Thermochemical hydrogen produced from a vanadium decomposition cycle

• US 20050013771A1
• Filed: 06/14/2004
• Published: 01/20/2005
• Est. