Polymeric amine sorbents for gas separation using a humidity swing regeneration process.

Abstract

Polymeric amine solid sorbents with improved stability to moisture and / or oxygen for sorptive gas separation processes are disclosed. The polymeric amine solid sorbents can be supported on a porous support or incorporated into a solid porous polymer network. Sorptive gas separators can use contactors with such polymeric amine solid sorbents to separate components from multicomponent gas streams.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present invention generally relate to solid amine sorbents, sorption contactors, and methods for sorptive gas separation of multicomponent fluid streams using same. More particularly, embodiments of the present invention relate to polymeric amine sorbents supported on inorganic porous supports or incorporated into solid porous polymer networks having improved stability to moisture and / or oxygen and rapid carbon dioxide adsorption capacity, sorption contactors having polymeric amine sorbents, and methods for sorptive gas separation of acid gases from multicomponent fluid streams using same. [Background technology]

[0002] Adsorption separation processes are common in industrial separation processes and are being considered for use in applications to mitigate the adverse effects of greenhouse gas emissions and associated climate change. For example, adsorption gas separation processes can be used to separate carbon dioxide from multicomponent fluid streams such as air, flue gas, or process gas. The cost of an adsorption separation process is heavily influenced by the amount of sorbent required to produce a certain throughput of purified product. This throughput per mass of sorbent is a simple product of the adsorption cycle capacity and the adsorption cycle time. In adsorption gas separation processes using thermal swing or chemical swing desorption mechanisms, desorption of the adsorbed molecules or components can be a relatively slow process because desorption energy must be introduced into the system and effectively transferred to the sorbent.

[0003] During the regeneration step of the adsorption gas separation process, steam can optionally be admitted to the adsorption separator to directly heat the adsorbent material and / or to purge separated components from the adsorption separator. Water in the product stream can then be separated from the product stream by condensation, thus increasing the purity of the remaining stream.

[0004] Humidity swing induced desorption of target components can provide a rapid and efficient means of desorbing the adsorbed components while resulting in a product stream that can be further purified by condensation of gaseous water from the product stream. Advantages of humidity swings or relative humidity swings for desorption include: 1) rapid introduction of energy by using the heat of adsorption or condensation of moisture to distribute the heat energy relatively evenly throughout the porous sorbent, 2) water can be vented to the atmosphere if desired and is tolerated if not significantly polluted, and 3) adsorbents with significant water adsorption capacity are fairly common.

[0005] Disadvantages of exposing conventional sorbent materials to water and / or steam during adsorptive separation processes include: 1) strongly adsorbed water on the sorbent material can result in energy-intensive and slow drying of the sorbent material, resulting in slow or long process cycle times; 2) the sorbent material can degrade in the presence of water (e.g., polymeric amine sorbents can migrate due to partial solvation, displacing amines and resulting in loss of amines from the sorbent material; with metal-organic framework (MOF) sorbents, their structures can undergo phase transitions in the presence of steam, resulting in pore collapse and / or loss of selective adsorption capacity); and / or 3) the water stability attributes of the sorbent material are often inversely proportional to one or more desirable attributes (e.g., target component adsorption capacity and / or reaction kinetics).

[0006] Furthermore, conventional adsorption gas separators and processes typically use adsorbents having a single adsorbent material, and the regeneration step can include admitting steam to the adsorbent bed via an inlet, flowing the steam in contact with the adsorbent material of the adsorbent bed, desorbing the target components to form a product stream, and recovering the product stream from the adsorbent bed via an outlet or port.

[0007] Polymeric amines are desirable for some adsorptive gas separation applications due to their high affinity, selectivity, large adsorption capacity, and kinetics for capturing target components, such as carbon dioxide (referred to herein as "CO2"), compared to other adsorbents. However, polymeric amines with high primary and secondary amine content are typically water-soluble polymers, which poses challenges when they are used as solid sorbents in processes that expose them to high relative humidity, condensation, and / or water, as moisture tends to leach out of the amines. This shortcoming limits conventional solid sorbents containing such polymeric amines to applications where the adsorbent is exposed to dry or low relative humidity conditions, such as gas chromatography applications. Furthermore, polymeric amines with high primary and secondary amine content tend to have limited stability when exposed to oxygen at high temperatures.

[0008] Commercial adoption of adsorptive gas separation requires reduced life cycle costs and improved sorbent durability. Therefore, enhanced adsorptive gas separation processes and sorbents that have desirable selectivity, high adsorption capacity, fast kinetics, and high durability are desirable. Summary of the Invention

[0009] In embodiments, a solid sorbent is disclosed that includes a polymeric amine having an average molecular weight of greater than 2000 Daltons, the solid sorbent being insoluble in water, forming a porous network, and in the form of particles or films or sheets.

[0010] In a broad aspect, a sorptive gas separation process for separating a first component from a multicomponent fluid stream having at least a first component and a second component at a first concentration includes 1) providing a solid sorbent comprising a polymeric amine having an average molecular weight greater than 2000 Daltons to a sorptive gas contactor, the solid sorbent being insoluble in water, forming a porous network, and in the form of particles or a film or sheet; 2) flowing the multicomponent fluid stream through the sorptive gas contactor; 3) adsorbing at least a portion of the first component from the multicomponent fluid stream onto the solid sorbent; 4) forming a first product stream; and 5) adsorbing the first component onto the solid sorbent. 4) recovering a first product stream from the gas contactor, wherein a concentration of the first component in the first product stream is less than the first concentration of the first component in the multicomponent fluid stream; 5) desorbing at least a portion of the first component adsorbed on the solid sorbent to form a second product stream; and 6) recovering a second product stream from the sorption gas contactor, wherein the second product stream is enriched in the first component relative to the multicomponent fluid stream such that a concentration of the desorbed first component in the second product stream is greater than the first concentration of the first component in the multicomponent fluid stream.

[0011] In an embodiment, the disclosed solid sorbent can include at least a polymeric amine formed into a porous solid having a CO2 equilibrium capacity. In an embodiment, the solid sorbent can have a CO2 equilibrium capacity to heat capacity ratio of 15-40 cc stp CO2 / (J / K) (stp=standard temperature and pressure) per unit heat capacity of the solid sorbent, the equilibrium capacity being measured at 50°C under a 15% CO2 feed mixture. In an embodiment, the solid sorbent can have a kinetic adsorption rate greater than 0.03 mmol / g / s when in contact with a CO2 mixture comprising 15% CO2 and a temperature between 30°C and 50°C, and a heat of adsorption of CO2 of 70 kj / mol to 120 kj / mol of CO2 adsorbed.

[0012] In an embodiment, the disclosed sorption gas contactor can include a plurality of sorbent sheets, each sheet including a solid sorbent. In an embodiment, each sorbent sheet can have a thickness in the range of 0.1 mm to 3 mm, or preferably in the range of 0.2 mm to 1 mm. The plurality of sheets can be arranged to form passages therebetween and to allow or otherwise permit flow of a gas stream between and through the passages of the plurality of sheets and to contact the sorbent sheets. In an embodiment, each of the plurality of solid sorbent sheets can have a sorbency of 0.2 g / cm or less. 3 ~0.8g / cm 3 and can include polymeric amine polymers having greater than 5 weight percent nitrogen from primary or secondary amine functionality, where the polymeric amine can be formed as a copolymer from vinyl amine monomers having a molecular weight less than 100 Daltons and divinyl monomers having a molecular weight greater than 100 Daltons, or can be formed from the reaction of a water soluble polymeric amine with a long chain alkyl (8 carbons or more) group. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1a is a perspective view of a pair of sorbent sheets, each sheet having a planar shape and defining a passageway therebetween, forming a pair of sorbent sheets. FIG. 1b is a cross-sectional view of the sorbent sheet shown in FIG. 1a along section AA, which has a flat or planar cross-section. FIG. 1c is a cross-sectional view of a sorbent sheet having a square wave cross-section. FIG. 1d is a cross-sectional view of a sorbent sheet having a curved wave cross-section. FIG. 1e is a cross-sectional view of a sorbent sheet having a triangular wave cross-section. FIG. 1f is a cross-sectional view of a sorbent sheet having a sawtooth cross-section. FIG. 1g is a cross-sectional view of a sorbent sheet having a corrugated cross-section. [Diagram 2] FIG. 1 is a process flow diagram of one embodiment of a sorptive gas separation process using a polymeric amine sorbent or a polymeric amine composite sorbent to separate a first component from a multicomponent fluid stream. [Diagram 3]Figure 3a is a surface view of a scanning electron micrograph of a sorbent sheet from polyethyleneimine supported on porous silica at a magnification of 500x, Figure 3b is a surface view of a scanning electron micrograph of a sorbent sheet from polyethyleneimine supported on porous silica at a magnification of 10,000x, and Figure 3c is a cross-sectional view of a scanning electron micrograph of a sorbent sheet from polyethyleneimine supported on porous silica at a magnification of 5,000x. [Figure 4] 1 is a plot of particle size and distribution for copolymers of allylamine and divinylbenzene (DVB) sorbent of Example 6b, where the y-axis shows volume percentage and the x-axis shows particle size in micrometers. [Diagram 5] Figure 5a is a bar graph comparing two different sorbents and their oxidative stability after 1 cycle and 20 cycles after exposure to air at 120° C. for 1 hour, and Figure 5b is a bar graph showing four different sorbents and their hydrothermal stability after immersion of the sorbent powders in hot water. [Figure 6] Figure 6a is a scanning electron micrograph of the sorbent powder at 55,000x magnification, and Figure 6b is a scanning electron micrograph of a cross-section of the sorbent sheet from Example 8 showing the polymer particles and porosity at 55,000x magnification. [Figure 7] 1 is a plot of temperature and mass of a sorbent sheet specimen over time. The mass of the specimen is the solid plot and the temperature is the dashed plot. Mass and temperature are shown on the right and left y-axes, respectively, and time is shown on the x-axis. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] [Definition]: Adsorbent: A porous solid material capable of adsorbing molecules by chemisorption and / or physisorption on and / or within the adsorbent material.

