Functionalized polymeric amine materials, synthesis, and use

Abstract

A functionalized polymeric amine material which can be used as a sorbent. The functionalized polymeric amine material can be attached to a substrate and / or to form a structured sorbent which can be used in a sorptive gas separation process. Functionalization of a polymeric amine material can be performed before or after the polymeric material is attached to a substrate or formed into a structured sorbent.

Description

[0001] FUNCTIONALIZED POLYMERIC AMINE MATERIALS, SYNTHESIS, AND USE

[0002] Field

[0003] Embodiment of the present invention generally relates to solid polymeric amine materials, synthesis of the materials, and use of the materials as a structured sorbent and for sorptive gas separation. More particularly, embodiments of the present invention relate to functionalized polymeric amine materials, synthesis of the materials, and the use of the materials as a structured sorbent for sorptive gas separation of an acid gas from a multi-component fluid mixture.

[0004] Background

[0005] Sorptive gas separation processes are amongst the most common of industrial separation processes and are considered for use in applications for mitigating the deleterious effects of greenhouse gas emissions, for example, sorptive gas separation of carbon dioxide from a multicomponent fluid stream such as an air, a flue gas, or a process gas stream. Cost of sorptive separation processes can be largely impacted by the amount of sorbent in a sorptive separator to produce a desired throughput of a purified product stream depleted in a target component.

[0006] During a regeneration step of a sorptive gas separation process, steam can be admitted into a sorptive separator to come in contact with and directly heat a sorbent material, thereby desorbing the sorbed components from the sorbent, and / or purging components from the sorptive separator. Water in a product stream recovered from the sorptive separator during the regeneration step can be separated by condensation from the product stream thus maintaining the purity of the separated gas component. Water sorbed on the sorbent material during the regeneration step can be removed during a subsequent step, for example, a conditioning step, of the sorptive gas separation process.

[0007] Moisture swing induced desorption of a target component can provide a fast and efficient means of desorbing sorbed components, while resulting in a product stream which can be easily further purified by condensation of water from the product stream. Benefits of partial pressure swing, moisture swing or relative humidity swing for desorption can include: rapid introduction of energy by using the heat of adsorption or condensation of the moisture to distribute heat energy relatively homogeneously amongst the porous sorbent; water, if environmentally friendly, can be discharged to the atmosphere if desired; and sorbents with significant water sorption capacity are fairly common due the hydrogen bonding capacity of water.

[0008] Drawbacks of conventional adsorbent materials exposed to water and / or steam during an adsorptive gas separation process can include: water adsorbed strongly onto an adsorbent material resulting in energy intensive and slow desorption and removal of water from the adsorbent material, the adsorbent material degrades in the presence of water (for example, polymeric amine adsorbents can migrate due to partial solvation making them mobile, and with MOF adsorbents, its structure undergoes phase transition in the presence of steam resulting in pore collapse and / or loss of selective adsorption capacity), and / or a water stability attribute of an adsorbent material is inversely related to one or more desirable attributes (for example, target molecule adsorption capacity and / or reaction kinetics).

[0009] Furthermore, conventional adsorptive gas separators and processes can use an adsorbent bed consisting of a single adsorbent material throughout the adsorbent bed where a regeneration step can include: admitting a steam stream into the adsorptive bed via an inlet, flowing the steam stream in contact with the adsorbent material through the adsorbent bed, desorbing a target molecule, producing a product stream, and recovering the product stream from the adsorbent bed via an outlet. A drawback of this approach is that an adsorbent material can be selected based on its water stability, which is often inversely related to one or more desirable attributes, including for example, target molecule adsorption capacity and / or reaction kinetics.

[0010] Polymeric amines are desirable for some adsorptive gas separation applications due to their high affinity and selectivity for acid gas components, large adsorptive capacity and rapid reaction kinetics for a target component relative to other adsorbents. However, polymeric amines with high primary and secondary amine content are water soluble polymers which entail considerable challenges in process design since this exposes them to high relative humidity, condensation, and / or water, as moisture leaches the amine. This shortcoming limits conventional solid adsorbents containing water soluble polymeric amines to applications where the adsorbents are exposed to dry or low relative humidity conditions, such as, gas chromatography applications. Furthermore, polymeric amines offer additional challenges including limited oxidation stability when exposed to oxygen under certain operating conditions.

[0011] PCT International Publication WO 2024 / 056715 titled “Epoxidation of Porous Amine-Based Phenylic Polymer Resins and Methods for Use for Carbon Dioxide Capture” teaches epoxidation of an amine resin (epoxy functionalized) to increase the oxidation stability and lifetime of a sorbent when exposed to oxygen under certain operating conditions.

[0012] For commercial adaptations of adsorptive gas separation, reduced life cycle costs and increased durability are required. An intensified adsorptive gas separation process and a sorbent with a desirable selectivity, large adsorption capacity, fast reaction kinetics and high durability are desired.

[0013] Summary

[0014] In a broad aspect of an invention, a functionalized polymeric amine material can comprise amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine having the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein, the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group is an alkyl with a formula CnHm where n is in a range of 2 to 12 and m is in a range of 2 to 25, and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkyl with a formula CnHm where n is in a range of 2 to 12 and m is in a range of 2 to 25, or a hydrogen atom. In a broad aspect of an invention, a functionalized polymeric amine material can comprise amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine having the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein, the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group is an alkene, an alkenyl, an aryl, a heteroatom substituted alkyl having a formula of CnHmYp wherein Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkene, an alkenyl, an aryl, a heteroatom substituted alkyl having a formula of CnHmYp wherein Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, or a hydrogen atom.

[0015] In a broad aspect of an invention, a functionalized polymeric amine material can comprise amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the at least one of the primary amine, the secondary amine and the tertiary amine is equal to or greater than 5% by weight of the amine groups, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine having the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group is an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl having a formula of CnHmFoClp wherein, n is in a range of 2 to 12, m is in a range of 2 to 25, o is in a range of 0 to 4, and p is in a range of 0 to 4; and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl having a formula of CnHmFoClp wherein, n is in a range of 2 to 12, m is in a range of 2 to 25, o is in a range of 0 to 4, and p is in a range of 0 to 4, or a hydrogen atom.

[0016] In a broad aspect of an invention, a functionalized polymeric amine material can be produced by reacting a polymer amine and at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, and a substituted alkyl halide of formula R2X, wherein,

[0017] R2 is an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl with a formula CnHmYp wherein

[0018] Y is one of a chlorine atom, a fluorine atom, or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25, and p is in a range of 0 to 4; and

[0019] X is a chlorine atom or a bromine atom.

[0020] In another broad aspect of the inventions functionalized polymeric amine structured sorbent can comprise the functionalized polymeric amine material disclosed herein and a substrate having a wetted surface area equal to or greater than 0.2 m2 / L of the substrate, wherein the surface area excludes a pore surface area of pores with a pore size of less than 150 microns. In another broad aspect of the inventions method of synthesizing a functionalized polymeric amine material can comprise: reacting at least one amine polymer with a solution and forming a mixture, wherein the at least one amine polymer comprises nitrogen equal to or greater than 4% by weight of the material and a surface area of equal to or greater than 2 m2 / g of the material, and wherein the solution comprises at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, a fluoro- or chloro substituted alkyl halide with a formula R2X, wherein

[0021] R2 is an alkyl group, an alkene group, an alkenyl group, an aryl group, a fluoro- or chloro substituted alkyl group a formula CnHmYp wherein Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, and

[0022] X is a chlorine atom or a bromine atom.

