Co2 capture sorbents with low regeneration temperature and high desorption rates — Susteon Inc. (US20240009613A1)

ABSTRACT

Abstract

A sorbent useful for CO2 capture is described, including a solid support with CO2-sorbing amine and ionic liquid thereon. The ionic liquid is catalytically effective to enhance sorbent characteristics such as (i) CO2 sorption capacity, (ii) CO2 sorption rate, (iii) CO2 desorption capacity, (iv) CO2 desorption rate, and (v) regeneration temperature, in relation to a corresponding sorbent lacking the ionic liquid. In specific implementations, the sorbent is regenerable at temperatures significantly below 100° C., thereby avoiding the need for steam heat desorption and enabling utilization of waste heat or other low energy thermal regeneration sources.

Description

CROSS-REFERENCE TO RELATED APPLICATION

The benefit under 35 USC § 119 of U.S. Provisional Patent Application 63/066,460 filed Aug. 17, 2020 in the names of Shaojun James Zhou and Raghubir Prasad Gupta for “CO 2 Capture Sorbents with Low Regeneration Temperature and High Desorption Rates” is hereby claimed. The disclosure of U.S. Provisional Patent Application 63/066,460 is hereby incorporated herein by reference, in its entirety, for all purposes.

FIELD

The present disclosure relates to sorbents useful for CO 2 capture, CO 2 capture systems including such sorbents, and to methods for making and using such sorbents.

DESCRIPTION OF THE RELATED ART

Carbon dioxide (CO 2 ) capture and sequestration is the focus of a vast spectrum of technological efforts to address the billions of tons of CO 2 that are generated annually by combustion engine vehicles, power generation plants, and other industrial and commercial processes.

The existing standard process for CO 2 capture employs aqueous amine solutions to absorb CO 2 from CO 2 -containing gases that are subjected to gas/liquid contacting with such solutions. Although such process for CO 2 capture utilizing aqueous amine solutions has achieved significant implementation, and although various efforts have been made to enhance such process, the liquid solution approach has a number of fundamental deficiencies.

These deficiencies include problems of aging and degradation of the amine in the solution, with the result that the amine solution must be reclaimed or changed out, with corresponding cessation or interruption of CO 2 capture operations.

Further, since the contacting of the CO 2 -containing gas must occur with the liquid solution, it is typically necessary to contact the CO 2 -containing gas with the liquid in a packed or tray column in order to generate the large gas/liquid interfacial area necessary for CO 2 removal via vapor/liquid equilibrium. The intimate and large interfacial area contact between the gas and the liquid causes entrainment of the liquid in the gas stream, foaming, and emission of the liquid into the surrounding environment. In addition, motors or other motive driver assemblies are required to recirculate liquid in the gas/liquid contacting vessel, at a sufficient rate to maintain effective CO 2 removal, and in the regeneration operation, the released CO 2 must be separated from the liquid solution, and in many instances, must be processed to remove water vapor therefrom to accommodate the further use or disposition of the CO 2 .

Accordingly, the aqueous liquid amine solution contacting of CO 2 -containing gas has a number of disadvantageous aspects and features related to the use of the aqueous liquid amine solution.

As a result of these deficiencies of conventional amine solution CO 2 capture processes, there have been intensive efforts to develop CO 2 -selective solid sorbents that have high sorption capacity for CO 2 and that can be repeatedly and easily regenerated without loss of such sorption capacity, and without the high levels of regeneration energy necessary in aqueous amine solution CO 2 scrubbing processes.

In these efforts, amine-doped solid sorbents have been developed, but the solid sorbents developed to date require high temperatures for regeneration and are correspondingly susceptible to thermal degradation or alternatively have low desorption rates that render them unsuitable for commercial applications.

In consequence, there is a continuing and critical need in the art for improved CO 2 capture materials and processes that overcome the aforementioned deficiencies.

SUMMARY

The present disclosure relates to sorbents useful for CO 2 capture, CO 2 capture systems including such sorbents, and methods for making and using such sorbents.

In one aspect, the disclosure relates to a sorbent useful for CO 2 capture, comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon.

In another aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising depositing CO 2 -sorbing amine and ionic liquid on a solid support.

In an additional aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising depositing ionic liquid on a solid support having an amine thereon.

In a further aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising:

depositing a CO 2 -sorbing amine on a solid support to form an aminated support; and

depositing ionic liquid on the aminated support to form the CO 2 capture sorbent comprising the solid support with the CO 2 -sorbing amine and ionic liquid thereon.

In a further aspect, the disclosure relates to a method of CO 2 capture, comprising contacting a CO 2 -containing gas with a sorbent comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, to produce CO 2 -reduced gas, and sorbent having CO 2 adsorbed thereon.

In yet another aspect, the disclosure relates to a CO 2 capture system comprising at least one sorption vessel containing a CO 2 capture sorbent comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, wherein the vessel is arranged for contacting of CO 2 -containing gas with the sorbent therein and discharge of CO 2 -reduced contacted gas.

Other aspects, features and embodiments of the disclosure will be more fully apparent from the ensuing description and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of relative CO 2 sorbent weight (wt %), showing sorbent weight gain as a function of time and number of cycles, for catalytic ionic liquid-enhanced CO 2 sorbents of the present disclosure, and for corresponding CO 2 sorbents without ionic liquid catalyst.

FIG. 2 is a graph of first cycle relative CO 2 sorbent weight gain as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, and for a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 3 is a graph of percentage increase of CO 2 adsorption as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, and for a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 4 is a graph of increase in adsorption rate as a function of time, for a catalytic CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 5 is a graph of relative weight of CO 2 desorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, and for a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 6 is a graph of increase in the relative amounts of CO 2 desorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 7 is a graph of increase in CO 2 desorption rate as a function of desorption time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, in relation to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 8 is a graph of CO 2 breakthrough curves for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 9 is a graph of increase in the amounts of CO 2 desorbed as a function of time and temperature, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 10 is a graph of increase in CO 2 desorption amount as a function of desorption time and temperature, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, in relation to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 11 is a graph of CO 2 breakthrough curves for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 12 is a graph of increase in the amounts of CO 2 adsorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 13 is a graph of CO 2 breakthrough curves for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst for several adsorption and desorption cycles.

