Method, synthesis, activation procedure and characterization of an oxygen rich activated porous carbon sorbent for selective removal of carbon dioxide with ultra high capacity

• US 10,232,342 B2
• Filed: 06/23/2017
• Issued: 03/19/2019
• Est. Priority Date: 07/01/2015
• Status: Active Grant

• Current Assignee: Apache Corporation (APA Corp.), Rice University
• Original Assignee: Apache Corporation (APA Corp.), Rice University
• Inventors: Ghosh, Saunab, Barron, Andrew R., Ho, Jason
• Primary Examiner(s): Hendrickson, Stuart L
• Application Number:
  US15/631,341
• Publication Number:
  US 20170304801A1
• Time in Patent Office: 634 Days
• CPC Class Codes: B01D 2253/102 Carbon
• CPC Class Codes: B01D 2253/306 Surface area, e.g. BET-specific surface
• CPC Class Codes: B01D 2253/311 Porosity, e.g. pore volume
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• 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 53/04 with stationary adsorbents B01D53/025 takes precedence
• 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 20/28076 being more than 1.0 ml/g
• CPC Class Codes: B01J 20/2808 being less than 2 nm, i.e. micropores or nanopores
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: C01B 32/30 Active carbon
• CPC Class Codes: C01B 32/342 characterised by non-gaseous activating agents
• CPC Class Codes: C10L 2290/542 Adsorption of impurities during preparation or upgrading of a fuel
• CPC Class Codes: C10L 3/104 Carbon dioxide
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The present disclosure pertains to materials for CO₂ adsorption at pressures above 1 bar, where the materials include a porous material with a surface area of at least 2,800 m²/g, and a total pore volume of at least 1.35 cm³/g, where a majority of pores of the porous material have diameters of less than 2 nm as measured from N₂ sorption isotherms using the BET (Brunauer-Emmett-Teller) method. The present disclosure also pertains to materials for separation of CO₂ from natural gas at partial pressures of either component above 1 bar, where the materials include a porous material with a surface area of at least 2,200 m²/g, and a total pore volume of at least 1.00 cm³/g, where a majority of pores of the porous material have diameters of greater than 1 nm and less than 2 nm as measured from N₂ sorption isotherms using the BET method.

Claims

1. A material for CO₂ adsorption at pressures above 1 bar comprising:

a porous material with a surface area of at least 2,800 m²/g, and a total pore volume of at least 1.35 cm³/g,

wherein more than 70% of pores of the porous material have diameters of less than 2 nm as measured from N₂ sorption isotherms using the BET (Brunauer-Emmett-Teller) method,

wherein the porous material has an oxygen content of more than about 7 wt % as measured by X-ray photoelectron spectroscopy, and

wherein the porous material has a CO₂ adsorption capacity of more than about 100 wt %.

2. The material of claim 1, wherein the porous material comprises a porous carbon material with a carbon content of between 80% and 95% as measured by X-ray photoelectron spectroscopy.

3. The material of claim 2, wherein the porous carbon material is prepared by heating an organic polymer precursor or biological material in the presence of KOH, wherein the temperature of activation is between 700°

C. and 800°

C.

4. The material of claim 3, wherein the organic polymer precursor or biological material comprises oxygen in a functional group.

5. The material of claim 4, wherein the functional group comprises a furyl.

6. The material of claim 5, wherein the organic polymer precursor polymerizes to form polyfurfuryl alcohol.

7. The material of claim 6, wherein the polyfurfuryl alcohol is prepared by the polymerization of furfuryl alcohol with a catalyst.

8. The material of claim 7, wherein the catalyst comprises iron(III) chloride.

9. The material of claim 3, wherein the biological material is chosen from at least one of the following:

sawdust and coconut husk.

10. The material of claim 4, wherein the functional group comprises an anisyl.

11. The material of claim 10, wherein the organic polymer precursor polymerizes to form polyanisyl alcohol.

12. The material of claim 11, wherein the polyanisyl alcohol is prepared by the polymerization of anisyl alcohol with a catalyst.

13. The material of claim 12, wherein the catalyst comprises a protic acid.

14. The material of claim 1, wherein more than 80% of pores of the porous material have diameters of less than 2 nm.

15. The material of claim 1, wherein the porous material has an oxygen content of more than about 10 wt % as measured by X-ray photoelectron spectroscopy.

16. The material of claim 1, wherein the molar CO₂:

CH₄ uptake ratio of the porous material is more than about 2.

17. A material for the separation of CO₂ from natural gas at partial pressures of either component above 1 bar comprising:

a porous material with a surface area of at least 2,200 m²/g, and a total pore volume of at least 1.00 cm³/g,

wherein more than 50% of pores of the porous material have diameters of greater than 1 nm and less than 2 nm as measured from N₂ sorption isotherms using the BET (Brunauer-Emmett-Teller) method, and

wherein the porous material has a CO₂ adsorption capacity of more than about 100 wt %.

18. The material of claim 17, wherein the porous material comprises a porous carbon material with a carbon content of between 80% and 95% as measured by X-ray photoelectron spectroscopy.

19. The material of claim 18, wherein the porous carbon material is prepared by heating an organic polymer precursor or biological material in the presence of KOH, wherein the temperature of activation is between 700°

C. and 800°

C.

20. The material of claim 19, wherein the organic polymer precursor comprises oxygen in a functional group.

21. The material of claim 20, wherein the functional group comprises a furyl.

22. The material of claim 21, wherein the organic polymer precursor polymerizes to form polyfurfuryl alcohol.

23. The material of claim 22, wherein the polyfurfuryl alcohol is prepared by the polymerization of furfuryl alcohol with a catalyst.

24. The material of claim 23, wherein the catalyst comprises iron(III) chloride.

25. The material of claim 19, wherein the biological material is chosen from at least one of the following:

sawdust and coconut husk.

26. The material of claim 20, wherein the functional group comprises an anisyl.

27. The material of claim 26, wherein the organic polymer precursor polymerizes to form polyanisyl alcohol.

28. The material of claim 27, wherein the polyanisyl alcohol is prepared by the polymerization of anisyl alcohol with a catalyst.

29. The material of claim 28, wherein the catalyst comprises a protic acid.

30. The material of claim 17, wherein more than 60% of pores of the porous material have diameters of greater than 1 nm and less than 2 nm.

31. The material of claim 17, wherein the porous material has an oxygen content of more than about 7 wt % as measured by X-ray photoelectron spectroscopy.

32. The material of claim 17, wherein the molar CO₂:

CH₄ uptake ratio of the porous material is more than about 2.

33. The material of claim 17, wherein the porous material has an oxygen content of more than about 10 wt % as measured by X-ray photoelectron spectroscopy.

34. A material for the separation of CO₂ from natural gas at partial pressures of either component above 1 bar comprising:

a porous material with a surface area of at least 2,200 m²/g, and a total pore volume of at least 1.00 cm³/g,

wherein more than 40% of pores of the porous material have diameters of greater than 1 nm and less than 2 nm as measured from N₂ sorption isotherms using the BET (Brunauer-Emmett-Teller) method, and

wherein the porous material has a CO₂ adsorption capacity of more than about 100 wt %.