# US 2019/0168185 A1 · Regenerative adsorbents of modified amines on solid supports

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- Number: US 2019/0168185 A1
- Document ID: US20190168185A1
- Status: Published application
- Kind: A1
- Application number: 16/271,245
- Filed: 2019-02-08
- Published: 2019-06-06
- Earliest claimed: 2015-01-12
- Assignees: University of Southern California
- Applicants: University of Southern California
- Inventors: Alain GOEPPERT; Hang ZHANG; George A. OLAH; G.K. Surya Prakash
- Web page: https://patentgrep.com/patent/US20190168185A1

## CPC

- B01J 20/103: {comprising silica}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- B01D 53/04: with stationary adsorbents {(B01D53/025 takes precedence)}
- B01J 20/262: {obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation (macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G)}
- B01J 20/28007: {with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like (carbon nanostructures B01J20/205)}
- B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing}
- B01J 20/3204: {Inorganic carriers, supports or substrates}
- B01J 20/3231: {characterised by the coating or impregnating layer}
- B01J 20/3272: {Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds}
- B01J 20/3425: {of sorbents or filter aids comprising organic materials}
- B01J 20/3483: {by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling}
- B01J 20/3491: {by pressure treatment}
- C07C 29/48: by oxidation reactions with formation of hydroxy groups
- C07C 41/01: Preparation of ethers
- C07C 51/16: by oxidation (C07C51/145 takes precedence)
- B01D 2253/202: Polymeric adsorbents
- B01D 2253/25: Coated, impregnated or composite adsorbents
- B01D 2257/504: Carbon dioxide
- Y02C 20/40: of CO2
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]

## Abstract

The invention relates to regenerative, solid sorbents for adsorbing carbon dioxide from a gas mixture, including air, with the sorbent including a modified polyamine and a solid support. The modified polyamine is the reaction product of an amine and an epoxide. The sorbent provides structural integrity, as well as high selectivity and increased capacity for efficiently capturing carbon dioxide from gas mixtures, including the air. The sorbent is regenerative, and can be used through multiple cycles of adsorption-desorption.

## Claims

### Claim 1

A method for capturing and separating carbon dioxide from a gas mixture, which comprises:
exposing a carbon dioxide sorbent to a gas mixture that contains carbon dioxide to effect adsorption of the carbon dioxide by the sorbent; and
treating the sorbent that contains adsorbed carbon dioxide under conditions sufficient to release the adsorbed carbon dioxide either at a higher carbon dioxide concentration or as purified carbon dioxide;
wherein the sorbent has a sufficiently high surface area for solid-gas contact and sufficient structural integrity for adsorbing carbon dioxide from the gas mixture without degrading, the sorbent comprising a modified polyamine which is supported upon and within a solid support, with the modified polyamine formed as a reaction product that includes amine functionalities from reaction of an excess of amine and an epoxide, and with the solid support being (a) a nano-structured support of silica, silica-alumina, alumina, titanium oxide, calcium silicate, carbon nanotubes, carbon, or a mixture thereof and having a primary particle size of less than about 100 nm; or (b) a natural or synthetic clay or a mixture thereof.

### Claim 2 (depends on 1)

The method of claim 1, wherein the sorbent is provided in a fixed, moving, or fluidized bed and the gas and bed are in contact for a sufficient time to trap the carbon dioxide in the sorbent, wherein the sorbent is treated with sufficient heat, reduced pressure, vacuum, gas purge, or a combination thereof to release a substantial amount or all of the adsorbed carbon dioxide.

### Claim 3 (depends on 1)

The method of claim 1, wherein the carbon dioxide is captured by the sorbent and separated from ambient air at low carbon dioxide concentrations of 200-5000 ppm.

### Claim 4 (depends on 1)

The method of claim 1, wherein the carbon dioxide is captured by the sorbent and separated from ambient air at moderate temperatures of less than 55° C.

### Claim 5 (depends on 1)

The method of claim 1, wherein the carbon dioxide sorbent is regenerative for capturing and separating carbon dioxide for at least one adsorption/regeneration cycle.

### Claim 6 (depends on 5)

The method of claim 5, wherein the carbon dioxide is captured from air having a carbon dioxide concentration of 200 to 5000 ppm.

### Claim 7 (depends on 5)

The method of claim 5, wherein the adsorbent regeneration temperature is less than 130° C.

