Claims
- 1. A method for producing single-wall carbon nanotubes, comprising:
(a) providing a supercritical fluid catalyst stream comprising
(i) a supercritical fluid, (ii) a catalyst precursor selected from the group consisting of multi-metallic catalyst precursors, mono-metallic catalyst precursors, and mixtures thereof that are dissolved, suspended, or both in the fluid, each multi-metallic catalyst precursor comprising at least two atoms, and each mono-metallic catalyst precursor comprising one atom, of at least one transition metal selected from the group consisting of Group VIb elements and Group VIIb elements, and (iii) a plurality of seed molecules selected from the group consisting of fullerenes, derivatized fullerenes, polycyclic aromatic compounds, derivatized polycyclic aromatic compounds, and mixtures thereof, wherein the supercritical fluid catalyst stream is at a temperature below the decomposition temperature of the catalyst precursor, below the minimum single-wall carbon nanotube formation initiation temperature and below the polymerization temperature of the seed molecule; (b) providing a carbon feedstock gas stream at a temperature above the minimum single-wall carbon nanotube formation initiation temperature; and (c) mixing the carbon feedstock gas stream with the supercritical fluid catalyst stream to form a mixed gas stream, wherein
(i) the catalyst precursor reaches a temperature above the decomposition temperature of the catalyst precursor, (ii) the temperature is sufficient to promote the initiation or growth of catalyst clusters, and (iii) the temperature is sufficient to promote the initiation and growth of single-wall carbon nanotubes on the catalyst clusters and on the seed molecules and to form the single-wall carbon nanotubes in the mixed gas stream.
- 2. The method of claim 1, further comprising providing a catalyst precursor gas stream at a temperature below the decomposition temperature of the catalyst precursor, and wherein the mixing step further comprises mixing the catalyst precursor gas stream with the carbon feedstock gas stream and the supercritical fluid catalyst stream to form the mixed gas stream.
- 3. The method of claim 1, wherein the derivatized fullerenes are halogenated fullerenes and the derivatized polycyclic aromatic compounds are halogenated polycyclic aromatic compounds.
- 4. The method of claim 1, wherein the seed molecules are selected from the group consisting of C60, C70, and mixtures thereof.
- 5. The method of claim 1, wherein the supercritical fluid comprises a compound selected from the group consisting of CO2, CO, and mixtures thereof.
- 6. The method of claim 5, wherein the supercritical fluid comprises CO2, and wherein PCO2 is at least about 73 atm.
- 7. The method of claim 1, wherein the multi-metallic catalyst precursor comprises a multi-metal carbonyl.
- 8. The method of claim 7, wherein the multimetal carbonyl is selected from the group consisting of Fe2(CO)9, Fe3(CO)12, Fe4C(CO)13, Fe5C(CO)15, Ru4C(CO)13, Ru5C(CO)15, Ru6C(CO)17, Os5C(CO)15, and mixtures thereof.
- 9. The method of claim 1, wherein the carbon feedstock gas is selected from the group consisting of CO, methane, or both.
- 10. The method of claim 1, wherein the carbon feedstock gas stream comprises CO, wherein PCO is between about 3 atm and about 1000 atm.
- 11. The method of claim 1, wherein the temperature of the mixed gas stream is at least about 850° C.
- 12. The method of claim 1, wherein the temperature of the mixed gas stream is at least about 900° C.
- 13. The method of claim 1, further comprising recovering a single-wall carbon nanotube product from the mixed gas stream.
- 14. The method of claim 13, wherein the recovering comprises passing the mixed gas stream through a gas-permeable filter.
- 15. The method of claim 13, wherein at least about 90% of the carbon in the single-wall carbon nanotube product is single-wall carbon nanotubes.
- 16. The method of claim 13, wherein at least about 95% of the carbon in the single-wall carbon nanotube product is single-wall carbon nanotubes.
- 17. The method of claim 13, wherein at least about 99% of the carbon in the single-wall carbon nanotube product is single-wall carbon nanotubes.
- 18. The method of claim 13, wherein less than about 7 atom % of the single-wall carbon nanotube product is metal catalyst.
- 19. The method of claim 13, wherein less than about 4 atom % of the single-wall carbon nanotube product is metal catalyst.
- 20. The method of claim 13, wherein less than about 2 atom % of the single-wall carbon nanotube product is metal catalyst.