FIG. 14 is a graph of the amounts of CO 2 adsorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst for two adsorption and desorption cycles.

FIG. 15 is a schematic representation of a multibed CO 2 capture system according to one embodiment of the present disclosure.

DETAILED DESCRIPTION

The present disclosure relates to sorbents useful for CO 2 capture, CO 2 capture systems including such sorbents, and methods of making and using such sorbents.

It will be appreciated from the subsequent description herein that the solid CO 2 sorbents, CO 2 capture systems, and CO 2 capture methods of the present disclosure may embody and be implemented with any of a wide variety of elements, features, and arrangements, among those disclosed herein. Correspondingly, it will be appreciated that such sorbents, systems, and methods may comprise, consist, or consist essentially of any of such elements, features, and arrangements, and that any of such elements, features, and arrangements may be modified or even absent in specific implementations and applications of the present disclosure.

For example, the ionic liquids utilized in the practice of the present disclosure may be restrictively specified in various embodiments, to exclude a specific one or specific ones from among the ionic liquids herein variously disclosed. Likewise, the CO 2 -sorbing amine utilized in the CO 2 capture sorbent of the present disclosure may be restrictively specified in various embodiments, to exclude a specific one or specific ones from among the CO 2 -sorbing amines variously described herein.

As an example, monoethanolamine may be excluded as a CO 2 -sorbing amine in various embodiments of the CO 2 capture sorbent, which are restrictively specified with regard to the particular CO 2 -sorbing amines designated for such embodiments. The CO 2 -sorbing amine utilized in the CO 2 capture sorbent may also be restrictively specified as to its association with the solid support, or a solid support surface thereof, as being covalently bonded to the support or support surface, being ionically bonded to the support or support surface, being impregnated in porosity of the support or support surface, being associated by van der Waals interaction with the support or support surface, and/or otherwise specifically associated with the support or support surface.

It will therefore be appreciated that the form, constitution, composition, arrangement, performance, and operation of the sorbents, systems, and methods of the present disclosure may be widely varied based on the substance and scope of the present disclosure, as implemented by persons ordinarily skilled in the art, in the field of the present disclosure.

The sorbents of the present disclosure are characterized by high CO 2 selectivity and high CO 2 capacity, and can be regenerated at temperatures below 100° C. in repeated sorption/desorption cycles, with high desorption rate and retention of high CO 2 selectivity and CO 2 capacity.

The present disclosure reflects the discovery that ionic liquids may be employed to enhance CO 2 sorption and desorption characteristics of amine-based CO 2 solid sorbents, including characteristics of sorption rate, sorption capacity, desorption rate, desorption capacity, and regeneration temperature, by catalytic action in the amine-based CO 2 solid sorbent. Ionic liquids, by virtue of their composition of inorganic cations and organic or inorganic anions, exhibit a number of favorable characteristics in the present application to amine-based CO 2 solid sorbents, including high chemical/thermal stability, tunable physiochemical characteristics (acid/base sites), low corrosivity, low heat capacity, and environmentally favorable characteristics. In

CROSS-REFERENCE TO RELATED APPLICATION

The benefit under 35 USC § 119 of U.S. Provisional Patent Application 63/066,460 filed Aug. 17, 2020 in the names of Shaojun James Zhou and Raghubir Prasad Gupta for “CO 2 Capture Sorbents with Low Regeneration Temperature and High Desorption Rates” is hereby claimed. The disclosure of U.S. Provisional Patent Application 63/066,460 is hereby incorporated herein by reference, in its entirety, for all purposes.

FIELD

The present disclosure relates to sorbents useful for CO 2 capture, CO 2 capture systems including such sorbents, and to methods for making and using such sorbents.

DESCRIPTION OF THE RELATED ART

Carbon dioxide (CO 2 ) capture and sequestration is the focus of a vast spectrum of technological efforts to address the billions of tons of CO 2 that are generated annually by combustion engine vehicles, power generation plants, and other industrial and commercial processes.

The existing standard process for CO 2 capture employs aqueous amine solutions to absorb CO 2 from CO 2 -containing gases that are subjected to gas/liquid contacting with such solutions. Although such process for CO 2 capture utilizing aqueous amine solutions has achieved significant implementation, and although various efforts have been made to enhance such process, the liquid solution approach has a number of fundamental deficiencies.

These deficiencies include problems of aging and degradation of the amine in the solution, with the result that the amine solution must be reclaimed or changed out, with corresponding cessation or interruption of CO 2 capture operations.

Further, since the contacting of the CO 2 -containing gas must occur with the liquid solution, it is typically necessary to contact the CO 2 -containing gas with the liquid in a packed or tray column in order to generate the large gas/liquid interfacial area necessary for CO 2 removal via vapor/liquid equilibrium. The intimate and large interfacial area contact between the gas and the liquid causes entrainment of the liquid in the gas stream, foaming, and emission of the liquid into the surrounding environment. In addition, motors or other motive driver assemblies are required to recirculate liquid in the gas/liquid contacting vessel, at a sufficient rate to maintain effective CO 2 removal, and in the regeneration operation, the released CO 2 must be separated from the liquid solution, and in many instances, must be processed to remove water vapor therefrom to accommodate the further use or disposition of the CO 2 .

Accordingly, the aqueous liquid amine solution contacting of CO 2 -containing gas has a number of disadvantageous aspects and features related to the use of the aqueous liquid amine solution.

As a result of these deficiencies of conventional amine solution CO 2 capture processes, there have been intensive efforts to develop CO 2 -selective solid sorbents that have high sorption capacity for CO 2 and that can be repeatedly and easily regenerated without loss of such sorption capacity, and without the high levels of regeneration energy necessary in aqueous amine solution CO 2 scrubbing processes.

