Finely divided metal catalyst and method for making same

• US 6,841,512 B1
• Filed: 03/13/2000
• Issued: 01/11/2005
• Est. Priority Date: 04/12/1999
• Status: Expired due to Fees

• Current Assignee: Chevron Texaco Corporation (Chevron Corp.)
• Original Assignee: Ovonic Battery Company, Inc (BASF SE)
• Inventors: Ovshinsky, Stanford R., Fetcenko, Michael A., Young, Kwo
• Primary Examiner(s): Nguyen, Cam N.
• Application Number:
  US09/523,820
• Time in Patent Office: 1,765 Days
• Field of Search: 502/66, 502/74, 502302-304, 502/308, 502/309, 502/314, 502/315, 502/326, 502/327, 502/331, 502335-338, 502/349, 502/350, 502/439, 420/451, 420/452, 429/223
• US Class Current: 502/335
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/76 combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• CPC Class Codes: B01J 25/00 Catalysts of the Raney type
• CPC Class Codes: B01J 25/02 Raney nickel
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C01B 3/001 characterised by the uptaking medium; Treatment thereof
• CPC Class Codes: C01B 3/0031 Intermetallic compounds; Metal alloys; Treatment thereof
• CPC Class Codes: C01B 3/0078 Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
• CPC Class Codes: C22C 14/00 Alloys based on titanium
• CPC Class Codes: C22C 16/00 Alloys based on zirconium
• CPC Class Codes: C22C 27/025 alloys based on vanadium
• CPC Class Codes: C22C 27/06 Alloys based on chromium
• CPC Class Codes: F17C 11/005 for hydrogen
• CPC Class Codes: H01M 10/345 Gastight metal hydride accumulators
• CPC Class Codes: H01M 2004/8684 Negative electrodes
• CPC Class Codes: H01M 2008/1095 Fuel cells with polymeric electrolytes
• CPC Class Codes: H01M 4/383 Hydrogen absorbing alloys
• CPC Class Codes: H01M 4/8605 : Porous electrodes
• CPC Class Codes: H01M 4/8652 : as mixture
• CPC Class Codes: H01M 4/90 : Selection of catalytic material
• CPC Class Codes: H01M 4/9041 : Metals or alloys H01M4/92 takes precedence
• CPC Class Codes: H01M 4/9075 : Catalytic material supported on carriers, e.g. powder carriers H01M4/8807, H01M4/881, H01M4/8814, H01M4/925 take precedence
• CPC Class Codes: H01M 4/9083 : on carbon or graphite
• CPC Class Codes: H01M 4/921 : Alloys or mixtures with metallic elements
• CPC Class Codes: H01M 8/04208 : Cartridges, cryogenic media or cryogenic reservoirs
• CPC Class Codes: H01M 8/08 : Fuel cells with aqueous electrolytes
• CPC Class Codes: H01M 8/083 : Alkaline fuel cells
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• 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

Abstract

An inexpensive, highly catalytic material preferably formed by a leaching process. The catalyst comprises a finely divided metal particulate and a support. The active material may be a nickel and/or nickel nickel alloy particulate having a particle size less than about 100 Angstroms. The support may be one or more metal oxides.

Claims

1. A catalyst powder, comprising:

a nickel or nickel alloy particulate having an average particle size of between about 10 and about 70 Angstroms, said particulate dispersed in a support matrix, said powder formed predominately of its nickel or nickel alloy particulate and support matrix.

2. The catalyst of claim 1, wherein said particulate has an average particle sire of between about 10 and about 50 Angstroms.

3. The catalyst of claim 1, wherein said particulate has an average particle size of between about 10 and about 40 Angstroms.

4. The catalyst of claim 1, wherein said particulate has an average particle size of between about 10 and about 30 Angstroms.

5. The catalyst of claim 1, wherein said particulate has an average particle size of between about 10 Angstroms and about 20 Angstroms.

6. The catalyst of claim 1, wherein said metal particulate is between about 0.0001% to about 99% by weight Df said catalyst.

7. The catalyst of claim 1, wherein said particulate has a particle proximity of between about 2 Angstroms and about 300 Angstroms.

8. The catalyst of claim 1, wherein said particulate comprises nickel alloy.

9. The catalyst of claim 8, wherein said nickel alloy comprises at least one element selected from the group consisting of Al, Co, Sn, Mn, Ti, and Fe.

10. The catalyst of claim 8, wherein said nickel alloy comprises at least one element selected from the group consisting of Al, Co, Sn, Mn, and Ti.

11. The catalyst of claim 8, wherein said nickel alloy is an alloy selected from the group consisting of NiCo alloy, NiMn alloy, NiCoAl alloy, NiCoMnTi alloy, and NiCoMnFe alloy.

12. The catalyst of claim 8, wherein said nickel alloy has an fcc crystal orientation.

13. The catalyst of claim 1, wherein said particulate comprises nickel metal.

14. The catalyst of claim 1, wherein said support comprises at least one inorganic oxide.

15. The catalyst of claim 1, wherein said support comprises at least one metal oxide.

16. The catalyst of claim 15, wherein said at least one metal oxide comprises at least one element selected from the group consisting of Ni, Co, Mn, Ti, Zr, Fe, and the rare earth elements.

17. The catalyst of claim 15, wherein said at least one metal oxide comprises at least one oxide selected from the group consisting of manganese oxide, nickel manganese oxide, and mixtures thereof.