[0015] The terms "sorbent," "adsorbent," and "absorbent" are used interchangeably herein.

[0016] The terms "sorption," "adsorption," and "absorption" are used interchangeably herein.

[0017] Resistant Sorbent: An adsorbent that meets or exceeds the definition of at least one of a steam-resistant sorbent, an oxidation-resistant sorbent, a nitrogen oxides (referred to herein as "NOx")-resistant sorbent, and / or a sulfur oxides (referred to herein as "SOx")-resistant sorbent.

[0018] Non-tolerant sorbent: A sorbent that does not meet or exceed the required definition for at least one of a steam-tolerant sorbent, an oxidation-resistant sorbent, a NOx-tolerant sorbent, and / or a SOx-tolerant sorbent.

[0019] Composite Sorbent: A sorbent comprising two or more adsorbent materials of different composition and / or different pore structure, e.g., at least one stable or resistant sorbent and at least one unstable or intolerant sorbent, combined to form a sorbent mixture in which the two or more sorbent materials can be substantially uniformly or non-uniformly distributed within the sorbent mixture.

[0020] Sorbent Sheet: A free-standing sheet, active layer, or laminate having a thickness between 0.1 and 3.0 millimeters and at least one other dimension being 100 times the thickness. The sorbent sheet can be cut into ribbons where the ribbon width is at least 10 times the sheet thickness.

[0021] Sorbent foam or formed composite sorbent: a solid object comprising at least one sorbent foam, e.g., an agglomerated powder formed with or without a binder or sorbent support into objects of at least 1 millimeter size or greater, such as pellets, beads, irregular particles, ribbons, rings, sheet segments, etc., which can be used in a contactor vessel or column or sorbent contactor and provide a passageway for a process fluid.

[0022] Supported composite sorbent: A composite sorbent on a sorbent support such as a sorbent sheet.

[0023] Steam-Stable Adsorbent: A porous solid material capable of maintaining less than a 10% loss in adsorption capacity, adsorption energetics, and adsorption kinetics after exposure to conditions of >95% relative humidity (herein referred to as "RH") at temperatures between 80 degrees Celsius (herein referred to as "°C") and 120°C for more than 100 hours (herein referred to as "h").

[0024] Steam-labile adsorbent: A porous solid material that exhibits greater than a 10% loss in adsorption capacity, adsorption energetics, and adsorption kinetics after exposure to temperatures between 80°C and 120°C for more than 100 hours and conditions greater than 95% RH.

[0025] Steam resistance: Able to maintain less than 10% loss in adsorption capacity, adsorption energetics, and / or adsorption kinetics after exposure to steam conditions at temperatures between 80°C and 120°C for more than 100 hours and greater than 95% relative humidity.

[0026] Oxidation resistance: capable of maintaining less than 10% loss in adsorption capacity, adsorption energetics and / or adsorption kinetics after exposure to air at a temperature of about 110° C. for more than 4 hours.

[0027] Target Cycle Capacity: The amount of desired target component captured during a separation cycle under steady-state operation per unit mass of sorbent.

[0028] Cycle Capacity: The amount of target component purified or extracted from a product stream during an adsorption-desorption separation cycle per unit mass of sorbent.

[0029] Heat Capacity (referred to herein as "Cp"): The heat capacity of the sorbent or sorbent mixture, its support, and other inert components that are in thermal contact with each other in the sorbent contactor.

[0030] Heat of Adsorption: The amount of energy released by taking a molecule from the gas phase and attaching it to a solid or supported liquid.

[0031] Water Sorbent Material: A porous solid material that may experience a weight gain of more than 5% when exposed to conditions exceeding 60% RH.

[0032] Target Compound Adsorbent Material: A porous solid material that can experience a weight gain of greater than 1% when exposed to conditions in which the feed gas stream or feed mixture is at temperatures between -10°C and 80°C.

[0033] Thickness: the smallest dimension of a three-dimensional object, for sheet-shaped materials, measured in a direction perpendicular to the plane of the sheet; for a sphere, it is the diameter of the sphere; for a ring, it is the difference between the outer and inner radii of the ring; for irregular particles, it is the shortest distance of a line passing from one side of the object through the other side of the object and through the center of mass of the object.

[0034] PEI: Polyethyleneimine having repeating units of iminoethylene arranged in a linear or branched configuration or [CH2CH2NH] n Polymer. Linear PEI contains all secondary amines, while branched PEI can contain primary, secondary and tertiary amine groups.

[0035] PAA: Polyallylamine or [CH2CHCH2NH2] n

[0036] Domain: A fragment of a molecule or polymer that can be considered separate from the rest of the molecule or polymer from a solubility standpoint.

[0037] Passage porosity: The porosity of the passages formed by the sorbent sheet or sorbent foam in a contactor. Passage porosity can be used interchangeably with the term channel porosity.

[0038] Particle: A piece of material having a volume of 1 cubic millimeter or less.

[0039] Particle Size: The dimension of a solid particle, defined when not specified as the equivalent diameter of a sphere of the same volume as the particle.

[0040] Film: A thin layer of material deposited on a carrier or material near the surface of a sheet of material.

[0041] Sheet: An object in which one dimension is much smaller than the other two dimensions, giving the object the appearance of a two-dimensional object or surface. As used in some embodiments described herein, a solid object is called a sheet if its smaller dimension, defined as the shortest distance between two points on either side of the object, is on average less than 1% of the length of any line following the object's surface connecting two opposing edges of the object.

[0042] Ribbon: an object with one dimension much smaller than the other two dimensions and with a large difference in the length of the object relative to the other two dimensions. A ribbon can be obtained by cutting a sheet into narrow strips. As used in some embodiments described herein, a ribbon has a flattened width that is at least 20 times smaller than the flattened length and a thickness that is less than 1% of the flattened length of the object. The ribbon can be bent, warped, pleated, or corrugated, for example, to aid in the formation of flow channels when assembled into a contactor.

[0043] Insoluble: Less than 100 ppm by weight of solid material when dissolved in an aqueous solution of pH 5-9 at temperatures between 10°C and 40°C in a suspension containing 1% solids per solvent.

[0044] Generally, a porous sorbent structure is disclosed. In an embodiment, the porous sorbent structure can include polymeric amine sorbent sites, optionally supported on an inorganic porous support or incorporated into a porous polymer network. In an embodiment, such a sorbent structure can be advantageously used in a sorptive gas separation process. More specifically, the composition and structure of such a sorbent structure can be used in a process for separating acid gases from a multicomponent fluid stream (e.g., a combustion gas stream, a flue gas stream, a process gas stream, an air stream, or other dilution source) during a sorptive gas separation process, in which the polymeric amine sorbent is exposed to at least one process gas stream (e.g., a feed stream and / or a regeneration gas stream) having a high relative humidity, e.g., a relative humidity of greater than about 30%.

[0045] The mediating effects of exposure of a polymeric amine sorbent to high relative humidity during at least a portion of a separation process cycle, which can lead to significant amounts of liquid water being adsorbed or filling a portion of the sorbent pores, are discussed.

[0046] Described herein are novel polymeric amine sorbents that have high adsorption capacity for at least one component and high stability and / or resistance to moisture, oxygen (referred to herein as "O"), and carbon dioxide (hereinafter "CO"), in some embodiments, such polymeric amine sorbents may be supported on a support material having a high pore volume.

[0047] Polymeric amines having high primary and secondary amine content are typically water-soluble polymers that are known to migrate or leach from the sorbent support and / or sorption contactor when exposed to high relative humidity. As described herein, chemical modification of the amine polymers can be used to modify the polarity of the polymeric amines, reduce the tendency of the amines to leach, and / or immobilize the amines within the porous solid support.

[0048] The use of known supported polymeric amine sorbents has generally been limited to applications where the sorbent is exposed only to dry or low relative humidity conditions and / or is protected from exposure to high relative humidity or water, such as in gas chromatography applications. As new applications for the separation of multi-component gas mixtures containing water and / or sorption processes using steam or hot water for regeneration develop, a need has been identified to develop more stable and robust sorbents.

[0049] Also disclosed are copolymerized amine monomers with large rigid copolymers that promote the formation of porous network structures that exhibit similar advantages in acid gas removal under wet conditions.

[0050] Described herein are preferred macroscopic arrangements of two-dimensionally structured polymeric amine sorbents that are used to build practical contactors with reduced flow resistance and improved acid gas recovery.

[0051] One aspect of the sorbent is the macroscopic or three-dimensional structure of the sorbent, which in some embodiments can exhibit a porous network morphology including a primary pore network having interconnected primary pores and a secondary pore network having interconnected secondary pores, the primary pore network being interconnected with the secondary pore network. In some embodiments, the primary pores have an average diameter in the range of about 1 micrometer to about 30 micrometers, and the secondary pores have an average pore diameter in the range of about 10 to about 200 nanometers.

[0052] Some enhanced rapid cycle sorption gas separation processes use a humidity swing desorption mechanism to regenerate a solid sorbent. Such sorption gas separation processes can be used to separate undesirable components, such as CO2, from gas mixtures to help address the challenges of greenhouse gas (GHG) emissions and associated climate change. Examples of such processes are described in WO 2017 / 165974.

[0053] Polymeric sorbents are desirable that have a high cycling capacity for adsorption and desorption of target molecules, as well as desirable chemical and structural stability of the active components when exposed to the process environment, maintaining both the functionality of the active sites and easy kinetic access to those sites.