In these efforts, amine-doped solid sorbents have been developed, but the solid sorbents developed to date require high temperatures for regeneration and are correspondingly susceptible to thermal degradation or alternatively have low desorption rates that render them unsuitable for commercial applications.

In consequence, there is a continuing and critical need in the art for improved CO 2 capture materials and processes that overcome the aforementioned deficiencies.

SUMMARY

The present disclosure relates to sorbents useful for CO 2 capture, CO 2 capture systems including such sorbents, and methods for making and using such sorbents.

In one aspect, the disclosure relates to a sorbent useful for CO 2 capture, comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon.

In another aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising depositing CO 2 -sorbing amine and ionic liquid on a solid support.

In an additional aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising depositing ionic liquid on a solid support having an amine thereon.

In a further aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising:

depositing a CO 2 -sorbing amine on a solid support to form an aminated support; and

depositing ionic liquid on the aminated support to form the CO 2 capture sorbent comprising the solid support with the CO 2 -sorbing amine and ionic liquid thereon.

In a further aspect, the disclosure relates to a method of CO 2 capture, comprising contacting a CO 2 -containing gas with a sorbent comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, to produce CO 2 -reduced gas, and sorbent having CO 2 adsorbed thereon.

In yet another aspect, the disclosure relates to a CO 2 capture system comprising at least one sorption vessel containing a CO 2 capture sorbent comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, wherein the vessel is arranged for contacting of CO 2 -containing gas with the sorbent therein and discharge of CO 2 -reduced contacted gas.

Other aspects, features and embodiments of the disclosure will be more fully apparent from the ensuing description and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of relative CO 2 sorbent weight (wt %), showing sorbent weight gain as a function of time and number of cycles, for catalytic ionic liquid-enhanced CO 2 sorbents of the present disclosure, and for corresponding CO 2 sorbents without ionic liquid catalyst.

FIG. 2 is a graph of first cycle relative CO 2 sorbent weight gain as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, and for a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 3 is a graph of percentage increase of CO 2 adsorption as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, and for a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 4 is a graph of increase in adsorption rate as a function of time, for a catalytic CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 5 is a graph of relative weight of CO 2 desorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, and for a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 6 is a graph of increase in the relative amounts of CO 2 desorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 7 is a graph of increase in CO 2 desorption rate as a function of desorption time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, in relation to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 8 is a graph of CO 2 breakthrough curves for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 9 is a graph of increase in the amounts of CO 2 desorbed as a function of time and temperature, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 10 is a graph of increase in CO 2 desorption amount as a function of desorption time and temperature, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure, in relation to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 11 is a graph of CO 2 breakthrough curves for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 12 is a graph of increase in the amounts of CO 2 adsorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst.

FIG. 13 is a graph of CO 2 breakthrough curves for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst for several adsorption and desorption cycles.

FIG. 14 is a graph of the amounts of CO 2 adsorbed as a function of time, for a catalytic ionic liquid-enhanced CO 2 sorbent of the present disclosure as compared to a corresponding CO 2 sorbent without ionic liquid catalyst for two adsorption and desorption cycles.

FIG. 15 is a schematic representation of a multibed CO 2 capture system according to one embodiment of the present disclosure.

DETAILED DESCRIPTION

The present disclosure relates to sorbents useful for CO 2 capture, CO 2 capture systems including such sorbents, and methods of making and using such sorbents.

It will be appreciated from the subsequent description herein that the solid CO 2 sorbents, CO 2 capture systems, and CO 2 capture methods of the present disclosure may embody and be implemented with any of a wide variety of elements, features, and arrangements, among those disclosed herein. Correspondingly, it will be appreciated that such sorbents, systems, and methods may comprise, consist, or consist essentially of any of such elements, features, and arrangements, and that any of such elements, features, and arrangements may be modified or even absent in specific implementations and applications of the present disclosure.

For example, the ionic liquids utilized in the practice of the present disclosure may be restrictively specified in various embodiments, to exclude a specific one or specific ones from among the ionic liquids herein variously disclosed. Likewise, the CO 2 -sorbing amine utilized in the CO 2 capture sorbent of the present disclosure may be restrictively specified in various embodiments, to exclude a specific one or specific ones from among the CO 2 -sorbing amines variously described herein.

As an example, monoethanolamine may be excluded as a CO 2 -sorbing amine in various embodiments of the CO 2 capture sorbent, which are restrictively specified with regard to the particular CO 2 -sorbing amines designated for such embodiments. The CO 2 -sorbing amine utilized in the CO 2 capture sorbent may also be restrictively specified as to its association with the solid support, or a solid support surface thereof, as being covalently bonded to the support or support surface, being ionically bonded to the support or support surface, being impregnated in porosity of the support or support surface, being associated by van der Waals interaction with the support or support surface, and/or otherwise specifically associated with the support or support surface.

It will therefore be appreciated that the form, constitution, composition, arrangement, performance, and operation of the sorbents, systems, and methods of the present disclosure may be widely varied based on the substance and scope of the present disclosure, as implemented by persons ordinarily skilled in the art, in the field of the present disclosure.

The sorbents of the present disclosure are characterized by high CO 2 selectivity and high CO 2 capacity, and can be regenerated at temperatures below 100° C. in repeated sorption/desorption cycles, with high desorption rate and retention of high CO 2 selectivity and CO 2 capacity.

The present disclosure reflects the discovery that ionic liquids may be employed to enhance CO 2 sorption and desorption characteristics of amine-based CO 2 solid sorbents, including characteristics of sorption rate, sorption capacity, desorption rate, desorption capacity, and regeneration temperature, by catalytic action in the amine-based CO 2 solid sorbent. Ionic liquids, by virtue of their composition of inorganic cations and organic or inorganic anions, exhibit a number of favorable characteristics in the present application to amine-based CO 2 solid sorbents, including high chemical/thermal stability, tunable physiochemical characteristics (acid/base sites), low corrosivity, low heat capacity, and environmentally favorable characteristics. In accordance with the present disclosure, ionic liquids are integrated as catalytic components in amine-containing solid sorbents to achieve a new generation of CO 2 capture sorbents with significantly improved adsorption/desorption performance and regeneration temperature requirements, e.g., regeneration temperatures on the order of 70° C.-100° C.

