Process for producing single wall nanotubes using unsupported metal catalysts

• US 6,221,330 B1
• Filed: 08/04/1997
• Issued: 04/24/2001
• Est. Priority Date: 08/04/1997
• Status: Expired due to Fees

• Current Assignee: Hyperion Catalysis International Incorporated
• Original Assignee: Hyperion Catalysis International Incorporated
• Inventors: Moy, David, Chishti, Asif
• Primary Examiner(s): Griffin, Steven P.
• Assistant Examiner(s): DiMauro, Peter
• Application Number:
  US08/910,495
• Time in Patent Office: 1,359 Days
• Field of Search: 423/447.3, 423/445.B, 423/447.2
• US Class Current: 423/447.3
• CPC Class Codes: B01J 19/121 Coherent waves, e.g. laser beams lasers per se H01S3/00
• CPC Class Codes: B01J 19/26 Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
• CPC Class Codes: B01J 2219/0875 Gas
• CPC Class Codes: B01J 3/04 Pressure vessels, e.g. autoclaves
• CPC Class Codes: B01J 3/042 in the form of a tube
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: D01F 9/127 by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
• CPC Class Codes: D01F 9/1278 Carbon monoxide
• CPC Class Codes: Y10S 977/742 Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/75 Single-walled
• CPC Class Codes: Y10S 977/842 for carbon nanotubes or fullerenes
• CPC Class Codes: Y10S 977/843 Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/896 Chemical synthesis, e.g. chemical bonding or breaking

Abstract

A process for producing hollow, single-walled carbon nanotubes by catalytic decomposition of one or more gaseous carbon compounds by first forming a gas phase mixture carbon feed stock gas comprising one or more gaseous carbon compounds, each having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms, optionally admixed with hydrogen, and a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms a metal containing catalyst which acts as a decomposition catalyst under reaction conditions; and then conducting said decomposition reaction under decomposition reaction conditions, thereby producing said nanotubes.

Claims

1. A method for producing hollow, single-walled carbon nanotubes by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of

(a) a carbon feedstock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms, optionally admixed with hydrogen, wherein 50% or more of said carbon feedstock gas is carbon monoxide; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms a metal containing catalyst which acts as a decomposition catalyst under reaction conditions;

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes.

2. The method defined in claim 1, wherein said carbon feedstock gas consists essentially of carbon monoxide.

3. The method defined in claim 1, wherein said decomposition reaction occurs at temperatures between approximately 400°

C. and approximately 1300°

C.

4. The method defined in claim 1, wherein said decomposition reaction occurs at temperatures between approximately 700°

C. and approximately 1100°

C.

5. The method defined in claim 1, wherein said decomposition reaction occurs at a pressure range of approximately 0 p.s.i.g. through approximately 100 p.s.i.g.

6. The method defined in claim 1, wherein said gas phase metal containing compound is produced by vaporizing a liquid or solid phase metal containing compound.

7. The method defined in claim 6, wherein said metal containing compound is vaporized into a flowing stream of carbon feedstock, wherein the temperature of said flowing stream is between approximately 400°

C. and approximately 1300°

C. and wherein said flowing stream is at a pressure range of approximately 0 p.s.i.g. through approximately 100 p.s.i.g.

8. The method defined in claim 1, wherein said gas phase metal containing compound is mixed with said feedstock by direct injection.

9. The method defined in claim 1, wherein said gas phase metal containing compound is in the form of an aerosol.

10. The method defined in claim 1, wherein said gas phase metal containing compound is Mo(CO)₆.

11. The method defined in claim 1, wherein said gas phase metal containing compound is Co₂(CO)₈.

12. The method defined in claim 1, wherein said gas phase metal containing compound is a volatile iron compound.

13. The method of claim 12, wherein said volatile iron compound is ferrocene.

14. The method defined in claim 1, wherein said gas phase metal containing compound is a volatile manganese compound.

15. The method of claim 14, wherein said volatile manganese compound is methylcyclopentadienyl manganese tricarbonyl.

16. The method defined in claim 1, wherein said gas phase metal containing compound is a volatile cobalt compound.

17. The method of claim 16, wherein said volatile cobalt compound is cyclopentadienyl cobalt dicarbonyl.

18. The method defined in claim 1, wherein said gas phase metal containing compound is a volatile nickel compound.

19. The method of claim 18, wherein said volatile nickel compound is nickel dimethylglyoxime.

20. The method defined in claim 1, wherein said gas phase metal containing compound is produced by subliming a solid phase metal containing compound.