[0054] The durability of the sorbent material to cyclic exposure to high relative humidity, condensation, water, and / or oxygen is important in several applications such as those disclosed above. Described herein are embodiments of polymeric amine sorbents with stable active adsorption sites within their porous structure where target gas components can be readily introduced and separated.

[0055] [Embodiment] In embodiments, the solid polymeric amine sorbent may have an average molecular weight greater than about 2000 Daltons, be insoluble in water, and be configured as a particle or film with a porous network. In embodiments, the solid polymeric amine sorbent may include a first sorbent domain (soluble domain) that is soluble in water and a second sorbent domain (insoluble domain) that is insoluble in water. In embodiments, the solid polymeric amine sorbent may also have a mass fraction of nitrogen greater than about 6% relative to the total mass of the polymer. In other embodiments, the solid polymeric amine sorbent may contain primary, secondary, and tertiary amine groups. In some embodiments, the tertiary amine groups represent less than about 20% mole fraction of nitrogen in the polymeric amine sorbent. In some embodiments, the primary and secondary amine groups represent more than about 80% mole fraction of nitrogen in the polymeric amine sorbent. In some embodiments, the solid polymeric amine sorbent may have an average pore volume greater than about 0.2 ml / g, or preferably within an average pore volume range of about 0.3 ml / g to about 1.5 ml / g. In an embodiment, the solid polymeric amine sorbent is about 4 m 2 / g~about 500m 2 / g, or more preferably about 20m 2 / g~about 300m 2The polymer may have an average BET (Brunauer, Emmett and Teller) surface area in the range of 100 nm / g, where the surface area is measured using, for example, a BET technique with liquid nitrogen.

[0056] In embodiments, the solid polymeric amine sorbent can have an average pore size in the range of about 10 to about 200 nanometers, as measured, for example, using a nitrogen adsorption isotherm. In some embodiments, the solid polymeric amine sorbent is in the form of particles having an average particle size in the particle size range of about 0.2 to about 40 micrometers. In some embodiments, the solid polymeric amine sorbents described herein can be unsupported to form a porous solid sorbent, or the sorbent can be configured on and / or in an inorganic porous support. In some embodiments, the polymeric amine sorbents described herein can be formed into a self-supported active layer comprising at least about 75 wt.% of the polymeric amine sorbent, the active layer having a thickness in the range of about 0.1 mm to about 3 mm, or in particular about 0.2 mm to about 1 mm.

[0057] In embodiments, the solid polymeric amine sorbent can be configured into a sorbent layer or other sorbent foam having a porous network geometry combining a primary pore network of interconnected primary pores that are also interconnected to a secondary pore network. In certain embodiments, the primary pore network has an average primary pore diameter range of about 1 micrometer to about 30 micrometers, and the secondary pore network has an average diameter range of about 10 nanometers to about 200 nanometers.

[0058] Such sorbent structures can be formed from porous particles having an average pore size of about 10 nanometers to about 200 nanometers and an average particle size in the range of about 0.2 micrometers to about 40 micrometers. During the manufacture of a sorbent layer or other sorbent foam, imperfect stacking of particles (which may be irregularly shaped) can form a network of pores between the particles having an average primary pore diameter in the average primary pore diameter range of about 1 micrometer to about 30 micrometers.

[0059] This hierarchy of interconnected pores can facilitate rapid exchange of gas between the sorbent and the process stream.

[0060] In embodiments, the solid polymeric amine composite sorbent may be a polymeric amine composite sorbent having an average molecular weight greater than about 2000 Daltons, insoluble in water, and configured into particles or films containing a porous network. In embodiments, the polymeric amine composite sorbent may include a first sorbent domain (soluble domain) that is soluble in water and a second sorbent domain (insoluble domain) that is insoluble in water. In some embodiments, the solid polymeric amine composite sorbent has a mass fraction of nitrogen greater than about 6% relative to the total polymer mass. In embodiments, the solid polymeric amine composite sorbent contains primary, secondary, and tertiary amine groups. In some embodiments, the tertiary amine groups represent less than about 20% mole fraction of nitrogen in the polymeric amine composite sorbent. In some embodiments, the primary amine and secondary amine groups represent more than about 80% mole fraction of nitrogen in the polymeric amine composite sorbent.

[0061] In an embodiment, the polymeric amine composite sorbent is 10 ~C 16 The functionalized polymer may include polyethyleneimine having a molecular weight of 2,000 to 12,000 daltons that reacts with a molecule containing an alkyl end chain and an electrophilic group capable of bonding to a primary or secondary amine to form a functionalized polymer. In an embodiment, the functionalized polymer has an average pore volume of 0.3 to 1.5 ml / g, an average pore volume of about 4 m 2 / g~about 500m 2 / g, or more preferably about 20m 2 / g~300m 2 The catalyst is deposited on a porous support having an average BET surface area in the range of 100 nm / g and an average pore diameter in the range of about 10 to 200 nanometers. Examples of such porous support materials include silica, alumina, zirconia, clays, aluminosilicates, their analogs and combinations thereof, so long as the pore size is sufficiently large, e.g., greater than 10 nm. The surface area can be measured using the BET technique with liquid nitrogen.

[0062] In embodiments, the polymeric amine composite sorbent composite can further include ethoxide. The solid composite sorbent can be unsupported or configured on and / or in an inorganic porous support. In embodiments of the polymeric amine composite sorbent, the polymeric amine can be at least one of a copolymer of vinyl amine and divinyl monomer containing primary and / or secondary amine groups having an interconnected porous structure.

[0063] In embodiments, the polymeric amine is a grafted alkylamine supported on a porous support, the porous support having an average pore volume of from about 0.3 ml / g to about 1.5 ml / g, or preferably from about 0.7 ml / g to about 1.5 ml / g, and the grafted functional group on the amine group comprises a hydrophobic group; C 10 ~C 16 Polyethylenimine functionalized with an alkyl alcohol and supported on a porous organic or inorganic solid support, and / or Functionalized polyethylenimines by reaction with alkyl epoxides At least one of the following is true:

[0064] The porous network polymeric amine composite sorbent can be formed into a self-supported active layer comprising at least about 75 wt. % of the polymeric amine composite sorbent, the active layer having a thickness ranging from about 0.1 mm to about 3 mm, or in particular from about 0.2 mm to about 1 mm.

[0065] In an embodiment, the polymeric amine composite sorbent can include a copolymer of vinylamine and a divinyl monomer having primary and / or secondary amine groups and an interconnected porous structure. In an embodiment, the polymeric amine composite sorbent includes a copolymer of allylamine and divinylbenzene (DVB).

[0066] In an embodiment, the polymeric amine composite sorbent may include copolymers of propyleneimine and divinylbenzene, and / or copolymers of ethyleneimine and divinylbenzene.

[0067] In embodiments, the above composite sorbents can be synthesized by controlling the reaction stoichiometry of electrophilic long-chain alkane-terminated reagents and PEI, reaction temperature and solvent composition. In embodiments, during the synthesis of poorly water-soluble PEI polymer derivatives or polymeric amine composite sorbents, the percentage of primary or secondary amines reacted with electrophilic molecules can be greater than about 5% and less than about 40%.

[0068] The resulting sorbents and composite sorbent examples exhibited CO2 adsorption capacities greater than 80% of the native PEI polymer under the same conditions, as described in more detail below. Briefly, however, Examples 1 and 2 provide the CO2 adsorption capacities of the sorbent powder and sorbent sheet, and demonstrate a reduction in CO2 capacity of less than 15% when the sorbent powder is incorporated into the sorbent sheet. This difference can be explained by the addition of non-CO2 adsorbing mass to the sorbent sheet composite.

[0069] Example 3 shows that the alkyl chain of the alkyl epoxide functionalizing agent must be long enough to prevent loss of CO2 capacity of the composite after immersion in pure water. Similarly, a minimum molecular weight of polyethyleneimine is necessary to prevent measurable leaching of the amine-containing polymer outside the silica support. Under cyclic adsorption / desorption conditions for CO2 separation using fast cycles with steam regeneration, filling of large membranes or pores with water typically does not occur, but slow migration of amines was observed in sorbent compositions that failed the liquid water exposure test. Three 1000-hour [or approximately 50,000 adsorption / desorption cycles] tests were performed using contactors made from PEI 2K-no epoxidation, PEI-2K-C4-epoxyalkyl functionalized, and PEI10K-C12-epoxyalkyl functionalized, respectively. The results of these tests correlated with the results in the pass / fail table shown in Example 3.

[0070] The sorption capacity of the composite sorbent is typically greater than about 2 mmol / g under typical input gas operating conditions and exposed to a stream containing 15% CO2 in nitrogen at 50°C. Furthermore, the disclosed composite sorbent also exhibits fast adsorption kinetics, as derived from the weight gain slope of the TGA data, with an initial adsorption rate of greater than about 0.03 mmol / g / s when exposed to 15% CO2 in nitrogen at 50°C, with an average sorbent particle size of less than 30 micrometers. Within the sorbent contactor, sorbent sheets exposed to high fluxes of CO2 per gram of sorbent exhibit similar magnitudes in terms of their average rates, as shown by the productivity rates in Examples 5 and 11. However, the local kinetic rates of CO2 adsorption are at least an order of magnitude faster compared to the global kinetic rates limited by the feed CO2 flux.

[0071] An example of a sorbent sheet comprised of a composite sorbent containing greater than about 75 wt. % amine-containing sorbent particles having an average particle size ranging from about 0.2 to about 40 micrometers as described herein demonstrated fast CO2 adsorption rates similar to a thin layer of free powder. Figures 3a and 6b show scanning electron micrographs of sorbent sheets using two different types of amine sorbent powders where the predominant material in the sheet was the sorbent powder.