Although it was not known or ascertainable, a priori, whether solid supports with CO 2 -sorbing amine and ionic liquid thereon could or would be effective for gas/solid sorbent CO 2 capture applications, the CO 2 solid sorbents of the present disclosure have demonstrated remarkably effective CO 2 capture capability and regeneration performance, as evidenced by the empirical results more fully described hereinafter.

In various specific implementations, regeneration temperatures on the order of 70° C.-95° C. may be utilized, such as regeneration temperatures of 75° C.-90° C. The regeneration may be carried out under temperature swing desorption conditions, pressure swing desorption conditions, or a combination of temperature swing and pressure swing desorption conditions. The pressure swing desorption conditions may include vacuum desorption conditions, or desorption at any suitable (atmospheric, sub-atmospheric, or super-atmospheric) pressure that is effective to remove previously adsorbed CO 2 and regenerate the sorbent for further contacting with CO 2 -containing gas.

The present disclosure thus provides a sorbent useful for CO 2 capture, comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon. Such CO 2 capture sorbent may be advantageously utilized in a wide variety of CO 2 removal and sequestration applications. For example, CO 2 capture applications in which the sorbent of the present disclosure can be employed to sorptively remove CO 2 from CO 2 -gas mixtures include the illustrative applications listed in Table 1 below, as identified with representative CO 2 concentrations encountered in such applications.

TABLE 1

Illustrative CO 2 Capture Applications

and Representative CO 2 Concentrations

CO 2 Concentration

Applications

in Gas Stream

Coal-fired power plant flue gas

10 to 15

vol %

Natural gas combined cycle (NGCC) power plant

3 to 5

vol %

flue gas

Blast furnace exhaust gas

17 to 21

vol %

Cement plant exhaust gas

15 to 25

vol %

Natural gas fired once through steam generator

8 to 10

vol %

Integrated gasification combined cycle (IGCC)

18 to 40

vol %

syngas

Syngas from steam methane reforming

18 to 25

vol %

Steam methane reforming flue gas

8 to 22

vol %

Steam methane pressure swing adsorption tail gas

40 to 50

vol %

Syngas from biomass gasification

9 to 25

vol %

Syngas from municipal waste gasification

20 to 30

vol %

Biogas

30 to 60

vol %

Direct air capture of CO 2

~400

ppmv

In the sorbent of the present disclosure, comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, the solid support may be of any suitable type and composition that is effective to support the amine and ionic liquid thereon. Illustrative solid support materials include, for example, carbon (e.g., carbon molecular sieves, activated carbon), silica, metal oxides (e.g., alumina, titania, zirconia, etc.), mixed metal oxides (multiple metal oxides combined), zeolites, aluminosilicates, metal organic frameworks (MOFs), clays (e.g., bentonite, montmorillonite, etc.), mesoporous materials, fabrics, non-woven materials, ceramic monoliths, metal monoliths, and ceramic-metal monoliths, polymers (e.g., polymeric sorbent resins such as polymethylmethacrylate, polystyrene, polystyrene-divinylbenzene, etc.), porous polymer networks, and mixtures, alloys, and combinations including any of the foregoing, but the disclosure is not limited thereto.

In specific embodiments, metal organic framework supports may be employed, such as for example: Zn 4 O(BTE)(BPDC) wherein BTE is 4,4′,4″-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate, and BPDC is biphenyl-4,4′-dicarboxylate; Zn 4 O(BTB) 2 , wherein BTB is 1,3,5-benzenetribenzoate; Zn 4 O(BBC) 2 , wherein BBC is 4,4′,4″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate; Zn 4 O(BDC) 3 , wherein BDC is 1,4-benzenedicarboxylate; Mn 3 [(Mn 4 Cl) 3 (BTT) 8 ] 2 , where BTT is benzene-1,3,5-tris(1H-tetrazole); or Cu 3 (BTC) 2 (H 2 O) 3 , wherein BTC is 1,3,5-benzenetricarboxylic acid.

The CO 2 -sorbing amine on the solid support likewise may be of any suitable type and composition that is effective in contact with a CO 2 -containing gas mixture to remove CO 2 therefrom. CO 2 -sorbing amines that may be advantageously employed in various embodiments of the present disclosure include primary, secondary, and tertiary alkylamines and alkanolamines, aromatic amines, mixed amines, polyamines, and combinations thereof. The amine is advantageously of a low volatility character wider the conditions wider which it is employed for CO 2 adsorption and desorption, and to which it is otherwise exposed, to minimize and preferably to avoid amine emissions that may contaminate the gas streams with which it is contacted, and/or reduce the effectiveness of the CO 2 sorption system over time.

By way of example, the CO 2 -sorbing amine in the sorbent of the disclosure may comprise one or more amine(s) such as monoethanolamine (MEA), triethanolamine (TEA), diethanolamine (DEA), diethylenetriamine (DETA), 2-(2-aminoethylamino)ethanol, diisopropanolamine, 2-amino-2-methyl-1,3-propanediol, pentaethylenehexamine, tetramethylenepentaamine, tetraethylenepentamine (TEPA), methyldiethanolamine (MDEA), polyallylamines, aminosilanes, tetraalkoxysilanes, aminoalkylalkoxysilanes (e.g., 3-aminopropyltriethoxysilane), hyperbranched aminosilica (HAS), and polymeric amines (e.g., polyethylenimines (PEI), etc.), as well as combinations and mixtures including one or more of the foregoing, but the disclosure is not limited thereto.

In specific embodiments of the sorbent, the CO 2 -sorbing amine comprises a polyalkyleneimine, e.g., polyethyleneimine or polypropyleneimine, or other suitable amine species. Polyethyleneimines are preferred in various embodiments because of their high proportion of secondary and primary amino functional groups and their low volatility. Polyethylenimines also provide a high nitrogen/carbon ratio which is advantageous for maximizing the amount of amino functional groups in the adsorbent.

