Fuel reformer catalyst and absorbent materials

• US 7,264,788 B2
• Filed: 11/24/2004
• Issued: 09/04/2007
• Est. Priority Date: 11/26/2003
• Status: Expired due to Fees

• Current Assignee: Cabot Corporation
• Original Assignee: Cabot Corporation
• Inventors: Brewster, James, Hampden-Smith, Mark J., Shen, Jian-Ping, Napolitano, Paul, Atanassova, Paolina
• Primary Examiner(s): Vanoy; Timothy C.
• Application Number:
  US10/996,791
• Publication Number:
  US 20050232858A1
• Time in Patent Office: 1,014 Days
• Field of Search: 423/220, 423/230, 423/231, 423/648.1, 423/651, 423/652, 423/653, 423/654, 423/655, 423/656
• US Class Current: 423/648.1
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3483 by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• CPC Class Codes: B01J 2220/42 Materials comprising a mixture of inorganic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: B01J 23/464 Rhodium
• CPC Class Codes: B01J 23/58 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 37/0045 Drying a slurry, e.g. spray drying
• CPC Class Codes: B01J 37/086 Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0425 In-situ adsorption process during hydrogen production
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 3/38 using catalysts
• CPC Class Codes: C01B 3/56 by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts
• CPC Class Codes: Y10S 502/514 Process applicable either to preparing or to regenerating or to rehabilitating catalyst or sorbent

Abstract

Materials that are useful for absorption enhanced reforming (AER) of a fuel, including absorbent materials and catalyst materials and methods for using the materials. The materials can be fabricated by spray processing. The use of the materials in AER can produce a H₂ product gas having a high H₂ content and a low level of carbon oxides.

Claims

1. A method for the conversion of a carbon-based fuel to a H₂-rich product gas, comprising the steps of:

(a) providing a carbon-based fuel;

(b) converting said carbon-based fuel to an intermediate gas product by contacting said carbon-based fuel with at least a first conversion catalyst;

(c) contacting said intermediate gas product with an absorbent material to absorb CO₂ and form a H₂-rich gas, said absorbent material having a theoretical absorption capacity for CO₂ and having an initial surface area of at least about 5 m²/g and an initial pore volume of at least about 0.01 cm³/g;

(d) extracting said H₂-rich gas from said contacting step;

(e) regenerating said absorbent; and

(f) repeating said steps (a), (b), (c), (d) and (e) at least 50 times, wherein said absorbent material retains at least about 50 mol. % of said theoretical absorption capacity after each of said repeating steps.

2. A method as recited in claim 1, wherein said converting step comprises steam reforming of said carbon-based fuel.

3. A method as recited in claim 2, wherein said first conversion catalyst is a steam reforming catalyst.

4. A method as recited in claim 1, wherein said converting step is selected from the group consisting of auto-thermal reforming, partial oxidation and catalytic partial oxidation of said carbon-based fuel.

5. A method as recited in claim 1, further comprising the step of contacting said H₂-rich gas with a water-gas shift catalyst.

6. A method as recited in claim 1, wherein said repeating step comprises repeating steps (a), (b), (c),(d) and (e) at least 100 times.

7. A method as recited in claim 1, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 500 times.

8. A method as recited in claim 1, wherein said absorbent material retains at least about 70 mol. % of said theoretical capacity after said repeating step.

9. A method as recited in claim 1, wherein said absorbent material retains at least about 90 mol. % of said theoretical capacity after said repeating step.

10. A method as recited in claim 1, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 200 times and wherein said absorbent material retains at least about 10 mol. % of said theoretical absorption capacity after said repeating step.

11. A method as recited in claim 1, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 200 times and wherein said absorbent material retains at least about 25 mol. % of said theoretical absorption capacity after said repeating step.

12. A method as recited in claim 1, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 200 times and wherein said absorbent material retains at least about 50 mol. % of said theoretical absorption capacity after said repeating step.

13. A method as recited in claim 1, wherein said absorbent material comprises at least one metal oxide selected from the group consisting of Group 1 and Group 2 metal oxides.

14. A method as recited in claim 1, wherein said absorbent material comprises a calcium-containing compound.

15. A method as recited in claim 1, wherein said absorbent material comprises CaO.

16. A method as recited in claim 1, wherein said absorbent material is selected from a group consisting of CaO:

MgO, CaO;

Al₂O₃, CaO;

TiO₂, CaO;

ZrO₂ and CaO;

Al₂O₃;

MgO.

17. A method as recited in claim 1, wherein said absorbent material comprises CaO:

Al₂O₃.