21. The method defined in claim 1, wherein said gas phase metal containing compound is produced by vaporizing a liquid phase metal containing compound.

48. The method as in any of claims 1 or 41-45, wherein said method provides a yield of hollow, single-walled carbon nanotubes greater than about 20 wt %.

49. The method as in any of claims 1 or 41-47, wherein said method provides a yield of hollow, single-walled carbon nanotubes greater than about 50 wt %.

52. The method as in any of claims 1 or 41-47, wherein said decomposition reaction occurs at temperatures between approximately 400°

C. and approximately 900°

C.

68. The method as in any of claims 1 or 41-47, wherein said gas phase mixture consists essentially of said carbon feed stock gas and said gas phase metal containing compound, optionally admixed with hydrogen, a diluent or mixtures thereof.

69. The method as in any of claims 1, 41 or 47, wherein said metal containing catalysts have diameters ranging from 1-10 nm.

70. The method as in any of claims 1, 41 or 47, wherein said carbon nanotubes have diameters less than about 10 nanometers.

71. The method as in any of claims 1, 41 or 47, wherein said carbon nanotubes have diameters less than about 3 nanometers.

72. The method as in any of claims 1, 22, 41-47 wherein said carbon nanotubes have diameters less than about 1 nanometer.

74. The method as in any of claims 1, 22 or 41-43 or 46-47, wherein said gas phase metal containing compound comprises a metal carbonyl.

75. The method as in any of claims 1, 22 or 41-43 or 46-47, wherein said gas phase metal containing compound comprises iron carbonyl.

22. A method for producing hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of;

(a) a carbon feed stock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms, optionally admixed with hydrogen, a diluent or mixtures thereof, wherein 50% or more of said carbon feedstock gas is carbon monoxide; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms metal containing catalysts which act as decomposition catalysts under reaction conditions; and

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers.

23. The method defined in claim 22, wherein said carbon feedstock gas consists essentially of carbon monoxide.

24. The method defined in claim 22, wherein said decomposition reaction occurs at temperatures between approximately 400°

C. and approximately 900°

C.

25. The method defined in claim 22, wherein said decomposition reaction occurs at a pressure range of approximately 0 p.s.i.g. through approximately 100 p.s.i.g.

26. The method defined in claim 22, wherein said gas phase metal containing compound is mixed with said feedstock by direct injection.

27. The method defined in claim 22, wherein said gas phase metal containing compound is in the form of an aerosol.

28. The method defined in claim 22, wherein said gas phase metal containing compound is Mo(CO)₆.

29. The method defined in claim 22, wherein said gas phase metal containing compound is Co₂(CO)₈.

30. The method defined in claim 22, wherein said gas phase metal containing compound is a volatile iron compound.

31. The method of claim 30, wherein said volatile iron compound is ferrocene.

32. The method defined in claim 22, wherein said gas phase metal containing compound is a volatile manganese compound.

33. The method of claim 32, wherein said volatile manganese compound is methylcyclopentadienyl manganese tricarbonyl.

34. The method defined in claim 22, wherein said gas phase metal containing compound is a volatile cobalt compound.

35. The method of claim 34, wherein said volatile cobalt compound is cyclopentadienyl cobalt dicarbonyl.

36. The method of claim 22, wherein said gas phase mixture consists essentially of said carbon feed stock gas and said gas phase metal containing compound, optionally admixed with hydrogen, a diluent or mixtures thereof.

37. The method of claim 22, wherein said carbon nanotubes have diameters ranging from about 1 to about 3 nanometers.

38. The method of claim 22, wherein said method provides a yield of single-walled carbon nanotubes greater than about 20 wt %.

39. The method of claim 22, wherein said method provides a yield of single-walled carbon nanotubes greater than about 50 wt %.

40. The method of claim 22, wherein said metal containing catalysts have diameters ranging from 1-10 nm.

50. The method as in any of claims 22 or 41-47, wherein said decomposition reaction occurs at temperatures between approximately 400°

C. and approximately 1300°

C.

51. The method as in any of claims 22 or 41-47, wherein said decomposition reaction occurs at temperatures between approximately 700°

C. and approximately 1100°

C.

