Application of amine-tethered solid sorbents to CO2 fixation from air

• US 8,491,705 B2
• Filed: 08/19/2010
• Issued: 07/23/2013
• Est. Priority Date: 08/19/2009
• Status: Active Grant

• Current Assignee: Global Thermostat Operations LLC
• Original Assignee: Christopher W. Jones, Jeffrey H. Drese, Peter M. Eisenberger, Ronald R. Chance, Sunho Choi
• Inventors: Choi, Sunho, Drese, Jeffrey H., Chance, Ronald R., Eisenberger, Peter M., Jones, Christopher W.
• Primary Examiner(s): Greene, Jason M
• Application Number:
  US12/859,650
• Publication Number:
  US 20110179948A1
• Time in Patent Office: 1,069 Days
• Field of Search: 951/14, 951/39, 951/48, 961/21, 961/43, 961/54
• US Class Current: 95/139
• CPC Class Codes: B01D 2252/2041 Diamines
• CPC Class Codes: B01D 2252/20421 Primary amines
• CPC Class Codes: B01D 2253/202 Polymeric adsorbents
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2258/06 Polluted air
• CPC Class Codes: B01D 2259/40088 by heating
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: B01J 20/28064 being in the range 500-1000 m2/g
• CPC Class Codes: B01J 20/28073 being in the range 0.5-1.0 ml/g
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3208 Polymeric carriers, supports or substrates
• CPC Class Codes: B01J 20/3219 involving a particular spacer or linking group, e.g. for attaching an active group
• CPC Class Codes: B01J 20/3255 comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
• CPC Class Codes: B01J 20/3257 the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
• CPC Class Codes: B01J 20/3272 Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3425 of sorbents or filter aids comprising organic materials
• CPC Class Codes: B01J 20/3483 by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

A method for capturing CO₂ from the ambient air by the use of solid tethered amine adsorbents, where the amine adsorbents are tethered to a substrate selected from the group of silica, metal oxides and polymer resins. The tethered amines are joined to the substrate by covalent bonding, achieved either by the ring-opening polymerization of aziridine on porous and non-porous supports, or by the reaction of mono-, di-, or tri-aminosilanes, with silica or a metal oxide having hydroxyl surface groups. The method includes the adsorption of CO2 from ambient air, the regeneration of the adsorbent at elevated temperatures not above 120° C. and the separation of purified CO₂, followed by recycling of the regenerated tethered adsorbent for further adsorption of CO₂ from the ambient atmosphere.

Claims

1. A method for the capture of C02 from dilute gas streams in a cyclical manner, the concentration of CO₂ in the gas stream being in the range of from 1-1000 ppm;

the process comprising passing the dilute-C02 gas stream over a solid adsorbent at a substantially ambient temperature of not greater than 120°

C., the solid adsorbent comprising an amine adsorbent tethered to a substrate, the tethered amine being selected from the group consisting of hyperbranched aminopolymers tethered to a substrate selected from the group consisting of a metal oxide, a porous silica and a porous hydrocarbon-based solid polymer support structure, wherein the amine is tethered to the substrate by covalent bonds; and

a tethered amine prepared by the reaction of a silyl amine with an oxide substrate; and

regenerating the solid adsorbent at a temperature of not substantially greater than about 120°

C., to obtain a substantially concentrated CO2 gas stream and a regenerated adsorbent; and

repeating the cycle.

2. The method of claim 1, wherein the substrate is a mesoporous silica.

3. The method of claim 2, wherein the tethered amine is a hyperbranched aminopolymer, forming a Class (iii) adsorbent with a substrate.

4. The method of claim 1, wherein the tethered amine is formed by the reaction of a silyl amine with a substrate selected from the group consisting of silica and metal oxides, to form a Class (ii) adsorbent.

5. The method of claim 4, wherein the silyl amme IS N-(3-(trimethoxysily I)propy 1)ethane-1,2-diamine.

6. The method of claim 1, wherein the tethered amine material comprises an aminefunctionalized porous polymer resin.

7. The method of claim 6, wherein the amine-functionalized porous polymer resin is a hydrocarbon polymer.

8. The method of claim 7, wherein the amine-functionalized porous polymer IS a porous poly(styrene) resin with benzylamine functional groups.

9. The method of claim 8 wherein the porous poly(styrene) resin with benzylamine functional groups is an aminomethylpolystyrene.

10. The method of claim 1 wherein the oxide substrate is a metal oxide.

11. The method of claim 10, wherein the oxide substrate-based tethered amine adsorbent is a metal oxide tethered to a hyperbranched aminopolymer.

12. The method of claim 11, wherein the hyperbranched aminopolymer results from the polymerization of aziridinc.

13. The method of claim 12, wherein the hyperbranched aminopolymer results from the reaction of aziridine and a porous silica substrate in the presence of a catalyst.

14. A cyclic process for the adsorption and capture of CO2 from ambient air, the process comprising cyclically passing air at ambient conditions through a bed of porous, solid material comprising an oxide substrate-based tethered amine adsorbent, to adsorb the CO2 from the air and form a CO2 loaded adsorbent, the adsorbent comprising a tethered amine derived from the group consisting of hyperbranched aminopolymers and a silylamine prepared by the reaction of a silyl diamine with an oxide substrate;

regenerating the tethered amine, by separating the CO₂ from the adsorbent, at a temperature of not greater than 120°

C. to form regenerated adsorbent and purified CO2; and

capturing the purified CO2; and

repeating the adsorption-regeneration process cycle.

15. The method of claim 14, wherein the substrate is a mesoporous silica.

16. The method of claim 14, wherein the tethered amine is a hyperbranched aminopolymer, forming a Class (iii) adsorbent with a substrate.

17. The method of claim 14 wherein the oxide substrate is a metal oxide.

18. The method of claim 17, wherein the oxide substrate-based tethered amine adsorbent is a metal oxide tethered to a hyperbranched aminopolymer.