Composites for carbon dioxide capture

• US 9,718,045 B2
• Filed: 01/11/2013
• Issued: 08/01/2017
• Est. Priority Date: 01/11/2012
• Status: Expired due to Fees

• Current Assignee: Rice University
• Original Assignee: William March Rice University
• Inventors: Tour, James M., Hwang, Chih-Chau
• Primary Examiner(s): HENDRICKSON, STUART L
• Application Number:
  US14/371,791
• Publication Number:
  US 20150056116A1
• Time in Patent Office: 1,663 Days
• CPC Class Codes: B01D 2251/00 Reactants
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2253/1124 Metal oxides
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2258/0283 Flue gases
• 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 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 20/28066 being more than 1000 m2/g
• CPC Class Codes: B01J 20/28078 Pore diameter
• CPC Class Codes: B01J 20/2808 being less than 2 nm, i.e. micropores or nanopores
• CPC Class Codes: B01J 20/28083 being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 20/28085 being more than 50 nm, i.e. macropores
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3236 containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/3248 the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
• CPC Class Codes: B01J 20/3293 Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
• CPC Class Codes: B01J 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3491 : by pressure treatment
• CPC Class Codes: C10L 2290/541 : Absorption of impurities during preparation or upgrading of a fuel
• CPC Class Codes: C10L 3/104 : Carbon dioxide
• 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 20/20 : of methane
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

Composite materials and methods of preparing C0₂ capture include: (1) a porous solid support comprising a plurality of porous channels; and (2) a nucleophilic source associated with the porous channels of the porous solid support. The nucleophilic source is capable of converting the captured C0₂ to poly(C0₂). Methods of capturing C0₂ from an environment include associating the environment with the aforementioned composite materials to lead to the capture of C0₂ from the environment. Such methods may also include a step of releasing the captured C0₂ from the composite material. The associating step comprises a conversion of the captured C0₂ to poly(C0₂) in the composite material. A releasing step may also include a depolymerization of the formed poly(C0₂).

Claims

1. A method of capturing CO₂ from an environment, wherein the method comprises:

contacting the environment with a composite material, wherein the composite material comprises;

a porous solid support comprising a plurality of porous channels, and

a nucleophilic source,

wherein the nucleophilic source is in contact with the porous channels of the porous solid support,

wherein the nucleophilic source is selected from the group consisting of sulfur-containing nucleophiles, metal oxides, metal nitrides, metal sulfides, metal selenides, and combinations thereof, and

wherein the contacting leads to the capture of CO₂ from the environment; and

releasing the captured CO₂ from the composite material, wherein the releasing occurs under one or more of the following conditions;

conditions comprising a reduction of pressure;

conditions comprising temperatures that range from about 15°

C. to about 30°

C.;

conditions comprising the absence of heating;

or

combinations thereof.

2. The method of claim 1, wherein the contacting comprises converting CO₂ to poly(CO₂) in the composite material.

3. The method of claim 1, wherein the CO₂ is in a gaseous state prior to conversion to poly(CO₂).

4. The method of claim 1, wherein the composite material captures CO₂ from the environment at a ratio of at least about 35% of the composite material'"'"'s weight.

5. The method of claim 1, wherein the environment comprises at least one of an industrial gas stream, natural gas stream, or a flue gas stream.

6. The method of claim 1, wherein the contacting occurs at pressures that range from about 1 atm to about 100 atm.

7. The method of claim 1, wherein the contacting occurs at pressures of at least about 10 atm.

8. The method of claim 1, wherein the contacting occurs at temperatures that range from about 15°

C. to about 30°

C.

9. The method of claim 1, wherein the releasing comprises a reduction of pressure.

10. The method of claim 9, wherein the pressure is reduced to less than about 10 atm.

11. The method of claim 1, wherein the releasing occurs at temperatures that range from about 15°

C. to about 30°

C.

12. The method of claim 1, wherein the releasing occurs in the absence of heating.

13. The method of claim 1, wherein the releasing occurs without exposing the composite material to electrical current or an applied voltage.

14. The method of claim 1,

wherein the contacting comprises converting CO₂ to poly(CO₂) in the composite material, and

wherein the releasing comprises a depolymerization of the formed poly(CO₂).

15. The method of claim 1, further comprising a step of reusing the composite material to capture CO₂ from an environment, wherein the reusing occurs after the releasing step.

16. The method of claim 1, wherein the porous solid support is selected from the group consisting of mesoporous carbon sources, glass, glass materials made from silicon oxide, metals, metal oxides, sulfur, metal nitrides, metal sulfides, metal selenides, and combinations thereof.

17. The method of claim 1, wherein the porous solid support comprises a mesoporous solid support.

18. The method of claim 1, wherein the porous solid support comprises a mesoporous carbon source, wherein the mesoporous carbon source is selected from the group consisting of amorphous carbons, carbon black, porous carbon black, activated carbons, graphene, expanded graphite, graphene nanoribbons, CMK-3, CMK-1, CMK-5, MCM-41, hydroxide-treated carbons and combinations thereof.

19. The method of claim 1, wherein the nucleophilic source comprises a metal oxide.

20. The method of claim 19, where the metal oxide comprises an iron oxide selected from the group consisting of FeO, α

-Fe₂O₃, β

-Fe₂O₃, γ

-Fe₂O₃, ε

-Fe₂O₃, Fe(OH)₂, Fe(OH)₃, α

-FeOOH, β

-FeOOH, γ

-FeOOH, δ

-FeOOH, Fe₅HO₈.nH₂O, 5Fe₂O₃.nH₂O, FeOOH.nH₂O, Fe₈O₈(OH)₆(SO₄).nH₂O, Fe³⁺₁₆O₁₆(OH,SO₄)_12-13.10-12H₂O, Fe^III_xFe^II_y(OH)<sub>3x+2y−

z</sub>(A⁻

)_z;

where A⁻

is Cl⁻

or 0.5SO₄²⁻

, FeO(OH).nH₂O, and combinations thereof.

21. The method of claim 1, wherein the nucleophilic source is in contact with the porous channels of the porous solid support through van der Waals interactions.

22. The method of claim 1, wherein the nucleophilic source is in contact with the porous channels of the porous solid support through covalent bonds.

23. The method of claim 1, wherein the composite material has a surface area of more than about 1,000 m²/g.

24. The method of claim 1, wherein the composite material has a surface area of at least about 2,500 m²/g.

25. The method of claim 1, wherein the capture of CO₂ comprises sorption of CO₂ to the composite material, wherein the sorption is selected from the group consisting of physisorption, chemisorption, absorption, adsorption and combinations thereof.

26. The method of claim 1, wherein the capture of CO₂ comprises absorption of CO₂ to the composite material.

27. The method of claim 1, wherein the nucleophilic source is selected from the group consisting of metal oxides, metal nitrides, metal sulfides, metal selenides, and combinations thereof.

28. The method of claim 1, wherein the nucleophilic source is selected from the group consisting of Fe₃O₄, FeS, and combinations thereof.

29. The method of claim 1, wherein the nucleophilic source comprises Fe₃O₄.

30. The method of claim 1, wherein the weight ratio of the nucleophilic source to the porous solid support is 1:

1.