### Claim 8 (depends on 1)

The method of claim 1, wherein the amine is a primary, secondary or tertiary alkyl- or alkanolamine, an aromatic amine, a mixed amine, tetraethylenepentamine, pentaethylenehexamine, triethylenetetramine, diethylenetriamine, ethylenediamine, hexaethyleneheptamine, a polyethylenimine, a polyvinylamine, polyallylamine, other polymeric amine compounds or combinations thereof, and wherein the epoxide is a simple epoxide, diepoxide, triepoxide, a polyepoxide compound, polymeric epoxide, ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, glycidol, butyl glycidyl ether, tert-butyl glycidyl ether, dodecyl and tetradecyl glycidyl ethers, octyl/decyl glycidyl ether, 1,2-epoxycyclohexane, epichlorohydrin, glycerol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, resorcinol diglycidyl ether, poly(propylene glycol) diglycidyl ether, 4,4′-isopropylidenediphenol diglycidyl ether, 1,2,5,6-diepoxycyclooctane, trimethylolpropane triglycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline, 4,4′-methylenebis(N,N-diglycidylaniline) or a mixture thereof.

### Claim 9 (depends on 1)

The method of claim 1, in which the modified polyamine is present in an amount of 1% to 90% by weight of the sorbent, or in an approximately equal amount by weight as the support.

### Claim 10 (depends on 1)

The method of claim 1, wherein the sorbent further comprises a polyethylene oxide, polyol or mixture thereof in an amount of 1 up to about 25% by weight of the sorbent, wherein the polyol is glycerol, oligomers of ethylene glycol or polyethylene glycol, and the polyethylene oxides may be present as their corresponding ethers.

### Claim 11 (depends on 1)

The method of claim 1, wherein the sorbent is prepared by combining the amine, epoxide, support and a solvent in a mixture, mixing and heating the mixture for a sufficient time to allow the amine and epoxide to combine as the reaction product and to be provided upon and within the support, followed by removal of the solvent to obtain the sorbent as a solid material.

### Claim 12 (depends on 1)

The method of claim 1, wherein the sorbent is prepared by dispersing the support in a solvent to form a suspension; dissolving the amine in the same solvent to form an amine solution; providing the epoxide in a solution with the same solvent or in a concentrated form; and combining the suspension, the amine solution, and the epoxide or epoxide solution in a mixture with agitation or stirring for a period of time to form a reaction product between the amine and the epoxide, with the solvent removed by heating the liquid reaction product, if necessary under vacuum, to obtain the sorbent as a solid.

### Claim 13 (depends on 12)

The method of claim 12, which further comprises adding a polyol or polyether to the mixture before removing of the solvent.

### Claim 14 (depends on 1)

The method of claim 1, wherein the sorbent is prepared by dissolving the amine in solvent to form an amine solution, adding the epoxide, in a concentrated form or in the form of a solution having the same solvent, to the amine solution to form a mixture; mixing the mixture at a temperature of 15 to 30° C. for 0.1 to 50 hours; then heating the mixture to allow for complete reaction between the amine and epoxide, followed by heating for 30 seconds to 300 minutes to remove part or all of the solvent, with any remaining solvent removed by heating, if necessary, under vacuum, to obtain the modified amine, dispersing the support in the same solvent to form a suspension; and forming the sorbent by adding the modified amine to the dispersion of the support with stirring to disperse the modified polyamine onto the support.

### Claim 15 (depends on 1)

The method of claim 1, which further comprises reacting the released carbon dioxide to form methanol, dimethyl ether, formic acid or carbon monoxide.

### Claim 16 (depends on 15)

The method of claim 15, which further comprises reacting the released carbon dioxide to form methanol, and dehydrating the methanol under conditions sufficient to produce dimethyl ether.

### Claim 17 (depends on 16)

The method of claim 16, which further comprises:
heating the dimethyl ether in the presence of an acidic-basic or zeolitic catalyst under conditions sufficient to form ethylene or propylene; and
converting the ethylene and/or propylene under conditions sufficient to higher olefins, synthetic hydrocarbons, aromatics, or a product produced therefrom, for use as a feedstock for chemicals or as transportation fuel; or
hydrating the ethylene or propylene under conditions sufficient to form ethanol or propanol.