Method for combustion synthesis of fullerenes

• US 7,396,520 B2
• Filed: 08/31/2002
• Issued: 07/08/2008
• Est. Priority Date: 08/31/2001
• Status: Active Grant

• Current Assignee: Nano-C, Inc.
• Original Assignee: Nano-C, Inc.
• Inventors: Howard, Jack B., Richter, Henning, Kronholm, David F., Modestino, Anthony J.
• Primary Examiner(s): Hendrickson; Stuart L.
• Assistant Examiner(s): MCCRACKEN, DANIEL
• Application Number:
  US10/489,846
• Publication Number:
  US 20050147552A1
• Time in Patent Office: 2,138 Days
• Field of Search: 423/445.B, 423/447.1, 4234491-459, 977/842, 977/843
• US Class Current: 423/445.00B
• CPC Class Codes: B01J 2219/00157 by means of a burner
• 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 32/15 Nano-sized carbon materials
• CPC Class Codes: C01B 32/154 Preparation
• CPC Class Codes: F23C 6/02 in parallel arrangement
• CPC Class Codes: F23C 99/00 Subject-matter not provided for in other groups of this subclass
• CPC Class Codes: Y02E 20/34 Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
• CPC Class Codes: Y10S 977/734 Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
• CPC Class Codes: Y10S 977/842 for carbon nanotubes or fullerenes

Abstract

A mod of combustion and a multi-component reactor to accomplish this mode of combustion are disclosed which produces fullerenes and fullerenic material by combustion. This mode consists of de-coupling an oxidation region of a flame from a post-flame region, thus giving greater control over operating parameters, such as equivalence ratio, temperature, and pressure; allows conditions of the operating parameters of the combustion reaction to be attained which would not be easily attained by conventional methods; and offers the ability to more easily stabilize the combustion reactions to allow for higher throughputs of fuel and oxidant. Several embodiments of a primary zone of a multicomponent reactor are also disclosed. Said primary zone serves as the oxidation region, operates on the principle of providing recycle to the reacting combustion mixture, and which may be operated as approximately a well-mixed reactor. A secondary zone is also disclosed which provides further residence time for reaction and the ability to control operating parameters, operates on the principle of minimizing recycle of the reacting combustion mixture. The secondary zone may be operated as approximately a plug-flow reactor. The primary and secondary zones may be operated in conjunction or either one alone.

Claims

1. A method comprising:

introducing carbon-containing fuel and oxidant at an introduction location into a primary chamber so that said fuel and said oxidant react to produce first combustion products, said first combustion products and unreacted residue being mixed using a non-turbulent flow and reacted with incoming carbon-containing fuel and oxidant and/or any newly formed combustion products and/or unreacted residue, thereby forming a combustion mixture; and

introducing said combustion mixture into a secondary chamber to produce fullerenic products by combustion.

2. The method of claim 1, wherein said combustion mixture comprises fullerenic products, and/or intermediates of fullerenic products and other material.

3. The method of claim 1, wherein said carbon-containing fuel and said oxidant are introduced into said primary chamber at multiple introduction locations.

4. The method of claim 1, wherein said carbon-containing fuel comprises fullerene-forming fuel, a non-fullerene forming fuel, or a combination thereof.

5. The method of claim 4, wherein said fullerene forming fuel comprises an unsaturated hydrocarbon.

6. The method of claim 5, wherein said unsaturated hydrocarbon is selected from the group consisting of acetylenes, polyacetylenes, aromatics, highly aromatic materials, and combinations thereof.

7. The method of claim 1, wherein said carbon-containing fuel comprises toluene.

8. The method of claim 1, further comprising introducing into said primary chamber

(i) an inert gas,

(ii) halogen containing compounds,

(iii) compounds containing alkali metals or alkaline earth metals,

(iv) compounds which contain the metals manganese, iron, or barium,

(v) compounds containing cyclic aromatic acid anhydrides,

(vi) compounds containing cobalt, iron, or nickel,

(vii) transition metals or

(viii) combinations thereof.

9. The method of claim 1, wherein the pressure in said primary chamber is in the range of from 10 to 400 torr.

10. The method of claim 9, wherein the overall equivalence ratio is in the range of 1.8 to 4.0.

11. The method of claim 10, wherein the temperature in said primary chamber is in the range of from 1500 K to 2500 K.

12. The method of claim 11, wherein the residence time in said primary chamber is in the range of 2 to 500 ms.

13. The method of claim 1, wherein the overall equivalence ratio is in the range of 1.8 to 4.0.

14. The method of claim 1, wherein the temperature in said primary chamber is in the range of from 1500 K to 2500 K.

15. The method of claim 1, wherein the residence time in said primary chamber is in the range of 2 to 500 ms.

16. The method of claim 1, wherein said primary chamber has at least one well-defined region wherein said fuel, oxidant, and combustion mixture each has at least one state variable which is approximately constant as a function of space.

17. The method of claim 16, wherein at least about 10% of said primary chamber is in said well-defined region.

18. The method of claim 1, further comprising:

allowing constituents of said combustion mixture in said secondary chamber to undergo reactions to produce second combustion products comprising fullerenic products and other material, wherein said second combustion products flow through said secondary chamber without substantial mixing between material from different regions corresponding to different residence times in said secondary chamber to produce fullerenic products.

