Amine-functionalized solid adsorbent materials and adsorbent composites for capturing carbon dioxide and methods of making the same

Abstract

Amine-functionalized solid adsorbent materials and adsorbent composites for capturing carbon dioxide and methods of making the same are provided.SOLUTION: Described herein are methods of making or rejuvenating a solid adsorbent composite comprising an amine and a porous support. The solid adsorbent composite exhibits a high adsorption capacity for carbon dioxide. The solid adsorbent composite exhibits desirable hydrothermal stability and cycling stability.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Described herein are methods for preparing or restoring solid sorbent composites comprising an amine and a porous support. The solid sorbent composites exhibit high adsorption capacity for carbon dioxide. The solid sorbent composites exhibit desirable hydrothermal and cycling stability. [Background technology]

[0002] The use of solid sorbent materials for carbon capture offers a viable and superior techno-economic alternative to conventional liquid amine-based carbon dioxide (CO2) capture processes. Solid sorbents tend to have better adsorption capacity, lower regeneration energy requirements, reduced system complexity, and reduced environmental and safety risks relative to activated liquid amines.

[0003] There are two types of adsorbent materials based on the underlying adsorption mechanism: physical adsorbents and chemical adsorbents. Physical adsorbents, such as activated carbon and zeolites, rely on van der Waals interactions, hydrogen bonding, or other electrostatic forces to adsorb gaseous species such as CO2 and water (HO). Chemical adsorbents, particularly amine-functionalized silica particles and metal-organic frameworks (MOFs), adsorb CO2 through reversible chemical reactions and the formation of ammonium carbamate, carbamic acid, ammonium carbonate, and / or ammonium bicarbonate. Although physical adsorbent materials are relatively mature compared to chemical adsorbent materials, one significant drawback of physical adsorbent materials is the significantly reduced CO2 adsorption capacity due to interference from other polar molecules, such as HO, which are inevitably present in the atmosphere and flue gases. In contrast, as a result of chemical bonding, chemisorbent materials generally have superior selectivity for CO adsorption over other interfering species such as nitrogen (N), oxygen (O), methane, and carbon monoxide (CO) relative to their physisorbent counterparts.

[0004] An ideal chemical sorbent material should have good CO2 adsorption capacity, fast adsorption kinetics, easy and fast desorption characteristics under practical desorption conditions, and good thermal and hydrothermal stability.

[0005] Amine-functionalized sorbents, presented in either pristine powder or heterocomposite formats, can degrade over time during storage or field operation. Degradation can result from oxidation in the presence of oxidizing species such as oxygen, loss of amine content due to evaporation or high airflow, and / or decomposition due to side reactions during field operation. It is necessary to revive the sorbent composite over time, compared to disposing of a composite-containing contactor with degraded performance.

[0006] In this disclosure, a solid adsorbent comprising an amine and a porous support has been developed and demonstrated that has high adsorption capacity for carbon dioxide. The solid adsorbent exhibits desirable hydrothermal and cycling stability. Summary of the Invention

[0007] In one aspect, a method of making or reviving an absorbent article is provided, the method including the steps of: (a) providing a starting article comprising a first amine having a first amine content, (b) providing a second amine, (c) contacting the starting article comprising the first amine with the second amine, and (d) obtaining a treated article having a second amine content, wherein the second amine content is higher than the first amine content.

[0008] These and other features, aspects, and advantages of the present disclosure will be better understood from the following detailed description taken in conjunction with the accompanying drawings, in which like reference numerals represent like parts throughout. [Brief explanation of the drawings]

[0009] [Figure 1] 1 illustrates an exemplary method for obtaining a treated article according to the present disclosure. [Figure 2]1 illustrates an exemplary method for making or reviving a sorbent powder according to the present disclosure. [Figure 3] 1 illustrates an exemplary method for creating or restoring a composite according to the present disclosure. [Figure 4] 1 illustrates an exemplary method for creating or restoring a composite using an amine solution according to the present disclosure. [Figure 5] 1 illustrates an exemplary method for preparing or reviving a composite coated contactor using an amine solution according to the present disclosure. [Figure 6] 1 illustrates an exemplary method for creating or reviving a composite using amine vapor according to the present disclosure. [Figure 7] 1 illustrates an exemplary method for creating or reviving a sorbent powder using an amine solution according to the present disclosure. [Figure 8] 1 illustrates an exemplary method for creating or reviving a sorbent powder containing partially covalently bonded amines using an amine solution according to the present disclosure. [Figure 9] 1 illustrates an exemplary method for creating or restoring a composite that includes a first amine that is not covalently bonded to the composite according to the present disclosure. [Figure 10] 1 illustrates an exemplary method of making or reviving a composite including a thermosetting binder and a first amine according to the present disclosure. [Figure 11] FIG. 1 shows an exemplary scheme for grafting (p-chloromethyl)phenyltrimethoxysilane (PCPT) onto γ-AlO to form an adsorbent containing covalently bound amines via amine alkylation using an amine and an alkylhalogen (—Cl) in accordance with the present disclosure. [Figure 12] 1 shows exemplary TGA traces of GE409, including γ-AlO, PCPT-grafted γ-AlO, PCPT-grafted γ-AlO with covalently bound spermine (GE351-SG2-39), and GE351-SG2-39 with additional impregnated PEHA, in accordance with the present disclosure. [Figure 13]FIG. 1 shows exemplary TGA traces of GE411-A3170B comprising γ-AlO, PCPT-grafted γ-AlO, PCPT-grafted γ-AlO with covalently bound spermine (GE351-SG2-39), and GE351-SG2-39 with additional impregnated PEHA and crosslinker (1,5-hexadiene diepoxide) in accordance with the present disclosure. [Figure 14] FIG. 1 shows exemplary TGA traces of GE417-A3167B comprising γ-AlO, PCPT-grafted γ-AlO, PCPT-grafted γ-AlO with covalently bound spermine (GE351-SG2-39), and GE351-SG2-39 with additional impregnated PEHA and crosslinker (1,5-hexadiene diepoxide) in accordance with the present disclosure. [Figure 15] 1 shows an exemplary NMR analysis of 0.27 1,2-epoxybutane:spermine (O / N) in 600 μL of CD3OD with residual methanol (3.35 ppm) in accordance with the present disclosure.

[0010] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the illustrated embodiments.

[0011] Unless otherwise indicated, the drawings provided herein are meant to illustrate features of embodiments of the present disclosure. These features are believed to be applicable in a wide variety of systems comprising one or more embodiments of the present disclosure. Thus, the drawings are not intended to include all conventional features known to those skilled in the art that are required for the practice of the embodiments disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0012] method.

[0013] Disclosed herein are methods for making or revitalizing absorbent articles. In some embodiments, the methods include: (a) providing a starting article comprising a first amine having a first amine content; (b) providing a second amine; (c) contacting the starting article comprising the first amine with the second amine; and (d) obtaining a treated article having a second amine content, wherein the second amine content is higher than the first amine content.

[0014] Referring to the drawings, according to one embodiment shown in FIG. 1, a method of making an article capable of adsorbing CO2 includes the steps of: (a) providing a starting article (100) comprising a first amine (101) having a first amine content (102); (b) providing a second amine (103); (c) contacting the starting article (100) comprising the first amine (101) with the second amine (103); and (d) obtaining a treated article (105) having a second amine content (104), wherein the second amine content (104) is higher than the first amine content (102).

[0015] Nitrogen (N) content in weight percent (N(wt%)) is used to quantify the amine content. N(wt%) can be quantitatively measured along with carbon (C) and hydrogen (H) content using inductively coupled plasma (ICP) elemental analysis, or commonly known as CHN analysis.

[0016] In one embodiment, the starting article (100) has a first amine content (102) that is zero. In another embodiment, the second amine content (104), expressed as N (wt%), is 0.1 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 0.5 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 1.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 1.0 to 30.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 1.0 to 20.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 1.0 to 5.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 5.0 to 25.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 5.0 to 20.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 5.0 to 15.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 5.0 to 10.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 10.0 to 20.0 wt% higher than the first amine content (102). In another embodiment, the second amine content (104), expressed as N (wt%), is 10.0 to 15.0 wt% higher than the first amine content (102).

[0017] The method may optionally include washing the starting article (100) comprising the first amine (101) having a first amine content (102) to extract or remove at least a portion of the first amine (101) or decomposed by-products prior to contacting the starting article (100) comprising the first amine (101) with the second amine (103). The method may optionally include a drying step to remove any solvent or any volatile species after contacting the starting article (100) comprising the first amine (101) with the second amine (103). The drying step may be carried out at ambient conditions using airflow or a purge gas, or any other conditions with different combinations of heat, airflow, vacuum, etc.

[0018] According to one embodiment, an adsorbent-containing film composite can be prepared by: (1) creating a slurry formulation containing a solvent, a functionalized adsorbent, and a binder. The solvent can be either aqueous or organic, or a mixture in any ratio. The binder can generally be a polymer or precursor, including a polymer, a mixture of monomers, etc., that crosslinks upon curing. (2) Optionally, additional additives can be incorporated as needed to improve the rheology and coating quality of the slurry. The additives should be compatible with the solvent and the functionalized adsorbent to facilitate adsorbent particle binding and even dispersion through the solvent. (3) applying the slurry onto a substrate by a coating technique such as, but not limited to, spray coating, dip coating, flow coating, spin coating, or drop coating; (4) drying to remove the solvent; and, optionally, (5) curing under irradiation, such as heat or UV light. The substrate may be selected from metals such as aluminum, copper, stainless steel, or ceramic materials, polymeric materials, or combinations thereof. Additionally, the substrate may have additional surface coatings for adhesion, corrosion protection, scratch resistance, etc., as known in the art. Substrates can be of any shape or form, including but not limited to, flat or non-flat plates, structured fin-and-tube such as heat exchangers, monolithic structures, 3D additive printed parts with any shape or geometry, etc.

[0019] According to another embodiment, the adsorbent composite coating can be prepared by: (1) creating a slurry formulation containing a solvent, a binder, an amine- or amine-free support, and at least one amine material. The solvent can be either aqueous or organic, or a mixture in any ratio. The binder material can generally be a polymer or precursor, including polymers, mixtures of monomers, etc., that crosslink upon curing. (2) Optionally, additional additives may be incorporated as needed to improve the rheology and coating quality of the slurry. The additives should be compatible with the solvent and the functionalized adsorbent to facilitate the binding and further dispersion of the adsorbent particles through the solvent. (3) applying the slurry onto a substrate by a coating technique such as, but not limited to, spray coating, dip coating, flow coating, spin coating, or drop coating; (4) drying to remove the solvent; and, optionally, (5) curing under irradiation, such as heat or UV light.

[0020] According to another embodiment shown in FIG. 2 , a method of making or reviving a sorbent powder includes the steps of: (a) providing a starting sorbent powder (200) comprising a first amine (201) having a first amine content (202); (b) providing a second amine (203); (c) contacting the starting sorbent powder (200) comprising the first amine (201) with the second amine (203); and (d) obtaining a treated sorbent powder (205) having a second amine content (204), wherein the second amine content (204) is greater than the first amine content (202).

