MANUFACTURING METHODS FOR THE PRODUCTION OF CARBON MATERIALS

• US 20110028599A1
• Filed: 04/08/2010
• Published: 02/03/2011
• Est. Priority Date: 04/08/2009
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: EnerG2 Technologies, Incorporated (BASF SE)
• Inventors: Scott, William D., Costantino, Henry R., Feaver, Aaron
• Granted Patent: US 8,293,818 B2
• Time in Patent Office: Days
• US Class Current: 523/309
• 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 32/336 characterised by gaseous activating agents
• CPC Class Codes: C08G 8/22 Resorcinol
• CPC Class Codes: C08G 8/28 Chemically modified polycondensates
• CPC Class Codes: C08J 3/12 Powdering or granulating
• CPC Class Codes: C08K 5/04 Oxygen-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: H01G 11/34 characterised by carbonisation or activation of carbon
• CPC Class Codes: H01M 4/96 Carbon-based electrodes
• CPC Class Codes: H01M 8/0234 Carbonaceous material
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02E 60/32 Hydrogen storage
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

The present application is generally directed to activated carbon materials and methods for making the same. The disclosed methods comprise rapidly freezing synthetically prepared polymer gel particles. The methods further comprise drying, pyrolyzing, and activating steps to obtain an activated carbon material of high porosity. The disclosed methods represent viable manufacturing processes for the preparation of activated carbon materials.

Claims

1. A method for making frozen polymer gel particles comprising rapidly freezing polymer gel particles, wherein the polymer gel particles have been generated from a polymer gel, and wherein the polymer gel has been prepared by reaction of one or more polymer precursers.

2. The method of claim 1, further comprising lyophilizing the frozen polymer gel particles to obtain polymer cryogel particles.

3. The method of claim 1, further comprising pyrolyzing polymer cryogel particles to obtain pyrolyzed polymer cryogel particles, wherein the polymer cryogel particles have been prepared by lyophilizing the frozen polymer gel particles.

4. The method of claim 1, further comprising activating pyrolyzed polymer cryogel particles to obtain activated polymer cryogel particles, wherein the pyrolyzed polymer cryogel has been prepared by pyrolyzing a polymer cryogel, and wherein the polymer cryogel has been prepared by lyophilizing the frozen polymer gel particles.

5. The method of claim 1, wherein rapidly freezing the polymer gel particles comprises immersing the polymer gel particles in a liquid having a temperature below about −

10°

C.

6. The method of claim 5, wherein rapidly freezing the polymer gel particles comprises immersing the polymer gel particles in a liquid having a temperature below about −

30°

C.

7. The method of claim 5, wherein the polymer gel particles are generated by grinding or milling the polymer gel.

8. The method of claim 5, wherein the liquid is liquid nitrogen.

9. The method of claim 5, wherein the liquid is ethanol.

10. The method of claim 5, wherein the polymer gel particles have an average particle size of less than about 30 mm.

11. The method of claim 10, wherein the polymer gel particles have an average particle size of about 0.5 mm to about 10 mm.

12. The method of claim 5, wherein the polymer gel particles are immersed in the liquid at a rate of about 5 grams/min.

13. The method of claim 1, wherein rapidly freezing the polymer gel particles comprises admixing the polymer gel particles with a cold solid.

14. The method of claim 13, wherein the cold solid is solid carbon dioxide.

15. The method of claim 1, wherein rapidly freezing the polymer gel particles comprises admixing the polymer gel particles with a gas having a temperature below about −

10°

C.

16. The method of claim 15, wherein the gas is nitrogen.

17. The method of claim 1, wherein the polymer gel particles are generated by grinding or milling the polymer gel in the presence of a cold solid.

18. The method of claim 17, wherein the cold solid is solid carbon dioxide.

19. The method of claim 1, wherein rapidly freezing the polymer gel particles comprises contacting the polymer gel particles with an atomized liquid having a temperature below about −

10°

C.

20. The method of claim 19, wherein rapidly freezing the polymer gel particles comprises contacting the polymer gel particles with an atomized liquid having a temperature below about −

30°

C.

21. The method of claim 19, wherein the atomized liquid is liquid nitrogen.

22. The method of claim 1, wherein rapidly freezing the polymer gel particles comprises contacting sprayed droplets comprising the polymer gel particles with a cold medium having a temperature below about −

10°

C. to obtain frozen droplets comprising the frozen polymer gel particles.

23. The method of claim 22, wherein the cold medium has a temperature below about −

30°

C.

24. The method of claim 22, wherein the sprayed droplets comprise a suspension of the polymer gel particles.

25. The method of claim 22, wherein the polymer gel particles comprise polymer gel having a viscosity of less than about 1000 cP.

26. The method of claim 22, wherein the polymer gel particles comprise incompletely polymerized polymer gel.

27. The method of claim 26, wherein polymerization of the polymer gel is completed after the sprayed droplets are contacted with the cold medium (i.e. after the freezing step).

28. The method of claim 27, further comprising lyophilizing the frozen droplets to obtain freeze-dried particles and completing the polymerization reaction within the freeze-dried particle.

