PROCESS AND APPARATUS FOR PRODUCING SINGLE-WALLED CARBON NANOTUBES

• US 20050042162A1
• Filed: 11/28/2001
• Published: 02/24/2005
• Est. Priority Date: 06/02/2000
• Status: Active Grant

• Current Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Original Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Inventors: Resasco, Daniel E., Balzano, Leandro, Alvarez, Walter E., Kitiyanan, Boonyarach
• Granted Patent: US 6,919,064 B2
• Time in Patent Office: Days
• US Class Current: 423/447.300
• CPC Class Codes: B01J 2208/00292 involving reactant solids
• CPC Class Codes: B01J 38/12 Treating with free oxygen-containing gas
• CPC Class Codes: B01J 38/60 using acids
• CPC Class Codes: B01J 38/64 using alkaline material; using salts
• CPC Class Codes: B01J 8/0055 using cyclones
• CPC Class Codes: B01J 8/388 externally, i.e. the particles leaving the vessel and subsequently re-entering it
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• 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 9/1271 Alkanes or cycloalkanes
• CPC Class Codes: D01F 9/1272 Methane
• CPC Class Codes: D01F 9/1278 Carbon monoxide
• CPC Class Codes: Y02P 20/584 Recycling of catalysts
• CPC Class Codes: Y10S 977/843 Gas phase catalytic growth, i.e. chemical vapor deposition

Abstract

A process and apparatus for catalytic production of single walled carbon nanotubes. Catalytic particles are exposed to different process conditions at successive stages wherein the catalytic particles do not come in contact with reactive (catalytic) gases until preferred process conditions have been attained, thereby controlling the quantity and form of carbon nanotubes produced. The process also contemplates processes and apparatus which recycle and reuse-the gases and catalytic particulate materials, thereby maximizing cost efficiency, reducing wastes, reducing the need for additional raw materials, and producing the carbon nanotubes, especially SWNTs, in greater quantities and for lower costs.

Claims

1-10. -10. (Cancelled)

11. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material, the catalytic particles effective in catalyzing the conversion of a carbon-containing gas into single-walled carbon nanotubes;

removing air from the catalytic particles by exposing the catalytic particles to a heated inert gas;

reducing the catalytic particles by exposing the catalytic particles to a heated reducing gas forming reduced catalytic particles; and

catalytically forming single-walled carbon nanotubes by exposing the reduced catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes.

12. The process of claim 11 wherein the catalytic material comprises cobalt and molybdenum.

13. The method process of claim 11 wherein the inert gas comprises a gas selected from the group consisting of He, Ar, and N₂.

14. The method process of claim 11 wherein the carbon-containing gas comprises a gas selected from the group consisting of CO, CH₄, C₂H₄, C₂H₂, or mixtures thereof.

15. The method process of claim 11 wherein the support material is selected from the group consisting of SiO₂, Al₂O₃, MgO, ZrO₂, zeolites, MCM-41, and Mg(Al)O.

16. The method process of claim 11 wherein the catalytic material comprises at least one of the metals selected from the group consisting of Co, Mo, Ni, Fe, W, or Nb.

17. The method process of claim 11 wherein the catalytic material comprises a Group VIII metal selected from the group consisting of Co, Ni, Ru, Rh, Pd, Ir, Fe, Pt, and mixtures thereof, and a Group VIb metal selected from the group consisting of Cr, Mo, W, and mixtures thereof and/or a Group Vb metal selected from the group consisting of V, Nb and Ta, and mixtures thereof.

18. The process of claim 11 wherein the reaction temperature is about 700°

C. to about 1000°

C.

19. The process of claim 11 wherein the reaction temperature is about 750°

C. to about 950°

C.

22. The process of claim 11 wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon.

23. The process of claim 22 wherein the carbon-containing gas further comprises a diluent gas.

20-21. -21. (Cancelled)

24. (Cancel)

25. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material, the catalyst effective in catalyzing the conversion of a carbon-containing gas into carbon nanotubes;

treating the catalytic particles with a reduction process;

heating the catalytic particles to a reaction temperature; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes.