[0023] In another broad aspect of the invention, a sorptive gas separation process can comprise: a. admitting a multi-component gas stream as a feed stream into a sorptive separator comprising a functionalized polymeric amine material described herein as a sorbent or a functionalized polymeric amine structured sorbent described herein, contacting the feed stream with the sorbent or structured sorbent, sorbing a first component from the feed stream on and / or in the sorbent or the structured sorbent thereby separating the first component from the feed stream and producing a first product stream depleted in a first component relative to the feed stream, and recovering the first product stream from the sorptive separator; and b. desorbing the first component from the sorbent or the structured sorbent in the sorptive separator by at least one of a temperature swing, a partial pressure swing, a moisture swing, a pressure swing, thereby producing a second product stream enriched in the first component relative to the feed stream, and recovering the second product stream from the sorptive separator. Brief Description of the Drawings

[0024] Figure 1a is a schematic diagram of an embodiment of the present invention illustrating a reaction of a commercially available polystyrene-divinylbenzene (referred herein as “SX”) and 1 -bromopropane, resulting in the alkylation of the SX;

[0025] Figure 1 b illustrates the reaction mechanisms of a secondary amine group into their alkylated derivative;

[0026] Figure 1c illustrates examples of resulting functionalized polymeric amines with a covalent bond to a carbon atom from an alkyl or substituted alkyl group;

[0027] Figure 2a is a process flow diagram of an embodiment of the present invention, illustrating an embodiment of a process of producing a functionalized polymeric amine structured sorbent by obtaining an un-functionalized amine polymer, producing a functionalized polymeric amine material, and forming the functionalized polymeric amine structured sorbent;

[0028] Figure 2b is a process flow diagram of an embodiment of the present invention, illustrating an embodiment of a process of producing a functionalized polymeric amine structured sorbent by obtaining an un-functionalized amine polymer, forming an un-functionalized polymeric amine structured sorbent, and functionalizing the un-functionalized polymeric amine structured sorbent;

[0029] Figure 3a is a graph showing a CO2 working sorptive capacity in cc / g at standard temperature and pressure (along the y-axis) versus a number of cycles (along the x-axis) comparing an unfunctionalized polymeric amine material “SX” to three functionalized polymeric amine materials “SX with 1-bromo-3-methylbutane.

[0030] Figure 3b is a graph showing a normalized CO2 sorptive capacity in cc / g at standard temperature and pressure (along the y-axis) versus a number of cycles (along the x-axis) for the same materials and conditions in Figure 3a.

[0031] Figure 4 illustrates the chemical structure of alkyl halide reagents: bromoethane, 1 -bromopropane, 2-bromopropane, 1 -bromobutane, 2-bromobutane, 1- bromo-2-methylpropane, 1-bromo-2-ethylbutane, 1 bromo-3-methylbutane, 2-bromo-2- methylpropane;

[0032] Figure 5 is a graph showing test results of sorption kinetics, with weight as a percent (along the y-axis) versus time in minutes (along the x-axis), for an alkyl- functionalized amine polymeric material produced as Example 1 , and three unfunctionalized amine polymeric materials using a 400 ppm CO2 gas mixture with 90% relative humidity at a temperature of 10°C.

[0033] Detailed Description

[0034] Definitions:

[0035] Sorbent: a porous solid material, with a single chemical formulation, capable of sorbing a component by chemisorption and / or physiosorption.

[0036] Sorbent sheet: a self-supported sheet, active layer, or laminate.

[0037] Binder: a material for attaching a sorbent to a substrate (which can also be referred to as “support” or “structure”).

[0038] Structured sorbent: a sorbent configured with or without a sorbent substrate into a physical form which can be used for defining flow channels for a gas stream in a contactor and / or a sorptive separator. The structured sorbents can be configured in a form of, for example, a sheet, a film, film segments, a ribbon, ribbon segments or string segments interconnected or in contact forming continuous solid object. A surface area of the structured sorbent can be defined as a wetted area or an area which is exposed to and comes in contact with an influent or feed stream of a sorptive separator excluding the area formed by pores within the structured sorbent.

[0039] Cyclic capacity: quantity of molecules separated from a gas stream during an adsorption-desorption cycle per unit mass of sorbent.

[0040] Heat capacity: amount of heat to be supplied to an object to produce a unit change in its temperature.

[0041] Heat of adsorption: energy released by adsorption of a molecule on a sorbent.

[0042] Wetted surface area: a surface area of a structured sorbent excluding sorbent pores and / or coating layer pores smaller than 10 microns.

[0043] One dimensional or two dimensional structured sorbent: a structured sorbent with one or two of the dimensions being at least 10Ox greater than the smaller dimension of the structured sorbent. For example, a structured sorbent configured in the shapes of a sheet with a thickness of 500 microns and a width and a length greater than 50 millimeters or a string with a diameter of 500 microns and a length of greater than 50 millimeters. Functionalized polymeric amine materials for use as a sorbent in sorptive gas separation processes, porous functionalized polymeric amine structured sorbents comprising functionalized polymeric amine materials supported on and / or in an inorganic porous substrate or integrated into a porous polymer network, methods of synthesis of the polymeric amine material, functionalization of structured sorbents comprising unfunctionalized polymeric amine materials, and a sorptive gas separation process using the structured sorbent with the polymeric amine material are disclosed herein. In particular, polymeric amine sorbent compositions, methods of synthesis, sorbent structures, for separation of a target component, for example an acid gas component from a gas stream, for example, a flue gas stream, a process gas stream, a biogas stream, an air stream, or an atmospheric air stream, are disclosed. In one aspect, during a sorptive gas separation process the polymeric amine sorbent can be exposed to at least one gas stream with high relative humidity, for example, greater than about 30% relative humidity, are disclosed.

[0044] The mediation of an amine sorbent to high relative humidity can result in a significant quantity of water to adsorb onto the adsorbent, thereby occupying sorbent pores and reducing the kinetics and / or capacity to sorb a target component. A functionalized polymeric amine material for use as a sorbent and a functionalized polymeric amine structured sorbent with a reduced rate of performance degradation when exposed to a high relative humidity are disclosed.

[0045] The functionalized polymeric amine materials disclosed herein can comprise high pore volumes and / or can be supported on porous substrates with high pore volumes, providing a high sorption capacity for at least one target acid gas component along with a high stability and / or tolerance to water or moisture, oxygen (herein referred to as “O2”) and carbon dioxide (herein referred to as “CO2”).

[0046] Polymeric amines with a high content of primary and secondary amines can typically be water soluble polymers and can be low molecular weight polymers which can leach out from a substrate and / or a structured sorbent when exposed to a high relative humidity or liquid water. In the present invention, chemical derivation of an amine polymer to desirably modify the polar nature of the polymer amine leading to the immobilization of the amine from a substrate and / or a structured sorbent, such as, a hydrophilic substrate are disclosed. Conventional polymeric amine sorbents supported on and / or in a substrate have been limited to applications with limited exposure to dry or low relative humidity conditions and / or are protected from exposure to high relative humidity or water, for example, gas chromatography applications. However, due to their large sorptive capacity and fast sorption kinetics of amine sorbents, it can be desirable to use amine sorbents in applications with one or more process gas streams and / or a regeneration stream comprising water or steam, if the problems of capacity degradation and stability when exposed to water are overcome.

[0047] Co-polymerized amine monomers with large rigid co-polymers favoring the formation of a porous network structure with similar benefits for acid gas separation applications under moist conditions are also disclosed.

[0048] Embodiments of the present invention is differentiated from the prior art teaching epoxy functionalization where in the present invention, alkyl-functionalization can be used for adding a functional group to an amine polymer through reaction of a hydrocarbon halide with a primary or a secondary amine to form a functionalized amine polymer which do not contain hydroxy groups.

[0049] Novel compositions and method of synthesizing amine polymers with improved performance and stability are also disclosed herein using an alkylation step of primary, secondary, and / or tertiary amines contained in the polymer or the amine monomer precursor(s).

[0050] Forming of a polymeric amine material cannot be sufficient for successful application at industrial scales. The polymeric amine material should be integrated into structured sorbents or a contactor for facilitating gas flow and contact between the sorbent and the gas stream comprising the target component to be separated. Macroscopic arrangement of the sorbent in one or two dimensions on a structured sorbent, while a plurality of structured sorbents can be employed to form three dimensional structures such as a contactor which can have a low gas flow resistance while maximizing the sorption kinetics for the target component such as an acid gas component are disclosed herein.

[0051] A sorptive gas separation process which can be cycled rapidly based on a temperature and / or a moisture swing desorption mechanism to regenerate the polymeric amine material used as a sorbent is also disclosed herein. The sorptive gas separation process can be used for separating a deleterious component, for example, an acid gas component or CO2, from a gas mixture, and to address the challenges of greenhouse gas (also known as “GHG”) emissions.

[0052] A sorbent with a high cyclic capacity for sorption and desorption of a target component is desirable as well as chemical, conformational and structural stability of an active polymer when exposed to its process environment, which preserves both active site function as well as kinetically facile access to those sites.

[0053] The durability of a material and a sorbent to cyclic exposure to high relative humidity and / or condensation, as well as oxygen, is critical in applications as disclosed above. Embodiments of the invention disclosed present methods of providing stable active sorption sites using amine functionality within a porous structure where a target gas component can be easily introduced and removed.

[0054] Functionalized Polymeric Amine Material

[0055] In an embodiment, a functionalized polymeric amine material can comprise amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine having the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein the R1 substituent group is a metal-organic framework (also referred to as a “MOF”), a covalent organic framework (also referred to as a “COF”), or a porous polymer, the R2 substituent group is an alkyl with a formula CnHm wherein n is in a range of 2 to 12 and m is in a range of 2 to 25, and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkyl with a formula CnHm where n is in a range of 2 to 12 and m is in a range of 2 to 25, or a hydrogen atom. In aspects of the functionalized polymeric amine material, the amine groups can comprise nitrogen, wherein the nitrogen can be equal to or greater than 4% by weight of the material or equal to or greater than 8% by weight of the material.

[0056] In further embodiments, the functionalized polymeric amine material can comprise at least one of: a surface area equal to or greater than 2 m2 / g of the material, equal to or greater than 5 m2 / g of the material, or equal to or greater than 10 m2 / g of the material, measured by Brunauer-Emmett-Teller (also referred to as “BET”) using liquid nitrogen and / or at a temperature of about 77° Kelvin; and pores within a pore size range of 2 nanometre (herein referred to as “nm”) to 400 nm, wherein the pores within the pore size range of 2 nm to 400 nm having a pore volume greater than 0.2 ml / g of the material, measured by mercury porosimetry.

[0057] In an embodiment, a functionalized polymeric amine material can comprise amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine having the R1 substituent group and at least one of a R2 substituent group or a R3 substituent group, wherein the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group is an alkene, an alkenyl, an aryl, a heteroatom substituted alkyl having a formula of CnHmYp wherein

[0058] Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkene, an alkenyl, an aryl, a heteroatom substituted alkyl having a formula of CnHmYp wherein Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25, and p is in a range of 0 to 5, or a hydrogen atom. In aspects of the functionalized polymeric amine material, the amine groups can comprise nitrogen, wherein the nitrogen can be equal to or greater than 4% by weight of the material or equal to or greater than 8% by weight of the material.

[0059] In further embodiments, the functionalized polymeric amine material can comprise at least one of: a surface area equal to or greater than 2 m2 / g of the material, equal to or greater than 5 m2 / g of the material, or equal to or greater than 10 m2 / g of the material, measured by Brunauer-Emmett-Teller (also referred to as “BET”) using liquid nitrogen and / or at a temperature of about 77° Kelvin; and pores within a pore size range of 2 nm to 400 nm, wherein the pores within the pore size range of 2 nm to 400 nm having a pore volume greater than 0.2 ml / g of the material, measured by mercury porosimetry.

[0060] In an embodiment, a functionalized polymeric amine material can comprise amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the at least one of the primary amine, the secondary amine and the tertiary amine, can be equal to or greater than 5% by weight of the amine groups, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine having the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer; the R2 substituent group is an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl having a formula of CnHmFoClp wherein n is in a range of 2 to 12, m is in a range of 2 to 25, o is in a range of 0 to 4, and p is in a range of 0 to 4; and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl having a formula of CnHmFoClp wherein n is in a range of 2 to 12, m is in a range of 2 to 25, o is in a range of 0 to 4, and p is in a range of 0 to 4, or a hydrogen atom.

[0061] In aspects of the functionalized polymeric amine material, wherein the amine groups comprise nitrogen, wherein the nitrogen can be equal to or greater than 4% by weight of the material or equal to or greater than 8% by weight of the material.

[0062] In further embodiments, the functionalized polymeric amine material can comprise at least one of: a surface area equal to or greater than 2 m2 / g of the material, equal to or greater than 5 m2 / g of the material, or equal to or greater than 10 m2 / g of the material, measured by Brunauer-Emmett-Teller (also referred to as “BET”) using liquid nitrogen and / or at a temperature of about 77° Kelvin; and pores within a pore size range of 2 nm to 400 nm, wherein the pores within the pore size range of 2 nm to 400 nm having a pore volume greater than 0.2 ml / g of the material, measured by mercury porosimetry.

[0063] In an embodiment, a functionalized polymeric amine material can be produced by reacting a polymer amine and at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, and a substituted alkyl halide of formula R2X, wherein

[0064] R2 is an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl with a formula CnHmYp wherein

[0065] Y is one of a chlorine atom, a fluorine atom, or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25, and p is in a range of 0 to 4; and

[0066] X is a chlorine atom or a bromine atom.