In like manner, the ionic liquid in the CO 2 capture sorbent of the present disclosure may be of any suitable type and composition that is effective in the sorbent to enhance CO 2 -sorption, CO 2 -desorption, and/or regeneration temperature characteristics of the CO 2 capture sorbent, as compared to a corresponding CO 2 capture sorbent lacking the ionic liquid therein. Thus, for example, the ionic liquid may be an ionic liquid that is interactive with the CO 2 -sorbing amine to enhance at least one of the sorbent characteristics of (i) CO 2 sorption capacity, (ii) CO 2 sorption rate, (iii) CO 2 desorption capacity, (iv) CO 2 desorption rate, and (v) regeneration temperature, in relation to a corresponding sorbent lacking the ionic liquid.

In the CO 2 capture sorbents of the present disclosure, ionic liquids enable high catalytic activity to be achieved, due to the Bronsted acid sites that are provided by the ionic liquids. As used in such context, a Bronsted acid is any substance (molecule or ion) that can donate a hydrogen ion (H + ). The parameter pKa measures how tightly a proton is held by a Bronsted acid. A pKa value may be a small, negative number, such as −3 or −5. It may be a larger, positive number, such as 30 or 50 or more. The lower the pKa of a Bronsted acid, the more easily it gives up its proton. Common Bronsted acids include organic acids such as acetic acid, phenols, organic sulfonic acids, and thiophenols.

Ionic liquids include ionic compounds that are liquid below 100° C. Ionic liquids may have melting points below ambient room temperatures, and even below 0° C. Preferred ionic liquids in the practice of the present disclosure include ionic liquids that are liquid over a wide temperature range, e.g., 300-400° C., from their melting point to their decomposition temperature. In general, ionic liquids have low symmetry, including at least one ion having a delocalized charge and an organic component, which prevent formation of stable crystal lattice structures, and cationic charge as well as anionic charge is distributed over a relatively large volume of the molecule by resonance.

The strong ionic (coulombic) interaction within ionic liquids results in a negligible vapor pressure other than under decomposition conditions, in addition to non-flammable character, and high thermal/mechanical/electrochemical stability. Ionic liquids also provide favorable solvent properties, and exhibit immiscibility with water or organic solvents that produces biphasic phenomena. The selection of the cation in the ionic liquid will have a strong impact on its properties, including its stability. The chemistry and functionality of the ionic liquid is generally controlled by the selection of the anion.

The ionic liquid in the CO 2 capture sorbent of the present disclosure may comprise one or more than one ionic liquid(s). The ionic liquid may for example comprise one or more ionic liquid(s) selected from among ammonium, imidazolium-, phosphonium-, pyridinium-, pyrrolidinium-, and sulfonium-based ionic liquids, as an ionic liquid comprising one or more cations of the following structures

and associated organic or inorganic anions of any suitable character. In various embodiments, anions such as the following may be employed

although a wide variety of other specific anions may be employed in the general practice of the present disclosure.

Illustrative ionic liquids that may be employed in various embodiments of the present disclosure include:

1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-ethyl-3-methylimidazolium tetrafluoroborate; 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide; 1-ethylpyridinium bromide; 1-hexyl-3-methylimidazolium triflate; 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide; 1,2-dimethyl-3-propylimidazolium bromide; 1,2-dimethyl-3-propylimidazolium iodide; 1,2-dimethylimidazole; 1,2-dimethylimidazolium chloride; 1,2-dimethylimidazolium bis(trifluoromethylsulfonyl)imide; 1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide; 1,3-diethylimidazolium bromide; 1,3-diethylimidazolium tetrafluoroborate; 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-benzyl-3-

methylimdiazolium

1,1,2,2-tetrafluoroethanesulfonate; 1-benzyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide; 1-decyl-3-methylimidazolium hexafluorophosphate; 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-ethyl-1-methylpyrrolidinium hexafluorophosphate; 1-ethyl-3-methylimidazolium hexafluorophosphate; 1-ethyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide; 1-heptyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-hexadecyl-3-methylimidazolium hexafluorophosphate; 1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide; 1-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-propyl-4-methylpyridinium bromide; bis(1-butyl-3-methylimidazolium) tetrathiocyanatocobaltate; diethylmethylsulfonium bis(trifluoromethylsulfonyl)imide; trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide; and triphenylcarbenium tetrakis(perfluoro-tert-butoxy) aluminate,

but the disclosure is not limited thereto.

In particular embodiments of the present disclosure, the ionic liquid may comprise an ionic liquid of the formula:

wherein each of R 1 and R 2 is independently selected from H, hydroxy, halo (F, Br, Cl, I), C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 carboxy, C 1 -C 12 haloalkyl, C 6 -C 12 aryl, C 6 -C 14 arylalkyl, C 5 -C 10 cycloalkyl, amino or substituted amino, thiol, phosphate, sulfate, phosphonate, and sulfonate. In particular embodiments, each of R 1 and R 2 is independently selected from C 1 -C 12 alkyl.

In still other embodiments, the ionic liquid may comprise an ionic liquid selected from the group consisting of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-2,3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-methyl acetyl, 3-methylimidazolium bis(trifluoro methyl sulfonyl)imide.

The ionic liquid in specific embodiments may include a substituted imidazolium group and a bis(trifluoromethylsulfonyl)imide group, wherein substituents of the substituted imidazolium group or of any suitable character for the particular application involved.

The ionic liquid may be present in any suitable concentration in the sorbent, which is effective to enhance the sorption and/or desorption characteristics and/or regeneration temperature characteristics thereof. In various embodiments, the ionic liquid may be present in the sorbent at concentration of from 1 to 5000 ppm by weight, based on total weight of the amine present on the sorbent. In other embodiments, the ionic liquid may be present in the sorbent at concentration of from 1 to 1000 ppm by weight, based on total weight of the amine present on the sorbent. In still other embodiments, the ionic liquid may be present in the sorbent at concentration of from 1 to 100 ppm by weight, based on total weight of the amine present on the sorbent. It will be appreciated that the concentration of the ionic liquid may be widely varied in the practice of the present disclosure.

