Activated carbon cryogels and related methods

• US 7,723,262 B2
• Filed: 11/21/2005
• Issued: 05/25/2010
• Est. Priority Date: 11/21/2005
• Status: Active Grant

• Current Assignee: BASF SE, Washington University In St Louis
• Original Assignee: EnerG2, LLC, University of Washington
• Inventors: Cao, Guozhong, Feaver, Aaron
• Primary Examiner(s): Silverman; Stanley S.
• Assistant Examiner(s): MCCRACKEN, DANIEL
• Application Number:
  US11/284,140
• Publication Number:
  US 20070113735A1
• Time in Patent Office: 1,646 Days
• Field of Search: 502416-439
• US Class Current: 502/416
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 20/28011 Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/28047 Gels
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28076 being more than 1.0 ml/g
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 3/0021 Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
• CPC Class Codes: C01B 32/00 Carbon; Compounds thereof C01B21/00, C01B23/00 take precedence; percarbonates C01B15/10; carbon black C09C1/48
• CPC Class Codes: F17C 11/005 for hydrogen
• CPC Class Codes: F17C 11/007 for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
• CPC Class Codes: Y02E 60/32 Hydrogen storage

Abstract

Carbon cryogels, methods for making the carbon cryogels, methods for storing a gas using the carbon cryogels, and devices for storing and delivering a gas using the carbon cryogels.

Claims

1. A carbon cryogel having a surface area of from about 1500 to about 3000 m²/g, wherein said cryogel has a pore size distribution comprising:

a) a peak for pores having a diameter less than 2 nm;

b) a peak for pores having a diameter of about 3 nm; and

c) a peak for pores having a diameter between 7 and 8 nm.

2. A carbon cryogel having a gravimetric methane storage capacity of 15-20%, a surface area of from about 2400 to about 2600 m²/g, and a total pore volume of from about 1.0 to about 1.5 cm³/g.

3. A carbon cryogel having a peak pore volume greater than about 0.1 cm³/g for pores having a diameter less than about 2 nm and having a peak pore volume greater than about 0.1 cm³/g for pores having a diameter of about 5 to about 12 nm.

4. The carbon cryogel of claim 3 further having a peak pore volume greater than about 0.04 cm³/g for pores having a diameter of about 2 to about 4 nm.

5. A carbon cryogel having a gravimetric methane storage capacity of about 0.009 to about 0.013 mol/g at room temperature and 500 psi, a surface area of from about 1500 to about 2500 m²/g, and a total pore volume of from about 1.2 to about 1.5 cm³/g.

6. The cryogel of claim 5, wherein said total pore volume is from about 1.4 to about 1.5 cm³/g.

7. The cryogel of claim 5, wherein the pore volume is from about 1.2 to about 1.4 cm³/g.

8. The carbon cryogel of claim 5 comprising mesopores having a diameter of about 5 to about 12 nm.

9. The carbon cryogel of claim 5 comprising mesopores having a diameter of about 2 to about 4 nm.

10. The carbon cryogel of claim 5, wherein said surface area is from about 1500 to about 2000 m²/g.

11. The carbon cryogel of claim 5, wherein said surface area is from about 2000 to about 2500 m²/g.

14. A method for making the carbon cryogel of claim 5, comprising:

(a) preparing a sol by mixing resorcinol, formaldehyde, and a catalyst in water;

(b) gelling the sol by heating at a temperature and for a time sufficient to provide a gel;

(c) washing the gel with acid to provide an acid-washed gel comprising an aqueous solvent;

(d) washing the acid-washed gel with a suitable organic solvent to exchange the aqueous solvent for an organic solvent to provide a solvent-exchanged gel;

(e) freeze drying the solvent-exchanged gel; and

(f) pyrolyzing the solvent-exchanged gel to provide a carbon cryogel.

15. The method of claim 14, wherein the molar ratio of resorcinol to catalyst is from about 10 to about 300.

16. The method of claim 14, wherein the catalyst is sodium carbonate.

17. The method of claim 14, wherein the weight ratio of resorcinol to water is from about 0.01 to about 2.0.

18. The method of claim 14, wherein gelling the sol comprises heating at a temperature and for a period of time sufficient to convert the sol to a crosslinked gel.

19. The method of claim 14, wherein gelling the sol comprises heating at about 900°

C. for from about 1 to about 7 days.

20. The method of claim 14, wherein washing the gel with acid comprises washing the gel with aqueous trifluoroacetic acid.

21. The method of claim 14, wherein washing the acid-washed gel comprises washing the gel with t-butanol.

22. The method of claim 14, wherein pyrolyzing the solvent-exchanged gel comprises heating at a temperature and for a period of time sufficient to convert the gel to a carbon cryogel.

23. The method of claim 14, wherein pyrolyzing the solvent-exchanged gel comprises heating at about 1050°

C. for about 4 hours under nitrogen.

24. The method of claim 14, wherein heating at a temperature and for a time sufficient to provide an activated carbon cryogel comprises heating at about 900°

C. under carbon dioxide.

25. The method of claim 14, further comprising heating the carbon cryogel at a temperature and for a time sufficient to provide an activated carbon cryogel.

26. The method of claim 25, wherein the temperature is about 900°

C. and the time is from about 10 to about 120 minutes.

27. The method of claim 25, wherein the activation is from about 5 to about 90%.

12. A gas storage vessel, comprising a vessel and a carbon cryogel having a gravimetric methane storage capacity of about 0.009 to about 0.013 mol/g at room temperature and 500 psi, a surface area of from about 1500 to about 2500 m²/g, and a total pore volume of from about 1.2 to about 1.5 cm³/g.

13. The gas storage vessel of claim 12, further comprising a gas adsorbed on said carbon cryogel wherein said gas is selected from the group consisting of methane, hydrogen, nitrogen, carbon monoxide, fluorine, nitric oxide, nitrogen trifluoride, silane, ethylene, boron trifluoride, phosphine, arsine, disilane, and carbon tetrafluoride.