[0067] In aspects of the functionalized polymeric amine material, the material can comprise amine groups wherein the amine groups comprise nitrogen, wherein the nitrogen can be equal to or greater than 4% of the material, or equal to or greater than 8% by weight of the material. In a further embodiment, the amine groups can comprise at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine having the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group with equal to or greater than 5% by weight of the amine groups wherein the R1 substituent group can be a metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group can be a linear alkyl with a formula CnHm whereinn is in the range of 2 to 6, and m is in the range of 5 to 15, and the R3 substituent group can be one of: the metal-organic framework, the covalent organic framework, the porous polymer, a linear alkyl group with a formula CnHm wherein n is in the range of 2 to 6, and m is in the range of 5 to 15, or a hydrogen atom.

[0068] In further embodiments, the functionalized polymeric amine material can comprise at least one of: a surface area a surface area equal to or greater than 2 m2 / g of the material, equal to or greater than 5 m2 / g of the material, or equal to or greater than 10 m2 / g of the material, measured by Brunauer-Emmett-Teller (“BET”) using liquid nitrogen and / or at a temperature of about 77° Kelvin; and pores within a pore size range of 2 nm to 400 nm, wherein the pores within the pore size range of 2 nm to 400 nm having a pore volume greater than 0.2 ml / g of the material, measured by mercury porosimetry.

[0069] In an embodiment, a functionalized polymeric amine material can be mixed with an aqueous liquid to form a slurry comprising the material, wherein the material can be equal to or greater than 80% by weight of the slurry on a dry basis. In another embodiment, a functionalized polymeric amine material can be mixed with an aqueous liquid and polymers acting as binders to form a slurry comprising the material, wherein the material can be equal to or greater than 80% by weight of the slurry on a dry basis.

[0070] In an embodiment, a slurry comprising a functionalized polymeric amine material can be deposited and / or attached onto a substrate with a surface area, excluding the surface area of pores having a pore size of less than 10 microns, of equal to or greater than 0.2 m2per liter of the substrate. In one aspect, the material can be attached, bounded, or included into the substrate by one or more methods of drying the slurry, precipitation of the material from the slurry, forming a solid cake on the substrate, and / or filling the pores of the substrate by filtration or other means to urge the material to the surface of the substrate and / or inside the substrate when the substrate is porous.

[0071] Functionalized Polymeric Amine Structured Sorbent

[0072] A functionalized polymeric amine structured sorbent can be formed by the methods disclosed herein and used in a sorptive separator in a sorptive gas separation process to selectively separate a target component, such as an acid gas component or CO2, from a gas mixture.

[0073] In an embodiment, a functionalized polymeric amine structured sorbent can comprise a functionalized polymeric amine material described herein which can comprise amine groups with nitrogen, wherein the nitrogen can be equal to or greater than 4% by weight of the material.

[0074] The reaction of alkylation using an alkyl halide can be carried out on substrates coated with an un-functionalized polymeric amine material, structured sorbents with an un-functionalized polymeric amine material, or sorbent contactors with an un-functionalized polymeric amine material. In embodiments, attaching and / or coating of the substrate with an un-functionalized polymeric amine and forming of the sorbent substrate or structured sorbent can be performed and achieved prior to functionalization.

[0075] A slurry comprising the un-functionalized polymeric amine material can be attached in and / or on a substrate and / or formed into a structured sorbent, before drying the slurry and at least one of the substrate and structured sorbent and contacting the un- functionalized polymeric amine material with a functionalizing agent in a solution, thereby forming a functionalized polymeric amine substrate and / or structured sorbent. For a structured sorbent, a side with the functionalized amine can be concentrated with the functionalized amine near the surface of the substrate by controlling reaction temperature, rate of addition, sequence of addition with, for example, filling pores with solvent with a mild acid before contacting a solution with a functionalizing agent mixed with a mild acid promoter. In an embodiment, a functionalized polymeric amine material for use as a sorbent can comprise a surface area equal to or greater than 2 m2 / g of the material, equal to or greater than 5 m2 / g of the material, or equal to or greater than 10 m2 / g of the material, measured by BET using liquid nitrogen and / or at a temperature of about 77° Kelvin.

[0076] In an embodiment, a functionalized polymeric amine material can comprise amine groups having nitrogen, wherein the nitrogen can be equal to or greater than 4% by weight of the material or equal to or greater than 8% by weight of the material, the amine group can be functionalized by a R2 substituent group wherein the R2 can be one of: an alkyl with a formula CnHm wherein n is in a range of 2 to 12 and m is in a range of 2 to 25; an alkene, an alkenyl, an aryl, or a heteroatom substituted alkyl having a formula of CnHmYp wherein

[0077] Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25, and p is in a range of 0 to 5; an alkyl, an alkene, an alkenyl, an aryl, or a fluoro- or chloro substituted alkyl having a formula of CnHmFoClp wherein n is in a range of 2 to 12, m is in a range of 2 to 25, o is in a range of 0 to 4, and p is in a range of 0 to 4; an alkyl, an alkene, an alkenyl, an aryl, or a fluoro- or chloro substituted alkyl with a formula CnHmYp wherein

[0078] Y is one of a chlorine atom, a fluorine atom, or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25, p is in a range of 0 to 4; and a linear alkyl with a formula CnHm where n is in a range of 2 to 6, and m is in a range of 5 to 15. In an embodiment, a functionalized polymeric amine polymer material can comprise a surface area, in a range of equal to or greater than 2 m2 / g of the material and equal to or less than 50 m2 / g of the material, measured by BET using liquid nitrogen and / or at a temperature of about 77° Kelvin. In another embodiment, a polymeric amine polymer material can comprise a surface area in a range of equal to or greater than 2 m2 / g of the material and equal to or less than 50 m2 / g of the material, measured by BET using liquid nitrogen and / or at a temperature of about 77° Kelvin, after drying the material at 110°C for 1 h.

[0079] In a further embodiment, a functionalized polymeric amine material can comprise pores within a pore size range of 2 nm to 400 nm measured, by mercury porosimetry, wherein the pores within the pore size range of 2 nm to 400 nm can have a pore volume of equal to or greater than 0.5 ml / g of the material, measured by mercury porosimetry.

[0080] In an embodiment, a functionalized polymeric amine material can comprise amine groups having nitrogen, wherein the nitrogen can be equal to or greater than 4% by weight of the material and functionalized by a R2 substituent group, wherein the R2 can be a linear alkyl group with a formula CnHm where n is in the range of 2 to 6, and m is in the range of 5 to 15. In one aspect, the polymeric amine polymer material can comprise pores in the range of 0.2 nm to 200 nm, wherein the pores in the range of 0.2 nm to 200 nm have a pore volume, in a range of equal to or greater than 0.2 ml / g and equal to or less than 2 ml / g of the material, measured by mercury porosimetry, after drying at 110°C for 1 h.