The use of ionic liquids in the CO 2 capture sorbents of the present disclosure enables the regeneration temperatures of the sorbent to be substantially reduced, as compared to a corresponding sorbent lacking the ionic liquid. This in turn imparts higher stability to the sorbent and achieves lower amine emissions from the sorbent, as compared to a corresponding sorbent lacking the ionic liquid and therefore requiring higher temperature regeneration, e.g., at temperatures significantly above 100° C. The lower regeneration temperature also enables utilization of lower grade heat sources such as waste heat from process plants, power plants, and other facilities.

A further advantage of the ionic liquid catalyzed CO 2 capture sorbents of the present disclosure as a consequence of their lowered regeneration temperatures is that water that is sorbed or otherwise present on the sorbent is not desorbed or otherwise volatilized at the lowered regeneration temperatures. Accordingly, the overall energy required for regeneration is reduced, and CO 2 capture costs are correspondingly lowered.

The CO 2 capture sorbent of the present disclosure may be provided in any suitable conformation that is efficacious for CO 2 capture from CO 2 -containing gas contacted with the sorbent. For example, the solid support may be of any suitable size and/or shape, or combination of suitable sizes and/or shapes, and the amine and ionic liquid thereon may be doped, deposited, impregnated, consolidated or otherwise integrated with the solid support in any suitable manner. Further, the CO 2 capture sorbent of the present disclosure may be combined with other sorbents, structures, components, agents, ingredients, etc. that further enhance the overall CO 2 capture that is achieved, or that provide suitable sorptive action and sorption capacity, or other removal capacity, for other constituents of the CO 2 -containing gas that are desirably removed in the processing of such gas. For example, the CO 2 capture sorbent of the present disclosure may be provided as a part of a laminated composite sorbent including a sorbent for nitrogenous gas species, hydrocarbon species, and/or other components of the CO 2 -containing gas.

The solid CO 2 capture sorbent of the present disclosure thus may comprise a solid support that is in any suitable form. The solid support may for example be in the form of particles, of geometrically regular or irregular shape, such as spherical, spheroidal, oblate, lobular, multi-lobular, or other forms or conformations of particles, in any suitable particle sizes and/or particle size distributions. Alternatively, the solid support may be in the form of platelets, flakes, films, sheets, discs, rods, fibers, filaments, rings, blocks, monoliths, parallelepipeds, composites, laminates, or in any other suitable forms, in any suitable sizes and/or size distributions. The solid support in various embodiments may be porous, non-porous, foraminous, channelized, or may be otherwise configured to provide appropriate surface and/or volume to accommodate desired amounts of CO 2 -sorbing amine and ionic liquid thereon.

By way of non-limiting illustrative examples, the solid support in various specific embodiments may be in the form of particles having a size in a range of from 2 μm to 50 mm, or particles having a size in a range of from 50 nm to 1 μm, or particles having a size in a range of from 100 nm to 10 mm, although the disclosure is not limited thereto and ranges including other lower and/or upper end point values, or other size dimensions, may be employed in specific applications, as necessary or desirable therein.

In another aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising depositing CO 2 -sorbing amine and ionic liquid on a solid support.

In an additional aspect, the disclosure relates to a method of making a CO 2 capture sorbent, comprising depositing ionic liquid on a solid support having an amine thereon.

The present disclosure in another aspect relates to a method of making a CO 2 capture sorbent, comprising:

depositing a CO 2 -sorbing amine on a solid support, to form an aminated support; and depositing ionic liquid on the aminated support to form the CO 2 capture sorbent comprising the solid support with the CO 2 -sorbing amine and ionic liquid thereon.

In such method, the depositing of ionic liquid on the aminated support may comprise contacting the aminated support with an alkanolic solution of the ionic liquid to impregnate the aminated support with the ionic liquid, recovering the ionic liquid-impregnated aminated support from the alkanolic solution, and removing alkanol from the recovered ionic liquid-impregnated aminated support to yield the CO 2 capture sorbent comprising the solid support with the CO 2 -sorbing amine and ionic liquid thereon. The removal of the alkanol from the recovered ionic liquid-impregnated aminated support may be carried out in any suitable manner, and may for example comprise evaporating the alkanol from the recovered ionic liquid-impregnated aminated support, by any suitable volatilization technique or procedure.

The disclosure in a further aspect relates to a method of CO 2 capture, comprising contacting a CO 2 -containing gas with a sorbent comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, to produce CO 2 -reduced gas, and sorbent having CO 2 adsorbed thereon.

Such CO 2 capture method may in specific embodiments further comprise regenerating the sorbent having CO 2 adsorbed thereon, to desorb CO 2 therefrom to form regenerated sorbent, and CO 2 desorbate; and recovering the CO 2 desorbate from the regenerated sorbent.

In specific embodiments, the foregoing CO 2 capture method may be conducted in a multi-bed system comprising multiple beds of the sorbent arranged for continuous CO 2 capture processing of the CO 2 -containing gas, wherein one or more of the multiple beds is on-stream for said contacting of the CO 2 -containing gas with the sorbent, and another or others of the multiple beds is off-stream and while off-stream said regenerating and recovering are carried out, with each of the multiple beds undergoing sequential on-stream and off-stream operations in a cyclic repeating sequence for said continuous CO 2 capture processing of the CO 2 -containing gas. The multi-bed system may be a pressure-swing adsorption (PSA) multi-bed system, or a thermal-swing adsorption (TSA) multi-bed system, or a pressure-swing adsorption/thermal-swing adsorption (PSA/TSA) multi-bed system.

