / g, 5 m2 / g, or 10 m2 / g; the contactor having an interpenetrating network formed by the porous amine polymer and the porous substrate, and the substrate can comprise carbon fiber or glass fiber.

[0180] Examples of embodiments of the inventive process for producing a contactor:

[0181] Example 1 : Laminate preparation by the in-situ polymerization reaction using the steps of: mixing a monomer, a crosslinker, an initiator and a pore forming agent, for forming a precursor mixture; incorporating or impregnating a substrate with the precursor mixture; polymerizing the polymers by heating the substrate, activating the polymers by hydrolysis for forming the laminate; washing the laminate; assembling the contactor by cutting, stacking and glueing the laminates for forming the contactor.

[0182] 1.26 g 1 ,1 '-azobis(cyclohexanecarbonitrile) was dissolved in 50 g N- vinylformamide, 20 g divinylbenzene-80 and 23.4 g N,N-dimethylformamide and mixed to form a substantially uniform precursor mixture. The precursor mixture was incorporated into a carbon-fiber-based non-woven substrate by immersing the substrate in the mixture, followed by a polymerization reaction at 110°C for 1 h in an inert environment to produce a laminate. After cooling to room temperature, the laminate was soaked in a 6 M NaOH mixture and activated at a temperature in a range of 95 °C to 100 °C for about 24 h. The laminate was washed with deionized water to remove byproducts, and excessive base until a neutral pH was achieved. The laminate was dried at room temperature. Figs. 1a and 1 b present pictures of the resulting activated laminate or substrate component activated laminate and drying at room temperature, with Fig. 1a before activation and Fig. 1 b after activation. In Fig. 1 b, a ruler is shown for scale and also shows the homogeneous coverage of the active component or sorbent on the non-woven carbon fiber substrate.

[0183] Example 2: During a component preparation and contactor assembly process, the laminate prepared as Example 1 was processed by adding spacers to the laminate, stacked, and assembled to form a sorbent contactor with the dimensions of 2 inches (L) x 1 inch (w) x 1 inch (h). The sorbent contactor is shown in Fig. 2a.

[0184] Example 3: A contactor was produced using an in-situ polymerization method of a substrate assembly which comprised the steps of: mixing a monomer, a crosslinker, an initiator and a pore-forming agent for forming a precursor mixture; assembling a substrate assembly from a plurality of substrates in the form of sheets, impregnating the substrate assembly with the precursor mixture; polymerizing the polymers; activating the polymers, for example, by hydrolysis, and washing. The method can comprise an additional step of functionalizing, for example, epoxidation or alkylation, after the activating step.

[0185] Substrates in the form of sheets were assembled with channels blocked or formed with the use of channel shapers producing a substrate assembly followed by conducting the in-situ polymerization reactions and activation. The precursor mixture as in Example 1 was produced and incorporated into the pre-shaped substrate assembly with channel spacers and a casing (for covering four sides of the substrate assembly) by immersing or submerging the substrate assembly into the precursor mixture. The substrate assembly was heated, increasing the temperature of the substrate assembly for conducting the polymerization reactions. The channel shapers were removed form the substrate assembly and the polymers were activated by hydrolysis and washed, forming a contactor. Functionalization for example, epoxidation or alkylation can be conducted after activation. The process creates a contactor or a self-supported monolith structure as shown in Fig. 2b.

[0186] Example 4: Breakthrough measurements were conducted for a contactor produced by the in-situ polymerization methods as described in Examples 1 and 2 referred to as PNP2(HT), and contactors produced by conventional methods of producing a solid active phase or sorbent with a polymerization reaction using amine materials from commercial sources followed by incorporating the sorbent into the substrate, referred to as Commercial resin-1 and Commercial resin-2. The dimensions of the contactors were 2 inches (L) x 1 inch (W) x 1 inch (H).