- 21. The method of claim 1, wherein the mono-metallic catalyst precursor comprises a metal carbonyl.
- 22. The method of claim 21, wherein the metal carbonyl is selected from the group consisting of Fe(CO)5, Ni(CO)4, and mixtures thereof.
- 23. The method of claim 1, further comprising mixing the supercritical fluid catalyst stream with a heating gas stream, wherein the supercritical fluid catalyst stream is heated to a temperature above the decomposition temperature of the catalyst precursor and sufficient to promote the initiation and growth of catalyst clusters and to form a supercritical fluid catalyst stream comprising a solution or suspension of catalyst clusters.
- 24. The method of claim 23, wherein the heating gas stream comprises a gas selected from the group consisting of CO, argon, nitrogen, and mixtures thereof.
- 25. The method of claim 23, wherein the temperature of the supercritical fluid catalyst stream comprising a solution or suspension of catalyst clusters is at least about 850° C.
- 26. The method of claim 23, wherein the temperature of the supercritical fluid catalyst stream comprising a solution or suspension of catalyst clusters is at least about 900° C.
- 27. The method of claim 1, further comprising subjecting the supercritical fluid catalyst stream to substantially coherent substantially monochromatic electromagnetic radiation, wherein the substantially coherent substantially monochromatic electromagnetic radiation provides sufficient energy to dissociate nonmetal atoms from the catalyst precursor and promote the initiation and growth of catalyst clusters and to form a supercritical fluid catalyst stream comprising a solution or a suspension of catalyst clusters.
- 28. The method of claim 27, wherein the substantially coherent substantially monochromatic electromagnetic radiation has a peak wavelength of about 200 nm to about 300 nm.
- 29. A method for producing single-wall carbon nanotubes, comprising:
(a) providing a plurality of seed molecules selected from the group consisting of C60, C70, derivatized C60, derivatized C70, short length tubular fullerenes, derivatized short length tubular fullerenes, open ended fullerenes, derivatized open ended fullerenes, single-wall carbon nanotubes with pre-attached catalyst particles, polycyclic aromatic compounds, derivatized polycyclic aromatic compounds, and mixtures thereof; (b) creating an aerosol of the seed molecules; (c) providing a fluid catalyst stream comprising a catalyst precursor comprising at least one atom of at least one transition metal selected from the group consisting of Group VIb elements and Group VIIb elements; (d) providing a carbon feedstock gas stream at a temperature above the minimum single-wall carbon nanotube formation initiation temperature; and (e) mixing the aerosol of the seed molecules, the fluid catalyst stream, and the carbon feedstock gas stream to form a mixed gas stream, wherein
(i) the catalyst precursor reaches a temperature above the decomposition temperature of the catalyst precursor, (ii) the temperature is sufficient to promote the initiation or growth of catalyst clusters, and (iii) wherein the temperature is sufficient to promote the initiation and growth of single-wall carbon nanotubes on the catalyst clusters and on the seed molecules and to form the single-wall carbon nanotubes in the mixed gas stream.
- 30. The method of claim 29, wherein at least some of the seed molecules are derivatized seed molecules, wherein the derivatized seed molecules comprise a halogen.
- 31. The method of claim 30, wherein the halogen is fluorine.
- 32. The method of claim 29, wherein the mixing step comprises:
(i) mixing the aerosol of seed molecules and the fluid catalyst stream to form a first mixture; and (ii) mixing the first mixture with the carbon feedstock gas stream to form the mixed gas stream.
- 33. The method of claim 29, wherein the creating step comprises:
(i) vaporizing the seed molecules in a hot carrier gas; and (ii) cooling the vaporized seed molecules in a cool carrier gas, to form the aerosol of seed molecules.
- 34. The method of claim 33, wherein the hot carrier gas is selected from the group consisting of CO, CO2, methane, argon, nitrogen, and mixtures thereof, and the cool carrier gas is selected from the group consisting of CO, CO2, methane, argon, nitrogen, and mixtures thereof.
- 35. The method of claim 34, wherein the hot carrier gas is CO and the cool carrier gas is CO.
- 36. The method of claim 33, wherein the temperature of hot carrier gas is at least about 500° C.
- 37. The method of claim 33, wherein the pressure of the hot carrier gas is between about 30 atmospheres and about 40 atmospheres.