[0021] According to another embodiment shown in FIG. 3, a method of making or reviving a composite includes the steps of: (a) providing a starting composite (300) comprising a first amine (301) having a first amine content (302); (b) providing a second amine (303); (c) contacting the starting composite (300) comprising the first amine (301) with the second amine (303); and (d) obtaining a treated composite (305) having a second amine content (304), wherein the second amine content (304) is higher than the first amine content (302).

[0022] In one embodiment, the starting composite (300) includes at least a polymer binder that is amine-free, resulting in a zero first amine content (302). In another embodiment, the starting composite (300) includes at least one thermosetting polymer binder that is cured with an amine-containing curing agent. The final binder after thermal curing includes amine groups from the curing agent at least partially covalently bonded to the binder, resulting in a non-zero first amine content (302). In another embodiment, the amine-functionalized sorbent presented as a composite includes at least one thermosetting polymer binder that is cured with an amine-containing curing agent and additional amine moieties that are not chemically bonded to the binder, also resulting in a non-zero first amine content (302).

[0023] According to another embodiment shown in FIG. 4 , a method of making or reviving a composite includes the steps of: (a) providing a starting composite (400) comprising a first amine (401) having a first amine content (402); (b) providing a second amine (403) in a solution (406) having a solvent (407); (c) contacting the starting composite (400) comprising the first amine (401) with the second amine (403) in the solution (406) having the solvent (407); and (d) obtaining a treated composite (405) having a second amine content (404), wherein the second amine content (404) is higher than the first amine content (402).

[0024] The method may optionally include a drying step to remove any solvent or any volatile species after contacting the starting composite (400) comprising the first amine (401) with the second amine (403). The drying step can be carried out at ambient conditions using air flow or a purge gas, or any other conditions with different combinations of heat, air flow, vacuum, etc.

[0025] According to another embodiment shown in FIG. 5 , a method of making or reviving a composite-coated contactor includes the steps of: (a) providing a contactor (508) coated with a starting composite (500) comprising a first amine (501) having a first amine content (502); (b) providing a second amine (503) in a solution (506) having a solvent (507); (c) contacting the starting composite (500) comprising the first amine (501) with the second amine (503) in the solution (506) having the solvent (507); and (d) obtaining a contactor (508) coated with a treated composite (505) having a second amine content (504), wherein the second amine content (504) is higher than the first amine content (502).

[0026] According to another embodiment shown in FIG. 6, a method of making or reviving a composite includes the steps of: (a) providing a starting composite (600) comprising a first amine (601) having a first amine content (602); (b) providing a second amine (603) in a vapor phase, optionally using a carrier gas such as N2 (606); (c) contacting the starting composite (600) comprising the first amine (601) with the second amine (603) in the vapor phase; and (d) obtaining a treated composite (605) having a second amine content (604), wherein the second amine content (604) is higher than the first amine content (602).

[0027] According to another embodiment shown in FIG. 7 , a method of making or reviving a sorbent powder includes the steps of: (a) providing a starting sorbent powder (700) comprising a first amine (701) having a first amine content (702); (b) providing a second amine (703) in a solution (706) having a solvent (707); (c) contacting the starting sorbent powder (700) comprising the first amine (701) with the second amine (703) in the solution (706) having the solvent (707); and (d) obtaining a treated sorbent powder (705) having a second amine content (704), wherein the second amine content (704) is greater than the first amine content (702).

[0028] According to another embodiment shown in FIG. 8 , a method of making or reviving a sorbent powder includes the steps of: (a) providing a starting sorbent powder (800) comprising a first amine (801) having a first amine content (802), wherein the first amine is at least partially covalently bonded to the sorbent powder (800); (b) providing a second amine (803) in a solution (806) having a solvent (807); (c) contacting the starting sorbent powder (800) comprising the first amine (801) with the second amine (803) in the solution (806) having the solvent (807); and (d) obtaining a treated sorbent powder (805) having a second amine content (804), wherein the second amine content (804) is higher than the first amine content (802).

[0029] According to another embodiment shown in FIG. 9 , a method of making or reviving a composite includes the steps of: (a) providing a starting composite (900) comprising a first amine (901) having a first amine content (902), wherein the first amine is at least partially covalently bonded to the composite (900); (b) providing a second amine (903) in a solution (906) having a solvent (907); (c) contacting the starting composite (900) comprising the first amine (901) with the second amine (903) in the solution (906) having the solvent (907); and (d) obtaining a treated composite (905) having a second amine content (904), wherein the second amine content (904) is higher than the first amine content (902).

[0030] According to another embodiment shown in FIG. 10, a method of making or reviving a composite comprises the steps of: (a) providing a starting composite (1000) comprising a first amine (1001) having a first amine content (1002) and a thermosetting binder (1005); (b) providing a second amine (1003) in an aqueous solution (1006); (c) contacting the starting composite (1000) comprising the first amine (1001) with the second amine (1003) in the aqueous solution (1006); and (d) obtaining a treated composite (1007) comprising a thermosetting binder (1005) and having a second amine content (1004), wherein the second amine content (1004) is higher than the first amine content (1002).

[0031] Adsorbent.

[0032] Described herein are solid adsorbents comprising an amine and a porous support. In some embodiments, the amine is at least partially covalently bound to the porous support. In some embodiments, the amine is covalently bound to the porous support. In some embodiments, the amine is not covalently bound to the porous support.

[0033] The solid adsorbent exhibits high adsorption capacity for carbon dioxide. The solid adsorbent exhibits desirable hydrothermal and cycling stability.

[0034] Sorbent materials are capable of binding specific fluids such as carbon dioxide (CO), water (HO), oxygen (O), or other gas molecules that may be present in air or in some other form as a result of decomposition reactions (e.g., combustion).

[0035] In general, solid adsorbents according to the present disclosure can be used with any suitable compositions, systems, and methods known in the art for facilitating solid adsorbents. The solid adsorbents are not limited to any particular embodiment disclosed herein. Exemplary compositions, systems, and methods can be found in International Application No. PCT / US2023 / 082729, the contents of which are incorporated herein by reference.

[0036] In general, the solid adsorbent can include any functionalizing ligand known in the art to facilitate solid adsorption.

[0037] In some embodiments, the functionalized ligand comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof, hi some embodiments, the functionalized ligand comprises at least one primary amine or at least one secondary amine.

[0038] In some embodiments, the functionalizing ligand comprises a polyamine. In some embodiments, the functionalizing ligand comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentaamines, hexaamines, polyamines, and combinations thereof.

[0039] Generally, the polyamine can contain any number of amine groups known in the art to be suitable for facilitating a solid adsorbent. In some embodiments, the polyamine contains a total number of amine groups in the range of about 2 to about 10. In some embodiments, the polyamine contains a total number of amine groups in the range of about 2 to about 6. In some embodiments, the polyamine contains a total number of amine groups in the range of about 2 to about 4. In some embodiments, the polyamine contains 2, 3, 4, 5, 6, 7, 8, 9, or 10 amine groups.

[0040] In some embodiments, the functionalized ligand is selected from the group consisting of polyamine ligands, aminosilicone ligands, amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentaamine ligands, hexaamine ligands, polyamine ligands, alkylamine ligands, and amino-alcohol ligands, comprising at least one cyclic unit. Exemplary ligands include, but are not limited to, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, di(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, di(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2- N,N'-bis(2-aminoethyl)-1,3-propanediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane(spermidine), triethylenetetramine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,4-diaminobutane(spermine), tetraethylenepentamine, and / or combinations thereof.

[0041] In some embodiments, the functionalizing ligand is selected from the group consisting of spermine, pentaethylenehexamine (PEHA), polyethyleneimine (PEI) of any molecular weight, epoxybutane-modified spermine, epoxybutane-modified PEHA, epoxybutane-modified PEI, and combinations thereof.

[0042] In some embodiments, the functionalized adsorbent has a Class-II, Class-III, or Class-IV isotherm with pure water. In some embodiments, the functionalized adsorbent has a Class-II isotherm with pure water. In some embodiments, the functionalized adsorbent has a Class-III isotherm with pure water. In some embodiments, the functionalized adsorbent has a Class-IV isotherm with pure water.

[0043] In some embodiments, the functionalized sorbent has a water uptake at high relative humidity of an average of <1 HO molecule per amine. In some embodiments, high relative humidity refers to a relative humidity of 50% or greater at ambient temperatures, such as, but not limited to, -20°C to 40°C. In some embodiments, high relative humidity refers to a relative humidity of 60% or greater at ambient temperatures, such as, but not limited to, -20°C to 40°C. In some embodiments, high relative humidity refers to a relative humidity of 70% or greater at ambient temperatures, such as, but not limited to, -20°C to 40°C. In some embodiments, high relative humidity refers to a relative humidity of 60% or greater at temperatures ranging from 40°C to 60°C. In some embodiments, high relative humidity refers to a relative humidity of 70% or greater at temperatures ranging from 40°C to 60°C. In some embodiments, high relative humidity refers to a relative humidity of 70% or greater at temperatures of 60°C or greater.

[0044] Generally, the functionalized sorbent can have any suitable desorption temperature known in the art to facilitate the functionalization of the sorbent. The desorption temperature refers to the temperature required to regenerate the sorbent material or sorbent composite to at least partially desorb CO and HO. Each desorption module or sub-module containing the functionalized sorbent can have a uniform temperature profile, a gradient temperature profile, or a discrete temperature profile.

[0045] In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 40°C to about 250°C. In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 120°C to about 250°C. In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 40°C to about 120°C. In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 40°C to about 100°C. In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 40°C to about 90°C.

[0046] In some embodiments, the functionalized sorbent has a desorption temperature of about 40°C or higher, about 50°C or higher, about 60°C or higher, about 70°C or higher, about 80°C or higher, about 90°C or higher, about 100°C or higher, about 110°C or higher, about 120°C or higher, about 130°C or higher, about 140°C or higher, about 150°C or higher, about 160°C or higher, about 170°C or higher, about 180°C or higher, about 190°C or higher, about 200°C or higher, about 210°C or higher, about 220°C or higher, about 230°C or higher, or about 240°C or higher. In some embodiments, the functionalized sorbent has a desorption temperature of about 50°C or less, about 60°C or less, about 70°C or less, about 80°C or less, about 90°C or less, about 100°C or less, about 110°C or less, about 120°C or less, about 130°C or less, about 140°C or less, about 150°C or less, about 160°C or less, about 170°C or less, about 180°C or less, about 190°C or less, about 200°C or less, about 210°C or less, about 220°C or less, about 230°C or less, about 240°C or less, or about 250°C or less.

[0047] Generally, the functionalized adsorbent can have any suitable adsorption temperature known in the art to facilitate the functionalized adsorbent. The adsorption temperature refers to the temperature required for the adsorbent material or adsorbent composite to at least partially adsorb CO and HO. The adsorption temperature refers to the temperature of the adsorbent material, the temperature of the gas stream, the temperature of the adsorption module or submodule, or a combination thereof. Each adsorption module or submodule containing the functionalized adsorbent can have a uniform temperature profile, a gradient temperature profile, or a discrete temperature profile.