53. The method as in any of claims 22 or 41-47, wherein said gas phase metal containing compound is produced by vaporizing a liquid or solid phase metal containing compound.

54. The method as in any of claims 22 or 41-47, wherein said gas phase metal containing compound is produced by vaporizing a liquid or solid phase metal containing compound into a flowing stream of carbon feedstock, wherein the temperature of said flowing stream is between approximately 400°

C. and approximately 1300°

C. and wherein said flowing stream is at a pressure range of approximately 0 p.s.i.g. through approximately 100 p.s.i.g.

64. The method as in any of claims 22 or 41-47, wherein said gas phase metal containing compound is produced by subliming a solid phase metal containing compound.

65. The method as in any of claims 22 or 41-47, wherein said gas phase metal containing compound is produced by vaporizing a liquid phase metal containing compound.

41. A method for producing hollow, single-walled carbon nanotubes by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of

(a) a carbon feedstock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms, wherein said carbon feedstock gas consists essentially of carbon monoxide; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms a metal containing catalyst which acts as a decomposition catalyst under reaction conditions;

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes.

55. The method as in any of claims 41-47, wherein said gas phase metal containing compound is mixed with said feedstock by direct injection.

56. The method as in any of claims 41-42 or 44-47, wherein said gas phase metal containing compound is in the form of an aerosol.

57. The method as in any of claims 41-44 or 46-47 wherein said gas phase metal containing compound comprises Mo(CO)₆.

58. The method as in any of claims 41-44 or 46-47, wherein said gas phase metal containing compound comprises Co₂(CO)₈.

59. The method as in any of claims 41-43 and 46-47, wherein said gas phase metal containing compound is a volatile iron compound.

60. The method as in any of claims 41-43 or 46-47, wherein said gas phase metal containing compound is a volatile iron compound and said volatile iron compound is ferrocene.

61. The method as in any of claims 41-43 or 46-47, wherein said gas phase metal containing compound comprises a volatile manganese compound.

62. The method as in any of claims 41-43 or 46-47, wherein said gas phase metal containing compound comprises a volatile cobalt compound.

63. The method as in any of claims 41-43 or 46-47, wherein said gas phase metal containing compound comprises a volatile nickel compound.

66. The method as in any of claims 41-47, wherein said carbon feedstock is admixed with hydrogen.

67. The method as in any of claims 41-47, wherein said carbon feedstock is admixed with hydrogen, a diluent or mixtures thereof.

73. The method as in any of claims 41-47, wherein said decomposition reaction occurs at a pressure range of approximately 0 p.s.i.g. through approximately 100 p.s.i.g.

42. A method for producing hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of;

(a) a carbon feed stock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms, wherein said carbon feedstock gas consists essentially of carbon monoxide; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms metal containing catalysts which act as decomposition catalysts under reaction conditions; and

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers.

43. A method for producing hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of;

(a) a carbon feed stock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms metal containing catalysts which act as decomposition catalysts under reaction conditions, wherein said gas phase metal containing compound is in the form of an aerosol; and

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers.

44. A method for producing hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of;

(a) a carbon feed stock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms metal containing catalysts which act as decomposition catalysts under reaction conditions, wherein said gas phase metal containing compound comprises Mo(CO)₆ or Co₂(CO)₈; and

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers.

45. A method for producing hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of;

(a) a carbon feed stock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms metal containing catalysts which act as decomposition catalysts under reaction conditions, wherein said gas phase metal containing compound comprises a volatile manganese compound; and

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers.

46. A method for producing hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of;

(a) a carbon feed stock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms metal containing catalysts which act as decomposition catalysts under reaction conditions; and

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes having diameters less than about 3 nanometers,

wherein said method provides a yield of hollow, single-walled carbon nanotubes greater than about 20 wt %.

47. A method for producing hollow, single-walled carbon nanotubes by catalytic decomposition of one or more gaseous carbon compounds comprising the steps of:

(1) forming a gas phase mixture of

(a) a carbon feedstock gas comprising one or more gaseous carbon compounds, each said compound having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms; and

(b) a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms a metal containing catalyst which acts as a decomposition catalyst under reaction conditions;

(2) conducting said decomposition reaction under decomposition reaction conditions and thereby producing said hollow, single-walled carbon nanotubes,

wherein said method provides a yield of hollow, single-walled carbon nanotubes greater than about 20 wt %.