- 38. The method of claim 33, wherein the temperature of the cool carrier gas is about room temperature.
- 39. The method of claim 33, wherein the seed molecules are provided to the process at a rate controlled by the temperature of the hot carrier gas.
- 40. The method of claim 33, wherein the seed molecules are provided to the process at a rate controlled by the temperature of the cool carrier gas.
- 41. The method of claim 33, wherein the seed molecules are provided to the process at a rate controlled by the ratio of the aerosol of seed molecules and the fluid catalyst stream.
- 42. The method of claim 33, wherein the seed molecules are selected from the group consisting of C60, C70, and mixtures thereof.
- 43. The method of claim 42, wherein the seed molecules is C60.
- 44. The method of claim 29, wherein the open ended fullerenes are fullerenes open at one end.
- 45. The method of claim 29, wherein the open ended fullerenes are fullerenes open at both ends.
- 46. The method of claim 29, wherein the polycyclic aromatic compound is corannulene.
- 47. The method of claim 29, wherein the m ono-metallic catalyst precursor comprises a metal carbonyl.
- 48. The method of claim 47, wherein the metal carbonyl is selected from the group consisting of Fe(CO)5, Ni(CO)4, and mixtures thereof.
- 49. The method of claim 329, further comprising recovering a single-wall carbon nanotube product from the mixed gas stream.
- 50. The method of claim 49, wherein the recovering comprises passing the mixed gas stream through a gas-permeable filter.
- 51. The method of claim 49, wherein at least about 90% of the carbon in the single-wall carbon nanotube product is single-wall carbon nanotubes.
- 52. The method of claim 49, wherein at least about 95% of the carbon in the single-wall carbon nanotube product is single-wall carbon nanotubes.
- 53. The method of claim 49, wherein at least about 99% of the carbon in the single-wall carbon nanotube product is single-wall carbon nanotubes.
- 54. The method of claim 49, wherein less than about 7 atom % of the single-wall carbon nanotube product is metal catalyst.
- 55. The method of claim 49, wherein less than about 4 atom % of the single-wall carbon nanotube product is metal catalyst.
- 56. The method of claim 49, wherein less than about 2 atom % of the single-wall carbon nanotube product is metal catalyst.
- 57. An apparatus for producing single-wall carbon nanotubes, comprising:
(a) a catalyst addition system, wherein the catalyst addition system is operable to provide a catalyst precursor gas stream comprising supercritical fluid catalyst stream comprising
(i) a supercritical fluid, (ii) a catalyst precursor selected from the group consisting of multi-metallic catalyst precursors, mono-metallic catalyst precursors, and mixtures thereof that are dissolved, suspended, or both in the fluid, each multi-metallic catalyst precursor comprising at least two atoms, and each mono-metallic catalyst precursor comprising one atom, of at least one transition metal selected from the group consisting of Group VIb elements and Group VIIb elements, and (iii) a plurality of seed molecules selected from the group consisting of fullerenes, derivatized fullerenes, polycyclic aromatic compounds, derivatized polycyclic aromatic compounds, and mixtures thereof, wherein the supercritical fluid catalyst stream is at a temperature below the decomposition temperature of the catalyst precursor, below the minimum single-wall carbon nanotube formation initiation temperature and below the polymerization temperature of the seed molecule; (b) a carbon feedstock gas source operable to provide a carbon feedstock gas stream at a temperature above the minimum single-wall carbon nanotube formation initiation temperature; and (c) a reactor, wherein the carbon feedstock gas stream and the supercritical fluid catalyst stream are mixed, wherein
(i) the catalyst precursor reaches a temperature above the decomposition temperature of the catalyst precursor, (ii) the temperature is sufficient to promote the initiation or growth of catalyst clusters, and (iii) wherein the temperature is sufficient to promote the initiation and growth of single-wall carbon nanotubes on the catalyst clusters and to form the single-wall carbon nanotubes in the mixed gas stream.