[0048] In some embodiments, the functionalized adsorbent has an adsorption temperature in the range of about -40°C to about 150°C. In some embodiments, the functionalized adsorbent has an adsorption temperature in the range of about 0°C to about 80°C. In some embodiments, the functionalized adsorbent has an adsorption temperature in the range of about 0°C to about 70°C. In some embodiments, the functionalized adsorbent has an adsorption temperature in the range of about 0°C to about 40°C.

[0049] In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 40° C. to about 120° C. In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 40° C. to about 100° C. In some embodiments, the functionalized adsorbent has a desorption temperature in the range of about 40° C. to about 90° C.

[0050] In some embodiments, the functionalized adsorbent has an adsorption temperature of about -40°C or higher, about -30°C or higher, about -20°C or higher, about -10°C or higher, about 0°C or higher, about 10°C or higher, about 20°C or higher, about 30°C or higher, about 40°C or higher, about 50°C or higher, about 60°C or higher, about 70°C or higher, about 80°C or higher, about 90°C or higher, about 100°C or higher, about 110°C or higher, about 120°C or higher, about 130°C or higher, or about 140°C or higher.

[0051] In some embodiments, the functionalized adsorbent has an adsorption temperature of about -30°C or less, about -20°C or less, about -10°C or less, about 0°C or less, about 10°C or less, about 20°C or less, about 30°C or less, about 40°C or less, about 50°C or less, about 60°C or less, about 70°C or less, about 80°C or less, about 90°C or less, about 100°C or less, about 110°C or less, about 120°C or less, about 130°C or less, about 140°C or less, or about 150°C or less.

[0052] Generally, the adsorbent can be any suitable adsorbent known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemistry, silica particles, zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), polyaromatic frameworks (PAFs), hydrogen-bonded framework (HOF) compounds, porous organic salts, activated carbon, molecular organic solids, and combinations thereof.

[0053] As used herein, MOF compounds are a class of compounds containing metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. The metal ions or clusters are connected by multidirectional organic ligands that act as connectors and linkers in the network structure. MOF compounds possess modularity that allows for synthetic tunability, resulting in fine chemical and structural control. Properties such as porosity, stability, particle morphology, and conductivity can be tailored to specific applications.

[0054] In many embodiments, the adsorbent is a MOF compound comprising a MOF metal or metal-containing cluster and a MOF linker.

[0055] In some embodiments, the MOF metal can be any suitable MOF metal known in the art that facilitates the solid adsorbents described herein. In other embodiments, the MOF metal is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof. In some embodiments, the MOF metal comprises Mg.

[0056] In some embodiments, the MOF metal-containing cluster can be any suitable MOF metal-containing cluster known in the art that facilitates the solid adsorbents described herein. In some embodiments, the MOF metal-containing cluster comprises a MOF metal node and a linker strut, where the MOF metal and linker are each defined as described herein. In other embodiments, the MOF metal-containing cluster comprises a MOF metal-oxycluster.

[0057] In some embodiments, the MOF linker can be any suitable MOF linker known in the art that facilitates the solid adsorbents described herein. Generally, the geometry and connectivity of the linker contribute to the structure of the resulting MOF compound. Adjusting the geometry, length, ratio, and functional groups of the linker can tune the size, shape, and internal surface properties of the MOF compound for targeted applications.

[0058] In some embodiments, the MOF linker is a linker selected from the group consisting of a polytopic linker, a ditopic linker, a tritopic linker, a tetratopic linker, a pentatopic linker, a hexatopic linker, a heptatopic linker, an octatopic linker, a mixed linker, a desymmetrized linker, a metal linker, an N-heterocyclic linker, and combinations thereof.

[0059] In some embodiments, the MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), their protonated, partially and fully deprotonated forms, and combinations thereof. As another example, in some embodiments, the MOF linker is a linker selected from the group consisting of dicarboxylates (e.g., terephthalic acid), tricarboxylates (e.g., 1,3,5-benzenetricarboxylic acid), azolates, tetrazolates, and combinations thereof.

[0060] As another example, in some embodiments, the MOF linker is selected from the group consisting of 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, and 2-methylquinoline-3,4-dicarboxylic acid. , Quinoline-2,4-dicarboxylic acid, Quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, Quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, Diimidedicarboxylic acid, Pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, Thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, Tetrahydropyran-4,4-dicarboxylic acid, Perylene-3,9-dicarboxylic acid, Perylene dicarboxylic acid, Pluriol E200 Dicarboxylic Acid, 3,6-Dioxaoctanedicarboxylic Acid, 3,5-Cyclohexadiene-1,2-dicarboxylic Acid, Octanedicarboxylic Acid, Pentane-3,3-carboxylic Acid, 4,4'-Diamino-1,1'-diphenyl-3,3'-dicarboxylic Acid, 4,4'-Diaminodiphenyl-3,3'-dicarboxylic Acid, Benzidine-3,3'-dicarboxylic Acid, 1,4-Bis-(phenylamino)benzene-2,5-dicarboxylic Acid, 1,1'-Dinaphthyl-8,8'-dicarboxylic Acid carboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-Dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E300 dicarboxylic acid, Pluriol E400 dicarboxylic acid, Pluriol E600 Dicarboxylic Acid, Pyrazole-3,4-dicarboxylic Acid, 2,3-Pyrazinedicarboxylic Acid, 5,6-Dimethyl-2,3-pyrazinedicarboxylic Acid, 4,4'-Diaminodiphenyletherdiimidedicarboxylic Acid, 4,4'-Diaminodiphenylmethanediimidedicarboxylic Acid, 4,4'-Diaminodiphenylsulfonediimidedicarboxylic Acid, 2,6-Naphthalenedicarboxylic Acid, 1,3-Adamantanedicarboxylic Acid, 1,8-Naphthalenedicarboxylic Acid, 2,3-Naphthalenedicarboxylic Acid, 8-Methoxy-2,3-naphthalenedicarboxylic Acid, 8-Nitro-2,3-naphthalenedicarboxylic Acid, 8-Sulfo-2,3-naphthalenedicarboxylic Acid, Anthracene-2,3-dicarboxylic Acid, 2'-3'-Diphenyl-p-terphenyl-4,4"-dicarboxylic Acid, Diphenylether-4,4'-dicarboxylic Acid Acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,The dicarboxylic acid linker is selected from the group consisting of 1,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, and combinations thereof.

[0061] As another example, in some embodiments, the MOF linker is a tricarboxylic acid linker selected from the group consisting of 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, and combinations thereof.

[0062] As another example, in some embodiments, the MOF linker is 1,1-dioxide-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, and a tetracarboxylic acid linker selected from the group consisting of 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and combinations thereof.

[0063] In an exemplary embodiment, the MOF linker is 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc) and / or 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- In some embodiments, dobpdc comprises 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenoxide form, its diphenoxide form, and combinations thereof.

[0064] In some embodiments, the MOF linker is the following linker: [ka] JPEG2026031461000003.jpg184109JPEG2026031461000004.jpg144151 and / or [ka] One or more of the following.

[0065] In some embodiments, the MOF compound is a MOF compound of the MOF-74 family. In some embodiments, the MOF compound is a MOF compound of the MOF-274 family. In some embodiments, the MOF compound is a MOF compound of the MOF-303 family. In some embodiments, the MOF compound is Mg2(dobpdc).

[0066] In some embodiments, the solid adsorbent does not comprise a MOF.

[0067] In some embodiments, the solid adsorbent comprises a non-MOF adsorbent. In some embodiments, the solid adsorbent comprises a mesoporous oxide support. In some embodiments, the solid adsorbent comprises a mesoporous oxide support selected from the group consisting of silica, alumina, zirconia, and combinations thereof. In some embodiments, the solid adsorbent comprises a porous polymer.

[0068] In some embodiments, the solid adsorbent does not include non-MOFs.

[0069] In general, amine-functionalized MOFs tend to have better CO2 capacity, expressed as the amount of CO2 captured per weight of adsorbent (e.g., gCO2 / g adsorbent or mmolCO2 / g adsorbent), at low CO2 concentrations, such as DAC-related conditions, compared to other adsorbents. Non-MOFs, such as mesoporous silica and alumina, may potentially offer lower cost and improved kinetics compared to other adsorbents.

[0070] The amine can be physically impregnated, which confers lower stability, or the amine can be chemically grafted, which provides higher stability but lower CO2 capacity depending on the amine selected and the grafting method.

[0071] One or more of reducing the particle size of the adsorbent, increasing the aspect ratio of the adsorbent, and synthesizing the aqueous adsorbent results in adsorbents with significantly improved CO2 uptake kinetics.

[0072] Generally, the adsorbent may comprise any suitable particle size known in the art that facilitates the functionalization of the adsorbents described herein. In some embodiments, the adsorbent has an average primary particle length of 50 μm or less. In some embodiments, the adsorbent has an average primary particle length of 30 μm or less. In some embodiments, the adsorbent has an average primary particle length of 10 μm or less. In some embodiments, the adsorbent has an average primary particle length of 5 μm or less. In some embodiments, the adsorbent has an average particle length of 3 μm or less, 2.9 μm or less, 2.8 μm or less, 2.7 μm or less, 2.6 μm or less, 2.5 μm or less, 2.4 μm or less, 2.3 μm or less, 2.2 μm or less, 2.1 μm or less, 2 μm or less, 1.9 μm or less, 1.8 μm or less, 1.7 μm or less, 1.6 μm or less, 1.5 μm or less, 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, or 0.1 μm or less. In some embodiments, the adsorbent has an average primary particle length of 5 μm or more. In some embodiments, the adsorbent has an average primary particle length of 3 μm or more, 2.9 μm or more, 2.8 μm or more, 2.7 μm or more, 2.6 μm or more, 2.5 μm or more, 2.4 μm or more, 2.3 μm or more, 2.2 μm or more, 2.1 μm or more, 2 μm or more, 1.9 μm or more, 1.8 μm or more, 1.7 μm or more, 1.6 μm or more, 1.5 μm or more, 1.4 μm or more, 1.3 μm or more, 1.2 μm or more, 1.1 μm or more, 1 μm or more, 0.9 μm or more, 0.8 μm or more, 0.7 μm or more, 0.6 μm or more, 0.5 μm or more, 0.4 μm or more, 0.3 μm or more, 0.2 μm or more, or 0.1 μm or more.

[0073] Generally, the adsorbent can comprise any suitable aspect ratio known in the art that facilitates the functionalization of the adsorbents described herein. As used herein, aspect ratio is the ratio of the average width of the adsorbent to the average length of the adsorbent. In some embodiments, the adsorbent has an aspect ratio ranging from about 0 to about 1. In some embodiments, the adsorbent has an aspect ratio of 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, or 0.1 or less. In some embodiments, the adsorbent has an aspect ratio of 0.9 or more, 0.8 or more, 0.7 or more, 0.6 or more, 0.5 or more, 0.4 or more, 0.3 or more, 0.2 or more, 0.1 or more, or 0 or more.