19. The method of claim 18, further comprising introducing an additive into said secondary chamber.

20. The method of claim 19, wherein said additive is selected from the group consisting of

(i) halogen containing compounds,

(ii) compounds containing alkali metals or alkaline earth metals,

(iii) compounds which contain the metals manganese, iron, or barium,

(iv) compounds containing cyclic aromatic acid anhydrides,

(v) compounds containing cobalt, iron, or nickel, and

(vi) combinations thereof.

21. The method of claim 18, wherein the temperature in said secondary chamber is in the range of from 1500 K to 2500 K.

22. The method of claim 18, wherein the residence time in said secondary chamber is in the range of 5 ms to 10 s.

23. The method of claim 18, wherein said primary chamber has at least one well-defined region wherein said fuel, oxidant and combustion mixture each has at least one state variable which is approximately constant as a function of space.

24. The method of claim 23, wherein at least about 10% of said primary chamber is in said well-defined region.

25. The method of claim 18, wherein said carbon-containing fuel and said oxidant are introduced into said primary chamber at multiple introduction locations.

26. The method of claim 18, wherein said combustion mixture in said secondary chamber are allowed to undergo reactions under conditions that favor fullerene production.

27. The method of claim 18, wherein said carbon-containing fuel comprises a fullerene-forming fuel, a non-fullerene-forming fuel, or a combination thereof.

28. The method of claim 27, wherein said fullerene-forming fuel comprises an unsaturated hydrocarbon.

29. The method of claim 28, wherein said unsaturated hydrocarbon is selected from the group consisting of acetylenes, polyacetylenes, aromatics, highly aromatic materials, and combinations thereof.

30. The method of claim 27, wherein said fullerene-forming fuel comprises benzene.

31. The method of claim 18, wherein the pressure in said primary chamber is in the range of from 10 to 400 torr.

32. The method of claim 31, wherein the overall equivalence ratio is in the range of from 1.8 to 4.0.

33. The method of claim 32, wherein the temperature in said primary chamber is in the range of from 1500 K to 2500 K.

34. The method of claim 33, wherein the temperature in said secondary chamber is in the range of from 1500 K to 2500 K.

35. The method of claim 34, wherein the residence time in said primary chamber is in the range of 2 to 500 ms.

36. The method of claim 35, wherein the residence time in said secondary chamber is in the range of 5 ms to 10 s.

37. The method of claim 18, wherein the overall equivalence ratio is in the range of from 1.8 to 4.0.

38. The method of claim 18, wherein the temperature in said primary chamber is in the range of from 1500 K to 2500 K.

39. The method of claim 18, wherein the residence time in said primary chamber is in the range of 2 to 500 ms.

40. A method comprising:

introducing carbon-containing fuel and oxidant at an introduction location into a primary chamber so that said fuel and said oxidant react to produce first combustion products, thereby forming a combustion mixture;

introducing said combustion mixture into a secondary chamber; and

allowing constituents of said combustion mixture in said secondary chamber to undergo reactions to produce second combustion products comprising fullerenic products and other material, wherein said second combustion products flow through said secondary chamber without substantial mixing between material from different regions corresponding to different residence times in said secondary chamber to produce fullerenic products.

41. The method of claim 40, wherein said carbon-containing fuel and said oxidant are introduced into said primary chamber at multiple introduction locations.

42. The method of claim 40, wherein said carbon-containing fuel comprises a fullerene-forming fuel, a non-fullerene-forming fuel or a combination thereof.

43. The method of claim 42, wherein said carbon-containing fuel comprises toluene.

44. The method of claim 42, wherein said fullerene-forming fuel comprises an unsaturated hydrocarbon.

45. The method of claim 44, wherein said unsaturated hydrocarbon is selected from the group consisting of acetylenes, polyacetylenes, aromatics, highly aromatic materials, and combinations thereof.

46. The method of claim 40, further comprising introducing an additive into said secondary chamber.

47. The method of claim 46, wherein said additive is selected from the group consisting of

(i) halogen containing compounds,

(ii) compounds containing alkali metals or alkaline earth metals,

(iii) compounds which contain the metals manganese, iron, or barium,

(iv) compounds containing cyclic aromatic acid anhydrides,

(v) compounds containing cobalt, iron, or nickel, and

(vi) combinations thereof.

48. The method of claim 40, wherein the overall equivalence ratio is in the range of from 1.8 to 4.0.

49. The method of claim 40, wherein the temperature in said primary chamber is in the range of from 1500 K to 2500 K.

50. The method of claim 40, wherein the temperature in said secondary chamber is in the range of from 1500 K to 2500 K.

51. The method of claim 40, wherein the residence time in said primary chamber is in the range of 2 to 500 ms.

52. The method of claim 40, wherein the residence time in said secondary chamber is in the range of 5 ms to 10 s.

53. The method of claim 40, wherein said combustion mixture in said secondary chamber are allowed to undergo reactions under conditions that favor fullerene production.

54. The method of claim 40, wherein the pressure in said primary chamber is in the range of from 10 to 400 torr.

55. The method of claim 54, wherein the overall equivalence ratio is in the range of 1.8 to 4.0.

56. The method of claim 55, wherein the temperature in said primary chamber is in the range of from 1500 K to 2500 K.

57. The method of claim 56, wherein the temperature in said secondary chamber is in the range of from 1500 K to 2500 K.

58. The method of claim 57, wherein the residence time in said primary chamber is in the range of 2 to 500 ms.

59. The method of claim 58, wherein the residence time in said secondary chamber is in the range of 5 ms to 10 s.