[0072] In embodiments, the polymeric amine sorbents and polymeric amine composite sorbents have a CO equilibrium capacity at 50° C. under a 15% CO feed mixture of 15-40 cc CO / (J / K) per unit heat capacity of the sorbent and a kinetic adsorption rate of greater than about 0.03 mmol / g / s when the sorbent (regenerated and ready for adsorption) is in contact with a 15% CO mixture at a temperature of 30° C. to 50° C.

[0073] Examples 2 and 8 show sorbent sheets made from two different sorbent materials containing amine polymers. The heat capacity (Cp) of the sorbent sheets shown in Examples 2 and 8 is between 1.7 and 2 J / gK, resulting in a CO2 volume / (J / K) sorbent sheet heat capacity of over 15 cc. This ratio strongly influences the amount of energy used to regenerate the sorbent when desorbing CO2. A larger ratio improves the economics of the process when other parameters are unchanged.

[0074] In an embodiment, the polymeric amine composite sorbent adsorbs CO2 with a CO2 heat of adsorption of 70 kj / mol to 120 kj / mol.

[0075] The CO2 heat of adsorption also impacts the energy cost of regenerating the sorbent. Lower heats of adsorption are preferred, but selective adsorption of CO2 requires a sufficient thermodynamic drive to remove CO2 from low CO2 partial pressure feeds.

[0076] In some embodiments, less than 10% of the adsorption capacity of the polymeric amine composite sorbent is lost after 50,000 cycles of operation, which includes a regeneration step under high temperature and humid conditions, for example, at temperatures between 90° C. and 130° C. and relative humidity in the range of 50% to 100%.

[0077] In some embodiments, the functional amine groups form greater than about 50% of the amine groups present in the amine polymer, and the functional amine groups are R1-CH2-NH2 R1-C2H4-NH2 R1-COR2-CH2-NH2 R1-NH-R2 R1-NH-CH2-COR2 may include at least one of wherein R1 and R2 are one of hydrogen, a polyamine, a copolymer of vinylamine and a rigid divinyl spacer group, an alkane, or a 10-16 carbon linear alkane chain.

[0078] In some embodiments, the polymeric amine sorbents can be formed as copolymers from short vinylamine monomers (having a molecular weight less than 100 Daltons) reacted with longer divinyl monomers (having a molecular weight greater than 100 Daltons).

[0079] A measure of the process intensity of a sorbent system can be expressed as metric tons per day of gas component captured from a gas mixture per metric ton of sorbent (referred to herein as "TPD / MT"). Important parameters that affect process intensity include the capacity and kinetics of the sorbent. Sorbents with high adsorption capacity and fast kinetics are typically desirable to increase process intensity. Examples of the productivity of two different sorbent contactors operating under fast cycling conditions are provided in Examples 5 and 11 described below.

[0080] In embodiments, contactors containing sheets of the novel sorbent, polymeric amine sorbent, or polymeric amine composite sorbent have demonstrated process intensities of over 30 metric tons of CO captured per day from a 10% CO concentration gas mixture per metric ton of sorbent when cycled between adsorption and desorption steps in less than 2 minutes.

[0081] [Sorbent sheet or foam and separator or contactor] An embodiment of the present invention includes a sorption contactor having a solid sorbent, particularly a polymeric amine sorbent, more particularly a polymeric amine composite sorbent, for separating components from a multi-component gas stream in the sorption contactor. The sorption contactor can include a plurality of sorbent sheets or sorbent foams stacked or arranged adjacent to each other. In one embodiment, the sorption contactor is a stack of a plurality of sorbent sheets arranged on top of each other, with at least one passageway formed between two adjacent stacked sorbent sheets or a pair of sorbent sheets, allowing a fluid to flow through the at least one passageway and thus through the contactor, where the fluid contacts the sorbent sheet or sorbent foam. Each sorbent sheet or sorbent foam can include a solid sorbent, such as the polymeric amine sorbent or polymeric amine composite sorbent described above. In an embodiment, at least 75% by weight of the sorbent in the sorbent sheet or sorbent foam is derived from a polymeric amine sorbent or polymeric amine composite sorbent, and the sorbent sheet or sorbent foam has a thickness ranging from about 0.1 mm to about 3 mm, or preferably from about 0.2 mm to about 1 mm. In an embodiment, the polymeric amine has greater than about 5% by weight of nitrogen from primary or secondary amine functional groups, based on the weight of the polymer. In an embodiment, each sorbent sheet or sorbent foam has a thickness of about 0.2 g / cm. 3 ~about 0.8g / cm 3 The density can range from 0.01 to 0.01.

[0082] In embodiments, the polymeric amine composite sorbent can be formed as a copolymer from short vinylamine monomers (having a molecular weight less than 100 Daltons) reacted with longer divinyl monomers (having a molecular weight greater than 100 Daltons).

[0083] In embodiments, the polymeric amine can be formed from the reaction of a water-soluble polymeric amine having a molecular weight greater than 2000 Daltons with a long chain alkyl (8 or more carbon atoms) ligand.

[0084] Referring to FIG. 1a, an exemplary set of sorbent foams or two sorbent sheets 12, which may include a polymeric amine sorbent or a polymeric amine composite sorbent, are shown stacked adjacent to (or on top of) each other to form voids or passages 14 therebetween to allow fluid to flow through the passages 14 and between and in contact with each of the sheets 12. Arrows 16 indicate the direction of flow of fluid, e.g., a feed stream, in the passages 14. The illustrated sorbent sheet 12 may be configured as a substantially flat plane, a flat sheet, or a foam in a planar configuration. Cross section AA of the sorbent sheet 12 is shown in FIG. 1b as a sheet cross section 20 (not shown to scale or aspect ratio relative to the sorbent sheet 12) having a thickness 22 of the sorbent foam or sorbent sheet. In an alternative configuration, the sorbent sheet or sorbent foam may have a thickness 22 and be non-planar. For example, the sheets may be configured to have alternative cross-sectional shapes, such as those shown in Figure 1c, such as a square wave 30 cross-section in Figure 1d, a curved or sinusoidal wave 31 cross-section, a triangular or delta wave 32 cross-section as shown in Figure 1e, a sawtooth or sawtooth wave 32 cross-section as shown in Figure 1f, or a corrugated or wavy 34 cross-section laminated with alternating flat and corrugated sheets as shown in Figure 1g. The thickness of the sorbent foam or sorbent sheet can be calculated by dividing the volume by the area of ​​the sorbent foam or sorbent sheet. The size, shape, and aspect ratio of the cross-section can be selectively configured to suit a particular application.

[0085] In an embodiment, the sorption contactor may have an enclosure or housing for substantially enclosing the plurality of sorbent sheets or sorbent foams and at least one passageway. The enclosure or housing may have at least one inlet port fluidly connected to the at least one passageway for entering the gas or fluid stream into the sorption contactor and at least one outlet port fluidly connected to the at least one passageway for withdrawing or discharging the product stream from the sorption contactor. In an embodiment, the sorption contactor may be comprised of a plurality of sorbent sheets or sorbent foams stacked together to form a repeatable stackable element having at least one passageway between the sorbent sheets or foams. In an embodiment, there may be passageways between the sorbent sheets or foams to form a plurality of passageways in the sorption contactor. In an embodiment, the plurality of passageways are substantially parallel to each other. In an embodiment, the plurality of passageways may not be substantially parallel to each other.

[0086] In an embodiment, the sorption contactor can have one or more spacers to create and / or maintain at least one passage between the sorbent sheets or sorbent foams. The spacers can be separate components disposed between each of a pair of sorbent sheets. In an embodiment, some of the sorbent sheets or sorbent foams can have features or protrusions thereon or can have cross-sectional geometries or shapes that are non-planar to function in a substantially similar manner as one or more spacers, for example as shown in Figures 1c-1g. That is, to create and / or maintain spacing between each of the sorbent sheets and at least one passage.

[0087] The protrusions can be made of a protrusion material that is substantially the same as the material of the sorbent sheet or sorbent foam, for example, the sorbent sheet can be embossed.

[0088] The sorption contactor can have one or more sorbent sheets or foams, which can be formed or comprised of at least one of a flat sheet, a pleated sheet, or a corrugated sheet.

[0089] A spacer, which is a separate component and made of a different material than the sorbent sheet or foam, can be attached to at least one sorbent sheet or foam or can be placed between the sorbent sheets or foams during assembly of the sorption contactor. The sorption contactor can include a sorbent sheet or sorbent foam with a spacer printed on the sorbent sheet or foam.

[0090] In embodiments, the sorption contactor can have a passage porosity (one or more passages created by the sorbent sheet or sorbent foam within the sorbent contactor, also known as "channel porosity") ranging from about 20% to about 80% porosity, or preferably from about 30% to about 75% porosity.

[0091] In embodiments, the sorbent sheets or sorbent foams included in the sorbent contactors disclosed herein comprise a porous network geometry having a primary pore network of interconnected primary pores that are also interconnected to a secondary pore network, the primary pore network having an average pore diameter ranging from about 1 micrometer to about 30 micrometers, and the secondary pore network having an average pore diameter range from about 10 nanometers to about 200 nanometers.

[0092] Such pore structures can be obtained by forming sorbent sheets or foams from porous particles of the compositions disclosed herein having an average particle size ranging from about 0.2 micrometers to about 40 micrometers.

[0093] During the fabrication of the sorbent bed, incomplete stacking of irregularly shaped particles can result in the formation of a network of pores between the particles having primary pore diameters having an average diameter range of about 1 micrometer to about 30 micrometers.

[0094] This hierarchy of interconnected pores can facilitate rapid exchange of gas between the sorbent layer and the process stream in the passages between the sorbent layers or sorbent foam.

