STRUCTURES INCLUDING CATALYTIC MATERIALS DISPOSED WITHIN POROUS ZEOLITE MATERIALS, SYSTEMS AND METHODS FOR USING THE SAME, AND METHODS OF FABRICATING CATALYTIC STRUCTURES

• US 20080045403A1
• Filed: 08/15/2006
• Published: 02/21/2008
• Est. Priority Date: 08/15/2006
• Status: Active Grant

• Current Assignee: Battelle Energy Alliance LLC (Battelle Memorial Institute)
• Original Assignee: Battelle Energy Alliance LLC (Battelle Memorial Institute)
• Inventors: Rollins, Harry W., Petkovic, Lucia M., Ginosar, Daniel M.
• Granted Patent: US 7,879,749 B2
• Time in Patent Office: Days
• US Class Current: 502/62
• CPC Class Codes: B01J 29/005 Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
• CPC Class Codes: B01J 29/035 Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
• CPC Class Codes: B01J 29/041 Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
• CPC Class Codes: B01J 29/061 containing metallic elements added to the zeolite
• CPC Class Codes: B01J 29/072 Iron group metals or copper
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/46 Iron group metals or copper
• CPC Class Codes: B01J 29/80 Mixtures of different zeolites
• 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: C07C 1/20 starting from organic compounds containing only oxygen atoms as heteroatoms
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2529/46 Iron group metals or copper
• CPC Class Codes: C07C 2529/84 Aluminophosphates containing other elements, e.g. metals, boron
• CPC Class Codes: C07C 2529/85 Silicoaluminophosphates (SAPO compounds)
• CPC Class Codes: C10G 2400/20 C2-C4 olefins
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10G 3/45 containing iron group metals or compounds thereof
• CPC Class Codes: C10G 3/47 containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 3/49 containing crystalline aluminosilicates, e.g. molecular sieves
• CPC Class Codes: C10G 3/50 in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: Y02P 30/40 : Ethylene production

Abstract

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing the formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing the formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by the crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Claims

1. A catalytic structure comprising:

a substantially crystalline zeolite material;

a first plurality of pores substantially defined by a crystal structure of the substantially crystalline zeolite material;

a second plurality of pores dispersed throughout the substantially crystalline zeolite material;

a metallic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores; and

a metal oxide material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores.

2. The catalytic structure of claim 1, wherein the metallic material comprises a plurality of metallic particles.

3. The catalytic structure of claim 2, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.

4. The catalytic structure of claim 1, wherein the metallic material comprises at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.

5. The catalytic structure of claim 1, wherein the metal oxide material comprises a plurality of metal oxide particles.

6. The catalytic structure of claim 1, wherein the plurality of metal oxide particles has an average particle size of less than about 500 angstroms.

7. The catalytic structure of claim 1, wherein the metal oxide material comprises at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.

8. The catalytic structure of claim 1, wherein the metal material comprise copper and the metal oxide material comprises zinc oxide.

9. The catalytic structure of claim 1, wherein the second plurality of pores comprises a plurality of elongated channels.

10. The catalytic structure of claim 9, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.

11. The catalytic structure of claim 9, wherein the second plurality of pores further comprises a plurality of generally spherical pores.

12. The catalytic structure of claim 1, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.

13. The catalytic structure of claim 12, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.

14. The catalytic structure of claim 13, wherein the zeolite material comprises ZSM-5.

15. The catalytic structure of claim 1, wherein the first plurality of pores comprises a plurality of micropores and the second plurality of pores comprises a plurality of mesopores.

16. A catalytic structure comprising:

a zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, the zeolite material comprising;

a first plurality of pores substantially defined by a crystal structure of the zeolite material; and

a second plurality of pores dispersed throughout the zeolite material;

at least one catalytic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores, the at least one catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.

17. The catalytic structure of claim 16, wherein the at least one catalytic material comprises a plurality of metallic particles.

18. The catalytic structure of claim 17, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.

19. The catalytic structure of claim 17, wherein each metallic particle of the plurality of metallic particles comprises at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.

20. The catalytic structure of claim 17, wherein the at least one catalytic material further comprises a plurality of metal oxide particles.

21. The catalytic structure of claim 20, wherein the plurality of metal oxide particles has an average particle size of less than about 500 angstroms.

