Fuel reformer catalyst and absorbent materials

• US 7,267,811 B2
• Filed: 11/26/2003
• Issued: 09/11/2007
• Est. Priority Date: 11/26/2003
• Status: Expired due to Fees

• Current Assignee: Cabot Corporation
• Original Assignee: Cabot Corporation
• Inventors: Hampden-Smith, Mark J., Shen, Jian-Ping, Napolitano, Paul, Brewster, James, Atanassova, Paolina
• Primary Examiner(s): Vanoy; Timothy C.
• Application Number:
  US10/723,424
• Publication Number:
  US 20050112056A1
• Time in Patent Office: 1,385 Days
• Field of Search: 423/230, 423/231, 423/648.1, 423/651, 423/652, 423/653, 423/654, 423/655, 423/656, 423/220
• US Class Current: 423/648.1
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• 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 20/3433 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 23/464 Rhodium
• CPC Class Codes: B01J 23/58 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• 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 2203/0227 containing a catalytic reforming step
• 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 2203/042 Purification by adsorption on solids
• 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 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 2203/1247 Higher hydrocarbons
• CPC Class Codes: C01B 3/38 : using catalysts
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/386 : Catalytic partial combustion
• 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

Abstract

Materials that are useful for absorption enhanced reforming (AER) of a fuel, including absorbent materials and catalyst materials, and methods for using such materials for the conversion of carbon-based fuels to a H₂-rich product gas. 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. The method for converting carbon-based fuels to a H₂-rich product gas includes forming an intermediate gas product from the carbon-based fuel using a catalyst and contacting the intermediate gas product with an absorbent to absorb CO₂. The absorbent can be regenerated while retaining a high absorption capacity.

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 selected from a liquid fuel and a gaseous 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;

(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 1, wherein said converting step is selected from the group consisting of autothermal reforming, partial oxidation and catalytic partial oxidation of said carbon-based fuel.

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

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

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

7. 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.

8. 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.

9. 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.

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 25 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) and (d) at least 200 times and wherein said absorbent material retains at least about 50 mol. % of said theoretical absorption capacity after said repeating step.

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

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

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

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

MgO.

16. A method as recited in claim 1, wherein said absorbent material comprises CaO and from about 1 wt. % to about 40 wt. % Al₂O₃.

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

C.

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

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

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

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

22. 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.

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

24. 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.

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

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

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

28. 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 selected from a liquid fuel and a gaseous 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 having a mass to absorb CO₂ and form a H₂-rich gas, said absorbent material having an theoretical absorption capacity for CO₂;

(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 mass of absorbent material retains at least about 40 grams CO₂ per 100 grams unreacted absorbent after each of said repeating steps.

29. A method as recited in claim 28, wherein said absorbent material retains at least 50 grams CO₂ per 100 grams unreacted absorbent after each of said repeating steps.

30. A method as recited in claim 28, wherein said absorbent material is pelletized.

31. A method as recited in claim 28, wherein said converting step comprises steam reforming of said carbon-based fuel.

32. A method as recited in claim 28, wherein said converting step is selected from the group consisting of autothermal reforming, partial oxidation and catalytic partial oxidation of said carbon-based fuel.

33. A method as recited in claim 28, further comprising the step of contacting said H₂-rich gas with a water-gas shift catalyst.

34. A method as recited in claim 28, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 50 times.

35. A method as recited in claim 28, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 100 times.

36. A method as recited in claim 28, wherein said repeating step comprises repeating steps (a), (b), (c), (d) and (e) at least 500 times.

37. A method as recited in claim 28, wherein said absorbent retains at least about 70 mol. % of said theoretical absorption capacity after said repeating step.

38. A method as recited in claim 28, wherein said absorbent retains at least about 90 mol. % of said theoretical absorption capacity after said repeating step.

39. A method as recited in claim 28, 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.

40. A method as recited in claim 28, 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.

41. A method as recited in claim 28, wherein said repeating step comprises repeating steps (a), (b), (c) and (d) at least 200 times and wherein said absorbent material retains at least about 50 mol. % of said theoretical absorption capacity after said repeating step.

42. A method as recited in claim 28, wherein said absorbent material comprises at least one metal-oxide selected from the group consisting of Group IA and Group IIA metal oxides.