18. A method as recited in claim 1, wherein said absorbent material comprises CaO:

TiO₂.

19. A method as recited in claim 1, wherein said absorbent material comprises at least 30 wt. % CaO.

20. A method as recited in claim 1, wherein said absorbent material comprises Li₂O.

21. A method as recited in claim 1, wherein said contacting step occurs at a temperature of not greater than about 800°

C.

22. A method as recited in claim 1, wherein said carbon-based fuel is a hydrocarbon-based fuel.

23. A method as recited in claim 1, wherein said carbon-based fuel is a gaseous fuel.

24. A method as recited in claim 1, wherein said carbon-based fuel comprises methane.

25. A method as recited in claim 1, wherein said carbon-based fuel comprises a liquid fuel.

26. A method as recited in claim 1, wherein said carbon-based fuel comprises a liquid fuel selected from the group consisting of diesel fuel, JP-8 aviation fuel, kerosene, ethanol and gasoline.

27. A method as recited in claim 1, wherein said H₂-rich gas comprises at least about 95 mol. % H₂ after each said repeating steps.

28. A method as recited in claim 1, wherein said regenerating step comprises heating said absorbent material to a temperature of at least about 700°

C.

29. A method as recited in claim 1, wherein said absorbent material is pelletized.

30. A method as recited in claim 1, wherein said absorbent material is in the form of a monolith.

31. A method as recited in claim 1, wherein said absorbent material is in the form of an extrudate.

32. A method as recited in claim 1, wherein said first conversion catalyst is pelletized.

33. A method as recited in claim 1, wherein said absorbent and said first conversion catalyst are formed into extrudates, at least a portion of said extrudates comprise both of said absorbent and said first conversion catalyst.

34. A method as recited in claim 1, wherein said absorbent material is coated on a support structure.

35. A method as recited in claim 1, wherein said absorbent material has substantially spherical morphology.

36. A method as recited in claim 1, wherein said absorbent material retains at least about 10 grams CO₂ per 100 grams unreacted absorbent compound after each of said repeating steps.

37. A method as recited in claim 1, wherein said absorbent material retains at least about 20 grams CO₂ per 100 grams unreacted absorbent compound after each of said repeating steps.

38. A method as recited in claim 1, wherein said absorbent material retains at least about 40 grams CO₂ per 100 grams unreacted absorbent compound after each of said repeating steps.

39. A method as recited in claim 1, further comprising providing steam with said carbon-based fuel.

40. A method as recited in claim 1, further comprising providing an oxygen-containing gas with said carbon-based fuel.

41. A method as recited in claim 1, wherein said absorbent material is pelletized and wherein said contacting step comprises contacting said intermediate gas product with said pelletized absorbent material having a first bulk density, wherein said repeating steps convert said pelletized absorbent material to a carbonized absorbent material having a second bulk density, and after said repeating steps said carbonized absorbent material has a third bulk density, wherein said third bulk density is greater than said first bulk density.

42. A method as recited in claim 41, wherein said third bulk density is up to about 140% of said first bulk density.

43. A method as recited in claim 1, wherein said carbon-based fuel comprises methane and wherein said first conversion catalyst comprises:

(a) a particulate support structure; and

(b) a metal dispersed on said support structure, wherein said conversion catalyst is capable of achieving at least about 90% of the theoretical thermodynamic conversion of methane to hydrogen at a temperature of 600°

C., a H₂O;

C ratio of 3;

1 and a gas hour space velocity (GHSV) of 5000 h<sup>−

1</sup> in the absence of an absorbent for CO₂.

44. A method as recited in claim 43, wherein said catalyst is capable of achieving at least about 95% of the theoretical thermodynamic conversion.

45. A method as recited in claim 43, wherein said catalyst is capable of achieving at least about 90% of the theoretical thermodynamic conversion of methane to hydrogen at a temperature of 600°

C., a H₂O;

C ratio of 3;

1 and a gas hour space velocity (GHSV) of 10000 h<sup>−

1</sup> in the absence of an absorbent for CO₂.

46. A method as recited in claim 43, wherein said catalyst is capable of achieving at least about 90% of the theoretical thermodynamic conversion of methane to hydrogen at a temperature of 600°

C., a H₂O;

C ratio of 3;

1 and a gas hour space velocity (GHSV) of 12500 h<sup>−

1</sup> in the absence of an absorbent for CO₂.

47. A method as recited in claim 43, wherein said support is selected from the group consisting of the metal oxides of aluminum, cerium, zirconium, lanthanum, silicon, magnesium, zinc and combinations thereof.