[0074] In some embodiments, the particle size is a discrete particle size. Discrete particle size measurements can be made according to any suitable means known in the art, for example, by measuring particle sizes in SEM images.

[0075] In some embodiments, the particle size measurement is an average particle size measurement. The average particle size measurement can be performed according to any suitable means known in the art, such as by analyzing particle size distribution information.

[0076] In general, the particle size of the adsorbent can be controlled, modified, or reduced according to any suitable technique known in the art to facilitate functionalizing adsorbents as described herein. In some embodiments, suitable techniques for controlling, modifying, or reducing particle size include mechanical milling (e.g., mortar and pestle) using a microfluidizer, dry milling, wet milling, chemical size reduction (e.g., incorporation of crystal growth inhibitors), acoustic cavitation, hydrodynamic cavitation, and combinations thereof.

[0077] Generally, the adsorbent may be in any suitable form known in the art that facilitates the functionalization of the adsorbents described herein. In some embodiments, the adsorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a film, a coating, an aqueous coating, a packed bed, a column, a monolith, and combinations thereof. An additional substrate may be present. For example, the adsorbent composite may be coated onto a flat substrate, a structured substrate, or a monolith substrate or support. The substrate may also have additional functionality, such as a heating plate, a heat exchanger, or a heat conductor.

[0078] Amine-functionalized adsorbent materials with improved amine utilization efficiency.

[0079] Described herein are functionalized sorbents comprising: (a) a support bound to a modifier according to Formula I; [ka] (b) a functionalized ligand comprising a polyamine; and (c) optionally a binder material.

[0080] In Formula I, the wavy line indicates the bond to the support, and X 1 is a first alkyl group, and X 2 is a second alkyl group, a is 1, 2 or 3, b is 0, 1 or 2, c is 0, 1 or 2, and a+b+c is equal to 3; A 1 is C, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, and A 2 is C, N, O, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, and A 3 is C, N, O, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; Y 1a , Y 1b , Y 2a , Y 2b , Y 3a , Y 3band Y are each independently hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, or branched alkyl hydrocarbon; n1, n2, n3, n4, n5, n6, and n7 are each independently 0 or 1; and d is an integer of 3 or greater.

[0081] In some embodiments, a is 3, b is 0, and c is 0. In these embodiments, there are three Si—O-support bonds in the functionalized adsorbent.

[0082] In some embodiments, a is 2, b is 1, and c is 0. In some embodiments, a is 2, b is 0, and c is 1. In these embodiments, there are two Si—O-support bonds in the functionalized adsorbent.

[0083] In some embodiments, a is 1, b is 2, and c is 0. In some embodiments, a is 1, b is 0, and c is 2. In some embodiments, a is 1, b is 1, and c is 1. In these embodiments, there is one Si—O-support bond in the functionalized adsorbent.

[0084] In some embodiments, the functionalized adsorbent comprises a plurality of modifiers according to Formula I. In some embodiments, the plurality of modifiers comprises the same modifier. In some embodiments, the plurality of modifiers comprises at least two different modifiers. In some embodiments, the plurality of modifiers comprises a random mixture of modifiers according to Formula I.

[0085] In some embodiments, the modifier-bonded support is formed by a silanization reaction. In some embodiments, the values ​​of a, b, and c can be adjusted by the silanization conditions used to form the modifier-bonded support, including, but not limited to, reaction conditions, reaction time, the density of surface hydroxy groups present in the starting support material, and other surface hydroxylation techniques, such as the use of acids (e.g., piranha acid solution and / or nitric acid), or the use of ultraviolet light / ozonolysis and water.

[0086] In some embodiments, the modifier-bonded support is formed by direct silanization, which occurs in a single step, hi some embodiments, the modifier-bonded support is formed by direct silanization, which comprises treating an alumina support with n-propyltrimethoxysilane (C3-TMS) and / or 3-[methoxy(polyethyleneoxy)6-9]propyltrimethoxysilane (PEG-TMS).

[0087] In some embodiments, the modifier-bonded support is formed by multi-step silanization occurring in two or more steps, hi some embodiments, the modifier-bonded support is formed by multi-step silanization including (1) modifying alumina with CPTMS bearing chlorine (—Cl) groups, and (2) attaching a Jeffamine material via an amine and —Cl alkylation reaction.

[0088] In some embodiments, the modifying agent comprises a trialkoxysilane-based compound further comprising an alkyl chain bonded to the Si atom, wherein the alkyl chain has a chain length of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms. In some embodiments, the modifying agent comprises a trimethoxysilane-based compound further comprising an alkyl chain bonded to the Si atom, wherein the alkyl chain has a chain length of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms.

[0089] In some embodiments, the modifying agent contains a heteroatom, such as, but not limited to, oxygen (O) or nitrogen (N). Exemplary O-containing trialkoxysilane materials include 3-[methoxy(polyethyleneoxy)(6-9)]propyltrimethoxysilane (PEG-TMS) with different repeating units. Exemplary amino(N)-containing trialkoxysilane materials include [3-(2-aminoethylamino)propyl]trimethoxysilane or [3-(diethylamino)propyl]trimethoxysilane.

[0090] In some embodiments, the modifying agent comprises an epoxy-functional trialkoxysilane material. Exemplary materials include, but are not limited to, (3-glycidoxypropyl)trimethoxysilane or [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane.

[0091] In some embodiments, the modifying agent comprises an acrylate or methacrylate functional trialkoxysilane material. Exemplary materials include, but are not limited to, (3-acrylamidopropyltrimethoxysilane), N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, or (3-methacrylamidopropyl)triethoxysilane.

[0092] In some embodiments, the first alkyl group is the same as the second alkyl group. In some embodiments, the first alkyl group is different from the second alkyl group. In some embodiments, the first alkyl group and the second alkyl group are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0093] Generally, the support can include any suitable adsorbent known in the art to facilitate functionalized adsorbents. In some embodiments, the support is any support described herein. In some embodiments, the support includes particles selected from the group consisting of solid particles, mesoporous particles, microporous particles, macroporous particles, and combinations thereof. In some embodiments, the support includes an inorganic support selected from the group consisting of oxides, alumina, silica, zirconia, clay, carbon powder, and combinations thereof.

[0094] In some embodiments, the adsorbent is present in powder form or coated composite form.

[0095] Generally, the support can be any suitable size known in the art that facilitates functionalizing the adsorbent. In some embodiments, the support has any size described in this disclosure. In some embodiments, the support has a D50 particle size of less than 50 μm. In some embodiments, the support has a D50 particle size of less than 20 μm. In some embodiments, the support has a D50 particle size of less than 10 μm.

[0096] Generally, the functionalizing ligand can include any suitable functionalizing ligand known in the art that facilitates functionalizing adsorbents. In some embodiments, the functionalizing ligand is any functionalizing ligand described herein. In some embodiments, the functionalizing ligand is selected from the group consisting of linear alkyl polyamines, triamines, tetraamines, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), branched polyamines, tris(3-aminopropyl)amine, polymeric amines, linear or branched polyethyleneimine (PEI), linear or branched polypropyleneimine (PPI), epoxide-modified polyamines, oxygen-containing amines, amine-functionalized resins, amine-functionalized ion exchange resins, and combinations thereof.

[0097] In some embodiments, the polyamine comprises only primary amines. In some embodiments, the polyamine comprises only primary and secondary amines. In some embodiments, the polyamine comprises primary, secondary, and tertiary amines.

[0098] In some embodiments, the polyamine comprises 3 or more amine groups. In some embodiments, the polyamine comprises 4 or more amine groups. In some embodiments, the polyamine comprises 5 or more amine groups. In some embodiments, the polyamine comprises 6 or more amine groups.

[0099] In some embodiments, the portion of formula I to the right of the Si atom comprises an alkyl group having a number of carbon atoms in the range of from about 3 to about 18.

[0100] In some embodiments, the portion of Formula I to the right of the Si atom comprises an oxygen-containing group or a polyether group.

[0101] In some embodiments, the portion of formula I to the right of the Si atom comprises at least one halogen selected from the group consisting of F, Cl, Br, and I.

[0102] In some embodiments, the modifying agent is formed following direct silanization or multi-step silanization.

[0103] Generally, the binder material can include any suitable binder material known in the art that facilitates functionalized sorbents. In some embodiments, the binder material is any binder material described herein. In some embodiments, the binder material includes a material selected from the group consisting of polymers, copolymers, thermosetting polymers, crosslinkable polymers, and combinations thereof. In some embodiments, the binder material includes a material selected from the group consisting of epoxies, acrylates, methacrylates, and combinations thereof.

[0104] In some embodiments, the functionalized adsorbent is deposited on a substrate.

[0105] Generally, the substrate can include any suitable substrate known in the art that facilitates functionalized adsorbents. In some embodiments, the substrate is any substrate described herein. In some embodiments, the substrate is selected from the group consisting of a monolith substrate, a structured substrate, a heat exchanger, a positive temperature coefficient heating element, a self-regulating heater, a substrate thermally coupled to a positive temperature coefficient heating element or a self-regulating heater, and combinations thereof. In some embodiments, the substrate comprises a substrate surface selected from the group consisting of a fin-and-tube heat exchanger, a plate-and-tube heat exchanger, and combinations thereof.

[0106] In some embodiments, the functionalized sorbent is configured to adsorb one or more of CO and HO. In some embodiments, the functionalized sorbent is configured to adsorb CO. In some embodiments, the functionalized sorbent is configured to adsorb HO. In some embodiments, the functionalized sorbent is configured to adsorb CO and HO.

[0107] Described herein are contactors comprising functionalized adsorbents. Generally, the contactor can comprise any suitable contactor known in the art to facilitate functionalized adsorbents. In some embodiments, the contactor is any contactor described in this disclosure.

[0108] In some embodiments, the contactor includes two sets of thermally coupled but fluidly separated flow paths, one set of which includes the functionalized adsorbent, an inlet for the CO2-containing gas stream, and an outlet for the CO2-depleted gaseous steam produced during the adsorption mode of operation, and the other set of which includes a heating and cooling medium, an inlet for the heating and cooling medium to enter the contactor, and an outlet for the heating and cooling medium to exit the contactor. In some embodiments, the heating and cooling medium is selected from the group consisting of heating and cooling oil, gaseous steam, heating and cooling steam, and combinations thereof.

[0109] Sorbent systems.

[0110] Exemplary embodiments described herein include a sorbent system. Generally, the sorbent system can be any suitable sorbent system known in the art that facilitates the functionalized sorbents described herein. In some embodiments, the sorbent system includes a functionalized sorbent and, optionally, a binder. In some embodiments, the sorbent system is disposed on a polymer film.

[0111] In some embodiments, the sorbent system is in the form of a coating formulation. The coating formulation can be in the form of a solution, emulsion, slurry (i.e., soluble binder, insoluble sorbent), or a combination thereof. If in the form of a solution, the binder is water-soluble. If in the form of an emulsion, the binder is not water-soluble. The coating formulation can include a binder and optionally at least one additive. In some embodiments, the at least one additive is selected from the group consisting of silica particles, clay particles, alumina particles, and combinations thereof. In some embodiments, the binder includes at least one water-based binder selected from the group consisting of water-based epoxies, water-based acrylic resins, water-soluble polymers, and combinations thereof.

[0112] In some embodiments, the sorbent system includes at least one concentrator. The concentrator can be any suitable concentrator known in the art that facilitates the functionalized sorbents described herein. The concentrator can be a passive or active concentrator.

[0113] In some embodiments, the sorbent system includes at least one component configured to drive fluid flow. The component configured to drive fluid flow can be any suitable component configured to drive fluid flow known in the art to facilitate the functionalized sorbents described herein. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of a pump, a fan, and combinations thereof.

[0114] In some embodiments, the sorbent system includes at least one component configured to alter temperature. The component configured to alter temperature can be any suitable component configured to alter temperature known in the art to facilitate functionalized sorbents described herein. In some embodiments, the component configured to alter temperature is selected from the group consisting of a heater, a cooler, and combinations thereof.

[0115] In some embodiments, the sorbent system includes at least one component configured to convey a fluid. The component configured to convey a fluid can be any suitable component configured to convey a fluid known in the art that facilitates the functionalized sorbents described herein. In some embodiments, the component configured to convey a fluid is selected from the group consisting of tubing, perforated tubing, perforated plastic tubing, perforated polymeric tubing, perforated metal tubing, perforated composite tubing, and combinations thereof.

[0116] In some embodiments, the adsorbent system includes at least one contactor. In some embodiments, the adsorbent system includes two or more contactors. In some embodiments, the adsorbent system includes a contactor configured for an adsorption cycle and a contactor configured for a desorption cycle. The contactor can be any suitable contactor known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent is integrated into at least one channel of the contactor. In some embodiments, the contactor is fabricated from the adsorbent itself. In some embodiments, the contactor is coated with an adsorbent system. In some embodiments, the contactor includes two or more adsorbent coatings, and at least one adsorbent coating is an adsorbent system.

[0117] In some embodiments, the adsorbent system includes a frame. The frame can be any suitable frame known in the art that facilitates the functionalized adsorbents described herein. The frame can be included in a contactor or between two contactors. The frame can be comprised of one piece or two or more pieces. In some embodiments, the frame is an air frame. In some embodiments, the frame is in a configuration selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and combinations thereof. In some embodiments, the adsorbent system is mounted in the frame.

[0118] CO2 capture system.

[0119] Also described herein are CO capture systems for use with the adsorbents. Such CO capture systems are known in the art, for example, in International Application No. PCT / US2024 / 051937, the contents of which are incorporated herein by reference.

[0120] As described in detail below, various embodiments of a preferred CO2 capture system for use with a sorbent are presented. The preferred CO2 capture system includes at least one contactor for extracting CO2 from an ambient fluid, such as ambient air, using a sorbent and thermally enhanced capture efforts. The disclosed system solves the problem of high CO2 extraction costs by integrating the sorbent with the contactor and utilizing an air concentrator. The high surface area of ​​the sorbent-integrated contactor, the low pressure drop across the contactor, and the air concentrator contribute significantly to system performance. The sorbent can be any sorbent according to the present disclosure. The contactor is characterized by a design that includes at least two fluidly isolated, independent, massively parallel fluid domains: a) an sorbent-integrated fluid domain that provides ambient air flow and CO2 adsorption from the ambient air flow; b) a second fluid domain for promoting desorption via the transfer of sensible heat to the sorbent-integrated fluid domain; and c) an optional third fluid domain that may be sorbent-integrated or used to promote desorption.

[0121] The CO2 capture system of the present disclosure can include at least one contactor having a sorbent material. The system can utilize the sorbent material and the contactor at an appropriate partial pressure to absorb CO2 from an inlet gas or first fluid stream.

[0122] The use of alternating cycles of two contactors for continuous CO2 removal, with each contactor having a massively parallel fluid domain, results in low pressure drop, and fluid separation avoids contamination of the CO2 stream and provides indirect heat exchange. The contactors can be manufactured using additive technologies, such as binder-jetting technology or some other manufacturing means. The described system offers commercial advantages by providing the ability to operate with low energy requirements over a wide range of applications. This technology can be deployed in locations with higher wind speeds, such as on the roofs of commercial buildings where state-of-the-art technology cannot be deployed. Additional market opportunities may include consumer CO2, industrial CO2 capture, and desalination.

[0123] Various embodiments of the CO2 capture system described above dramatically improve the ability to extract CO2 from an inlet gas, such as ambient air, using less energy and therefore at lower cost. The use of a concentrator combined with a low pressure drop across the contactor allows the CO2 capture system to operate in a passive mode, thus reducing energy requirements. The integration of the adsorbent with the contactor and the transfer of sensible heat to the adsorbent channels to support desorption produces a CO2 stream that is not contaminated with the fluid used to provide the sensible heat. As an example, the use of a multi-branched contactor design, which allows for thermally enhanced recovery of CO2 in the inlet gas, reduces the overall system operating costs. The use of alternating cycles of at least two contactors for continuous CO2 removal, each including a multi-branched design, more specifically, including massively parallel channels, results in low pressure drop and provides the indirect heat exchange described above, which aids in effective energy transfer in the CO2 capture system. Thus, various embodiments of the CO2 capture system and contactor design described above present a fuel-efficient two-cycle system architecture for producing a CO2 stream from an inlet gas stream.

[0124] How to use.

[0125] In general, the solid sorbents may be used according to any suitable purpose known in the art that facilitates the use of the solid sorbents described herein. In some embodiments, the solid sorbents are used in sorbent systems. In some embodiments, the solid sorbents are used in carbon capture sorbent systems. In some embodiments, the solid sorbents are used in moisture sorbent systems. In some embodiments, the solid sorbents are used in carbon capture sorbent systems in the presence of water. In some embodiments, the solid sorbents are used to capture gases. In some embodiments, the solid sorbents are used in post-combustion capture of CO2 and / or direct air capture of CO2.

[0126] In some embodiments, the method includes the steps of (I) receiving a gas source containing at least one gas in a solid sorbent, and (II) capturing a quantity of the at least one gas in the solid sorbent.

[0127] Generally, the gas source can be any suitable gas source known in the art that facilitates the methods described herein. In some embodiments, the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0128] Generally, the at least one gas can be any suitable gas known in the art that facilitates the methods described herein. In some embodiments, the at least one gas is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0129] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 100% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 40% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 15% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount greater than 10% (v / v).

[0130] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 100 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 300 ppmv to about 5000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 500 ppmv.

[0131] In some embodiments, the at least one gas does not include water vapor.

[0132] In some embodiments, at least one gas comprises water vapor. In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 15% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 4% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 4% (v / v) to about 15% (v / v).

[0133] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount greater than about 10% (v / v) and in the presence of water vapor. In some embodiments, water vapor is present in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.5% (v / v) to about 10% (v / v).

[0134] In some embodiments, capturing a quantity of at least one gas with a solid sorbent comprises adsorbing a quantity of at least one gas with the solid sorbent. In some embodiments, capturing a quantity of at least one gas with the solid sorbent comprises adsorbing a quantity of at least one gas with the solid sorbent in the presence of water vapor.

[0135] In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 1% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 10% (v / v) to about 90% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 20% (v / v) to about 80% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 30% (v / v) to about 70% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 40% (v / v) to about 60% (v / v) of the at least one gas present in the source gas.

[0136] In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 1% (v / v) to about 25% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 1% (v / v) to about 20% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 1% (v / v) to about 15% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 1% (v / v) to about 10% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 1% (v / v) to about 5% (v / v) of the at least one gas present in the source gas.

[0137] In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 80% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 85% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 90% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured by the solid adsorbent ranges from about 95% (v / v) to about 100% (v / v) of the at least one gas present in the source gas.

[0138] In some embodiments, the source gas is modified to modify the amount of water vapor. In some embodiments, modifying the amount of water vapor includes increasing the amount of water vapor. In some embodiments, modifying the amount of water vapor includes decreasing the amount of water vapor. In some embodiments, increasing the amount of water vapor includes adding or injecting water vapor into the source gas. In some embodiments, decreasing the amount of water vapor includes removing water vapor from the source gas by evaporation, condensation, and / or pre-adsorption. In some embodiments, modifying the amount of water vapor includes exhaust gas recirculation (EGR) and / or blending.

[0139] In many embodiments, the solid adsorbent, the source gas, the at least one gas, or a combination thereof, is at a particular temperature. Each temperature may be varied to facilitate the methods described herein. Each temperature may have a uniform temperature profile, a gradient temperature profile, a discrete temperature profile, or a combination thereof.

[0140] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, at least one of the solid adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature ranging from about −40° C. to about 150° C. during the gas adsorption cycle. In some embodiments, at least one of the solid adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature ranging from about 60° C. to about 250° C. during the gas desorption cycle. Each adsorption module or submodule can have a uniform temperature profile, a gradient temperature profile, or a discrete temperature profile. In some embodiments, the method includes varying the pressure during the desorption cycle to facilitate desorption. During the desorption step, a vacuum is optionally applied to facilitate the process. In one embodiment, the pressure in the adsorbent-integrated channels 158 is between 0.8 bar and 1.2 bar. In another embodiment, the pressure in the adsorbent-integrated channels 158 is between 0.4 bar and 0.8 bar. In another embodiment, the pressure in the adsorbent-integrated channels 158 is between 0.1 bar and 0.4 bar. In another embodiment, the pressure in the adsorbent-integrated channels 158 is less than 0.1 bar.

[0141] In some embodiments, the method includes controlling the temperature. The temperature may be controlled for the solid adsorbent, the source gas, the at least one gas, or a combination thereof.

[0142] SUMMARY OF THE INVENTION Exemplary embodiments described herein include a method for collecting at least one gas from a gas source. [Example]

[0143] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. Therefore, the following examples should be construed as merely illustrative and in no way limit the present disclosure. The starting materials in the following examples may not necessarily have been prepared by the specific preparation procedures described in other examples. Furthermore, any numerical range recited herein is understood to include all values ​​from the lower value to the upper value. For example, if a range is stated as 10 to 50, it is intended that values ​​such as 12 to 30, 20 to 40, or 30 to 50 are explicitly recited herein. These are merely examples of what is specifically intended, and all possible combinations of values ​​between the recited lowest and highest values, including the recited lowest and highest values, should be considered to be expressly stated in this application.

[0144] Two sets of experiments were performed to demonstrate the applicability of this disclosure. One set of experiments involved reviving adsorbent powders and other heterogeneous composites. This disclosure is also applicable to other types of adsorbent materials and adsorbent composites in different form factors and shapes, including, but not limited to, powders, films, gels, homogeneous composites, structured articles containing different adsorbents and composites, composites with homogeneous and heterogeneous compositions, etc.

[0145] Example 1 General test procedures.

[0146] The CO2 and HO adsorption performance was studied using a gravimetric dynamic vapor sorption analyzer (DVS). In the experiments presented in this disclosure, the gas and vapor used are CO2 and water, respectively. The DVS vacuum analyzer is designed to accurately measure the mass change of a sample as it adsorbs precisely controlled concentrations of water and / or gas molecules. The sample is placed in a sample pan suspended from a microbalance (typically, an empty pan is suspended on the other side of the microbalance as a reference). The DVS vacuum simultaneously controls and measures the inflow and outflow of sorbent while recording the change in sample mass. The primary instrument, the microbalance (UltraBalance™), is housed in a precisely controlled temperature-controlled enclosure (called an incubator). This ensures a highly stable instrument baseline and accurate vapor generation control at the experimental temperature.

[0147] The gravimetric DVS method can accurately measure the isotherms of pure H2O and pure CO2. A two-cycle continuous adsorption test protocol has been developed for wet CO2 adsorption. At the start of each test, the adsorbent material of interest is loaded onto a 10 -5 The sample is subjected to an activation (or regeneration) step at 120°C for 60 minutes under a vacuum of less than 100 mbar. A set water partial pressure is introduced under vacuum at a given temperature without carrier gas interference. The weight of the sample is measured directly and continuously using the Ultra Precision Micro-Balance of the Surface Measurement System with a resolution of 0.1 μg. All sorption measurements in this disclosure were performed in mass balance mode, with the mass balance criterion set as a mass change per minute (dm / dt less than 0.0035). When water adsorption reaches equilibrium, CO2 gas is introduced with a preset partial pressure target. The CO2 partial pressure can be adjusted to reflect the application conditions, i.e., 400 vppm for direct air capture (DAC) or 4.5 v% for post-combustion capture (PCC).

[0148] CO2 and HO adsorption performance can also be studied using a homemade breakthrough test rig. The test rig has a sample chamber containing the test sample in either powder or coated form, with separate calibrated CO2 and relative humidity (RH) sensors located at both the gas inlet before the sample chamber and the gas outlet after the sample chamber. The test rig can measure individual breakthrough curves for CO2 and HO under dry or humid CO2 conditions at preset RH levels. Uptake can be calculated by integrating the breakthrough curves over time.

[0149] Dry CO isotherms are measured at 25°C using the gravimetric DVS method to assess CO uptake at different CO partial pressures. Similarly, HO isotherms are measured to assess HO uptake at different relative humidity (RH) levels.

[0150] The adsorption performance is measured under DAC-relevant co-adsorption conditions (25°C, 50% RH, and 400 vppm CO2) using a breakthrough test rig. The CO2 desorption characteristics are studied by monitoring the CO2 desorption signal while gradually increasing the test bed temperature. For each experiment, the adsorbent is subjected to adsorption under DAC-relevant conditions, i.e., 25°C, 400 vppm CO2, and 50% RH, until complete equilibrium.

[0151] CO2 uptake or capacity is expressed as grams of CO2 adsorbed per gram of adsorbent (gCO2 / g adsorbent). Similarly, HO uptake or capacity is expressed as grams of HO adsorbed per gram of adsorbent (gHO / g adsorbent). CO2 and HO uptake can generally be viewed as an exponential increase over time, which

number

[0152] Nitrogen (N) content in weight percent (N(wt%)) is used to relatively quantify the amine content. N(wt%) can be quantitatively measured along with carbon (C) and hydrogen (H) content using inductively coupled plasma (ICP) elemental analysis, or commonly known as CHN analysis.

[0153] Example 2 Adsorbent regeneration.

[0154] Sorbent powder containing covalently bound amine (GE351-SG2-39).

[0155] GE351-SG2-39 was synthesized according to Figure 11. First, 4 g of γ-AlO (thermally preactivated at 100 °C) was added to a three-neck round-bottom flask. The particle sizes of the γ-AlO measured by Horiba light scattering technology were 5.06 / 8.44 / 14.17 μm for D10 / D50 / D90, respectively. 20 ml of toluene and 200 μl of water were added to the flask. Once a homogeneous mixture was formed, after stirring, 4 g of the grafting agent (hereinafter referred to as the grafting agent) (p-chloromethyl)phenyltrimethoxysilane (PCPT) was added dropwise to the slurry. The reaction mixture was heated to reflux and stirred at 90 °C overnight. After cooling to room temperature, the excess toluene was removed. The slurry was transferred to a 50 ml centrifuge tube containing fresh toluene. It was washed three times with fresh toluene to remove excess physisorbed PCPT. The residue was then placed in a vacuum oven at 90 °C to obtain PCPT-grafted γ-AlO. Next, spermine (4.04 g, 0.02 mmol) was dissolved in toluene (50 ml) and PCPT-grafted γ-AlO (2 g, 0.002 mmol of PCPT) was added. The reaction mixture was stirred at 90 °C for 72 hours. The reaction mixture was then cooled to room temperature, and excess toluene was removed. The resulting residue was washed three times with methanol and then dried under vacuum at 90 °C to obtain GE351-SG2-39 containing covalently bound spermine.

[0156] The CO2 and H2O adsorption performance measured under DAC-relevant co-adsorption conditions (25 °C, 50% RH, and 400 vppm CO2) for GE351-SG2-39 is summarized in Table 1, along with a description of N (wt%) and chemical composition.

[0157] [Table 1]

[0158] Example 3 Treatment of sorbent powder with amine solution (GE409-A3169D), corresponding to the embodiment of Figures 1, 2, 7 and 8.

[0159] In a 20 mL scintillation vial, 0.100 g of GE351-SG2-39, containing PCPT-grafted γ-Al2O3 with covalently bound spermine (24.9% organics), was slurried in 5 mL of methanol. Next, 67 wt % pentaethylenehexamine (PEHA, 0.067 g) was added to the vial and stirred at room temperature for 16 hours. The methanol was removed by rotary evaporation, and the material was dried in a vacuum oven at 90 °C for 8 hours to yield 166.6 mg of GE409. TGA was used to characterize the amount of amine impregnated into the porous support. The total organic mass loss was 44.6%, thus resulting in a total impregnated amine mass loss of 19.7%. The elemental analysis composition was 26.56% C, 4.88% H, and 10.49% N.

[0160] Exemplary TGA traces of GE409-A3169D containing γ-AlO, PCPT-grafted γ-AlO, PCPT-grafted γ-AlO with covalently bound spermine (GE351-SG2-39), and GE351-SG2-39 with additional impregnated PEHA are shown in Figure 12. Clearly, treating GE351-SG2-39 with PEHA further improves the CO adsorption performance (Table 1).

[0161] Example 4 Treatment of sorbent powder with amine solution (GE411-A3170B), corresponding to the embodiment of Figures 1, 2, 7 and 8.

[0162] In a 20 mL scintillation vial, 0.100 g of GE351-SG-2-39, containing PCPT-grafted γ-AlO with covalently bound spermine (24.9% organics), was slurried in 5 mL of methanol. Next, 67 wt. % pentaethylenehexamine (PEHA, 0.067 g) and 4 equivalents of a crosslinker, e.g., 1,5-hexadiene diepoxide (0.0168 g), were added to the vial and stirred at room temperature for 16 hours. The methanol was removed by rotary evaporation, and the material was dried in a vacuum oven at 90 °C for 8 hours to yield 178 mg of GE411. TGA was used to characterize the amount of amine impregnated and crosslinked into the porous support. The total organic mass loss was 51.0%, and therefore the impregnated amine mass loss totaled 26.1%. The elemental analysis composition is 31.16% C, 6.25% H and 12.36% N.

[0163] Figure 13 shows the TGA traces of GE411-A3170B containing γ-AlO, PCPT-grafted γ-AlO, PCPT-grafted γ-AlO with covalently bound spermine (GE351-SG2-39), and GE351-SG2-39 with additional impregnated PEHA and crosslinker (1,5-hexadiene diepoxide). Clearly, treating GE351-SG2-39 with PEHA further improved its CO adsorption performance (Table 1).

[0164] Example 5 Treatment of sorbent powder with amine solution (GE417-A3176B), corresponding to the embodiment of Figures 1, 2, 7 and 8.

[0165] In a 20 mL scintillation vial, 0.100 g of GE351-SG-2-39, containing PCPT-grafted γ-Al2O3 with covalently bound spermine (24.9% organics), was slurried in 5 mL of methanol. Next, 4 equivalents of 1,5-hexadiene diepoxide (0.0168 g) were added to the vial and stirred for 1 hour. Then, 67 wt. % pentaethylenehexamine (PEHA, 0.067 g) was added to the vial, and the slurry was stirred at room temperature for 16 hours. The methanol was removed by rotary evaporation, and the material was dried in a vacuum oven at 90 °C for 8 hours to yield 183.8 mg of GE417. TGA was used to characterize the amount of amine impregnated and crosslinked into the porous support. The total organic mass loss was 51.5%, and therefore the impregnated amine mass loss totaled 26.6%. The elemental analysis composition is 30.04% C, 5.84% H and 11.05% N.

[0166] Figure 14 shows TGA traces for GE417-A3167B containing γ-AlO, PCPT-grafted γ-AlO, PCPT-grafted γ-AlO with covalently bound spermine (GE351-SG2-39), and GE351-SG2-39 with additional impregnated PEHA and crosslinker (1,5-hexadiene diepoxide). The difference between GE409-A3170B and GE417-A3167B lies in when and how the crosslinker (1,5-hexadiene diepoxide) was added. In the case of GE409-A3170B, the crosslinker was added together with the PEHA amine, while in the case of GE417-A3167B, the crosslinker was added and stirred for 1 hour before the PEHA amine was added. Clearly, both methods of treating GE351-SG2-39 with PEHA and crosslinker resulted in increased N (wt%) and CO adsorption performance.

[0167] Example 6 Extraction of amines from composite coatings containing thermosetting binders corresponding to the embodiments of Figures 1, 3, 4, 9 and 10.

[0168] In this example, epoxide-modified spermine was used as an example. The general methodology for modifying amines such as spermine using epoxides is disclosed in U.S. Patent Application No. 18 / 606,176, which is incorporated herein by reference.

[0169] According to the general method, a 20 mL scintillation vial was charged with 1 equivalent of 17% by weight amine and methanol. Then, 0.01 to 4 equivalents of functionalized oxirane (epoxide) were added to the methanol solution. The solution was stirred overnight at room temperature. After at least 12 hours, the solvent was removed by rotary evaporation. The amine was dried in a vacuum oven at 80 °C for 4 hours. NMR samples were prepared in deuterated methanol (CD3OD) to determine the functionalization ratio. For example, 1 equivalent of spermine (2 mmol, 0.405 g) was added to a 20 mL scintillation vial and dissolved in 3 mL of methanol. Then, 1 equivalent of 1,2-epoxybutane (2 mmol, 174 μL) was added, and the solution was stirred at room temperature for 18 hours. The methanol was removed by rotary evaporation, resulting in a quantitative yield of 0.27 1,2-epoxybutane:spermine.

[0170] A general method for analyzing oxygen to amine (O / N) ratios using NMR is also disclosed in US patent application Ser. No. 18 / 606,176, which is incorporated herein by reference.

[0171] Typically, functionalized amines were dissolved in 600 μL of CD3OD, and the oxygen-to-nitrogen ratio was determined by H NMR based on the parent amine. For the NMR in Figure 15, the peak at 1.66 ppm was set to 4 based on the protons highlighted by (C). The amount of functionalization can be determined by the CH3 peak at δ 0.96 ppm (E) or the hydrogen attached to the beta (β)-alcohol at δ 3.58 ppm (A).

number

[0172] Step 1. Preparation of composite films.

[0173] Westcoat-11, a two-part epoxy, is used as an example binder to illustrate this disclosure. Part A is oxirane, 2,2'-[(1-methylethylidene)bis(4,1-phenyleneoxymethylene)] bis-homopolymer, having a CAS number of 25085-99-8, and Part B is a mixture of tetraethylenepentamine, having a CAS number of 112-57-2, and propylene glycol diamine, 2-amino-, diether, with propylene, having a CAS number of 9046-10-0. 0.25 g of spermine modified with 1,2-epoxybutane was dissolved in 1.5 g of water. 0.25 g of γ-Al2O3 was added to the solution, and the mixture was stirred at room temperature for 2 hours. The particle sizes of the γ-Al2O3 measured by Horiba light scattering technology are 5.06 / 8.44 / 14.17 μm for D10 / D50 / D90, respectively. To this mixture, 144 mg of Westcoat-11-Part A mixed with 72 mg of Westcoat-11-Part B was directly added. The slurry was sonicated for 5 minutes and then drop-cast onto a 2" x 2" aluminum coupon to produce an adsorbent composite film (Sample ID: GE455-MCF286). The film was cured at room temperature for 24 hours and then dried in a 90°C oven for 1 hour. The composite film contains two amine sources: (1) butane epoxide-modified spermine starting material and (2) Westcoat-11 Part B.

[0174] Step 2. Cleaning the composite film with H2O.

[0175] The sample (GE455_F01-MCF286) was initially sprayed with water and then immersed in 30 mL of DI water for 1 hour. The pH of the DI water was measured at approximately 12 after the first wash, indicating that the amines present in the original coating had been at least partially extracted. The film was again immersed in fresh 30 mL of DI water for 15 minutes. No change in pH was recorded during the second wash, indicating that most, if not all, of the leachable amines had been extracted. The film was then removed from the DI water, air-dried, and then further dried in a 90°C oven for 1 hour. The washed film sample has a sample ID of GE455-MCF286W.

[0176] Adsorption performance.

[0177] The CO2 and HO adsorption performance measured under DAC-relevant co-adsorption conditions (25 °C, 50% RH, and 400 vppm CO2) for both samples is summarized in Table 2. As can be seen from Table 2, washing with HO is able to at least partially extract the amines present in the composite films, leading to a decrease in the amine content and subsequently a decrease in the CO2 capacity.

[0178] [Table 2]

[0179] Example 7 11 is an example of the preparation or revival of a composite coating comprising a thermosetting binder, corresponding to the embodiments of FIGS. 1, 3, 4, 9 and 10. FIG.

[0180] Step 1. Preparation of composite films.

[0181] 288 mg of Westcoat EC-11 Part A and 144 mg of Westcoat EC-11 Part B were added to 2 g of water and mixed. To this solution, 3 g of alumina was added, and the slurry was vortexed and then sonicated for 5 minutes. The slurry was drop-cast onto a clean 2" x 2" aluminum coupon (MCF304). The coupon was air-dried at room temperature for 1 day to cure, then dried in an oven at 90°C for 1 hour.

[0182] Step 2. Amine impregnation.

[0183] 0.3 g of PEHA was dissolved in water and drop-cast onto MCF304. The sample was air-dried overnight and then dried in an oven at 90 °C for 1 hour. The mass of the loaded film (MCF304L) increased by 0.15 g. This increase indicates that PEHA was loaded onto the alumina film at an alumina-to-PEHA weight ratio of 1:0.4.

[0184] Adsorption performance.

[0185] The CO2 and HO adsorption performance measured under DAC-relevant co-adsorption conditions (25 °C, 50% RH, and 400 vppm CO2) for both samples is summarized in Table 3. As can be seen from Table 3, treating the samples in an amine-containing bath can increase the amine content in the film, which subsequently leads to an increase in CO2 capacity.

[0186] [Table 3]

[0187] Example 8 Adsorbent composite coatings containing different adsorbent materials.

[0188] The adsorbent composite coating may include one type of adsorbent material. As described in more detail herein, adsorbent materials generally include materials capable of binding specific fluids, such as carbon dioxide (CO), water (HO), oxygen (O), or other gas molecules that may be present in air or as a result of decomposition reactions (e.g., combustion). For example, adsorbent materials may include metal-organic frameworks (MOFs) and / or covalent organic frameworks (COFs). In some embodiments, adsorbent materials may include polymeric resins, silica, zeolites, and other materials capable of capturing the fluids discussed herein. Exemplary adsorbent materials further include, but are not limited to, amine-functionalized porous inorganic supports such as alumina and silica, amine-functionalized mesoporous polymer supports, amine-functionalized MOFs, amine-functionalized COFs, amine-functionalized ion-exchange resins, and amine-functionalized aerogels.

[0189] Alternatively, the adsorbent composite coating may comprise at least two different types of adsorbent materials. Suitable adsorbent materials may include MOFs, COFs, polymeric resins, amine-functionalized mesoporous inorganic supports such as silica, zeolites, alumina, and silica, amine-functionalized mesoporous polymeric supports, amine-functionalized MOFs, amine-functionalized COFs, and amine-functionalized polymeric resins.

[0190] A sorbent article capable of sorbing CO2 is presented as a contactor in a CO2-containing flow path or air flow path. The sorbent article can be in any form, including, but not limited to, a sorbent powder, a composite mixed with at least one binder material as a film or coating, a packed bed, a floating bed, a column, and the like. In one embodiment, the amine-functionalized sorbent is presented as a composite film or coating (hereinafter referred to as a composite) comprising an amine-bearing moiety and at least one binder. In another embodiment, the amine-functionalized sorbent is presented as a composite comprising an amine-bearing moiety and at least one polymer binder. In another embodiment, the amine-functionalized sorbent presented as a composite comprises at least one thermosetting polymer binder cured by an amine-containing curing agent. In another embodiment, the amine-functionalized sorbent presented as a composite comprises at least one thermosetting polymer binder cured by an amine-containing curing agent and additional amine moieties not chemically bonded to the binder. In another embodiment, the amine-functionalized sorbent is presented as a composite, comprising at least one thermosetting epoxy-based binder, the epoxy binder being a two-part epoxy comprising an epoxy moiety and an amine-based curing agent. In another embodiment, the amine-functionalized sorbent is presented as a composite comprising an amine-bearing moiety, at least one polymer binder, and at least one additive, including, but not limited to, clay particles, silica particles, alumina particles, and the like. In another embodiment, the amine-functionalized sorbent is presented as a composite prepared using an organic solvent, including, but not limited to, xylene, p-xylene, o-xylene, ketones, ethanol, isopropyl alcohol, and the like. In another embodiment, the amine-functionalized sorbent is presented as a composite prepared using water as the solvent.

[0191] Additional substrates may be present. For example, the adsorbent article can be coated as a composite coating including a binder material on a flat, structured, or monolithic substrate or support. The substrate can also have additional functions, such as a heating plate, heat exchanger, or heat conductor. In one embodiment, the adsorbent composite is provided as a coating on a monolithic substrate made of a ceramic material, including but not limited to silica and alumina, or a metallic material, including aluminum, copper, or stainless steel or other alloys, or a polymeric material. In one embodiment, the adsorbent composite is provided as a coating on a heating substrate whose temperature can be adjusted by applying a voltage or current. Examples of heating substrates include positive temperature coefficient heating elements (PTC heating elements) or self-regulating heaters. In another embodiment, the adsorbent composite is provided as a coating on a heat exchanger containing two sets of thermally coupled but fluidically separated flow paths. One set of the two sets of thermally coupled but fluidly separated flow paths includes the adsorbent composite, an inlet for the CO2-containing gas stream, and an outlet for the CO2-depleted gaseous steam during the adsorption mode of operation, and the other set of the two sets of thermally coupled but fluidly separated flow paths includes a heating and cooling medium, such as heating / cooling oil, heating and cooling gas vapor, or heating and cooling steam, an inlet to the heat exchanger for the heating and cooling medium, and an outlet for the heating and cooling medium exiting the heat exchanger.

[0192] overview.

[0193] Described herein is a solid adsorbent comprising an amine and a porous support. The solid adsorbent exhibits high adsorption capacity for carbon dioxide. The solid adsorbent exhibits desirable hydrothermal and cycling stability.

[0194] Definition.

[0195] As used herein, references to an "exemplary embodiment" or "one embodiment" or "some embodiments" of the present disclosure are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.

[0196] When introducing elements of various embodiments disclosed herein, the articles "a," "an," "the," and "said" are intended to mean that there are one or more elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0197] Unless otherwise indicated, approximation language, such as "generally," "substantially," and "about," used herein indicates that the modified term may apply only to an approximate degree, as recognized by one of ordinary skill in the art, rather than to an absolute or complete degree. Thus, values ​​modified by one or more terms, such as "about," "approximately," and "substantially," are not limited to the exact value specified. In at least some cases, approximation language may correspond to the precision of an instrument for measuring the value. Additionally, unless otherwise indicated, terms such as "first," "second," and "second" are used herein merely as labels and are not intended to impose any ordering, positioning, or hierarchical requirements on the items they refer to. Furthermore, for example, a reference to a "second" item does not require or exclude the presence of, for example, a "first" item or lower-numbered items, or a "third" or higher-numbered item.

[0198] As used herein, the term "alkyl," used alone or in compound words such as "haloalkyl," includes functional groups that contain carbon chains. Alkyl groups can contain aliphatic carbon chains, aryl carbon chains, or combinations thereof. An alkyl defined by a number of carbon atoms, e.g., a C alkyl, is understood to have that number of carbon atoms, but is not otherwise limited.

[0199] As used herein, "amine-containing unit" means a functional group that includes an amine group, such as a primary amine, a secondary amine, a tertiary amine, a cyclic amine, or a combination thereof.

[0200] As used herein, "OH-containing unit" refers to a functional group that includes a hydroxy (-OH) group. The -OH group may be a primary -OH group, where the -OH group is attached to a primary carbon atom to form a primary alcohol, a secondary -OH group, where the -OH group is attached to a secondary carbon atom to form a secondary alcohol, or a tertiary -OH group, where the -OH group is attached to a tertiary carbon atom to form a tertiary alcohol.