43. A method as recited in claim 28, wherein said absorbent material comprises a calcium-containing compound.

44. A method as recited in claim 28, wherein said absorbent material comprises CaO.

45. A method as recited in claim 28, wherein said absorbent material comprises CaO:

MgO.

46. A method as recited in claim 28, wherein said absorbent material comprises CaO and from about 1 wt. % to about 40 wt. % Al₂O₃.

47. A method as recited in claim 28, wherein said contacting step occurs at a temperature of not greater than about 800°

C.

48. A method as recited in claim 28, wherein said carbon-based fuel is a hydrocarbon-based fuel.

49. A method as recited in claim 28, wherein said carbon-based fuel is a gaseous fuel.

50. A method as recited in claim 28, wherein said carbon-based fuel comprises methane.

51. A method as recited in claim 28, wherein said carbon-based fuel is a liquid fuel.

52. A method as recited in claim 28, wherein said carbon-based fuel comprises a liquid selected from the group consisting of diesel fuel, JP-8 aviation fuel, kerosene, ethanol and gasoline.

53. A method as recited in claim 28, wherein said H₂-rich gas comprises at least about 95 mol. % H₂ after said repeating step.

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

C.

55. A method as recited in claim 28, wherein said absorbent material is pelletized.

56. A method as recited in claim 28, wherein said absorbent material is coated on a support structure.

57. A method as recited in claim 28, wherein said absorbent material has substantially spherical morphology.

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

(a) providing a carbon-based fuel selected from a liquid fuel and a gaseous fuel, and steam;

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

(c) contacting said intermediate gas product with an absorbent material to absorb CO₂ and form an H₂-rich gas, said absorbent material having a theoretical absorption capacity and wherein at least said absorbent material is pelletized;

(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 60 mol. % of its theoretical CO₂ absorption capacity after each of said repeating steps.

59. A method as recited in claim 58, wherein said absorbent material retains at least about 90 mol. % of said theoretical CO₂ absorption capacity after each of said repeating steps.

60. A method as recited in claim 58, wherein said absorbent material retains at least 10 grams CO₂ per 100 grams unreacted absorbent material after each of said repeating steps.

61. A method as recited in claim 58, wherein said absorbent material retains at least 20 grams CO₂ per 100 grams unreacted absorbent material after each of said repeating steps.

62. A method as recited in claim 58, wherein said absorbent material retains at least 30 grams CO₂ per 100 grams unreacted absorbent material after each of said repeating steps.

63. A method as recited in claim 58, wherein said absorbent material retains at least 40 grams CO₂ per 100 grams unreacted absorbent material after each of said repeating steps.

64. A method as recited in claim 58, wherein said absorbent material is regenerated at least about 100 times and wherein said absorbent material retains at least about 20 mol. % of said theoretical CO₂ absorption capacity.

65. A method as recited in claim 58, wherein said absorbent material has substantially spherical morphology.

66. A method as recited in claim 58, wherein said first conversion catalyst is a steam reforming catalyst.

67. A method as recited in claim 58, further comprising the step of contacting said H₂-rich product gas with a water-gas shift catalyst.

68. A method as recited in claim 58, wherein said absorbent material comprises at least one metal oxide selected from the group consisting of Group IA and Group IIA metal oxides.

69. A method as recited in claim 58, wherein said absorbent material comprises a calcium-containing compound.

70. A method as recited in claim 58, wherein said absorbent material comprises CaO.

71. A method as recited in claim 58, wherein said absorbent material comprises CaO and from about 1 wt. % to about 40 wt. % Al₂O₃.

72. A method as recited in claim 58, wherein said absorbent comprises CaO and a metal oxide selected from the group consisting of Al₂O₃ and MgO.

73. A method as recited in claim 58, wherein said first conversion catalyst comprises a metal selected from the group consisting of Rh, Ni, Ru, Pt, and Pd.

74. A method as recited in claim 58, wherein said contacting step occurs at a temperature of not greater than about 800°

C.

75. A method as recited in claim 58, wherein said regenerating step comprises heating said absorbent material to a temperature of at least about 700°

C.

76. A method as recited in claim 58, wherein said conversion catalyst is pelletized with said absorbent material.

77. A method as recited in claim 58, wherein said H₂-rich product gas comprises at least about 95 mol. % H₂.