In specific embodiments, the CO 2 capture method of the disclosure may be carried out wherein the CO 2 -containing gas is air, e.g., atmospheric air, in a direct air capture application, or the CO 2 -containing gas may be supplied from a combustion process, e.g., wherein the CO 2 -containing gas comprises effluent from an electrical power-generating plant or other CO 2 -containing gas resulting from combustion of fossil fuel, syngas from organic matter gasification, blast furnace exhaust gas from steel making, cement kiln exhaust gas, effluent from a motive vehicle, etc.

In other embodiments, wherein the CO 2 -containing gas is supplied from an oxidation process, such as a biological oxidation process, or other process in which oxidative action or chemical reaction is conducted.

In various other embodiments, the CO 2 -containing gas may comprise one or more of: coal-fired power plant flue gas;

natural gas combined cycle power plant flue gas; blast furnace exhaust gas; cement plant exhaust gas; natural gas fired once through steam generator gas; steam methane reformer syngas; steam methane reformer flue gas; steam methane reformer PSA tail gas; dry reforming syngas; integrated gasification combined cycle (IGCC) syngas; biogas; biomass gasification syngas; municipal waste gasification syngas; and atmospheric gas.

The disclosure in yet another aspect relates to a CO 2 capture system comprising at least one sorption vessel containing a CO 2 capture sorbent comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, wherein the vessel is arranged for contacting of CO 2 -containing gas with the sorbent therein and discharge of CO 2 -reduced contacted gas.

In such CO 2 capture system, the vessel in various embodiments may be constituted and arranged for regeneration of the sorbent after at least partial loading of CO 2 thereon resulting from said contacting. In various embodiments, the system may comprise multiple sorption vessels constituted and arranged for cyclic repeating operation comprising adsorption operation and desorption regeneration operation, e.g., for thermal swing operation, for pressure swing operation, e.g., pressure/vacuum swing operation, or for combined thermal swing and pressure swing operation, e.g., thermal swing and pressure/vacuum swing operation.

The advantages and features of the disclosure are further illustrated with reference to the following examples, which are not to be construed as in any way limiting the scope of the disclosure but rather as illustrative of various embodiments thereof in specific applications thereof.

Example 1

0.005 wt % (50 ppmw) ionic liquid was added to an amine-doped silica sorbent by dissolving the ionic liquid (IL) in an alcohol solvent and immersing the solvent in the ionic liquid/alcohol solution for several hours. The alcohol solvent was then evaporated in a Rotavapor® rotary evaporator (BUCHI Corporation, New Castle, Delaware, USA) to remove all of the solvent. The resulting IL-treated amine-doped silica sorbent after evaporation of all solvent was tested for CO 2 adsorption and desorption capacity as a function of time, against corresponding amine-doped silica sorbent without IL treatment.

The tests were performed with a feed gas containing 10% CO 2 and 90% N 2 . The test conditions were as follows:

<u

CLAIMS

Claims ( 31 )

1 . A sorbent useful for CO 2 capture, comprising a solid support with CO 2 -sorbing amine and ionic liquid thereon, wherein the ionic liquid is interactive with the CO 2 -sorbing amine to enhance at least one of the sorbent characteristics of (i) CO 2 sorption capacity, (ii) CO 2 sorption rate, (iii) CO 2 desorption capacity, (iv) CO 2 desorption rate, and (v) regeneration temperature, in relation to a corresponding sorbent lacking the ionic liquid.

2 . The sorbent of claim 1 , wherein the solid support comprises one or more material(s) selected from the group consisting of: carbon, silica, porous silicon, zeolites, metal oxides, mixed metal oxides, aluminosilicates, metal organic frameworks (MOFs), clays, mesoporous materials, fabrics, non-woven materials, ceramic monoliths, metal monoliths, ceramic-metal monoliths, polymers, porous polymer networks, and mixtures, alloys, and combinations including any one or more of the foregoing.

3 .- 4 . (canceled)

5 . The sorbent of claim 1 , wherein the solid support comprises one or more metal organic frameworks (MOFs), wherein the one or more MOFs comprise(s) at least one selected from the group consisting of: Zn 4 O(BTE)(BPDC) wherein BTE is 4,4′,4″-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate, and BPDC is biphenyl-4,4′-dicarboxylate; Zn 4 O(BTB) 2 , wherein BTB is 1,3,5-benzenetribenzoate Zn 4 O(BBC) 2 , wherein BBC is 4,4′,4″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate; Zn 4 O(BDC) 3 wherein BDC is 1,4-benzenedicarboxylate; Mn 3 [(Mn 4 Cl) 3 (BTT) 8 ] 2 , where BTT is benzene-1,3,5-tris(1H-tetrazole); and Cu 3 (BTC) 2 (H 2 O) 3 , wherein BTC is 1,3,5-benzenetricarboxylic acid.

6 . (canceled)

7 . The sorbent of claim 1 , wherein the CO 2 -sorbing amine comprises:

(i) one or more amine(s) selected from the group consisting of primary, secondary and tertiary alkylamines and alkanolamines, aromatic amines, mixed amines, polyamines and combinations thereof; (ii) one or more amine(s) selected from the group consisting of monoethanolamine (MEA), triethanolamine (TEA), diethanolamine (DEA), diethylenetriamine (DETA), 2-(2-aminoethylamino)ethanol, diisopropanolamine, 2-amino-2-methyl-1,3-propanediol, pentaethylenehexamine, tetramethylenepentaamine, tetraethylenepentamine (TEPA), methyldiethanolamine (MDEA), polyallylamines, aminosilanes, tetraalkoxysilanes, aminoalkylalkoxysilanes, hyperbranched aminosilica (HAS), polymeric amines, and combinations and mixtures including one or more of the foregoing; (iii) one or more polyalkyleneimine(s); or (iv) one or more polyethyleneimine(s).

8 .- 10 . (canceled)

11 . The sorbent of claim 1 , wherein the CO 2 -sorbing amine comprises polyethylene imine, tetraethylenepentamine, or polypropyleneimine.

