# US 12,005,422 B2 · Gas capture using polymeric particles

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- Number: US 12,005,422 B2
- Document ID: US12005422B2
- Status: Granted
- Kind: B2
- Application number: 16/312,903
- Filed: 2017-06-23
- Published: 2019-05-30
- Granted: 2024-06-11
- Earliest claimed: 2016-06-23
- Assignees: Charmstar Cambridge Limited
- Applicants: Charmstar Cambridge Limited
- Inventors: Seyed Ali Nabavi; Goran Vladisavljevic; Vasilije Manovic
- Web page: https://patentgrep.com/patent/US12005422B2

## CPC

- B01J 20/267: {Cross-linked polymers}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- B01J 20/268: {Polymers created by use of a template, e.g. molecularly imprinted polymers}
- B01J 20/28016: {Particle form}
- B01J 20/28019: {Spherical, ellipsoidal or cylindrical}
- B01J 20/3057: {Use of a templating or imprinting material (molecularly imprinted polymers B01J20/268); filling pores of a substrate or matrix followed by the removal of the substrate or matrix}
- B01J 20/3071: {Washing or leaching}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- B01D 2253/202: Polymeric adsorbents
- B01D 2257/108: Hydrogen
- B01D 2257/302: Sulfur oxides
- B01D 2257/404: Nitrogen oxides other than dinitrogen oxide
- B01D 2257/502: Carbon monoxide
- B01D 2257/504: Carbon dioxide
- 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)}
- 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)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]

## Abstract

Disclosed herein is a method of making a polymeric material for selective adsorption of a gas. The method comprises dissolving a monomer comprising a functional group having an affinity for the gas in a solvent with a cross-linker and an initiator; emulsifying the solution in a liquid which is immiscible with the first solvent; and agitating and heating the emulsion to cause polymerization of the monomer into a cross-linked polymer having nanocavities with functional groups covalently-incorporated on walls thereof. Also disclosed are polymeric particles, an apparatus for forming the particles and a method of adsorbing a selected gas.

## Claims

### Claim 1

A method of making a polymeric material for selective adsorption of carbon dioxide, the method comprising:
dissolving a monomer comprising a functional group having a greater affinity for carbon dioxide molecules than other molecules in a mixed gas stream in a solvent with a cross-linker and an initiator to form a solution, wherein the dissolving comprises mixing with a template comprising molecules that are structurally similar to molecules of the mixed gas stream such that monomer-template complexes are formed, the molecules of the template being a structural analogue of one or more molecules of the mixed gas stream;
emulsifying the solution in a liquid that is immiscible with the solvent to form an emulsion; and
agitating and providing thermal or light energy to the emulsion to cause polymerization of droplets of the solution into particles of a cross-linked polymer having nanocavities with carbon dioxide-philic functional groups covalently-incorporated on walls thereof onto which molecules of carbon dioxide are able to be selectively adsorbed, the particles having a specific surface area SBET of 328-443 m2/g, wherein the carbon dioxide-philic functional groups are one of an amide group, an amine group, a carboxyl group, and a hydroxyl group,
wherein each of the nanocavities is sized and shaped to be structurally complementary with two carbon dioxide molecules due to a distance between the carbon dioxide-philic functional groups within the nanocavities sufficient for two kinematic diameters of 0.33 nm to facilitate selective adsorption of the carbon dioxide molecules by entrapment and bonding of the carbon dioxide molecules into the nanocavities.

### Claim 2 (depends on 1)

The method of claim 1, wherein the emulsion includes acetonitrile as a dispersed phase and mineral oil as a continuous phase.

### Claim 3 (depends on 1)

The method of claim 1, further comprising washing the cross-linked polymer by mechanical agitation and/or ultrasonic agitation to remove unreacted reagents and a continuous phase of the emulsion.

### Claim 4 (depends on 1)

The method of claim 1, wherein the emulsifying comprises forcing the solution through a porous membrane and forming substantially uniformly-sized droplets by controlling a rate of flow through the porous membrane and a shear force imposed on a surface of the porous membrane.

### Claim 5 (depends on 1)

The method of claim 1, further comprising removing the template, thereby leaving the nanocavities with the carbon dioxide-philic functional groups having an affinity to carbon dioxide molecules.

### Claim 6 (depends on 1)

The method of claim 1, wherein the solvent comprises a porogenic solvent in which the monomer, the template, the cross-linker and the initiator have a solubility that promotes homogeneity of the solution.

