Low-temperature hydrogen production from oxygenated hydrocarbons

• US 20030099593A1
• Filed: 11/29/2001
• Published: 05/29/2003
• Est. Priority Date: 11/29/2001
• Status: Active Grant

• Current Assignee: Wisconsin Alumni Research Foundation (University of Wisconsin System)
• Original Assignee: Wisconsin Alumni Research Foundation (University of Wisconsin System)
• Inventors: Dumesic, James A., Cortright, Randy D.
• Granted Patent: US 6,699,457 B2
• Time in Patent Office: Days
• US Class Current: 423/648.1
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0277 containing a catalytic decomposition step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0495 the impurity being water
• CPC Class Codes: C01B 2203/1047 Group VIII metal catalysts
• CPC Class Codes: C01B 2203/1064 Platinum group metal catalysts
• CPC Class Codes: C01B 2203/107 Platinum catalysts
• CPC Class Codes: C01B 2203/1082 Composition of support materials
• CPC Class Codes: C01B 2203/1211 Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/22 by decomposition of gaseous or liquid organic compounds C01B3/0005 takes precedence ; coking liquid carbonaceous materials C10B55/00
• CPC Class Codes: C01B 3/326 characterised by the catalyst
• CPC Class Codes: C01B 3/501 by diffusion
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

Disclosed is a method of producing hydrogen from oxygenated hydrocarbon reactants, such as glycerol, glucose, or sorbitol. The method can take place in the vapor phase or in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon having at least two carbon atoms, in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIII transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.

Claims

1. A method of producing hydrogen comprising:

reacting water and a water-soluble oxygenated hydrocarbon having at least two carbon atoms, in the presence of a metal-containing catalyst, wherein the catalyst comprises a metal selected from the group consisting of Group VIII transitional metals, alloys thereof, and mixtures thereof.

2. The method of claim 1, wherein the water and the oxygenated hydrocarbon are reacted at a temperature of from about 100°

C. to about 450°

C., and at a pressure where the water and the oxygenated hydrocarbon are gaseous.

3. The method of claim 1, wherein the water and the oxygenated hydrocarbon are reacted at a temperature of from about 100°

C. to about 300°

C., and at a pressure where the water and the oxygenated hydrocarbon are gaseous.

4. The method of claim 1, wherein the water and the oxygenated hydrocarbon are reacted at a temperature not greater than about 400°

C., at a pressure where the water and the oxygenated hydrocarbon remain condensed liquids.

5. The method of claim 1, wherein the water and the oxygenated hydrocarbon are reacted at a pH of from about 4.0 to about 10.0.

6. The method of claim 1, wherein the catalyst comprises a metal selected from the group consisting of nickel, palladium, platinum, ruthenium, rhodium, iridium, alloys thereof, and mixtures thereof.

7. The method of claim 1, wherein the catalyst is further alloyed or mixed with a metal selected from the group consisting of Group IB metals, Group IIB metals, and Group VIIb metals.

8. The method of claim 1, wherein the catalyst is further alloyed or mixed with a metal selected from the group consisting of copper, zinc, and rhenium.

9. The method of claim 1, wherein the catalyst is adhered to a support.

10. The method of claim 9, wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, and boron nitride.

11. The method of claim 9, wherein the support is surface-modified to remove surface moieties selected from the group consisting of hydrogen and hydroxyl.

12. The method of claim 9, wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali compounds, and alkali earth compounds.

13. The method of claim 9, wherein the support is silica modified with trimethylethoxysilane.

14. The method of claim 9, wherein the support is a zeolite.

15. The method of claim 9, wherein the support is a carbon nanotube or a carbon fullerene.

16. The method of claim 9, wherein the support is a nanoporous support.

17. The method of claim 1, wherein the water and the oxygenated hydrocarbon are reacted at a temperature not greater than about 400°

C., at a pressure where the water and the oxygenated hydrocarbon remain condensed liquids, and further comprising reacting the water and the water-soluble oxygenated hydrocarbon in the presence of a water-soluble salt of an alkali or alkali earth metal.

18. The method of claim 17, wherein the water-soluble salt is selected from the group consisting of an alkali or an alkali earth metal hydroxide, carbonate, nitrate, or chloride salt.

19. The method of claim 1, wherein the water-soluble oxygenated hydrocarbon has a carbon-to-oxygen ratio of 1:

1.

20. The method of claim 1, wherein the water-soluble oxygenated hydrocarbon has from 2 to 12 carbon atoms.

21. The method of claim 1, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols.

22. The method of claim 1, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of aldohexoses and corresponding alditols.