[0095] In an embodiment, the adsorption separator can include at least one sorption contactor as described above. In certain embodiments, the adsorption separator can have an enclosure or housing for substantially enclosing the at least one sorption contactor or multiple sorption contactors, the enclosure or housing having at least one inlet port fluidly connected to at least one passage of the sorption contactor for entering the gas or fluid stream into the adsorption separator and the sorption contactor, and at least one outlet port fluidly connected to at least one passage of the sorption contactor for withdrawing or discharging a product stream from the sorption contactor and the adsorption separator.

[0096] An embodiment of the present invention can include a sorbent bed having a solid sorbent, particularly a polymeric amine sorbent, more particularly a polymeric amine composite sorbent, for separating multi-component gas streams. The sorbent bed can include a vessel, an inlet port on the vessel, an outlet port on the vessel, and a plurality of sorbent pellets including a solid sorbent, for example, a polymeric amine sorbent or a polymeric amine composite sorbent, as described herein. The polymeric amine sorbent or polymeric amine composite sorbent can be configured on and / or in a sorbent support. The sorbent bed can be a fixed bed or a fluidized bed.

[0097] [Solid sorbent use process] Solid sorbents, such as polymeric amine sorbents or solid sorbent compositions having different sorption and / or adsorption properties disclosed herein, can be used for the purpose of separating a first component (e.g., acid gas, carbon dioxide, nitrogen oxides, and / or sulfur oxides) from a multi-component gas stream for industrial or practical hazardous effluent reduction, and to provide a concentrated stream of an acid gas component, such as CO, that can be further utilized for sequestration or other industrial uses.

[0098] In embodiments, sorbent separators, sorbent beds and / or sorbent contactors comprising polymeric amine sorbents and / or polymeric amine composite sorbents having different sorbent and adsorption properties can be used in an adsorption process to separate a first component from a multi-component gas stream.

[0099] In an embodiment, a sorption gas separation process is provided for the sorption gas separation of a multi-component fluid stream comprising at least a first component (which may include, for example, carbon dioxide, nitrogen oxides, and / or sulfur oxides) and a second component. In one such embodiment, the sorption process is capable of separating at least a portion of the first component from the multi-component fluid stream.

[0100] FIG. 2 illustrates one embodiment of a sorptive gas separation process 100 for separating a multi-component fluid stream including at least a first component and a second component.

[0101] As shown in Figure 2, a first step 101 includes providing a sorption gas contactor having at least a polymeric amine sorbent and / or a polymeric amine composite sorbent as described herein. The process 100 uses a sorption gas contactor including a plurality of sorbent sheets or sorbent foams stacked together to form passages between each pair of adjacently stacked sorbent sheets or sorbent foams and to form one or more channels or passages for allowing fluid to flow through the contactor, as described herein. In an embodiment, a plurality of spacers may be placed or otherwise disposed between each of the plurality of sorbent sheets to form passages therebetween.

[0102] In embodiments, the sorption gas contactor can have a plurality of sorbent sheets or forms, each of the plurality of sorbent sheets forming passageways with adjacent sorbent sheets. In embodiments, each of the sorbent sheets can have the polymeric amine sorbent and / or polymeric amine composite sorbent described above. In embodiments, at least 75% by weight of the sorbent on the sorbent sheet or form is the polymeric amine sorbent or polymeric amine composite sorbent. In some embodiments, the sorbent sheet or form has a thickness ranging from about 0.1 mm to about 3 mm, or preferably from about 0.2 mm to about 1 mm, and a density of about 0.2 g / cm. 3 ~about 0.8g / cm 3 An example of the thickness of the sorbent sheet is shown in FIG.

[0103] A multicomponent gas stream (e.g., a combustion gas stream, a flue gas stream, a process gas stream, an acid gas stream, or an air stream) having at least a first component (e.g., carbon dioxide, oxides of sulfur, or oxides of nitrogen) and a second component (e.g., nitrogen) can be used as a feed stream and enter the contactor during the adsorption step 110. In an embodiment, the multicomponent gas stream can also include moisture. As the multicomponent gas stream flows through the contactor, the multicomponent gas stream contacts the polymeric amine sorbent and / or the polymeric amine composite sorbent and at least a portion of the first component of the multicomponent gas stream is adsorbed in and / or on the sorbent. In an embodiment, the multicomponent gas stream can enter and / or contact the polymeric amine sorbent and / or the polymeric amine composite sorbent at a pressure of about 1 bar absolute to about 2 bar absolute. In an embodiment, the feed stream can enter the contactor at a temperature of about 10°C to about 90°C. Although not specifically shown, the remaining components of the multicomponent stream, or components not adsorbed in and / or on the sorbent material, e.g., a second component such as nitrogen, flows through the contactor and exits the contactor in the form of a first product stream and is recovered.

[0104] In some embodiments, during the adsorption step 110, the polymeric amine sorbent and / or polymeric amine composite sorbent may be exposed to a first relative humidity that may be about 20% relative humidity (RH) or greater. In embodiments, this RH may be measured in the sorbent sheet or foam, particularly within the pore volume of the sorbent sheet or foam when the gas and sorbent within the pores are approximately in thermal equilibrium.

[0105] Thermal equilibrium may be defined, for example, as when the temperature of the gas within the pores and the temperature of the sorbent are at a temperature difference of about 2 degrees Kelvin or less.

[0106] In an embodiment, the polymeric amine sorbent and / or polymeric amine composite sorbent and / or the contactor are at the adsorption temperature during the adsorption step 110. The adsorption step 110 can be terminated and a subsequent step, such as a regeneration step 111, can be initiated before or when the polymeric amine sorbent or polymeric amine composite sorbent reaches a predetermined adsorption capacity and / or before or during breakthrough of the first component in the first product stream.

[0107] In embodiments, the first product stream is at least periodically depleted in a first component relative to the feed stream and also includes a second component, such as nitrogen. In some embodiments, the first product stream is also enriched in the second component relative to the feed stream. In embodiments, the first product stream is recovered from the contactor during a regeneration step.

[0108] During the regeneration step 111, at least a portion of the first component adsorbed in and / or on the polymeric amine sorbent and / or polymeric amine composite sorbent can be desorbed by at least one of a temperature swing mechanism and a partial pressure swing mechanism to form a second product stream. In an embodiment, during the regeneration step 111, the polymeric amine sorbent and / or polymeric amine composite sorbent is exposed to and / or contacted with a regeneration stream that increases the relative humidity in the contactor to a second relative humidity that is greater than or equal to the first relative humidity. In an embodiment, the second relative humidity is greater than the first relative humidity or about 20% relative humidity measured within the pores of the sorbent when the gas and sorbent within the pores are in near thermal equilibrium, e.g., when the temperature of the gas and the temperature of the sorbent within the pores are at a temperature difference of about 2 degrees Kelvin or less.

[0109] During the regeneration step 111, the polymeric amine sorbent and / or polymeric amine composite sorbent and / or contactor are allowed to reach a regeneration temperature, which is higher than the adsorption temperature.

[0110] In an embodiment, a first regeneration stream containing a third component, e.g., water or steam, can be flowed into the contactor, contacted with the polymeric amine sorbent and / or the polymeric amine composite sorbent, and flowed through the contactor. The first regeneration stream can be actively or passively controlled to have a partial vapor pressure of about 0.3 bar absolute or greater, and / or can enter the contactor with a partial vapor pressure of about 0.3 bar absolute or greater. As a result, at least a portion of the first regeneration stream or the third component can be adsorbed in and / or on the sorbent, generating a heat of adsorption. This heat of adsorption is the result of, for example, a phase change undergone by water from a gas phase (e.g., steam) to a liquid phase (e.g., liquid water) or to an adsorbed state on the surface of a solid (physisorption).

[0111] In an embodiment, the first recycle stream consists primarily of steam. This is a preferred embodiment in applications and / or processes where it is desirable to separate and recover a product stream containing a first component, e.g., an acid gas or CO2, in high purity. In other embodiments, the first recycle stream comprises a mixture of steam and the first component, e.g., an acid gas component such as CO2.

[0112] In one embodiment, the regeneration stream is a steam stream at a pressure between 30 kPa and 120 kPa absolute and a temperature between 60°C and 110°C.

[0113] The structure formed from the porous thin sheets with porous solid sorbent material that is stable to steam and liquid water enables a rapid adsorption / desorption process for separating CO2 from other CO2-containing gases, including flue gas or ambient air, i.e., Direct Air Capture (DAC). Examples 5 and 11 are provided below to illustrate the demonstrated rapid adsorption / desorption kinetic capabilities. At productivity above 10 TPD / T sorbent, a large amount of CO2-containing gas comes into contact with the solid sorbent in a short period of time.

[0114] Typical contact times for CO2-containing gas flowing through the structure contactor are less than 1 second, or less than 0.5 seconds, more preferably less than 0.2 seconds. The high CO2 capture indicates that the majority of the sorbent material is accessible to the inlet CO2 within a fraction of a second. The present invention combines the benefits of the structured sorbent design disclosed in PCT Patent Application WO 2021 / 240476 with the benefits of a tailored amine-based sorbent powder to enable CO2 capture at low CO2 concentrations (less than 10% CO2) down to 400 ppm CO2 in air (DAC) while extending the life of the solid sorbent in applications that use a steam addition step for rapid regeneration.

[0115] In one embodiment, the capture cycle time is less than 120 seconds, preferably less than 60 seconds, and more preferably less than 40 seconds.