[0201] As used herein, the terms "halogen" or "halide," alone or in compound words such as "haloalkyl," include fluorine, chlorine, bromine, or iodine. Additionally, when used in compound words such as "haloalkyl," said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of "haloalkyl" include CF, ClCH, CFCH, and CFCCl. Terms such as "haloalkoxy" are defined analogously to the term "haloalkyl." Examples of "haloalkoxy" include CF, CClCHO, CFHCHCHO, and CFCHO.

[0202] As used herein, the term "polyamine" refers to a chemical compound having at least two amine groups. Thus, polyamines can include diamines, triamines, tetraamines, pentaamines, hexaamines, and combinations thereof.

[0203] H NMR spectra are reported in ppm downfield from tetramethylsilane, where "s" means singlet, "d" means doublet, "dd" means doublet of a doublet, "ddd" means doublet of a doublet of a doublet, "t" means triplet, "m" means multiplet, and "br s" means broad singlet.

[0204] As used herein, the term "fluid" includes any medium or material that flows, including, but not limited to, air, gas, liquid, and steam.

[0205] As used herein, the term "D50 particle size" refers to the median particle size. In other words, D50 is the size that divides the particle size distribution between the upper and lower halves of this diameter. Exemplary methods for measuring particle size include dynamic light scattering, optical microscopy, scanning electron microscopy, sedimentation, etc. A laser diffraction particle size analyzer (Horiba LA-960) was used to determine particle size in this disclosure.

[0206] Although specific features of various embodiments of the invention may be shown in some drawings and not in others, this is for convenience only, and in accordance with the principles of the invention, any feature of a drawing may be referenced and / or claimed in combination with any feature of any other drawing.

[0207] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.

[0208] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system, and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements that do not differ substantially from the literal language of the claims.

[0209] Exemplary embodiments.

[0210] The individual aspects of the present disclosure may be combined in any combination or permutation. Selected exemplary embodiments are described in the following clauses. These embodiments are non-limiting.

[0211] Further aspects of the invention are provided by the subject matter of the following clauses, which may be combined in any permutation or combination, including between embodiments.

[0212] 1. A method of making or reviving an absorbent article, comprising: (a) providing a starting article comprising a first amine having a first amine content; (b) providing a second amine; (c) contacting a starting article comprising the first amine with a second amine; (d) obtaining a treated article having a second amine content, the second amine content being higher than the first amine content; A method comprising:

[0213] 2. The method of clause 1, wherein the starting article comprises a sorbent powder functionalized with a first amine, the sorbent powder being capable of absorbing CO2, H2O, or a combination thereof.

[0214] 3. The method of clause 2, wherein the adsorbent powder comprises a MOF, an amine-functionalized MOF, an amine-functionalized porous support, an amine-functionalized resin, an amine-functionalized ion exchange resin, or a combination thereof.

[0215] 4. The method of any one of clauses 1 to 3, wherein the starting article comprises a support, and the first amine is at least partially covalently bonded to at least a portion of the support in the starting article.

[0216] 5. The method of any one of clauses 1 to 4, wherein the starting article comprises a support and the first amine is not covalently bonded to at least a portion of the support in the starting article.

[0217] 6. The method of any one of clauses 1 to 5, wherein the starting article comprises a support, and the support is a porous support comprising porous silica, porous alumina, porous clay, porous polymer, porous carbon powder, or a combination thereof.

[0218] 7. The method of any one of clauses 1 to 6, wherein the second amine is present in a gas or vapor phase optionally comprising a carrier gas optionally comprising air, N2, dry air, steam, or a combination thereof.

[0219] 8. The method of any one of clauses 1 to 7, wherein the second amine has at least one more amine group per unit than the first amine.

[0220] 9. The method of any one of clauses 1 to 8, wherein the second amine is provided in the liquid phase.

[0221] 10. The method of any one of clauses 1 to 9, wherein the second amine is provided as a solution comprising a solute dissolved in a solvent.

[0222] 11. The method of clause 10, wherein the solvent comprises HO, an alcohol-containing solvent, a ketone-containing solvent, an ether-containing solvent, an aromatic-containing solvent, or a combination thereof.

[0223] 12. The method of any one of clauses 1 to 11, wherein the first amine and the second amine each contain two or more amine groups per unit.

[0224] 13. The method of any one of clauses 1 to 12, wherein the two or more amine groups per unit comprise only primary amine groups.

[0225] 14. The method of any one of clauses 1 to 13, wherein the two or more amine groups per unit include a primary amine group and a secondary amine group.

[0226] 15. The method of any one of clauses 1 to 14, wherein the two or more amine groups per unit include a primary amine group, a secondary amine group, and a tertiary amine group.

[0227] 16. The method of any one of clauses 1 to 15, wherein the first amine is the same as the second amine.

[0228] 17. The method of any one of clauses 1 to 16, wherein the starting article comprises a composite capable of absorbing CO2, H2O, or a combination thereof.

[0229] 18. The method of clause 17, wherein the composite comprises a binder selected from the group consisting of a polymer, a copolymer, a mixture of two or more polymers, a thermosetting material, a crosslinkable material, and combinations thereof.

[0230] 19. The method of any one of clauses 1 to 18, wherein at least a portion of the first amines are covalently bonded to the binder.

[0231] 20. The method of any one of clauses 1 to 19, wherein the second amine is provided in a composite form with a binder that is the same as or different from the binder provided in the starting article.

[0232] 21. The method of any one of clauses 1 to 20, wherein the starting article is in the form of a contactor, the contactor comprising a substrate surface to which the composite is applied.

[0233] 22. The method of clause 21, wherein the contactor comprises a monolith substrate, a structured substrate, a heat exchanger, or a combination thereof.

[0234] 23. The method of any one of clauses 1 to 22, wherein the substrate surface is a positive temperature coefficient heating element or a self-regulating heater, or the substrate surface is a substrate thermally coupled to a positive temperature coefficient heating element or a self-regulating heater.

[0235] 24. The method of any one of clauses 1 to 23, wherein the contactor comprises a fin-and-tube heat exchanger, a plate-and-tube heat exchanger, or a combination thereof.

[0236] 25. The method of any one of clauses 1 to 24, wherein the contactor comprises two sets of thermally coupled but fluidly separated flow paths, one set of the thermally coupled but fluidly separated flow paths comprising the adsorbent composite, an inlet for a CO2-containing gas stream, and an outlet for a CO2-depleted gas stream during an adsorption mode of operation, and the other set of the thermally coupled but fluidly separated flow paths comprising a heating and cooling medium optionally comprising heating and cooling oil, gaseous vapor, or heating and cooling steam, an inlet to the contactor for the heating and cooling medium, and an outlet for the heating and cooling medium exiting the contactor. [Explanation of symbols]

[0237] 100 Starting Items 101 First Amine 102 First Amine Content 103 Secondary Amine 104 Secondary Amine Content 105 Treated items 200 Starting sorbent powder 201 First Amine 202 First Amine Content 203 Secondary Amine 204 Secondary Amine Content 205 Treated sorbent powder 300 Departure Composite 301 First Amine 302 First Amine Content 303 Secondary Amine 304 Secondary Amine Content 305 Treated Composite 400 Departure Composite 401 First Amine 402 First Amine Content 403 Secondary Amine 404 Secondary Amine Content 405 Treated Composite 406 Solution 500 Departure Composite 501 First Amine 502 First Amine Content 503 Secondary Amine 504 Secondary Amine Content 505 Treated Composite 506 Solution 507 Solvent 508 Contactor 600 Departure Composite 601 First Amine 602 First Amine Content 603 Secondary Amine 604 Secondary Amine Content 605 Treated Composite 606 N2 700 Starting sorbent powder 701 First Amine 702 First Amine Content 703 Secondary Amine 704 Secondary Amine Content 705 Treated Composite 706 Solution 707 Solvent 800 Starting sorbent powder 801 First Amine 802 First Amine Content 803 Secondary Amine 804 Secondary Amine Content 805 Treated sorbent powder 806 Solution 807 Solvent 900 Departure Composite 901 First Amine 902 First Amine Content 903 Second Amine 904 Secondary Amine Content 905 Treated Composite 906 Solution 907 Solvent 1000 Departure Composite 1001 First Amine 1002 First amine content 1003 Secondary Amine 1004 Secondary Amine Content 1005 Thermosetting binder 1006 Aqueous solution 1007 Treated Composite

Claims

1. 1. A method of making or reviving an absorbent article, comprising: (a) providing a starting article (100) comprising a first amine (101) having a first amine content (102); (b) providing a second amine (103); (c) contacting said starting article (100) comprising a first amine (101) with said second amine (103); (d) obtaining a treated article (105) having a second amine content (104), said second amine content (104) being higher than said first amine content (102); A method comprising:

2. The starting article (100) comprises a sorbent powder functionalized with the first amine (101), the sorbent powder being capable of reacting with CO ２ , H ２ 2. The method of claim 1, wherein the cellulose is capable of absorbing cellulose, cellulose acetate, cellulose esters, cellulose acetate, cellulose acetate derivatives ...

3. 3. The method of claim 2, wherein the adsorbent powder comprises an MOF, an amine-functionalized MOF, an amine-functionalized porous support, an amine-functionalized resin, an amine-functionalized ion exchange resin, or a combination thereof.

4. 10. The method of claim 1, wherein the starting article (100) comprises a support, and the first amine (101) is at least partially covalently bonded to at least a portion of the support in the starting article (100).

5. 10. The method of claim 1, wherein the starting article (100) comprises a support, and the first amine (101) is not covalently bonded to at least a portion of the support in the starting article (100).

6. 10. The method of claim 1, wherein the starting article (100) comprises a support, the support being a porous support comprising porous silica, porous alumina, porous clay, porous polymer, porous carbon powder, or a combination thereof.

7. The second amine (103) is oxidized in air, N ２ 10. The method of claim 1, wherein the oxidized carbon dioxide is in a gas or vapor phase optionally comprising a carrier gas optionally comprising dry air, steam, or a combination thereof.

8. 2. The method of claim 1, wherein the second amine (103) has at least one more amine group per unit than the first amine (101).

9. The method of claim 1 , wherein the second amine (103) is provided in a liquid phase.

10. The method of claim 1 , wherein the second amine (103) is provided as a solution comprising a solute dissolved in a solvent.

11. The solvent is H ２ 11. The method of claim 10, comprising: O, an alcohol-containing solvent, a ketone-containing solvent, an ether-containing solvent, an aromatic-containing solvent, or a combination thereof.

12. 2. The method of claim 1, wherein the first amine (101) and the second amine (103) each contain two or more amine groups per unit.

13. 13. The method of claim 12, wherein the two or more amine groups per unit comprise only primary amine groups, or the two or more amine groups per unit comprise primary and secondary amine groups, or the two or more amine groups per unit comprise primary, secondary, and tertiary amine groups.

14. 2. The method of claim 1, wherein the first amine (101) is the same as the second amine (103).

15. The starting article (100) is ２ , H ２ 2. The method of claim 1, comprising a composite capable of absorbing oxygen, nitrogen, argon ...

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