[0187] Fig. 3 is a graph comparing breakthrough plots from a contactor produced by the novel in-situ polymerization methods referred to as PNP2(HT) or a plot 51 , and contactors produced by conventional methods (polymerization reaction of materials from commercial sources followed by incorporation into the substrate) , as Commercial resin-1 or a plot 53 and Commercial resin-2 or a plot 52. The x-axis represents time in seconds. The y-axis represents breakthrough of CO2 from an outlet end of a contactor in 1-y / yO, wherein “y” is a concentration of CO2 in an effluent stream from a sorptive separator, and “yO” is a concentration of CO2 in an influent stream from the sorptive separator. Tests were conducted using a source of CO2 with 400 ppm CO2 and a flow rate of 200 ml / min. The area under the plots from time 0 until the CO2 breakthrough (when the plots are at about 0 on the y-axis) corresponds to the sorptive capacity of the sorbents or contactors. The slope of plots is indicative of an increase in CO2 concentration corresponding to CO2 breakthrough of the sorbents for a given thickness, which is related to the kinetics of the sorbent at the thickness of the laminate and the length of the transient zone in the contactors. A greater slope of a plot can be indicative of a shorter transient zone which corresponds to faster kinetics. This example illustrates that the contactor of Example 2 produced using the novel method can offer the advantages of a greater t sorbent capacity, faster kinetics, and a simplified manufacturing process relative to contactors produced using conventional methods.

[0188] Fig. 4a illustrates the normalized sorption capacity for CO2 as a percentage by weight while Fig. 4b illustrates the normalized sorbent capacity for water as a percentage by weight at various humid conditions and various temperatures measured by a dynamic vapor sorption test (a thermo-gravimetric type of measurement). Figs. 4a and 4b compare a prior art reference sample produced using convention methods and the sample produced using novel in-situ polymerization methods described in Examples 2 or 3. In Fig. 4a, the sorption capacities for CO2 for a prior art reference sample or columns 61 are compared to the PNP2 samples or columns 62. In Fig. 4b, the sorption capacities for water for a prior art reference sample or columns 63 are compared to the PNP2 sample or columns 64. Fig. 4a demonstrates that the contactor produced by the in-situ polymerization method has a comparable or greater sorption capacity for CO2 relative to the prior art reference sample at the three test conditions. Fig. 4b demonstrates the in-situ polymerization method has a greater sorption capacity for water and is relatively hydrophilic relative to the prior art reference sample.

[0189] Fig. 5 is a column chart comparing the sorptive capacities of laminates at an initial (dry) condition (columns filled with solid color) versus after wet oxidation testing (columns filled with horizontal lines) for six different laminates with PNP2. Laminates 1 , 2, and 3 were produced using the novel methods of incorporating the polymer precursor on and / or in a substrate followed by polymerization reaction (in-situ polymerization method), while laminates 4, 5, and 6 were produced using the conventional method of incorporating the solid active phase layer on and / or in a substrate after polymerization reaction. Sorptive capacity testing was conducted by exposing the laminates to a gas mixture of about 15% CO2 with about 85% N2 for about 120 minutes. Wet oxidation testing was conducted by exposing the laminates to a gas mixture with 95% relative humidity at 90°C for about 4 days. After wet oxidation testing of the laminates 1 , 2, and 3 produced using the in-situ polymerization method retained about 88.6% to 89.9% of their original sorptive capacity, laminates 4, 5, and 6 produced using conventional methods retained about 39% to about 70.1 % of their original sorptive capacity. Fig. 5 illustrates the in-situ polymerization method advantageously increases the wet oxidation stability or performance of the sorbent.

Claims

CLAIMS:1 . A method for producing a laminate, the method comprising:(a) forming a precursor mixture having a monomer, a crosslinker, and an initiator;(b) incorporating the precursor mixture in and / or on a substrate;(c) polymerizing the precursor mixture and forming a polymer in and / or on the substrate, and(d) activating the polymer to produce the laminate.

2. The method of claim 1 , wherein the monomer is at least one of N- vinylformamide, N-vinyl acetamide, N-vinyl phthalimide, and N-vinylsuccinimide.

3. The method of claim 1 or 2, wherein the crosslinker is a chemical having multiple double-bonds with at least two double-bonds.