[0116] In embodiments, the heat of adsorption resulting from the adsorption of water on the polymeric amine sorbent and / or polymeric amine composite sorbent can be used as at least a portion of the heat of desorption to desorb at least a portion of the first component adsorbed in and / or on the sorbent. The desorbed first component can form a second product stream with other components in the gas phase. Thus, in some embodiments, the second product stream can be at least periodically enriched in the first component with respect to the feed stream. That is, the concentration of the first component desorbed from the sorbent material in the second product stream can be higher than the concentration of the first component in the multi-component stream. The second product stream can then be discharged or recovered from the contactor.

[0117] In embodiments, in sorptive gas separation processes using contactors including polymeric amine sorbents and / or polymeric amine composite sorbents as disclosed herein where steam is used as a recycle stream and / or where water may be adsorbed onto and / or within the sorbent sheet, leaching or vaporization of the amine from the sorbent and / or sorbent sheet is reduced or substantially eliminated.

[0118] In an embodiment, during the regeneration step 111, at least a portion of the first component adsorbed in and / or on the polymeric amine sorbent and / or polymeric amine composite sorbent can be desorbed by a pressure swing mechanism, or a pressure swing mechanism in combination with a temperature swing mechanism, and / or a partial pressure swing mechanism.

[0119] In an embodiment, during the conditioning step 112, a third component, such as water, adsorbed on and / or in the polymeric amine sorbent and / or polymeric amine composite sorbent can be desorbed from the sorbent by at least one of a temperature swing mechanism and a partial pressure swing mechanism to form a third product stream. In a preferred embodiment, during the conditioning step 112, the polymeric amine sorbent and / or polymeric amine composite sorbent is exposed to or to a third relative humidity, the third relative humidity being less than the second relative humidity. By introducing the conditioning stream into a sorbent contactor, the sorbent can be exposed to a swing or reduction in relative humidity during the conditioning step 112 relative to the regeneration step 111 to desorb the adsorbed moisture on and / or in the sorbent, which can then form at least a portion of the third product stream. In embodiments, the conditioning stream flows into a contactor where it is then contacted with a polymeric amine sorbent and / or a polymeric amine composite sorbent, the conditioning stream having a third relative humidity, the third relative humidity being lower than the second relative humidity. The conditioning stream can be, for example, at least one of an air stream, an inert gas stream, and / or a nitrogen stream. Thus, in some embodiments, the third product stream can be at least periodically enriched with a third component relative to the conditioning stream. The components desorbed from the sorbent during the conditioning step 112 can form a third product stream that can be discharged or recovered from the contactor.

[0120] In other embodiments, desorption of the third component or water adsorbed on and / or within the sorbent can be performed or assisted by applying a vacuum to reduce the pressure in the contactor to a pressure below the saturation pressure of the third component, steam, or water in the contactor.

[0121] Additional optional subsequent steps (not shown in FIG. 2) can occur, for example, after a cooling step, in which the temperature of the polymeric amine sorbent and / or polymeric amine composite sorbent can be reduced before repeating the adsorption step 110. The cycle of adsorption step 110, regeneration step 111, and optional conditioning step 112 (and any optional subsequent steps) can be repeated as desired.

[0122] In an embodiment, a sorption gas separation process for separating at least a first component from a multicomponent gas stream includes providing a contactor as described herein; flowing the multicomponent gas stream as a feed stream into the sorption contactor via an inlet port; adsorbing at least a portion of the first component from the feed stream onto a polymeric amine sorbent; at least periodically recovering a first product stream from the sorption contactor via an outlet port, the first product stream being enriched in a second component relative to the feed stream; optionally flowing a first regeneration stream having a steam content purity of greater than 80% (mole fraction) and a steam partial pressure of about 0.3 bar absolute or greater into the sorbent contactor; adsorbing steam or water onto the polymeric amine sorbent and / or polymeric amine composite sorbent, and optionally generating heat of adsorption or condensation; and optionally allowing water to adsorb onto the sorbent. If the amount of energy released when the first component is desorbed is greater than the energy desired to desorb the first component from the polymeric amine sorbent and / or polymeric amine composite sorbent, the method may include desorbing at least a portion of the first component adsorbed on the sorbent, forming a second product stream at least periodically enriched in the first component relative to the feed stream, recovering the second product stream from the sorbent contactor, and optionally desorbing water adsorbed in the adsorber by allowing a conditioning stream, e.g., an air stream, an inert gas stream, and / or a nitrogen stream having a third relative humidity, where the third relative humidity is less than the second relative humidity, and / or by applying a vacuum to reduce the pressure in the contactor to a pressure less than the saturation pressure of at least one of the third component, steam, and / or water in the contactor.

[0123] In sorptive gas separation processes, particularly where steam is used in the regeneration stream and / or the sorptive gas separation process where water can be adsorbed onto and / or into the sorbent sheet during the regeneration step, the use of the polymeric amine sorbents and / or polymeric amine composite sorbents disclosed above provides the advantage of reducing leaching or vaporization of the amine from the sorbent, resulting in increased durability of the sorbent and contactor. EXAMPLES

[0124] Example 1a: Supported amine polymer. Preparation of PEIDS. High pore volume silica [1.2 ml / g] was mixed with PEI polymer (10 K Daltons) functionalized by reaction with 1,2 epoxy-dodecane (ED) in isopropanol (IPA) for 1 h at 20 °C. Before adding the silica, additional inorganic antioxidant salt dispersed in water was added at 1.6% weight fraction of the dry sorbent powder dissolved in water to obtain an IPA / water mixed solvent mass ratio of 9 / 1. Finally, high pore volume silica was slowly mixed into the solution to achieve the following mass ratio of PEI / ED / SiO2 in the dry powder: 85 / 51 / 100. The formed slurry was stirred for another 20 h at room temperature. The solvent was then removed in a rotary evaporator at 60 °C. The collected powder was placed in a drying oven at 100 °C for 1 h. The recovered power was then tested for CO2 capacity in a TGA instrument and the measured CO2 adsorption capacity of the powder was 44±2 cc / g CO2 at 50°C, with 10% CO2 in the remaining nitrogen feed.

[0125] Example 1b: Preparation of Sorbent Sheets The powder of Example 1a was mixed with water and a polymeric binder and dispersant in a weight ratio of 64.8 / 32 / 2.5 / 0.7 water / powder / binder / dispersant. The binder was a styrene acrylic binder added to the slurry as a 45 wt% solution, and the dispersant was a mixture of an antifoam agent and a surfactant to stabilize the suspension.

[0126] The suspension was placed in a high shear mixer for 1 hour and then placed in a ball mill drum containing stabilized zirconia grinding balls and rotated for 24 hours. The slurry was then distributed to a slot die coater apparatus fitted with a 300 mm web width nonwoven (NW) carbon substrate (17 g / m2, 0.2 mm thickness) operating at 2 m / min. The slurry temperature was maintained between 20 °C and 25 °C during the coating process as the slurry impregnated the NW carbon substrate. The slurry pump speed was adjusted to limit the overcoat and removal of the slurry by the doctor blade before drying the sheet downstream of the slot die slurry injection. Partial drying of the coated sheet was achieved between the coating station and the collection roller with a transit time of two out of three minutes through a forced air convection oven section set at 60 °C. The collected sheet was further dried in an oven at 100 °C for 1 hour and stored at room temperature pending further processing. The resulting sheets had a thickness of 0.275±0.015 mm and an average density of 0.59 g / ml, and an adsorption capacity of 38±2 cc / g of CO2 at 50° C. with 10% CO2 in a balance nitrogen feed.

[0127] Example 2: Scanning electron microscope (SEM) pictures of sheets of polyethylimine supported on porous silica from Example 1b and impregnated onto a NW carbon film substrate are shown in Figures 3a, 3b and 3c. The sorbent sheet surface views are shown in Figures 3a and 3b, and the cross-sectional view is shown in Figure 3c.

[0128] In Figure 3a, large scale features such as cracks in the sorbent film on the surface of the sheet and sorbent-coated carbon fibers protruding from the surface of the film can be observed. Figure 3b shows an enlarged cross section of a sorbent sheet surface film showing the porous structure of the denser regions. Figure 3c shows a cross section of a sorbent sheet with a distribution of interconnected small and large pores that facilitates rapid transport of fluid components within the sorbent sheet.

[0129] Example 3: A specimen of the sorbent sheet from Example 2 was placed in a thermogravimetric analyzer (TGA) and dried and conditioned by removing the adsorbed CO2 from exposure to air and moisture by contacting the sample with nitrogen while maintaining the sample at 100°C for 1 hour. The specimen was then cooled to 50°C in nitrogen and the flow was switched to 10% CO2 in the remaining nitrogen stream. The weight gain of the specimen was recorded and converted to adsorption capacity per gram of sample once an equilibrium plateau was obtained. The measured capacity of the sheet at 50°C for CO2 under an atmosphere of 10% CO2 in nitrogen was 38±2 cc / g. For reference, the CO2 adsorption capacity of the sorbent powder alone under the same test conditions was 45±2 cc / g.

[0130] Example 4: (0='Fail'; 1='Pass') Water stability test. [Table 1]

[0131] Pass / Fail Cold Water Stability Test: 0.2g of powder is placed in 10g of DI water at 20°C and mixed for 1 hour. The liquid is filtered off and the powder is dried before testing. CO2 adsorption capacity tests are performed on a set of samples prepared with the same molar ratio of PEI / nitrogen in epoxy-alkane and the same weight ratio of silica to amine polymer as in Example 1, "0", which shows a loss of CO2 capacity of more than 5%. "1" indicates no loss is detected (within 1cc / g CO2 capacity or 2% measurement error). Each row corresponds to a different polymer molecular mass and each column corresponds to the carbon number of the alkyl chain in the epoxy-alkane used to functionalize the PEI. Water Exposure Stability Table.

