IP Library Granted Patent US 7,618,612
Granted Patent B2
US 7,618,612 · App. 11/124,717 · Granted Nov 17, 2009

Low-temperature hydrogen production from oxygenated hydrocarbons

Assignee: Wisconsin Alumni Research Foundation
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Quick Facts
Patent No.
US 7,618,612
App. No.
11/124,717
Granted
Nov 17, 2009
Kind
B2
Abstract

Disclosed is a method of producing hydrogen from oxygenated hydrocarbon reactants, such as methanol, glycerol, sugars (e.g. glucose and xylose), or sugar alcohols (e.g. sorbitol). The method takes place in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIIIB 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 (44)

1. A method of producing hydrogen comprising:

reacting water and a water-soluble oxygenated hydrocarbon selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, alditols, and mixtures thereof, at a pressure of from about 0.1 atm to about 53.29 atm;

in the presence of a catalyst comprising an alloy, mixture, or combination of at least one Group VIII transition metal and a metal selected from the group consisting of silver, gold, Group IIB metals, Group VIIB metals, Group IVA metals, and Group VA metals; and

wherein the catalyst is adhered to a support.

2. The method of claim 1 , wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, boron nitride, and mixtures thereof.

3. The method of claim 1 , wherein the support is a zeolite.

4. The method of claim 1 , wherein the support is a carbon nanotube or a fullerene.

5. The method of claim 1 , further comprising reacting the water and the water-soluble oxygenated hydrocarbon in the presence of a water-soluble salt of an alkali or alkaline earth metal.

6. The method of claim 5 , wherein the water-soluble salt is an alkali or an alkaline earth metal hydroxide, carbonate, nitrate, or chloride salt.

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

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

9. The method of claim 1 , wherein the catalyst comprises ruthenium, palladium, or platinum.

10. The method of claim 1 , wherein the catalyst comprises a metal selected from the group consisting of Group IIB metals, and Group VIIB metals.

11. The method of claim 1 , wherein the catalyst comprises a metal selected from the group consisting of zinc, germanium, tin, and bismuth.

12. The method of claim 11 , wherein the catalyst comprises rhenium.

13. The method of claim 1 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol and glycerol, and the at least one Group VIII transition metal(s) is selected from the group consisting of palladium and platinum.

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

15. The method of claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the condensed liquid phase.

16. The method of claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the vapor phase.

17. The method of claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 450° C.

18. The method of claim 1 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 275° C.

19. The method of claim 1 , wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali metal compounds, and alkaline earth compounds.

20. A method of producing hydrogen comprising:

reacting water and a water-soluble oxygenated hydrocarbon selected from the group consisting of ethanediol, ethanedione, glycerol, glyceraldehyde, aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, alditols, and mixtures thereof, at a pressure of from about 0.1 atm to about 53.29 atm;

in the presence of a catalyst comprising at least one metal selected from the group consisting of palladium, platinum, mixtures thereof, combinations thereof, and alloys thereof, and in the presence of a water-soluble salt of an alkali or alkaline earth metal;

wherein the catalyst is adhered to a support.

21. The method of claim 20 , wherein the support is selected from the group consisting of silica, alumina, zirconia, titania, ceria, carbon, silica-alumina, silica nitride, boron nitride, and mixtures thereof.

22. The method of claim 20 , wherein the support is a zeolite.

23. The method of claim 20 , wherein the support is a carbon nanotube or a fullerene.

24. The method of claim 20 , wherein the water-soluble salt is an alkali or an alkaline earth metal hydroxide, carbonate, nitrate, or chloride salt.

25. The method of claim 20 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of aldotetroses, aldopentoses, aldohexoses, ketotetroses, ketopentoses, ketohexoses, and alditols.

26. The method of claim 20 , wherein the catalyst comprises platinum.

27. The method of claim 20 , wherein the catalyst further comprises a metal selected from the group consisting of silver, gold, Group IIB metals, and Group VIIb metals.

28. The method of claim 20 , wherein the catalyst further comprises a metal selected from the group consisting of zinc, germanium, tin, and bismuth.

29. The method of claim 20 , wherein the catalyst comprises rhenium.

30. The method of claim 20 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of ethanediol and glycerol.

31. The method of claim 20 , wherein the water-soluble oxygenated hydrocarbon is selected from the group consisting of sucrose, glucose, mannitol, and sorbitol.

32. The method of claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the condensed liquid phase.

33. The method of claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted in the vapor phase.

34. The method of claim 20 , wherein the catalyst further comprises nickel or ruthenium.

35. The method of claim 20 , wherein the catalyst comprises more than one Group VIII transition metal.

36. The method of claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 450° C.

37. The method of claim 20 , wherein the water and the water-soluble oxygenated hydrocarbon are reacted at a temperature of from 100° C. to 275° C.

38. The method of claim 20 , wherein the support is modified by treating it with a modifier selected from the group consisting of silanes, alkali metal compounds, and alkaline earth compounds.

Assignments (1)
CONFIRMATORY LICENSE Recorded Dec 6, 2021
From: UNIVERSITY OF WISCONSIN-MADISON
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 058740/0569 →
Continuity (3)
Continuation 1030625800 · Nov 27, 2002
Continuation In Part 0999855200 · Nov 29, 2001
Related Publication 20050207971A1 · Sep 22, 2005