23. The method of claim 1, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of glucose and sorbitol.

24. The method of claim 1, wherein the water-soluble oxygenated hydrocarbon is sucrose.

25. A method of producing hydrogen comprising:

reacting water and a water-soluble oxygenated hydrocarbon having at least two carbon atoms, at a temperature not greater than about 400°

C., at a pressure where the water and the oxygenated hydrocarbon remain condensed liquids, and in the presence of a metal-containing catalyst, wherein the catalyst comprises a metal selected from the group consisting of Group VIII transitional metals, alloys thereof, and mixtures thereof.

26. The method of claim 25, wherein the catalyst comprises a metal selected from the group consisting of nickel, palladium, platinum, ruthenium, rhodium, iridium, alloys thereof, and mixtures thereof.

27. The method of claim 25, wherein the catalyst is further alloyed or mixed with a metal selected from the group consisting of Group IB metals, Group IIB metals, and Group VIIb metals.

28. The method of claim 25, wherein the catalyst is further alloyed or mixed with a metal selected from the group consisting of copper, zinc, and rhenium.

29. The method of claim 25, wherein the catalyst is adhered to a support.

30. The method of claim 29, wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, and boron nitride.

31. The method of claim 29, wherein the support is surface-modified to remove surface moieties selected from the group consisting of hydrogen and hydroxyl.

32. The method of claim 31, wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali compounds, and alkali earth compounds.

33. The method of claim 29, wherein the support is silica modified with trimethylethoxysilane.

34. The method of claim 29, wherein the support is a zeolite.

35. The method of claim 29, wherein the support is a carbon nanotube or a carbon fullerene.

36. The method of claim 29, wherein the support is a nanoporous support.

37. The method of claim 25, further comprising reacting the water and the water-soluble oxygenated hydrocarbon in the presence of a water-soluble salt of an alkali or alkali earth metal.

38. The method of claim 37, wherein the water-soluble salt is selected from the group consisting of an alkali or an alkali earth metal hydroxide, carbonate, nitrate, or chloride salt.

39. The method of claim 25, wherein the water-soluble oxygenated hydrocarbon has a carbon-to-oxygen ratio of 1:

1.

40. The method of claim 25, wherein the water-soluble oxygenated hydrocarbon has from 2 to 12 carbon atoms.

41. The method of claim 25, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols.

42. The method of claim 25, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of aldohexoses and corresponding alditols.

43. The method of claim 25, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of glucose and sorbitol.

44. The method of claim 25, wherein the water-soluble oxygenated hydrocarbon is sucrose.

45. A method of producing hydrogen comprising:

reacting water and a water-soluble oxygenated hydrocarbon having at least two carbon atoms, at a temperature of from about 100°

C. to about 450°

C., and at a pressure where the water and the oxygenated hydrocarbon are gaseous, in the presence of a metal-containing catalyst, wherein the catalyst comprises a metal selected from the group consisting of Group VIII transitional metals, alloys thereof, and mixtures thereof, the catalyst being adhered to a support.

46. The method of claim 45, wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, and boron nitride, modified to remove surface moieties selected from the group consisting of hydrogen and hydroxyl.

47. The method of claim 46, wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali compounds, and alkali earth compounds.

48. The method of claim 45, wherein the support is silica modified with trimethylethoxysilane.

49. The method of claim 45, wherein the water-soluble oxygenated hydrocarbon has a carbon-to-oxygen ratio of 1:

1.

50. The method of claim 45, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols.

51. A method of producing hydrogen comprising:

reacting water and a water-soluble oxygenated hydrocarbon having at least two carbon atoms, at a temperature of not greater than about 400°

C., and at a pressure where the water and the oxygenated hydrocarbon remain condensed liquids, in the presence of a metal-containing catalyst, wherein the catalyst comprises a metal selected from the group consisting of Group VIII transitional metals, alloys thereof, and mixtures thereof, the catalyst being adhered to a support.

52. The method of claim 51, wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, and boron nitride, modified to render to remove surface moieties selected from the group consisting of hydrogen and hydroxyl.

53. The method of claim 52, wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali compounds, and alkali earth compounds.

54. The method of claim 51, wherein the support is silica modified with trimethylethoxysilane.

55. The method of claim 51, wherein the water-soluble oxygenated hydrocarbon has a carbon-to-oxygen ratio of 1:

1.

56. The method of claim 51, wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols.