Hydrogen generation catalyst

• US 20020083643A1
• Filed: 10/26/2001
• Published: 07/04/2002
• Est. Priority Date: 01/07/2000
• Status: Active Grant

• Current Assignee: Protonex Technology Corporation (Honeywell International Inc.)
• Original Assignee: Millennium Fuels USA LLC
• Inventors: Kelly, Michael T., Amendola, Steven C., Binder, Michael, Petillo, Phillip J., Sharp-Goldman, Stefanie L.
• Granted Patent: US 6,683,025 B2
• Time in Patent Office: Days
• US Class Current: 48/61
• CPC Class Codes: B01J 23/462 Ruthenium
• CPC Class Codes: B01J 31/08 Ion-exchange resins
• CPC Class Codes: B01J 37/16 Reducing
• CPC Class Codes: B01J 37/348 Electrochemical processes, e.g. electrochemical deposition or anodisation
• CPC Class Codes: C01B 3/065 from a hydride
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The present invention relates to a composition and method for storage and controlled release of hydrogen. In particular, the present invention relates to the use of borohydride based solutions as a hydrogen storage source and a catalyst system to release hydrogen therefrom.

Claims

1. A process for producing a supported hydrogen generation catalyst, comprising:

(A) contacting a substrate with a solution comprising a transition metal ion; and

(B) contacting the resulting substrate of (A) with a reducing agent.

2. The process according to claim 1, wherein

the substrate comprises a material selected from the group consisting of ceramics, plastics, polymers, glass, fibers, ropes, nonwovens, wovens, textiles, fabrics, carbons, carbon-fibers, ion exchange resins, metals, alloys, wires, wires, meshes, and combinations thereof;

the transition metal ion is an anion, a cation, an anion complex or a cation complex of a transition metal selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof; and

the reducing agent is selected from the group consisting of metal hydrides, hydrazine, hydrogen gas, glucose, hydroxylamine, carbon monoxide, dithionate, sulfur dioxide, borohydride, alcohols, and mixtures thereof.

3. The process according to claim 1, wherein the substrate is an anionic exchange resin, and the solution comprises an anionic complex of a transition metal.

4. The process according to claim 3, wherein the solution is obtained by reacting a transition metal salt with an acid having the corresponding anion of said transition metal salt.

5. The process according to claim 3, wherein the anionic complex of a transition metal is characterized by the chemical formula [M^y+X₆]^(y−

6), wherein, M is a transition metal, y is the valence of the transition metal, and X is an anion with a single negative charge.

6. The process according to claim 1, wherein the substrate is a cationic exchange resin, and the solution comprises a transition metal cation and a non-complexing anion.

7. The process according to claim 6, wherein the solution has a pH of greater than or equal to about 0.

8. The process according to claim 6, wherein the solution is obtained by the following process:

(A) reacting a transition metal salt with a compound having a non-complexing anion to thereby promote precipitation of the anion, originally associated with the transition metal salt, and the cation, originally associated with the non-complexing anion; and

(B) separating out the precipitate.

9. The process according to claim 6, wherein the non-complexing anion is selected from the group consisting of perchlorate (ClO₄₋

), hexaflourophosphate (PF₆₋

), tetrafluoroborate (BF₄₋

), and mixtures thereof.

10. The process according to claim 1, further comprising drying the resulting substrate of step (A) before contacting the substrate with the reducing agent, wherein the substrate comprises a material selected from the group consisting of ceramics, plastics, polymers, glass, fibers, ropes, nonwovens, wovens, textiles, fabrics, carbons, carbon-fibers, ion exchange resins, metals, alloys, wires, meshes, and combinations thereof.

11. A supported hydrogen generation catalyst obtained by the process according to claim 1.

12. A supported hydrogen generation catalyst obtained by the process according to claim 3.

13. A supported hydrogen generation catalyst obtained by the process according to claim 6.

14. A supported hydrogen generation catalyst obtained by the process according to claim 10.

16. The process according to claim 15, wherein the voltage is a varying voltage, and wherein the resulting transition metal coating is a transition metal black coating.

17. The process according to claim 15, wherein the transition ion is a an anion, a cation, an anion complex or a cation complex of a transition metal selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof.

18. A supported hydrogen generation catalyst obtained by the process according to claim 15.

20. The supported catalyst according to claim 19, wherein

the substrate comprises a material selected from the group consisting of ceramics, plastics, polymers, glass, fibers, ropes, nonwovens, wovens, textiles, fabrics, carbons, carbon-fibers, ion exchange resins, metals, alloys, wires, meshes, and combinations thereof;

and

the hydrogen generation catalyst comprises a transition metal selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof.

21. The supported catalyst according to claim 19, wherein

the substrate is selected from the group consisting of ceramics, zeolites, pervoskites, phosphates, fibers, fibrous materials, meshes, cationic exchange resins, and anionic exchange resins;

and

the hydrogen generation catalyst comprises a transition metal selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof.