### Claim 7

A material for selective adsorption of carbon dioxide, the material comprising particles of polymerized droplets of uniform or substantially uniform sphericity formed from a cross linked polymer and having nanocavities with carbon dioxide-philic functional groups having a greater affinity for carbon dioxide molecules than other molecules in a mixed gas stream, the particles having a specific surface area SBET of 328-443 m2/g, the carbon dioxide-philic functional groups covalently incorporated on walls of the nanocavities, onto which molecules of carbon dioxide are able to be selectively adsorbed,
wherein each of the nanocavities is sized and shaped to be structurally complementary with two carbon dioxide molecules due to a distance between the carbon dioxide-philic functional groups within the nanocavities sufficient for two kinematic diameters of 0.33 nm to facilitate selective adsorption of the carbon dioxide molecules by entrapment of the carbon dioxide molecules into the nanocavities,
wherein the carbon dioxide-philic functional groups is one of an amide group, an amine group, a carboxyl group, and a hydroxyl group.

### Claim 8 (depends on 7)

The material of claim 7, wherein the nanocavities are smaller than 2 nm.

### Claim 9 (depends on 7)

The material of claim 7, wherein the particles are insoluble in water and able to regenerate by removal of adsorbed carbon dioxide molecules using temperature and pressure manipulations.

### Claim 10

A material for selective adsorption of carbon dioxide, the material comprising particles of polymerized droplets of irregular, rounded shape formed from clustered and partially-fused spherical or substantially spherical polymer particles and having nanocavities with carbon dioxide-philic functional groups having a greater affinity for carbon dioxide molecules than other molecules in a mixed gas stream, the particles having a specific surface area SBET of 328-443 m2/g, the carbon dioxide-philic functional groups covalently incorporated on walls of the nanocavities, onto which molecules of carbon dioxide are able to be selectively adsorbed,
wherein each of the nanocavities is sized and shaped to be structurally complementary with two carbon dioxide molecules due to a distance between the carbon dioxide-philic functional groups within the nanocavities sufficient for two kinematic diameters of 0.33 nm to facilitate selective adsorption of the carbon dioxide molecules by entrapment of the carbon dioxide molecules into the nanocavities,
wherein the carbon dioxide-philic functional groups is one of an amide group, an amine group, a carboxyl group, and a hydroxyl group.

### Claim 11 (depends on 10)

The material of claim 10, wherein the particles comprise a structure formed from multiple partially-coalesced droplets clustered together, each of the droplets comprising multiple monomer molecules.

### Claim 12 (depends on 11)

The material of claim 11, wherein each of the droplets is a mixture additionally comprising a template, a solvent, an initiator, and a across linker, the solvent, the initiator, and the cross-linker having been used to form the particles.

### Claim 13 (depends on 10)

The material of claim 10, wherein the particles are insoluble in water and are able to regenerate by removal of adsorbed gas molecules using temperature and pressure manipulations.

### Claim 14 (depends on 10)

A method of adsorbing a selected gas from a gas stream comprising a mixture of gases, the method comprising flowing the gas stream past the material of claim 10.

### Claim 15 (depends on 7)

The material of claim 7, wherein the carbon dioxide-philic functional groups are incorporated on the walls of the nanocavities in a spatial arrangement that forms a cavity having a shape, size, and the carbon dioxide-philic functional groups complementary to and able to receive the two carbon dioxide molecules, such that each carbon dioxide molecule is able to be adsorbed by one of the carbon dioxide-philic functional groups.

### Claim 16 (depends on 7)

The material of claim 7, wherein the nanocavities are formed by molecular imprinting using a template comprising a molecule that is a structural analogue to the two carbon dioxide molecules.

### Claim 17 (depends on 16)

The material of claim 16, wherein the template is low molecular weight carboxylic acid having a molecular weight of between approximately 46 g/mole and 200 g/mole.

### Claim 18 (depends on 17)

The material of claim 17, wherein the template is oxalic acid or formic acid.

### Claim 19 (depends on 16)

The material of claim 16, wherein each carbon dioxide-philic functional group within the nanocavities is spaced a distance from one another in a range suitable for two carbon dioxide molecules to each be adsorbed by a carbon dioxide-philic functional group within each of the nanocavities.

### Claim 20 (depends on 7)

The material of claim 7, wherein at least half of the particles by volume have a diameter of approximately 350 microns to 800 microns.

### Claim 21 (depends on 7)

The material of claim 7, wherein the material is an adsorbent for low-temperature post-combustion capture of carbon dioxide by chemisorption and at a heat of adsorption that is greater than 40 kJ mol.

### Claim 22 (depends on 7)

The material of claim 7, wherein the carbon dioxide-philic functional groups within each of the nanocavities have a polarity and quadrupole moment that attract and result in hydrogen bonds with carbon dioxide molecules.

### Claim 23 (depends on 7)

The material of claim 7, wherein the material has a carbon dioxide adsorption capacity that ranges from at least 0.28 mmol/g to 0.62 mmol/g at temperatures ranging from 25° C. to 80° C. in the mixed gas stream.

### Claim 24 (depends on 7)

The material of claim 7, wherein the cross-linked polymer is formed by polymerization of a monomer selected from the group consisting of acrylamide, methacrylamide, allylamine, 4-vinylaniline, N-Allylaniline, diallylamine, and triallylamine.