12 . (canceled)

13 . The sorbent of claim 1 , wherein the ionic liquid comprises one or more ionic liquid(s) selected from the group consisting of ammonium-, imidazolium-, phosphonium-, pyridinium-, pyrrolidinium-, and sulfonium-based ionic liquids.

14 . The sorbent of claim 1 , wherein the ionic liquid comprises one or more ionic liquid(s) selected from the group consisting of ionic liquids comprising one or more of cations

and associated organic or inorganic anions.

15 . The sorbent of claim 14 , wherein the organic or inorganic anions are selected from the group consisting of

16 . The sorbent of claim 1 , wherein the ionic liquid comprises one or more ionic liquid(s) selected from the group consisting of:

1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-ethyl-3-methylimidazolium tetrafluoroborate; 1-ethyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide; 1-ethylpyridinium bromide; 1-hexyl-3-methylimidazolium triflate; 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide; 1,2-dimethyl-3-propylimidazolium bromide; 1,2-dimethyl-3-propylimidazolium iodide; 1,2-dimethylimidazole; 1,2-dimethylimidazolium chloride; 1,2-dimethylimidazolium bis(trifluoromethylsulfonyl)imide; 1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide; 1,3-diethylimidazolium bromide; 1,3-diethylimidazolium tetrafluoroborate; 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-benzyl-3-methylimdiazolium 1,1,2,2-tetrafluoroethanesulfonate; 1-benzyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide; 1-decyl-3-methylimidazolium hexafluorophosphate; 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-ethyl-1-methylpyrrolidinium hexafluorophosphate; 1-ethyl-3-methylimidazolium hexafluorophosphate; 1-ethyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide; 1-heptyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-hexadecyl-3-methylimidazolium hexafluorophosphate; 1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide; 1-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-propyl-4-methylpyridinium bromide; bis(1-butyl-3-methylimidazolium) tetrathiocyanatocobaltate; diethylmethylsulfonium bis(trifluoromethylsulfonyl)imide; trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide; and triphenylcarbenium tetrakis(perfluoro-tert-butoxy) aluminate.

17 . The sorbent of claim 1 , wherein the ionic liquid comprises

wherein each of R 1 and R 2 is independently selected from H, hydroxy, halo (F, Br, Cl, I), C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 12 carboxy, C 1 -C 12 haloalkyl, C 6 -C 12 aryl, C 6 -C 14 arylalkyl, C 5 -C 10 cycloalkyl, amino or substituted amino, thiol, phosphate, sulfate, phosphonate, and sulfonate.

18 . (canceled)

19 . The sorbent of claim 1 , wherein the ionic liquid comprises a substituted imidazolium group and a bis(trifluoromethylsulfonyl)imide group, wherein substituent(s) of the substituted imidazolium group are each independently selected from among organo substituents.

20 . The sorbent of claim 1 , comprising from 1 to 5000 ppm by weight of the ionic liquid, based on total weight of the amine present on the solid support.

21 .- 24 . (canceled)

25 . A method of making a CO 2 capture sorbent, comprising:

depositing a CO 2 -sorbing amine on a solid support, to form an aminated support; and depositing ionic liquid on the aminated support to form the CO 2 capture sorbent comprising the solid support with the CO 2 -sorbing amine and ionic liquid thereon, wherein said depositing ionic liquid on the aminated support comprises contacting the aminated support with an alkanolic solution of the ionic liquid to impregnate the aminated support with the ionic liquid, recovering the ionic liquid-impregnated aminated support from the alkanolic solution, and removing alkanol from the recovered ionic liquid-impregnated aminated support to yield the CO 2 capture sorbent comprising the solid support with the CO 2 -sorbing amine and ionic liquid thereon, and wherein said removing alkanol from the recovered ionic liquid-impregnated aminated support comprises evaporating the alkanol from the recovered ionic liquid-impregnated aminated support.

26 .- 27 . (canceled)

28 . A method of CO 2 capture, comprising contacting a CO 2 -containing gas with a sorbent according to claim 1 , to produce CO 2 -reduced gas, and sorbent having CO 2 adsorbed thereon.

29 . The method of claim 28 , further comprising:

regenerating the sorbent having CO 2 adsorbed thereon, to desorb CO 2 therefrom to form regenerated sorbent, and CO 2 desorbate; and recovering the CO 2 desorbate from the regenerated sorbent.

30 . The method of claim 29 , wherein the method is conducted in a multi-bed system comprising multiple beds of the sorbent arranged for continuous CO 2 capture processing of the CO 2 -containing gas, wherein one or more of the multiple beds is on-stream for said contacting of the CO 2 -containing gas with the sorbent, and another or others of the multiple beds is off-stream and while off-stream said regenerating and recovering are carried out, with each of the multiple beds undergoing sequential on-stream and off-stream operations in a cyclic repeating sequence for said continuous CO 2 capture processing of the CO 2 -containing gas.

31 .- 33 . (canceled)

34 . The method of claim 28 , wherein the CO 2 -containing gas is air.

35 .- 39 . (canceled)

40 . The method of claim 28 , wherein the CO 2 -containing gas comprises CO 2 -containing gas produced by combustion of fossil fuel.

41 .- 43 . (canceled)

44 . The method of claim 28 , wherein the CO 2 -containing gas comprises one or more of:

coal-fired power plant flue gas; natural gas combined cycle power plant flue gas; blast furnace exhaust gas; cement plant exhaust gas; natural gas fired once through steam generator gas; steam methane reformer syngas; steam methane reformer flue gas; steam methane reformer PSA tail gas; dry reforming syngas; integrated gasification combined cycles (IGCC) syngas; biogas; biomass gasification syngas; municipal waste gasification syngas; and atmospheric gas.

45 . A sorbent according to claim 1 , as disposed in a CO 2 capture system comprising at least one sorption vessel containing the sorbent, wherein the vessel is arranged for contacting of CO 2 -containing gas with the sorbent therein and discharge of CO 2 -reduced contacted gas.

46 .- 50 . (canceled)

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