4. The method of any one of claims 1 to 3, wherein the initiator generates free radicals triggered by at least one of heat, an oxidative-reduction reaction, and light-induced decomposition.

5. The method of any one of claims 1 to 4, wherein the polymer can be a polymeric compound.

6. The method of any one of claims 1 to 5, further comprising during step (a) forming the precursor mixture having a pore-forming agent.

7. The method of claim 6, wherein the pore-forming agent is at least one of a solvent, silica particles, sugar, and a salt.

8. The method of any one of claims 1 to 7, further comprising during step (d) converting amide to amine.

9. The method of any one of claims 1 to 8, further comprising after step (d) functionalizing the polymer by epoxidation or alkylation.

10. The method of any one of claims 1 to 9, further comprising conducting the polymerization by at least one of at a temperature in a temperature range of 60°C to 160°C or exposing the precursor mixture to light.

11. A method for producing a contactor, the method comprising:(a) forming a precursor mixture having a monomer, a crosslinker, and an initiator;(b) incorporating the precursor mixture in and / or on a substrate;(c) polymerizing the precursor mixture and forming a polymer in and / or on the substrate, and(d) activating the polymer to produce a laminate, and(e) assembling a plurality of laminates to produce the contactor.

12. The method of claim 11 , wherein the monomer is at least one of N- vinylformamide, N-vinyl acetamide, N-vinyl phthalimide, and N-vinylsuccinimide.

13. The method of claim 11 or 12, wherein the crosslinker is a chemical having multiple double-bonds with at least two double-bonds.

14. The method of any one of claims 11 to 13, wherein the initiator generates free radicals triggered by at least one of heat, an oxidative-reduction reaction, and light-induced decomposition.

15. The method of any one of claims 11 to 14, wherein the polymer can be a polymeric compound.

16. The method of any one of claims 11 to 15, further comprising during step (a) forming the precursor mixture having a pore-forming agent.

17. A method for producing a contactor, the method comprising:(a) configuring at least one substrate to produce a substrate assembly;(b) forming a precursor mixture of a monomer, a crosslinker, and an initiator;(c) incorporating the precursor mixture in and / or on the substrate assembly;(d) polymerizing the precursor mixture and forming a polymer in and / or on the substrate assembly, and(e) activating the polymer to produce the contactor.

18. The method of claim 17, wherein the monomer is at least one of N- vinylformamide, N-vinyl acetamide, N-vinyl phthalimide, and N-vinylsuccinimide.

19. The method of claim 17 or 18, wherein the crosslinker is a chemical having multiple double-bonds with at least two double-bonds.

20. The method of any one of claims 17 to 19, wherein the initiator generates free radicals triggered by at least one of heat, an oxidative-reduction reaction, and light-induced decomposition.

21. The method of any one of claims 17 to 20, wherein the polymer can be a polymeric compound.

22. The method of any one of claims 17 to 21 , further comprising during step (a) forming the precursor mixture having a pore-forming agent.

23. The method of claim 22, wherein the pore-forming agent is at least one of a solvent, silica particles, sugar, and a salt.

24. The method of any one of claims 17 to 23, further comprising during step (d) converting amide to amine.

25. The method of any one of claims 17 to 24, further comprising after step (d) functionalizing the polymer by epoxidation or alkylation.

26. The method of any one of claims 17 to 25, further comprising conducting the polymerization by at least one of at a temperature in a temperature range of 60°C to 160°C or exposing the precursor mixture to light.

27. A contactor, the contactor comprising:(a) at least one substrate formed or assembled to produce a substrate assembly, the substrate assembly further comprising a plurality of passages, and(b) a polymer in and / or on the at least one substrate, wherein the polymer sets and / or bonds the at least one substrate in a ridged structure or a self-supported structure.

28. The contactor of claim 27, wherein the polymer is a polymeric compound.

29. The contactor of claim 27, wherein the polymer is at least one of a sorbent, a porous polymeric amine sorbent, an amine sorbent, and a PNP based sorbent.

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