[0081] In an embodiment, a functionalized polymeric amine structured sorbent can comprise a functionalized polymeric amine material disclosed herein and a substrate having a wetted surface area equal to or greater than 0.2 m2per liter of the substrate, wherein the surface area excludes a pore surface area of pores with a pore size of less than 150 microns. In aspects, the surface area can be measured by BET using liquid nitrogen and / or at a temperature of about 77° Kelvin.

[0082] In further embodiments, a functionalized polymeric amine structured sorbent can comprise at least one of a binder; a binder having a polymer; a wetted surface area equal to or greater than 0.2 m2 / L of the structured sorbent; and amine groups having nitrogen covalently bonded to at least one R2 substituent group, wherein the nitrogen can be equal to or greater than 4% by weight of the structured sorbent.

[0083] In embodiments of a functionalized polymeric amine structured sorbent, the functionalized polymeric amine material can comprise at least one of: amine groups having nitrogen, wherein the nitrogen is equal to or greater than 4% by weight of the structured sorbent; pores within a pore size range of 2 nm to 400 nm, wherein the pores within the pore size range of 2 nm to 400 nm having a pore volume of equal to or greater than 0.2 ml / g of the material measured by mercury porosimetry, and pores within a pore size range of 0.2 nm to 200 nm, wherein the pores within the pore size range of 0.2 nm to 200 nm having a pore volume in a range of 0.2 ml / g to 2 ml / g of the material measured by mercury porosimetry.

[0084] Method of Synthesizing a Functionalized Polymeric Amine Material

[0085] In an embodiment, a functionalized polymeric amine material can comprise amine groups with nitrogen, wherein the nitrogen with equal to or greater than 4% by weight of the material or equal to or greater than 8% by weight of the material. In one aspect, the functionalized polymeric amine material can comprise a surface area equal to or greater than 2 m2 / g of the material, equal to or greater than 5 m2 / g of the material, or equal to or greater than 10 m2 / g of the material, measured by BET using liquid nitrogen and / or at a temperature of about 77° Kelvin. The functionalized polymeric amine material can be synthesized with the following embodiments.

[0086] In an embodiment, a method of synthesizing a functionalized polymeric amine material can comprise the following steps: contacting and reacting at least one amine polymer with a solution comprising at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, and a heteroatom substituted alkyl halide of formula R2X, forming a mixture and forming a functionalized polymeric amine material.

[0087] In one aspect, the material can comprise a polymeric amine with amine groups wherein the amine groups can be equal to or greater than 4% by weight of the material and the amine group having nitrogen, wherein the nitrogen can be covalently bonded to at least one R2 substituent group. In a further embodiment the method can further comprise the step of reacting the at least one amine polymer with a base by adding a base to the mixture. In one aspect, the base can be potassium carbonate. The presence of base can neutralize the formed hydrogen halide acid from the reaction of the alkyl or derived alkyl halide molecule with the amine groups in the polymer.

[0088] In a further embodiment, the method can comprise the step of reacting the at least one amine polymer with a non-aqueous solvent at a temperature in a range of - 10°C to 50°C. In one aspect, the method can comprise the step of reacting the at least one amine polymer at a pressure equal to or less than 2 bar absolute, or preferably at atmospheric pressure. In a further embodiment, the method can comprise adding an aqueous solution to the mixture. In one aspect, adding an aqueous solution to the mixture for terminating a reaction between the halide and the amine functions in the amine polymer.

[0089] In a further embodiment, the synthesis method can comprise the step of washing the solids by adding a liquid, for example, water, to remove the solvent, salt formed, and / or the base.

[0090] In an embodiment, a functionalized polymeric amine material can be mixed with an aqueous liquid to form a slurry comprising the material, wherein the material can be equal to or greater than 80% by weight of the slurry on a dry basis. In another embodiment, a functionalized polymeric amine material can be mixed with an aqueous liquid and polymers acting as binders to form a slurry comprising the material, wherein the material can be equal to or greater than 80% by weight of the slurry on a dry basis.

[0091] In an embodiment, a slurry comprising a functionalized polymeric amine material can be deposited and / or attached onto a substrate with a surface area, excluding the surface area of pores having a pore size of less than 10 microns, of equal to or greater than 0.2 m2per liter of the substrate. In one aspect, the material can be attached, bounded, or included into the substrate by one or more methods of drying the slurry, precipitation of the material from the slurry, forming a solid cake on the substrate, and / or filling the pores of the substrate by filtration or other means to urge the material to the surface of the substrate and / or inside the substrate when the substrate is porous.

[0092] In an embodiment, a method of synthesizing a functionalized polymeric amine material, the method can comprise the following steps: reacting at least one amine polymer with a solution and forming a mixture, wherein the at least one amine polymer comprises nitrogen equal to or greater than 4% by weight of the material and a surface area of equal to or greater than 2 m2 / g, equal to or greater than 5 m2 / g of the material, or equal to or greater than 10 m2 / g of the material, measured by Brunauer-Emmett-Teller (BET) using liquid nitrogen and / or at a temperature of about 77° Kelvin, and wherein the solution comprises at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, a fluoro- or chloro substituted alkyl halide with a formula R2X, wherein

[0093] R2 is an alkyl group, an alkene group, an alkenyl group, an aryl group, a fluoro- or chloro substituted alkyl group a formula CnHmYp where Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, and

[0094] X is a chlorine or bromine atom.

[0095] In an embodiment, a method of synthesizing a functionalized polymeric amine material, the method can further comprise at least one of: during the reacting, adding a base to the mixture; during the reacting, adding a base to the mixture, wherein the base is potassium carbonate; the reacting is at a temperature in a range of -10°C to 50°C; the reacting is at a pressure of equal to or less than 2 bar absolute; the reacting is at a pressure of atmospheric pressure; the reacting is at least one of: at a temperature in a range of -10°C to 50°C, and at a pressure of equal to or less than 2 bar absolute or at atmospheric pressure; during the reacting, adding an aqueous solution to the mixture; during the reacting, adding an aqueous solution to the mixture for terminating the reacting between the halide and the amine functions; after the reacting, adding an aqueous solution and a polymer as a binder for forming a slurry; after the reacting, adding an aqueous solution and a polymer as a binder for forming a slurry, wherein the material is equal to or greater than 80% by weight of the slurry on a dry basis; and at least one of: drying the slurry, precipitating the material from the slurry, filtering the material from the slurry, and depositing the material in and / or on a substrate.

[0096] Functionalization of coated substrates, structured sorbents, or sorbent contactors

[0097] In an embodiment, a method of forming a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent, which can comprise a wetted surface area of equal to or greater than 0.2 m2 / L, and at least one amine polymer with nitrogen wherein the nitrogen can be equal to or greater than 4% by weight of the functionalized polymeric amine substrate and / or the functionalized polymeric amine structured sorbent, is disclosed herein.

[0098] In an embodiment, a method of forming a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent can comprise contacting a substrate or a structured sorbent with a solution comprising at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, a fluoro- or chloro substituted alkyl halide of formula R2X, wherein,

[0099] R2 is an alkyl group, an alkene group, an alkenyl group, an aryl group, a fluoro- or chloro substituted alkyl group a formula CnHmYp, wherein Y is one of a chlorine atom, a fluorine atom, or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, and

[0100] X is a chlorine atom or a bromine atom.