32. The hydrogen generation system according to claim 27, wherein the hydrogen generation catalyst is obtained by the process according to claim 1.

33. The hydrogen generation system according to claim 27, wherein the hydrogen generation catalyst is obtained by the process according to claim 15.

35. The hydrogen generation system according to claim 34, wherein the hydrogen-consuming device is selected from the group consisting of a fuel cell, a combustion engine, a gas turbine, and combinations thereof.

37. The process according to claim 36, wherein

the substrate comprises a material selected from the group consisting of ceramics, plastics, polymers, glass, fibers, ropes, nonwovens, wovens, textiles, fabrics, carbons, carbon-fibers, ion exchange resins, metals, alloys, wires, wires, meshes, and combinations thereof;

the transition metal ion is an anion, a cation, an anion complex or a cation complex of a transition metal selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof;

the reducing agent is selected from the group consisting of metal hydrides, hydrazine, hydrogen gas, glucose, hydroxylamine, carbon monoxide, dithionate, sulfur dioxide, borohydride, alcohols, and mixtures thereof; and

the chemical vapor deposition complexing compound is 2, 4 pentane dione.

38. A supported hydrogen generation catalyst obtained by the process according to claim 36.

15. A process for producing a supported hydrogen generation catalyst, comprising:

(A) placing a conductive substrate in a solution comprising a transition metal ion; and

(B) applying a voltage to the substrate to thereby electrochemically plate a transition metal coating onto the substrate.

19. A supported hydrogen generation catalyst, comprising (i) a substrate;

and (ii) molecules of a hydrogen generation catalyst bound to, entrapped within, and/or coated onto said substrate.

22. A hydrogen generation system, comprising:

(A) a metal hydride solution, comprising a metal hydride and water; and

(B) a hydrogen generation catalyst system, comprising a hydrogen generation catalyst.

23. The hydrogen generation system according to claim 22, wherein the metal hydride is selected from the group consisting of sodium borohydride, lithium borohydride, potassium borohydride, ammonium borohydride, tetramethyl ammonium borohydride, and mixtures thereof.

24. The hydrogen generation system according to claim 22,

wherein the metal hydride solution further comprises a stabilizing agent to provide a pH of greater than or equal to about 7;

and

wherein the catalyst system further comprises a containment system that separates the catalyst from the reacted metal hydride.

25. The hydrogen generation system according to claim 24, wherein the stabilizing agent is selected from the group consisting of hydroxide-containing compounds selected from the group consisting of sodium hydroxide, lithium hydroxide, and potassium hydroxide;

compounds containing a soft metal selected from the group consisting of lead, tin, cadmium, zinc, gallium, and mercury; and

compounds containing a non-metal selected from the group consisting of sulfur; and

mixtures thereof.

26. The hydrogen generation system according to claim 25, wherein the stabilizing agent is selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium sulfide, thiourea, carbon disulfide, sodium zincate, sodium gallate, and mixtures thereof.

27. The hydrogen generation system according to claim 24, wherein the hydrogen generation catalyst, comprises (i) a substrate;

and (ii) molecules of a transition metal bound onto, entrapped within, and/or coated onto the substrate.

28. The hydrogen generation system according to claim 27, wherein

the substrate comprises a material selected from the group consisting of ceramics, plastics, polymers, glass, fibers, ropes, nonwovens, wovens, textiles, fabrics, carbons, carbon-fibers, ion exchange resins, metals, alloys, wires, meshes, and combinations thereof;

and

the hydrogen generation catalyst comprises a transition metal selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof

29. The hydrogen generation system according to claim 28, wherein

the substrate is selected from the group consisting of ceramics, zeolites, pervoskites, phosphates, fibers, fibrous materials, meshes, cationic exchange resins, and anionic exchange resins;

and

the hydrogen generation catalyst comprises a transition metal selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof.

30. The hydrogen generation system according to claim 22, wherein the catalyst is selected from the group consisting of ruthenium, iron, cobalt, nickel, copper, manganese, rhodium, rhenium, platinum, palladium, chromium, silver, osmium, iridium, borides thereof, alloys thereof, and mixtures thereof.

31. The hydrogen generation system according to claim 22, wherein the hydrogen generation catalyst system, comprises a flexible tubing and a hydrogen generation catalyst in the flexible tubing.

34. The hydrogen generation system according to claim 22, wherein the stabilized metal hydride solution further comprises water obtained from the reaction product of a hydrogen-consuming device.

39. The hydrogen generation system according to claim 27, wherein the hydrogen generation catalyst is obtained by the process according to claim 36.

36. A process for producing a supported hydrogen generation catalyst, comprising:

(A) evaporating a transition metal complex comprising a transition metal ion and a chemical vapor deposition complexing compound;

(B) recondensing the transition metal complex onto a substrate; and

(C) applying a reducing agent to the transition metal complex that is deposited on the substrate.