[0132] Example 5: The sorbent sheet from Example 2 was placed in a flat screen printer to deposit an area of ​​1.6 mm diameter, 0.3±0.015 mm high epoxy resin dots, which were then thermally cured in air at 100° C. for 1 hour [crosslinking of the epoxy resin]. Strips 1.2 m long and 1 inch wide were cut and stacked to form structured sorbent beds encased in 1.6 mm thick polymer (ULTEM) panels and loaded into a test apparatus for delivery of synthetic feeds of CO2 flue gas, steam and nitrogen and cyclic recovery of depleted CO2 synthetic flue gas, purified CO2 streams and wet nitrogen streams.

[0133] The synthetic feed stream [10% CO2, 3% H2O in remaining N2] had a pressure of 105 kPa - 115 kPa absolute and a temperature of 40 ± 2 °C, the steam stream had a pressure of 90 kPa - 100 kPa and a temperature of 110 ± 5 °C (superheated), and the nitrogen stream had a pressure of 105 kPa - 115 kPa and was split into two streams at temperatures of 110 ± 5 °C and 80 ± 5 °C.

[0134] The bed samples were placed in a temperature controlled jacket set at 80 °C to minimize the effect of heat loss through the sides of the bed and to better represent the performance of a larger bed operating with negligible parasitic heat loss through the sides of the bed.

[0135] Rapid cycling between these four feed streams resulted in purification of CO. The duration and flow rate of each addition was adjusted until a satisfactory CO capture efficiency and CO product purity was achieved. Typically, cycle lengths were between 40 s and 90 s.

[0136] [Table 2]

[0137] Productivity is calculated as TPD / m 3) or tons of CO2 purified per day per ton of structured bed (TPD / T). CO2 recovery is defined as the percentage of CO2 in the product stream relative to the amount of CO2 introduced into the sorbent bed with the feed. CO2 purity refers to the product stream after water removal.

[0138] Example 6a: The sequential polymerization can be seen in Scheme 1 below.

[0139] (1) Salt formation [ka]

[0140] A 250 ml round bottom three neck glass flask equipped with a condenser, nitrogen inlet and outlet, and a Teflon coated stir bar was utilized for this reaction. The flask was flushed with nitrogen and immersed in an ice bath. It was then charged with 40 g of isopropanol and 18 g of hydrochloric acid (concentration 36-37%). The mixture was then cooled to a temperature below 10°C, and 10 g of 98% pure allylamine was added dropwise with stirring while maintaining the temperature below 20°C. 0.5 g of DVB and 1.3 g of V-50 were then added and the temperature was raised to 55°C. An additional aliquot of 1.5 g of DVB was then added to the flask in three separate batches at 1 hour, 2 hours, and 3 hours. The reaction temperature was then raised to 65°C and maintained at that temperature for an additional 3 hours. The product was then diluted with 20 g of methanol and filtered through a Buchner funnel. The solid portion of the mixture was then suspended in 40 g of DI water and 8 g of NaOH was added under stirring. After 30 minutes, the solid was filtered and washed twice with DI water. It was then further washed with methanol. The powder was then dried overnight in a vacuum oven at 60° C. The workup for the solid powder was the same as in Example 1. A 20% yield was obtained and the CO2 capacity of 36.8 cc / g resin was measured at 50° C. using 10% CO2 and 90% He flow gas. Then, 4 g of DVB-80 (DVB Aldritch) comonomer and 0.85 g of 2,2'-azobis(2-amidinopropane) dihydrochloride (V-50) initiator were added and the temperature was increased to 55° C. and maintained at that temperature for 18 hours with stirring. The product was then diluted with 20 g of methanol and filtered through a Buchner funnel. The solid portion was then suspended in 40 g of DI water and 8 g of NaOH was added with stirring. After 30 minutes, the solid was filtered and washed twice with DI water. This was further washed with methanol. The resulting powder was then dried overnight in a vacuum oven at 60°C.

[0141] [Table 3]

[0142] Example 6b: The reaction was carried out in a 500 ml round bottom three neck glass flask equipped with mechanical stirring with Teflon coated shaft and blade, nitrogen inlet and outlet, and a thermometer. The flask was immersed in an ice bath and flushed with nitrogen, followed by charging with 165 g HCl (36-37%) and 1.65 g NaCl. The mixture was then cooled to a temperature of about 15°C and 110 g allylamine was added slowly with stirring while maintaining the temperature below 30°C. After cooling to 15-20°C, 17.5 g citric acid was added slowly and the resulting pH was measured at 5.5. 18 g V-50 and 6 g DVB were then added and the temperature was increased to 65°C. 44 g DVB was added by syringe pump over 4.3 hours while maintaining the temperature at 67-70°C. After the DVB addition, the temperature was increased to 82°C and the reaction continued for an additional 2.5 hours. Work-up on the solid powder was the same as in Example 14 below. A yield of 46.3% was obtained, with a CO2 capacity of 46.9 cc / g resin at 50°C using 10% CO2 and 90% He flow gas. The particle size and distribution is shown in Figure 4. This is a broad, unimodal distribution curve with a peak around 4 μm and a tail out to 70 μm. Scanning electron micrographs (SEM) demonstrate that the solid polymer consists primarily of aggregates of nanoparticles.

[0143] Example 6c: Three repeat polymerization reactions were carried out on a larger scale in a 5 L round bottom 3-neck glass flask equipped with Teflon coated shaft and blade mechanical stirring. The flask was flushed with nitrogen and charged with 1004 g of cold (approximately 8-10°C) dilute aqueous HCl solution containing 68 g allylamine, 6.6 g NaCl, and 96 g citric acid. The pH of the reaction solution was approximately 6. 72 g V-50 and 24 g DVB were then added and the temperature was raised to 65°C. 176 g DVB was then added by syringe pump over 4.25 hours while maintaining the temperature at 67-70°C and diluting by adding 640 g water when the viscosity increased. After the DVB addition, the temperature was raised to 80°C and the reaction continued for an additional 1.5 hours.

[0144] [Table 4] CO2 adsorption capacity of replicate scale-up samples in 10% CO2 in He at 50 °C.

[0145] [Table 5] Composition of the dried polymer from elemental analysis.

[0146] Example 7: Repeated exposure cycles to air at 120° C. for 1 hour were performed on representative samples of the allylamine co-DVB polymers presented herein as well as a reference commercial amine-doped resin containing phenylamine [Lewatit 1065]. Between each cycle, the CO2 capacity of the materials was measured at 50° C.

[0147] Figure 5a compares the CO2 capacity of samples after one and 20 air exposure cycles. CO2 capacity at 50 °C per gram of sorbent under 10% CO2 in N2 is shown on the y-axis, and amine-doped resin containing phenylamine [Lewatit1065] sorbent and allylamine co-DVB polymer sorbent is shown along the x-axis. The unshaded bars show the CO2 capacity after one cycle, and the shaded bars show the CO2 capacity after 20 cycles. The adsorbed CO2 volume is reported at STP (standard temperature and pressure).

[0148] FIG. 5b shows the CO2 adsorption capacity before and after water immersion for a reference amine-containing resin [Lewatit1065] and a porous polymer disclosed herein. The CO2 capacity at 50° C. per gram of sorbent under 10% CO2 in N2 is shown on the y-axis, and amine-doped resins containing phenylamine [Lewatit1065] sorbent and allylamine co-DVB polymer sorbents 180420, 180423, and 180425 are shown along the x-axis. The unshaded bars show the CO2 capacity before immersion, and the shaded bars show the CO2 capacity after immersion. The adsorbed CO2 volume is reported at STP.

[0149] Two of the prepared porous amine sorbent samples showed no CO2 volume loss and superior adsorption capacity compared to the reference, indicating effective incorporation of amine monomers into the porous copolymer with almost no unreacted monomer remaining in the solid sorbent.

[0150] The sample of Example 6a is significantly more oxidatively stable than the reference amine resin material. Hydrothermal stability was tested by comparing the CO2 capacity of the resin before and after soaking the powder under mixing for 1 hour.

[0151] Example 8: Preparation of sorbent sheets: 164 g of the sample from Example 6c before drying (containing 81% dry polymer) was mixed with 300 g water and 54 g polyvinyl alcohol polymer (molecular weight approximately 200 kDaltons) (43 wt% suspension) in a high shear mixer for 1 hour, then transferred to a ball mill grinding vessel containing zirconia stabilizing beads and spun for 24 hours. The slurry was then dispensed into a slot die coater apparatus fitted with a 300 mm web width NW carbon substrate (17 g / m2, 0.2 mm thickness) operating at 2 m / min. The slurry temperature was maintained between 20°C and 25°C during the coating process as the slurry impregnated the NW carbon substrate. The slurry pump speed was adjusted to limit overcoat and removal of slurry by the doctor blade before drying the sheet downstream of the slot die slurry injection. Partial drying of the coated sheet occurred between the coating station and the collection roller due to a 3 minute transfer through a forced air convection oven section set at 60°C. The recovered sheets were further dried in an oven at 100° C. for 1 hour and stored at room temperature until further processing. The resulting sheets had a thickness of 0.18±0.01 mm and an average density of 0.47 g / ml, and an adsorption capacity of 30±2 cc / g of CO at 50° C. with 10% CO in a residual nitrogen feed.

[0152] Example 9: Figure 6a shows a powder scanning electron microscope (SEM) image of Example 6b, and Figure 6b shows a cross-sectional SEM image of the sorbent sheet of Example 8. Sub-micrometer diameter polymer particles can be observed in Figure 6a, while a porous network with pores in the micrometer size range can be observed in Figure 6b (dark areas). The interstices between the polymer particles are preserved upon coating.