22. The catalytic structure of claim 20, wherein each metal oxide particle comprises at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.

23. The catalytic structure of claim 16, wherein the at least one catalytic material comprises copper and zinc oxide.

24. The catalytic structure of claim 16, wherein the second plurality of pores comprises a plurality of elongated channels.

25. The catalytic structure of claim 24, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.

26. The catalytic structure of claim 24, wherein the second plurality of pores further comprises a plurality of generally spherical pores.

27. The catalytic structure of claim 16, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.

28. The catalytic structure of claim 27, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.

29. The catalytic structure of claim 28, wherein the zeolite material comprises ZSM-5.

30. The catalytic structure of claim 16, wherein the first plurality of pores comprises a plurality of micropores and the second plurality of pores comprises a plurality of mesopores.

31. A method of fabricating a catalytic structure, the method comprising:

forming a zeolite material at least partially around at least one template structure, the zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol;

removing the at least one template structure from within the zeolite material;

introducing at least one catalytic material into the zeolite material, the at least one catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.

32. The method of claim 31, wherein introducing at least one catalytic material into the zeolite material comprises introducing a plurality of metallic particles into the zeolite material.

33. The method of claim 32, wherein introducing a plurality of metallic particles into the zeolite material comprises introducing a plurality of metallic particles having an average particle size of less than about 500 angstroms into the zeolite material.

34. The method of claim 32, further comprising selecting each metallic particle of the plurality of metallic particles to comprise at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.

35. The method of claim 32, wherein introducing at least one catalytic material into the zeolite material further comprises introducing a plurality of metal oxide particles into the zeolite material.

36. The method of claim 35, wherein introducing a plurality of metal oxide particles into the zeolite material comprises introducing a plurality of metal oxide particles having an average particle size of less than about 200 angstroms into the zeolite material.

37. The method of claim 35, further comprising selecting each metal oxide particle of the plurality of metal oxide particles to comprise at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.

38. The method of claim 31, wherein introducing at least one catalytic material into the zeolite material comprises introducing copper and zinc oxide into the zeolite material.

39. The method of claim 38, wherein introducing copper into the zeolite material and introducing zinc oxide into the zeolite material each comprise introducing a nitrate solution into the zeolite material and heating the zeolite material in air to temperatures of greater than about 100°

C.

40. The method of claim 31, wherein forming a zeolite material at least partially around at least one template structure comprises forming a zeolite material around a plurality of elongated template structures, and wherein removing the at least one template structure from within the zeolite material comprises forming a plurality of elongated channels in the zeolite material.

41. The method of claim 40, wherein forming a plurality of elongated channels comprises forming a plurality of generally cylindrical channels having an average diameter in a range extending from about 20 angstroms to about 500 angstroms in the zeolite material.

42. The method of claim 40, wherein forming a zeolite material at least partially around at least one template structure further comprises forming a zeolite material around a plurality of generally spherical template structures, and wherein removing the at least one template structure from within the zeolite material comprises forming a plurality of generally spherical pores in the zeolite material.

43. The method of claim 31, wherein forming a zeolite material comprises forming a zeolite material having a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.

44. The method of claim 43, wherein forming a zeolite material comprises forming an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.

45. The method of claim 44, wherein forming a zeolite material comprises forming ZSM-5.

46. The method of claim 31, wherein forming a zeolite material at least partially around at least one template structure comprises forming a zeolite material at least partially around at least one template structure comprising at least one of a plurality of carbon nanoparticles and a plurality of carbon nanowires.

47. The method of claim 31, wherein forming a zeolite material at least partially around at least one template structure comprises forming a zeolite material at least partially around each of a plurality of carbon nanotubes.

48. The method of claim 47, wherein introducing a first catalytic material comprises impregnating at least one carbon nanotube of the plurality of carbon nanotubes with a solution comprising at least one element of at least one of the first catalytic material and the second catalytic material.

49. A method of synthesizing hydrocarbon molecules having two or more carbon atoms, the method comprising:

contacting hydrogen and at least one of carbon monoxide and carbon dioxide with a catalytic structure at a temperature greater than about 200°

C. and a pressure greater than about 0.5 megapascals, the catalytic structure comprising;

a zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, the zeolite material comprising;

a first plurality of pores substantially defined by interstitial spaces within a crystal structure of the zeolite material; and

a second plurality of pores dispersed throughout the zeolite material; and

at least one catalytic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores, the first catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.