[0101] In one aspect, the method forms a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent, which can comprise a polymeric amine having amine groups with nitrogen, wherein the nitrogen can be equal to or greater than 4% by weight of the sorbent substrate or structured sorbent and the nitrogen can be covalently bonded to one or more R2 substituent group. In an embodiment, a method of forming a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent, which can comprise a wetted surface area of equal to or greater than 0.2 m2 / L of the substrate or structured sorbent, can comprise at least one amine polymer with nitrogen wherein the nitrogen can be equal to or greater than 4% by weight of the substrate or structured sorbent.

[0102] In an embodiment, a method of forming a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent can comprise contacting a substrate having at least one amine polymer, or a structured sorbent having at least one amine polymer, with a solution comprising at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, a fluoro- or chloro substituted alkyl halide of formula R2X. In one aspect, the method forms a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent, which can comprise a polymeric amine having amine groups with nitrogen wherein the nitrogen can be equal to or greater than 4% by weight of the substrate or structured sorbent and the amine groups having nitrogen, wherein the nitrogen can be covalently bonded to one or more R2 substituent group.

[0103] In an embodiment, a method of forming a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent can comprise contacting a substrate or a structured sorbent having at least one amine polymer material or un-functionalized polymeric amine material with a solution, wherein the at least one amine polymer comprises nitrogen equal to or greater than 4% by weight of the material and a surface area of equal to or greater than 2 m2per gram of the material measured by Brunauer-Emmett-Teller (BET) using liquid nitrogen and / or at a temperature of about 77° Kelvin, wherein the solution can comprise at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, a fluoro- or chloro substituted alkyl halide of formula R2X, wherein

[0104] R2 is an alkyl group, an alkene group, an alkenyl group, an aryl group, a fluoro- or chloro substituted alkyl group a formula CnHmYp, wherein Y is one of a chlorine atom, a fluorine atom, or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, and

[0105] X is a chlorine atom or a bromine atom. Description of a sorptive gas separation application

[0106] A functionalized polymeric amine material disclosed herein can be used as a sorbent and configured with a substrate or structured sorbent, for forming a functionalized polymeric amine substrate or a functionalized polymeric amine structured sorbent, which can be used for a sorptive gas separation process, such as, separating a target component for example, an acid gas component such as CO2, from a multicomponent gas stream. For example, the multi-component gas stream can be, a flue gas stream, a process gas stream, a biogas stream, a bio-methane gas stream, an air stream, or an atmospheric air stream.

[0107] In an embodiment, a sorptive gas separation process can comprise the following steps:

[0108] (a) admitting a multi-component gas stream as a feed stream into a sorptive separator comprising at least one of a functionalized polymeric amine material as a sorbent, a functionalized polymeric amine substrate, and a functionalized polymeric amine structured sorbent, contacting the feed stream with the at least one of the sorbent, the substrate, and the structured sorbent, sorbing a first component from the feed stream on and / or in the at least one of the sorbent, the substrate, and the structured sorbent in the sorptive separator thereby separating the first component from the feed stream and producing a first product stream depleted in a first component relative to the feed stream, and recovering the first product stream from the sorptive separator, and

[0109] (b) desorbing the first component from the at least one of the sorbent the substrate, and the structured sorbent in the sorptive separator by at least one of a temperature swing, a partial pressure swing, a moisture swing, a pressure swing, thereby producing a second product stream enriched in the first component relative to the feed stream, and recovering the second product stream from the sorptive separator.

[0110] In embodiments, the sorptive gas separation process can comprise at least one of the following steps: after step (b) repeating steps (a) and (b); after step (b) further comprising: a step (c) conditioning the at least one of the sorbent, the substrate, and the structured sorbent by at least one of: reducing a temperature of the at least one of the sorbent, the substrate, and the structured sorbent relative to a temperature of the at least one of the sorbent, the substrate, and the structured sorbent during step (b), desorbing water from the at least one of the sorbent, the substrate, and the structured sorbent, and increasing a pressure at the at least one of the sorbent, the substrate, and the structured sorbent relative to a pressure of the at least one of the sorbent, the substrate, and the structured sorbent during step (b); after step (c) repeating steps (a), (b), and (c).

[0111] In embodiments, the sorptive gas separation process can comprise at least one of: the sorbent, the substrate, or the structured sorbent having a functionalized polymeric amine material disclosed herein, the multi-component gas stream is at least one of a flue gas stream, a process gas stream, a biogas stream, a bio-methane gas stream, an air stream, or an atmospheric air stream; the first component is acid gas component or CO2.

[0112] Fig. 1a illustrates the novel synthesis reaction of a commercially available amine-rich polymer resin (polystyrene-divinylbenzene, referred herein as “SX”) and 1- bromopropane resulting in the alkylation of the SX. As shown in Fig. 1a, a SX resin 1 can be reacted with a weak base 2, resulting in an alkylated SX 3. Fig. 1 b illustrates the reaction mechanism during synthesis, showing a secondary amine 4 reacting with a halogenoalkane 5 resulting in an alkyl-substituted amine 6 and a halogen acid 7. Fig. 1c illustrates the resulting functionalized amine polymer with a covalent bond to a carbon atom from an alkyl or substituted alkyl group.

[0113] Figs. 2a and 2b are process flow diagrams illustrating two methods and sequence of steps for producing a functionalized polymeric amine structured sorbent.

[0114] Fig 2a illustrates a method which can comprise the steps of: obtaining an un-functionalized amine polymer material in an obtaining step 20; functionalizing the amine polymer in a functionalizing material step 22; and a forming the functionalized polymeric amine structured sorbent in a forming step 24. The amine polymer material can be supplied in a form of a powder. During the functionalizing material step 22, a functionalized polymeric amine material is produced. During the forming step 24 the functionalized polymeric amine material can be attached to and / or formed into and / or onto a substrate, a structured sorbent, and / or a contactor.

[0115] Fig. 2b illustrates a method which can comprise the steps of: obtaining an un-functionalized amine polymer material in an obtaining step 20; forming an unfunctionalized polymeric amine structured sorbent in a forming step 26; and functionalizing the un-functionalized polymeric amine structured sorbent in a functionalizing step 28.

[0116] The amine polymer material can be supplied in a form of a powder. During the forming step 26, the un-functionalized amine polymer material can be attached to and / or formed into and / or onto a substrate, a structured sorbent, and / or a contactor. During the functionalizing step 28, a solution comprising alkyl halide or substituted alkyl halide can be used to functionalize the amine polymer material, for producing a functionalized polymeric amine structured sorbent.

[0117] Example 1

[0118] With reference to Fig. 1 b, a reaction between a commercial amine-rich polymer resin SX, 1 -bromopropane and 1-bromo-3-methylbutane (Sigma-Aldrich, 99%) was performed by the steps of: mixing 3 g of SX with 0.6 g of K2CO3 in 20 mL of acetonitrile forming a mixture, adding 0.48g of 1 -bromopropane or 0.6g of 1-bromo-3-methylbutane to the mixture, stirring the mixture for 20 hour at room temperature or approximately 20°C, quenching the reaction by adding water to the mixture, separating and recovering solids from the mixture by vacuum filtration, washing the solids with deionized water, washing the solids with methanol, and drying the solids in a vacuum oven at 70°C for 16 hours, thereby producing a functionalized polymeric amine material (in a form of a powder) which can be used as a sorbent.