[0153] Figure 6b is a powder SEM image of a cross section of the sorbent sheet of Example 8 showing the porosity of the polymer particles and the sorbent membrane. The darker areas are voids remaining between the sorbent particles after formation of the sorbent sheet. These voids or pores are interconnected in a three-dimensional network, allowing for rapid diffusion and transport of fluid or gas components to the surface of the individual sorbent particles.

[0154] Example 10: A specimen of the sorbent sheet from Example 9 was placed in a thermogravimetric analyzer (TGA) and dried and conditioned by contacting the sample with nitrogen while maintaining the sample at 140° C. for 20 minutes to remove adsorbed CO2 from exposure to air and moisture. The specimen was then cooled to 50° C. in nitrogen and the flow was switched to 10% CO2 in the remaining nitrogen stream. The weight gain of the specimen was then recorded and converted to adsorption capacity per gram of sample once an equilibrium plateau was obtained. The measured capacity of the sheet at 50° C. for CO2 in an atmosphere of 10% CO2 in the remaining nitrogen was 30±2 cc / g. For reference, the CO2 adsorption capacity of the sorbent powder alone under the same test conditions was 35±2 cc / g. FIG. 7 shows the mass change of the sorbent sheet specimen during the TGA test with the sample weight on the right axis versus time, as well as the temperature near the specimen on the left axis. The sample is first exposed to nitrogen at 140° C. for 20 minutes to dry the material and remove adsorbed CO2 from exposure to air.

[0155] The gas composition in the TGA furnace was switched to 10% CO2 in N2 at 51 min. 80% of the weight gain of the sample sheet was observed in less than 2 min, indicating rapid adsorption of CO2 in the sorbent sheet. A 6% mass change of the sample 20 min after the introduction of CO2 corresponds to an adsorption capacity of approximately 30 cc / g STP.

[0156] Example 11: The sorbent sheet from Example 10 was placed in a flat screen printer to deposit an area of ​​1.6 mm diameter epoxy resin dots with a height of 0.25±0.01 mm, which was then thermally cured at 100° C. in air for 1 hour [crosslinking of the epoxy resin]. Strips 1.2 m long and 1 inch wide were cut and stacked to form a structured sorbent bed encased in 1.6 mm thick ULTEM panels and loaded into a test apparatus for delivery of synthetic feeds of CO2 flue gas, steam and nitrogen, with periodic withdrawal of depleted CO2 synthetic flue gas, purified CO2 stream and wet nitrogen stream.

[0157] The synthetic feed stream [10% CO2, 3% H2O in balance nitrogen] had a pressure of 105 kPa to 115 kPa absolute and a temperature of 40±2°C, the steam stream had a pressure of 90 kPa to 100 kPa and a temperature of 110±5°C (superheated), and the nitrogen stream had a pressure of 105 kPa to 115 kPa and was split into two streams with temperatures of 110°C±5°C and 80°C±5°C.

[0158] The bed samples were placed in a temperature controlled jacket set at 80°C to minimize the effect of heat loss through the sides of the bed and to better represent the performance of a larger bed operating with negligible parasitic heat loss through the sides of the bed.

[0159] Rapid cycling between these four feed streams resulted in the purification of CO. The duration and flow rate of each addition were adjusted until a satisfactory CO capture efficiency and CO product purity was achieved. Typical cycle lengths were between 40 and 120 seconds.

[0160] [Table 6]

[0161] Productivity is defined as tons of CO2 purified per cubic meter of structured bed volume or per ton of structured bed per day. CO2 recovery is defined as the percentage of CO2 in the product stream relative to the amount of CO2 introduced into the sorbent bed with the feed. CO2 purity refers to the product stream after water removal.

[0162] The exemplary embodiments described herein are not intended to be exhaustive or to limit the scope of the invention to the precise forms disclosed, but are chosen and described to explain the principles of the invention and its application and practice so as to enable others skilled in the art to understand its teachings.

[0163] As will be apparent to those skilled in the art in light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the scope of the invention (including combinations of the various described embodiments or portions thereof). Accordingly, the scope of the invention should be construed in accordance with the material defined by the claims.

Claims

1. A solid sorbent comprising: Polymeric amines having an average molecular weight greater than 2000 Daltons Including, the solid sorbent is insoluble in water and forms a porous network; the solid sorbent is in the form of particles or a film or a sheet; the polymeric amine comprises a first soluble domain and a second insoluble domain; A solid sorbent wherein the polymeric amine comprises primary amines and secondary amines, and the combined mass fraction of the primary amines and the secondary amines is greater than 6% mass fraction of nitrogen relative to the mass of the polymeric amine.

2. the solid sorbent has an average pore size in the range of 10 to 200 nanometers as measured using a nitrogen adsorption isotherm; 10. The solid sorbent of claim 1, wherein the solid sorbent is in the form of particles, the particles having an average particle size in the range of 0.2 to 40 micrometers.

3. 3. The solid sorbent of claim 1 or 2, wherein the polymeric amine comprises a copolymer formed from the reaction of a vinylamine with a divinyl monomer and further comprises an interconnected porous structure.

4. The solid sorbent of any one of claims 1 to 3, wherein the polymeric amine is supported on a porous support.

5. The polymeric amine is C １０ ~C １６ 5. The solid sorbent of claim 4 comprising polyethyleneimine functionalized with an alkyl alcohol.

6. 6. The solid sorbent of claim 5, wherein the molar ratio of long chain alkane groups to amine groups ranges from 10% to 25%.

7. 6. The solid sorbent of claim 5, wherein the polyethyleneimine is functionalized by reaction with an alkyl-epoxide.

8. The solid sorbent of any one of claims 1 to 7, wherein the solid sorbent is a self-supporting sheet or sorbent foam having a thickness in the range of 0.1 mm to 3 mm.

9. The solid sorbent has a heat capacity of 15 to 40 cc stp CO per unit heat capacity of the solid sorbent. ２ / (J / K)'s CO ２ and an equilibrium capacity to heat capacity ratio, the equilibrium capacity being 15% CO at 50°C. ２ The solid sorbent of any one of claims 1 to 8, measured under the feed mixture.

10. 1. A solid sorbent comprising a polymeric amine formed in a porous solid, (a) CO ２ an equilibrium capacity, wherein the solid sorbent has an equilibrium capacity of 15 to 40 cc stp CO per unit heat capacity of the solid sorbent; ２ / (J / K)'s CO ２ and an equilibrium capacity to heat capacity ratio of 15% CO ２ CO measured at 50°C under the feed mixture ２ equilibrium capacity, (b) the kinetic adsorption rate of CO ２ When in contact with the mixture, the kinetic adsorption rate is greater than 0.03 mmol / g / s, and the CO ２ The mixture is 15% CO ２ and a kinetic adsorption rate, including a temperature of 30°C to 50°C; (c) CO ２ wherein the heat of adsorption is between 70 kJ / mol and 120 kJ / mol of adsorbed CO ２ CO ２ wherein the polymeric amine is a copolymer of vinylamine and divinyl monomer having primary and / or secondary amine groups and an interconnected porous structure; A solid sorbent comprising:

11. 11. The solid sorbent of claim 10, wherein the polymeric amine further comprises a grafted alkylamine supported on a porous support, the porous support having a pore volume in the range of 0.7 to 1.5 ml / g, and the grafted functional groups on the amine groups comprise hydrophobic groups.

12. 1. A sorption gas contactor comprising: A plurality of sorbent sheets each comprising the solid sorbent of any one of claims 1 to 11, the plurality of sorbent sheets having a thickness in the range of 0.1 mm to 3 mm, and arranged to form passages between the plurality of sorbent sheets to allow flow of a gas stream between and in contact with the sorbent sheets. a sorption gas contactor comprising:

13. 1. A sorption gas contactor comprising: a plurality of sorbent sheets, each of the plurality of sorbent sheets comprising a solid sorbent, each of the sorbent sheets having a thickness in a range of 0.1 mm to 3 mm, and arranged to form passages between the plurality of sorbent sheets to permit flow of a gas stream between and in contact with the sorbent sheets; Including, The solid sorbent sheet has a density of 0.2 g / cm ３ ~0.8g / cm ３ and having greater than 5 wt. % nitrogen from primary or secondary amine functional groups, said polymeric amine being formed as a copolymer from vinylamine monomers having a molecular weight less than 100 Daltons and divinyl monomers having a molecular weight greater than 100 Daltons, or formed from the reaction of a water-soluble polymeric amine with a long chain alkyl (8 or more carbon atoms) group. Sorption gas contactor.

14. 14. The sorption gas contactor of claim 13 having passage porosity between said plurality of said sorbent sheets, said passage porosity being in the range of 20% to 80%.

15. 1. A sorption gas separation process for separating a first component from a multi-component fluid stream comprising at least a first component and a second component, the process comprising: (a) providing a sorption gas contactor comprising the solid sorbent of any one of claims 1 to 10; (b) flowing the multicomponent fluid stream through the sorption-gas contactor to adsorb at least a portion of the first component from the multicomponent fluid stream onto the solid sorbent to form a first product stream, and recovering the first product stream from the sorption-gas contactor, wherein the first product stream is depleted in the first component relative to the multicomponent fluid stream; (c) desorbing at least a portion of the first component adsorbed onto the solid sorbent to form a second product stream and recovering the second product stream from the sorption-gas contactor, the second product stream being enriched in the first component relative to the multi-component fluid stream; A sorption gas separation process comprising:

16. In step (b), further comprising exposing the solid sorbent to a first relative humidity, the first relative humidity being at least 20% relative humidity measured at an inlet of the sorption gas contactor; In step (c), the method further comprises controlling the regeneration stream to have a vapor partial pressure of 0.3 bar absolute or greater before entering the regeneration stream into the sorption gas contactor.

16. The process of claim 15.

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