50. The method of claim 49, wherein contacting at least one of carbon monoxide and carbon dioxide with a catalytic structure comprises supplying a mixture of hydrogen and at least one of carbon monoxide and carbon dioxide to a reactor containing the catalytic structure.

51. The method of claim 49, further comprising:

removing reaction products and unreacted reactants from the reactor;

cooling the reaction products and unreacted reactants; and

separating unreacted reactants from the reaction products, the reaction products comprising hydrocarbon molecules having two or more carbon atoms.

52. The method of claim 51, further comprising recombining the separated unreacted reactants with the mixture supplied to the reactor.

53. The method of claim 49, wherein the catalytic structure comprises a plurality of pellets each comprising the zeolite material and the at least one catalytic material.

54. The method of claim 49, wherein the at least one catalytic material comprises a plurality of metallic particles.

55. The method of claim 54, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.

56. The method of claim 54, further comprising selecting each metallic particle of the plurality of metallic particles to comprise at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.

57. The method of claim 54, wherein the at least one catalytic material further comprises a plurality of metal oxide particles.

58. The method of claim 57, wherein the plurality of metal oxide particles has an average particle size of less than about 500 angstroms.

59. The method of claim 57 further comprising selecting each metal oxide particle to comprise at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.

60. The method of claim 49, wherein the at least one catalytic material comprises copper and zinc oxide.

61. The method of claim 49, wherein the second plurality of pores comprises a plurality of elongated channels.

62. The method of claim 61, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.

63. The method of claim 61, wherein the second plurality of pores further comprises a plurality of generally spherical pores.

64. The method of claim 49, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.

65. The method of claim 64, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.

66. The method of claim 65, wherein the zeolite material comprises ZSM-5.

67. The method of claim 49, wherein the first plurality of pores comprises a plurality of micropores and the second plurality of pores comprises a plurality of mesopores.

68. A system for synthesizing hydrocarbon molecules having two or more carbon atoms from hydrogen and at least one of carbon monoxide and carbon dioxide, the system comprising:

a reactor configured to receive a reactant mixture comprising hydrogen and at least one of carbon monoxide and carbon dioxide; and

a catalytic structure disposed within the reactor, the catalytic structure comprising;

a zeolite material capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, the zeolite material comprising;

a first plurality of pores substantially defined by a crystal structure of the zeolite material; and

a second plurality of pores dispersed throughout the zeolite material; and

at least one catalytic material disposed within at least one pore of at least one of the first plurality of pores and the second plurality of pores, the first catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen.

69. The system of claim 68, further comprising a device configured to heat the catalytic structure to a temperature of greater than about 200°

C.

70. The system of claim 69, further comprising a device configured to pressurize the reactor to a pressure of greater than about 0.5 megapascals.

71. The system of claim 68, wherein the at least one catalytic material comprises a plurality of metallic particles.

72. The system of claim 71, wherein the plurality of metallic particles has an average particle size of less than about 500 angstroms.

73. The system of claim 71, wherein each metallic particle of the plurality of metallic particles comprises at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, or cesium.

74. The system of claim 71, wherein the at least one catalytic material further comprises a plurality of metal oxide particles.

75. The system of claim 74, wherein the plurality of metal oxide particles has an average particle size of less than about 200 angstroms.

76. The system of claim 74, wherein each metal oxide particle comprises at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide.

77. The system of claim 68, wherein the at least one catalytic material comprises copper and zinc oxide.

78. The system of claim 68, wherein the second plurality of pores comprises a plurality of elongated channels.

79. The system of claim 78, wherein each elongated channel of the plurality of elongated channels is generally cylindrical and has an average diameter in a range extending from about 20 angstroms to about 500 angstroms.

80. The system of claim 78, wherein the second plurality of pores further comprises a plurality of generally spherical pores.

81. The system of claim 68, wherein the zeolite material has a framework type selected from MFI, BEA, FAU, MOR, FER, ERI, OFF, CHA and AEI.

82. The system of claim 81, wherein the zeolite material comprises an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.

83. The system of claim 82, wherein the zeolite material comprises ZSM-5.

84. The system of claim 68, wherein the first plurality of pores comprises a plurality of micropores and the second plurality of pores comprises a plurality of mesopores.