18. The catalyst of claim 15, wherein said at least one metal oxide is multivalent.

19. The catalyst of claim 15, wherein said at least one metal oxide comprises an oxide of Mn, Ni, Co, and Ti.

20. The catalyst of claim 15, wherein said at least one metal oxide comprises an oxide of Mn, Ni, Co, Ti, and Fe.

21. The catalyst of claim 15, wherein said at least one metal oxide comprises an oxide of Mn, Co, and Ti.

22. The catalyst of claim 15, wherein said at least one metal oxide comprises fine-grained oxides and course-grained oxides.

23. The catalyst of claim 15, wherein said at least one metal oxide is microcrystalline.

24. The catalyst of claim 1, wherein said support comprises carbon.

25. The catalyst of claim 1, further comprising zeolite.

26. The catalyst of claim 1, wherein said catalyst is compositionally graded within said support.

27. The catalyst of claim 1, wherein said particulate is substantially uniformly distributed throughout said support.

28. The catalyst of claim 1, wherein said catalyst is formed by leaching at least a substantial portion of the bulk of a hydrogen storage alloy.

29. A catalyst particle, comprising:

a nickel and/or nickel alloy particulate having an average particle size of between about 10 and about 70 Angstroms, said particulate disposed in a support, said particulate and said support forming at least 25% by volume of said catalyst particle, said nickel alloy lacking platinum and palladium.

30. The catalyst of claim 29, wherein said particulate has an average particle size of between about 10 and about 50 Angstroms.

31. The catalyst of claim 29, wherein said particulate has an average particle size of between about 10 and about 40 Angstroms.

32. The catalyst of claim 29, wherein said particulate has an average particle size of between about 10 and about 30 Angstroms.

33. The catalyst of claim 29, wherein said particulate has an average particle size of between about 10 and about 20 Angstroms.

34. The catalyst of claim 29, wherein said particulate is about 0.0001 to about 99% by weight of said catalyst.

35. The catalyst of claim 29, wherein said particulate has a particle proximity of between about 2 Angstroms and about 300 Angstroms.

36. The catalyst of claim 29, wherein said nickel alloy comprises at least one element selected from the group consisting of Al, Co, Sn, Mn, Ti, and Fe.

37. The catalyst of claim 29, wherein said nickel alloy comprises at least one element selected from the group consisting of Al, Co, Sn, Mn, and Ti.

38. The catalyst of claim 29, wherein said nickel alloy is an alloy selected from the group consisting of NiCo alloy, NiMn alloy, NiCoAl alloy, NiCoMnTi alloy, and NiCoMnFe alloy.

39. The catalyst of claim 29, wherein said nickel alloy has an fcc crystal orientation.

40. The catalyst of claim 29, wherein said support comprises at least one inorganic oxide.

41. The catalyst of claim 29, wherein said support comprises at least one metal oxide.

42. The catalytic material of claim 41, wherein said at least one metal oxide comprises at least one element selected from the group consisting of Ni, Co, Mn, Ti, Zr, Fe, and the rare earth elements.

43. The catalytic material of claim 41, wherein said at least one metal oxide comprises an oxide of Mn.

44. The catalyst of claim 41, wherein said at least one metal oxide comprises an oxide of Mn and Ni.

45. The catalyst of claim 41, wherein said at least one metal oxide comprises an oxide of Mn, Ni, Co, and Ti.

46. The catalyst of claim 41, wherein said at least one metal oxide comprises an oxide of Mn, Ni, Co, Ti, and Fe.

47. The catalyst of claim 41, wherein said at least one metal oxide comprises an oxide of Mn, Co, and Ti.

48. The catalyst of claim 41, wherein said at least one metal oxide comprises fine-grained oxides and course-grained oxides.

49. The catalyst of claim 29, wherein said support material comprises carbon.

50. The catalyst of claim 29, further comprising zeolite.

51. The catalyst of claim 29, wherein the density of said particulate is graded within support.

52. The catalyst of claim 29, wherein said particulate is substantially uniformly distributed throughout said support.

53. The catalyst of claim 29, wherein said catalyst is formed by leaching at least a substantial portion of the bulk of a hydrogen storage alloy.

54. The catalyst of claim 29, wherein said particulate and said support form at least 50% of the volume of said catalyst particle.

55. The catalyst of claim 29, wherein said particulate and said support form at least 75% of the volume of said catalyst particle.

56. The catalyst of claim 29, wherein said particulate and said support form at least 90% of the volume of said catalyst particle.

57. The catalyst of claim 29, wherein said particulate and said support form substantially the entire catalyst particle.

58. A catalyst, comprising:

a metal particulate having an average particle size of between about 10 and about 70 Angstroms, said metal particulate comprising a nickel alloy, said nickel alloy lacking platinum and palladium, said nickel alloy comprising at least one element selected from the group consisting of Al, Co, Sn, Mn, Ti, and Fe; and

a support.

59. The catalyst of claim 58, wherein said particulate has an average particle size of between about 10 and about 50 Angstroms.

60. The catalyst of claim 58, wherein said particulate has an average particle size of between about 10 and about 40 Angstroms.

61. The catalyst of claim 58, wherein said particulate has an average particle size of between about 10 and about 30 Angstroms.

62. The catalyst of claim 58, wherein said particulate has an average particle size of between about 10 and about 20 Angstroms.

63. The catalyst of claim 58, wherein said nickel alloy comprises Co.

64. The catalyst of claim 58, wherein said nickel alloy comprises Mn.

65. The catalyst of claim 58, wherein said nickel alloy is an alloy selected from the group consisting of NiCo alloy, NiCoAl alloy, NiCoMnTi alloy, NiCoMnFe alloy, and NiMn alloy.

66. The catalyst of claim 58, wherein said support comprises at least one oxide.