[0119] The functionalized polymeric amine material was analyzed by placing the functionalized polymeric amine material in a thermogravimetric analysis (also referred to as “TGA”) instrument and cyclically exposing the functionalized polymeric amine material to a nitrogen and CO2 gas mixture with 15% by volume CO2 and 85% by weight nitrogen at 50°C, dry air, a gas mixture with 20.9% by volume oxygen at 110°C for 1 hour, and air for cooling the functionalized polymeric amine material to 50°C. Sorption capacities of the functionalized polymeric amine material for a gas mixture with 15% by volume of CO2 at 50°C was recorded over a number of cycles and an oxidative degradation of the functionalized polymeric amine material was compared to an unfunctionalized polymeric amine powder under the same conditions.

[0120] Fig. 3a is a graph showing CO2 working sorptive capacity in cc / g at standard temperature and pressure (also referred to as “STP”) (along the y-axis) versus a number of cycles (along the x-axis), comparing an unfunctionalized polymeric amine material “SX” shown as a plot 30 and three functionalized polymeric amine materials SX with 1-bromo-3-methylbutane, shown as a plot 32, a plot 34 and a plot 36. The conditions were described above and 10 cycles had a cumulative time of 10 hours or an equivalent of 1 hour per cycle.

[0121] Fig. 3b is a graph showing a CO2 normalized sorptive capacity as a percentage of an initial capacity (along the y-axis) versus a number of cycles (along the x-axis) of the same materials (unfunctionalized polymeric amine material “SX” shown as a plot 30 and three functionalized polymeric amine materials SX with 1-bromo-3- methylbutane, shown as a plot 32, a plot 34 and a plot 36), and conditions in Fig. 3a.

[0122] A degradation in sorptive capacity of a material or sorbent can be defined as a difference between a sorptive capacity of a fresh sorbent and a sorptive capacity of a sorbent after use. Fig. 3b shows after 10 cycles, a degradation in sorptive capacity of a functionalized polymeric amine material as shown by plot 32 can be about 42% less than a degradation in sorptive capacity of an unfunctionalized polymeric amine material as shown by plot 30.

[0123] Table 1 below compares a sorbent’s sorptive capacity for H2O and CO2 as a change in percentage (%) by mass, referred to herein as “H2O uptake” and “CO2 uptake” for the functionalized polymeric amine materials listed as “Epoxy-SX” (epoxy functionalized) and “Alkylation-SX” (alkyl functionalized) and three different reference materials listed as “S4+”, “PNP-1” and “-SX”. The Alkylation-SX material was described as Example 1 above. The tests were conducted in the TGA instrument using a nitrogen stream with 400 ppm CO2 at a temperature of 10°C and a relative humidity of 90%.

[0124] Table 1 - Comparison of H2O uptake and CO2 uptake of various sorbents

[0125] Table 1 shows a CO2 sorptive capacity of the Alkylation-SX (alkyl- functionalized amine polymeric material) is similar to the SX (un-functionalized amine polymeric material), while a sorptive capacity for water of the Alkylation-SX was reduced by about 15% relative to the SX. The reduction in sorptive capacity for water is desirable for sorptive gas separation applications where one or more influent streams supplied to a sorptive gas separator can comprise elevated levels of moisture, as excessive water adsorption on a sorbent can interfere with diffusion of a target component from a feed stream to the sorbent as well as an undesirably increasing a mass and a heat capacity of the sorbent which can result in consuming additional energy for raising a temperature of the sorbent desired for regeneration. Table 1 shows the Alkylation-SX material having the least uptake of H2O relative to the sorbents tested as well as a greater uptake of CO2 relative to the Epoxy-SX or epoxy-functionalized amine polymeric material.

[0126] Example 2

[0127] Additional alkyl-functionalized amine polymeric materials were prepared with the same conditions and molar ratios of bromide to amine groups as in Example 1 . The SX material was reacted with the following alkyl halide reagents: bromoethane, 1- bromopropane, 2-bromopropane, 1 -bromobutane, 2-bromobutane, 1-bromo-2- methylpropane, 1-bromo-2-ethylbutane, 1 bromo-3-methylbutane, 2-bromo-2- methylpropane.

[0128] The additional alkyl-functionalized amine polymeric materials were tested for sorptive capacity for CO2 versus a number cycles under the same conditions as described above. A comparison of the SX unfunctionalized amine polymeric material with the additional alkyl-functionalized amine polymeric materials are shown in Table 2.

[0129] Table 2 -Comparison of SX with additional alkyl-functionalized amine polymeric materials

[0130] Fig. 4 illustrates the chemical structure of the alkyl halide reagents: bromoethane, 1 -bromopropane, 2-bromopropane, 1 -bromobutane, 2-bromobutane, 1- bromo-2-methylpropane, 1-bromo-2-ethylbutane, 1 bromo-3-methylbutane, 2-bromo-2- methylpropane.

[0131] It is notable that the linear alkyl chain addition provides a reduced sorptive capacity loss and can offer a greater oxidative protection while some branched alkyl substituents showed some degree of oxidative protection while others do not. Alkyl groups sterically hindering the amine can be less likely to form tertiary amine with multiple branched groups attached to the same nitrogen.

[0132] Example 3

[0133] An aliquot of the material prepared in Example 1 in a form of a powder was tested for adsorption kinetics in a dynamic vapor sorption (also referred to as “DVS”) unit with a feed gas comprising an air stream with a CO2 concentration of 400 ppm, and a relative humidity of 90%, and at a temperature of 10°C. After exposing the material to the feed stream the CO2 was desorbed from the sorbent by heating the material to 85°C while flushing the material with nitrogen for one hour.

[0134] Fig. 5 is a graph showing test results of sorption kinetics in weight as a percent (along the y-axis) versus time in minutes (along the x-axis) for an alkylation-SX sorbent compared to three others amine-based sorbents: the unfunctionalized resin designated as “SX”, a copolymer of divinyl benzene and vinyl ethyl amine designed at “PNP-1” and a polyethylenimide supported on high pore volume Silica substrate designed as “S4+”. A SX plot 50 shows the unfunctionalized amine polymeric material SX, an alkylation-SX plot 52 shows the alkyl-functionalized amine polymeric material produced as Example 1 , a PNP-1 plot 54 shows the poly(allylamine-co-divinylbenzene) material, and a S4+ plot 56 shows the polyethylenimine material impregnated into a porous silica substrate or support.

[0135] Fig. 5 shows alkylation-SX plot 52 or the alkyl-functionalized amine polymeric material having an increased rate of CO2 adsorption or at the test conditions relative to the SX, PNP-1 , and S4+ materials tested. The adsorption rate for the

[0136] Alkylation-SX material is about 50% faster than for the SX material or unfunctionalized amine polymeric material.