26. The process of claim 25 wherein the catalytic material comprises cobalt and molybdenum.

27. The process of claim 25 wherein the step of heating the catalytic particles comprises exposing the catalytic particles to a heated inert gas.

28. The process of claim 25 further comprising the step of flushing the carbon-containing gas from the reacted catalytic particles.

29. The process of claim 25 further comprising the step of cooling the reacted catalytic particles.

30. The process of claim 25 further comprising the step of removing amorphous carbon from the reacted catalytic particles and treating the reacted catalytic particles to obtain the single-walled carbon nanotubes.

31. The process of claim 25 wherein the catalytic material is a metallic catalyst.

32. The process of claim 25 wherein the reaction temperature is about 700°

C. to about 1000°

C.

33. The process of claim 25 wherein the reaction temperature is about 750°

C. to about 950°

C.

34. The process of claim 25 wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon.

35. The process of claim 25 wherein the carbon-containing gas further comprises a diluent gas.

36. The process of claim 25 comprising the additional step of treating the reacted catalytic particles to obtain the single-walled carbon nanotubes.

37-62. -62. (Cancel)

63. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material comprising Co and Mo;

heating the catalytic particles to a reaction temperature wherein the reaction temperature is about 750°

C. to about 950°

C.; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes.

64. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

treating the catalytic particles with a reduction process;

heating the catalytic particles to a reaction temperature wherein the reaction temperature is about 750°

C. to about 950°

C.; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes.

65. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature wherein the reaction temperature is about 750°

C. to about 950°

C., and wherein the catalytic particles are heated by exposing the catalytic particles to a heated inert gas; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes.

66. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature wherein the reaction temperature is about 750°

C. to about 950°

C.;

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes; and

flushing the carbon-containing gas from the reacted catalytic particles.

67. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature wherein the reaction temperature is about 750°

C. to about 950°

C.;

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes; and

removing amorphous carbon from the reacted catalytic particles to obtain the single-walled carbon nanotubes.

68. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature wherein the reaction temperature is about 750°

C. to about 950°

C.; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, wherein the carbon-containing gas further comprises a diluent gas.

69. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature wherein the reaction temperature is about 750°

C. to about 950°

C.;

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes; and

treating the reacted catalytic particles to obtain the single-walled carbon nanotubes.

70. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material comprising Co and Mo;

heating the catalytic particles to a reaction temperature; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, and wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon.

71. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

treating the catalytic particles with a reduction process;

heating the catalytic particles to a reaction temperature; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, and wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon.

72. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature by exposing the catalytic particles to a heated inert gas; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, and wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon.

73. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, and wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol and/or an aromatic hydrocarbon, and flushing the carbon-containing gas from the reacted catalytic particles.

74. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature;

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, and wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon; and

removing amorphous carbon from the reacted catalytic particles and treating the reacted catalytic particles to obtain the single-walled carbon nanotubes.

75. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature; and

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, and wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon and wherein the carbon-containing gas further comprises a diluent gas.

76. A process for producing single-walled carbon nanotubes, comprising:

disposing catalytic particles into a reactor wherein the catalytic particles comprise a support material and a catalytic material;

heating the catalytic particles to a reaction temperature;

catalytically forming single-walled carbon nanotubes by exposing the catalytic particles to a carbon-containing gas for a duration of time and at a temperature sufficient to cause catalytic production of the single-walled carbon nanotubes thereby forming reacted catalytic particles bearing the single-walled carbon nanotubes, and wherein the carbon-containing gas comprises carbon monoxide, a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an oxygenated hydrocarbon, an alcohol, and/or an aromatic hydrocarbon; and

treating the reacted catalytic particles to obtain the single-walled carbon nanotubes.