48. A method as recited in claim 43, wherein said dispersed metal is selected from the group consisting of Rh, Ni, Ru, Pt, Pd and alloys thereof.

49. A method as recited in claim 43, wherein said dispersed metal comprises Rh.

50. A method as recited in claim 43, wherein said conversion catalyst comprises from about 0.1 wt. % to about 5 wt. % of said metal.

51. A method as recited in claim 43, wherein said support structure comprises Al₂O₃ and said dispersed metal comprises Rh.

52. A method as recited in claim 43, wherein said conversion catalyst is pelletized.

53. A method as recited in claim 43, wherein said conversion catalyst is coated on a support.

54. A method as recited in claim 43, wherein said conversion catalyst has substantially spherical morphology.

55. A method as recited in claim 43, further comprising the step of contacting said intermediate gas phase with a water-gas shift catalyst.

56. A method as recited in claim 55, wherein said water-gas shift catalyst comprises a metal dispersed on a support phase, said metal being selected from the group consisting of Fe, Co, Cu and Cr.

57. A method as recited in claim 1, wherein said absorbent material and said first conversion catalyst are in the form of a particulate composite material, said particulate composite material comprising a first phase comprising said absorbent material, and a second phase comprising said conversion catalyst.

58. A method as recited in claim 57, wherein the mass ratio of said first phase to said second phase is greater than 1:

1.

59. A method as recited in claim 57, wherein the mass ratio of said first phase to said second phase is from about 20:

1 to about 3;

1.

60. A method as recited in claim 57, wherein the mass ratio of said first phase to said second phase is from about 9:

1 to about 5;

1.

61. A method as recited in claim 57, wherein said particulate composite material is pelletized.

62. A method as recited in claim 57, wherein said particulate composite material is coated on a support structure.

63. A method as recited in claim 57, wherein said particulate composite material is a monolithic structure.

64. A method as recited in claim 57, wherein said particulate composite material has an average particle size (d₅₀) of from about 1 μ

m to about 50 μ

m.

65. A method as recited in claim 1, wherein said initial surface area is at least about 10 m²/g.

66. A method as recited in claim 1, wherein said initial surface area is at least about 15 m²/g.

67. A method as recited in claim 1, wherein said initial pore volume is at least about 0.04 cm³/g.

68. A method as recited in claim 1, wherein said initial pore volume is at least about 0.15 cm³/g.

69. A method as recited in claim 1, wherein said absorbent material is fabricated by spray processing.

70. A method for the conversion of a carbon-based fuel to a H₂-rich product gas, comprising the steps of:

(a) providing a carbon-based fuel;

(b) converting said carbon-based fuel to an intermediate gas product by contacting said carbon-based fuel with at least a first conversion catalyst;

(c) contacting said intermediate gas product with an absorbent material selected from the group consisting of CaO;

Al₂O₃, CaO;

TiO₂, Li₂O to absorb CO₂ and form a H₂-rich gas, said absorbent material having a theoretical absorption capacity for CO₂ and having an initial surface area of at least about 5 m²/g and an initial pore volume of at least about 0.01 cm³/g;

(d) extracting said H₂-rich gas from said contacting step;

(e) regenerating said absorbent; and

(f) repeating said steps (a), (b), (c), (d) and (e) at least 10 times, wherein said absorbent material retains at least about 50 mol. % of said theoretical absorption capacity after each of said repeating steps.

71. A method as recited in claim 70, wherein said absorbent material comprises CaO:

Al₂O₃.

72. A method as recited in claim 70, wherein said absorbent material comprises CaO:

TiO₂.

73. A method as recited in claim 70, wherein said absorbent material comprises Li₂O.

74. A method as recited in claim 70, wherein said absorbent material retains at least about 70 mol. % of said theoretical capacity after said repeating step.

75. A method as recited in claim 70, wherein said absorbent material retains at least about 90 mol. % of said theoretical capacity after said repeating step.

76. A method as recited in claim 70, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 200 times and wherein said absorbent material retains at least about 10 mol. % of said theoretical absorption capacity after said repeating step.

77. A method as recited in claim 70, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 200 times and wherein said absorbent material retains at least about 25 mol. % of said theoretical absorption capacity after said repeating step.

78. A method as recited in claim 70, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 200 times and wherein said absorbent material retains at least about 50 mol. % of said theoretical absorption capacity after said repeating step.

79. A method as recited in claim 70, wherein said carbon-based fuel is a gaseous fuel.

80. A method as recited in claim 70, wherein said carbon-based fuel is a liquid fuel.