29. The method of claim 27, further comprising completing the polymerization of the polymer gel within the frozen droplets.

30. The method of claim 22, wherein the sprayed droplets further comprise microspheres comprising the polymer gel particles.

31. The method of claim 30, wherein the microspheres comprise an emulsion selected from a water-in-oil (w/o) emulsion, oil-in-water (o/w) emulsion, oil-in-water-oil (o/w/o) emulsion, water-in-oil-in-water (w/o/w) emulsion, and water-in-oil-in-oil (w/o/o) emulsion.

32. The method of claim 31, wherein the emulsion comprises a surfactant selected from non-ionic, cationic, non-ionic polymeric, and non-ionic polymeric fluorinated surfactants.

33. The method of claim 22, wherein the cold medium is liquid nitrogen or ethanol.

34. The method of claim 1, wherein rapidly freezing the polymer gel particles comprises rapidly puling a vacuum on the polymer gel particles.

35. The method of claim 1, wherein the one or more polymer precursors are selected from phenolic compounds and aldehydes.

36. The method of claim 35, wherein the one or more polymer precursors are selected from resorcinol and formaldehyde.

37. The method of claim 36, further comprising adding a basic catalyst to a mixture of resorcinol and formaldehyde.

38. The method of claim 37, wherein the basic catalyst is sodium carbonate.

39. The method of claim 38, wherein the molar ratio of resorcinol to catalyst is from about 50 to 1 to about 100 to 1.

40. The method of claim 38, wherein the molar ratio of resorcinol to catalyst is from about 25 to 1 to about 50 to 1.

41. The method of claim 36, further comprising adding water as a solvent to a mixture of resorcinol and formaldehyde, and wherein the ratio of resorcinol to water is from about 0.05 to 1 to about 0.70 to 1.

42. The method of claim 41, further comprising adding water as a solvent to a mixture of resorcinol and formaldehyde, and wherein the ratio of resorcinol to water is from about 0.15 to 1 to about 0.35 to 1.

43. The method of claim 1, wherein the polymer gel comprises less than about 1000 ppm of organic solvent.

44. The method of claim 2, wherein lyophilizing the frozen polymer gel particles comprises placing the frozen polymer gel particles in a lyophilizer having a shelf temperature of between about 10°

C. and about 25°

C.

45. The method of claim 2, wherein lyophilizing the frozen polymer gel particles comprises placing the frozen polymer gel particles under reduced pressure of between about 50 mTorr and about 1000 torr.

46. The method of claim 3, wherein pyrolyzing the polymer cryogel particles comprises heating the polymer cryogel particles for between about 0 and about 60 minutes.

47. The method of claim 3, wherein pyrolyzing the polymer gel particles comprises heating the polymer gel particles at temperatures from about 700°

C. to about 1200°

C.

48. The method of claim 47, wherein pyrolyzing the polymer gel particles comprises heating the polymer gel particles at temperatures from about 850°

C. to about 1050°

C.

49. The method of claim 4, wherein activating the pyrolyzed polymer gel particles comprises heating the pyrolyzed polymer gel particles for between about 1 minute and about 10 minutes.

50. The method of claim 4, wherein activating the pyrolyzed polymer gel particles comprises contacting the pyrolyzed polymer gel particles with an activating gas.

51. The method of claim 4, wherein activating the pyrolyzed polymer gel particles comprises heating the pyrolyzed polymer gel particles at temperatures from about 800°

C. to about 1300°

C.

52. The method of claim 51, wherein activating the pyrolyzed polymer gel particles comprises heating the pyrolyzed polymer gel particles at temperatures from about 900°

C. to about 1050°

C.

53. The method of claim 4, wherein activating the pyrolyzed polymer gel particles comprises activating the pyrolyzed polymer gel particles to a degree of activation from about 5% to about 90%.

61. Activated polymer cryogel particles prepared according to claim 4, wherein the activated polymer cryogel particles have a specific surface area of at least about 1000 m²/g.

62. Pyrolyzed polymer cryogel particles prepared according to claim 3, wherein the pyrolyzed polymer cryogel particles have a specific surface area of about 500 to about 800 m²/g.

63. The pyrolyzed polymer cryogel particles of claim 62, wherein the pyrolyzed polymer cryogel particles have a tap density of between about 0.40 cc/g and about 0.60 cc/g.

54. A polymer cryogel comprising less than about 1000 ppm of organic solvent.

55. The polymer cryogel of claim 54, wherein the organic solvent is t-butanol.

56. The polymer cryogel of claim 54, wherein the organic solvent is acetone.

57. The polymer cryogel of claim 54, wherein the polymer cryogel has a tap density of between about 0.10 cc/g and about 0.60 cc/g.

58. The polymer cryogel of claim 55, wherein the polymer cryogel has a tap density of between about 0.15 cc/g and about 0.25 cc/g.

59. The polymer cryogel of claim 54, wherein the polymer cryogel has a BET specific surface area of between about 150 m²/g to about 700 m²/g.

60. The polymer cryogel of claim 59, wherein the polymer cryogel has a BET specific surface area of between about 400 m²/g to about 700 m²/g.