- 58. An apparatus for producing single-wall carbon nanotubes, comprising:
(a) a seed molecule source operable to provide a plurality of seed molecules selected from the group consisting of C60, C70, derivatized C60, derivatized C70, short length tubular fullerenes, derivatized short length tubular fullerenes, open ended fullerenes, derivatized open ended fullerenes, single-wall carbon nanotubes with pre-attached catalyst particles, polycyclic aromatic compounds, derivatized polycyclic aromatic compounds, and mixtures thereof; (b) a carrier gas source, wherein the carrier gas source is operable to provide a carrier gas that mixes with the seed molecules to form an aerosol of the seed molecules; (c) a catalyst addition system, wherein the catalyst addition system is operable to provide a catalyst precursor gas stream comprising a catalyst precursor, wherein the catalyst precursor comprises at least one atom of at least one transition metal selected from the group consisting of Group VIb elements and Group VIIb elements; (d) a carbon feedstock gas source operable to provide a carbon feedstock gas stream at a temperature above the minimum single-wall carbon nanotube formation initiation temperature; and (e) a reactor, wherein the aerosol of the seed molecules, the fluid catalyst stream, and the carbon feedstock gas stream are mixed to form a mixed gas stream, wherein
(i) the catalyst precursor reaches a temperature above the decomposition temperature of the catalyst precursor, (ii) the temperature is sufficient to promote the initiation or growth of catalyst clusters, and (iii) wherein the temperature is sufficient to promote the initiation and growth of single-wall carbon nanotubes on the catalyst clusters and to form the single-wall carbon nanotubes in the mixed gas stream.
- 59. A method for producing single-wall carbon nanotubes, comprising:
(a) providing a catalyst stream comprising
(i) a catalyst precursor comprising a multi-metallic catalyst precursor that is dissolved, suspended, or both in the catalyst stream, wherein the multimetallic catalyst precursor comprising at least two atoms of at least one transition metal selected from the group consisting of Group VIb elements and Group VIIIb elements, and (ii) a plurality of seed molecules selected from the group consisting of fullerenes, derivatized fullerenes, polycyclic aromatic compounds, derivatized polycyclic aromatic compounds, and mixtures thereof, wherein the catalyst stream is at a temperature below the decomposition temperature of the catalyst precursor, below the minimum single-wall carbon nanotube formation initiation temperature and below the polymerization temperature of the seed molecule; (b) providing a carbon feedstock gas stream at a temperature above the minimum single-wall carbon nanotube formation initiation temperature; and (c) mixing the carbon feedstock gas stream with the catalyst stream to form a mixed gas stream, wherein
(i) the catalyst precursor reaches a temperature above the decomposition temperature of the catalyst precursor, (ii) the temperature is sufficient to promote the initiation or growth of catalyst clusters, and (iii) the temperature is sufficient to promote the initiation and growth of single-wall carbon nanotubes on the catalyst clusters and on the seed molecules and to form the single-wall carbon nanotubes in the mixed gas stream.
- 60. The method of claim 59, wherein the catalyst stream further comprises a mono-metallic catalyst precursor, wherein the mono-metallic catalyst precursor comprises one atom of a transition metal selected from the group consisting of Group VIb elements and Group VIIIb elements, and the catalyst stream is at a temperature below the decomposition temperature of the mono-metallic catalyst precursor.
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims priority from U.S. provisional applications, Serial Nos. 60/265,646, filed Jan. 31, 2001, No. 60/287,894, filed May 1, 2001, and No. 60/302,956, filed Jul. 3, 2001, which applications are each incorporated herein by reference.
[0002] This patent application is related to U.S. patent application Ser. No. _________, “PROCESS UTILIZING TWO ZONES FOR MAKING SINGLE-WALL CARBON NANOTUBES,” to Smalley et al., (Attorney Docket No. 11321-P040US), filed concurrently herewith, and U.S. patent application Ser. No. _________, “PROCESS UTILIZING PRE-FORMED CLUSTER CATALYSTS FOR MAKING SINGLE-WALL CARBON NANOTUBES,” to Smalley et al. (Attorney Docket No. 11321-P041US), filed concurrently herewith. Both of these U.S. Patent Applications are also incorporated herein by reference.
Government Interests
[0003] The present invention was made in connection with research pursuant to grant numbers NCC9-77 and R51480 from the National Aeronautics and Space Administration; grant number 36810 from the National Science Foundation; and grant numbers 99 003604-055-1999 and R81710 from the Texas Advanced Technology Program.
Provisional Applications (3)
|
Number |
Date |
Country |
|
60265646 |
Jan 2001 |
US |
|
60287894 |
May 2001 |
US |
|
60302956 |
Jul 2001 |
US |