Claims

Claims:1 . A functionalized polymeric amine material comprising amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine further comprising the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group is an alkyl with a formula CnHm where n is in a range of 2 to 12 and m is in a range of 2 to 25, and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkyl with a formula CnHm where n is in a range of 2 to 12 and m is in a range of 2 to 25, or a hydrogen atom.

2. A functionalized polymeric amine material comprising amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine further comprising the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group is an alkene, an alkenyl, an aryl, a heteroatom substituted alkyl having a formula of CnHmYp wherein Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer,an alkene, an alkenyl, an aryl, a heteroatom substituted alkyl having a formula of CnHmYp wherein Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, or a hydrogen atom.

3. A functionalized polymeric amine material comprising amine groups having at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the at least one of the primary amine, the secondary amine and the tertiary amine is equal to or greater than 5% by weight of the amine groups, and the primary amine further comprising a R1 substituent group, the secondary amine and the tertiary amine further comprising the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group, wherein the R1 substituent group is a metal-organic framework, a covalent organic framework, or a porous polymer; the R2 substituent group is an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl having a formula of CnHmFoClp wherein n is in a range of 2 to 12, m is in a range of 2 to 25, o is in a range of 0 to 4, and p is in a range of 0 to 4; and the R3 substituent group is one of: the metal-organic framework, the covalent organic framework, the porous polymer, an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl having a formula of CnHmFoClp wherein n is in a range of 2 to 12, m is in a range of 2 to 25, o is in a range of 0 to 4, and p is in a range of 0 to 4, or a hydrogen atom.

4. A functionalized polymeric amine material produced by reacting a polymer amine and at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, and a substituted alkyl halide of formula R2X, whereinR2 is an alkyl, an alkene, an alkenyl, an aryl, a fluoro- or chloro substituted alkyl with a formula CnHmYp wherein Y is one of a chlorine atom, a fluorine atom, or a nitrogen atom, and n is in a range of 2 to 12, m is in a range of 2 to 25, and p is in a range of 0 to 4; andX is a chlorine atom or a bromine atom.

5. The material of claim 4, wherein the material comprises amine groups comprising at least one of a primary amine, a secondary amine, and a tertiary amine, wherein the primary amine further comprises a R1 substituent group, the secondary amine and the tertiary amine further comprising the R1 substituent group and at least one of a R2 substituent group and a R3 substituent group with equal to or greater than 5% by weight of the amine groups wherein the R1 substituent group is aa metal-organic framework, a covalent organic framework, or a porous polymer, the R2 substituent group is a linear alkyl with a formula CnHm wherein n is in the range of 2 to 6, and m is in the range of 5 to 15, and the R3 substituent group can be one of: the metal-organic framework, the covalent organic framework, the porous polymer, a linear alkyl group with a formula CnHm where n is in the range of 2 to 6, and m is in the range of 5 to 15, or a hydrogen atom.

6. The material of any one of claims 1 to 5, wherein the amine groups comprise nitrogen, and wherein the nitrogen is equal to or greater than 4% by weight of the material.

7. The material of any one of claims 1 to 6, further comprising a surface area equal to or greater than 2 m2 / g of the material.

8. The material of any one of claims 1 to 5, further comprising pores having a pore size in a range of 2 nm to 400 nm, wherein the pores have a pore volume greater than 0.2 ml / g of the material.

9. A functionalized polymeric amine structured sorbent comprising the material of any one of claims 1 to 8 and a substrate having a wetted surface area equal to or greater than 0.2 m2 / L of the substrate, wherein the surface area excludes a pore surface area of pores with a pore size of less than 150 microns.

10. The structured sorbent of claim 9, further comprising a binder.11 . The structured sorbent of claim 9 or 10, wherein the material further comprises amine groups having nitrogen, and wherein the nitrogen is equal to or greater than 4% by weight of the structured sorbent.

12. The structured sorbent of any one of claims 9 to 11 , wherein the material comprises pores having a pore size in a range of 2 nm to 400 nm, wherein the pores have a pore volume of equal to or greater than 0.2 ml / g of the material.

13. The structured sorbent of any one of claims 9 to 12, wherein the material comprises pores within a pore size range of 0.2 nm to 200 nm, wherein the pores have a pore volume in a range of 0.2 ml / g to 2 ml / g of the material.

14. The structured sorbent of any one of claims 9 to 13, further comprising a wetted surface area equal to or greater than 2 m2 / L of the structured sorbent.

15. The structured sorbent of any one of claims 9 to 14, further comprising at least one of: amine groups having nitrogen, wherein the nitrogen iscovalently bonded to at least one R2 substituent group, and the nitrogen is equal to or greater than 4% by weight of the structured sorbent.

16. A method of synthesizing a functionalized polymeric amine material, the method comprising: reacting at least one amine polymer with a solution and forming a mixture, wherein the at least one amine polymer comprises nitrogen equal to or greater than 4% by weight of the material, and has a surface area of equal to or greater than 2 m2 / g of the material, and wherein the solution comprises at least one of an alkyl halide, an alkene halide, an alkenyl halide, an aryl halide, a fluoro- or chloro substituted alkyl halide with a formula R2X, wherein the R2 is an alkyl group, an alkene group, an alkenyl group, an aryl group, a fluoro- or chloro substituted alkyl group a formula CnHmYp, where Y is one of a chlorine atom, a fluorine atom or a nitrogen atom, n is in a range of 2 to 12, m is in a range of 2 to 25 and p is in a range of 0 to 5, andX is a chlorine atom or a bromine atom.

17. The method of claim 16, further comprising adding a base during the reaction.

18. The method of claim 16 or 17, wherein the reacting is at least one of: at a temperature in a range of -10°C to 50°C, and at a pressure of equal to or less than 2 bar absolute.

19. The method of any one of claims 16 to 18, further comprising adding an aqueous solution during the reaction.

20. The method of any one of claims 16 to 19, further comprising adding an aqueous solution and a polymer as a binder for forming a slurry, wherein the material is equal to or greater than 80% by weight of the slurry on a dry basis.21 . The method of claim 20, further comprising at least one of: drying the slurry, precipitating the material from the slurry, filtering the material from the slurry, and depositing the material in and / or on a substrate.

22. A sorptive gas separation process, the process comprising: a. admitting a multi-component gas stream as a feed stream into a sorptive separator comprising a functionalized polymeric amine material of any one of claims 1 to 8 as a sorbent or a functionalized polymeric amine structured sorbent of any one of claims 9 to 15, contacting the feed stream with the sorbent or structured sorbent, sorbing a first component from the feed stream on and / or in the sorbent or the structured sorbent thereby separating the first component from the feed stream and producing a first product stream depleted in a first component relative to the feed stream, and recovering the first product stream from the sorptive separator, and b. desorbing the first component from the sorbent or the structured sorbent in the sorptive separator by at least one of a temperature swing, a partial pressure swing, a moisture swing, a pressure swing, thereby producing a second product stream enriched in the first component relative to the feed stream, and recovering the second product stream from the sorptive separator.

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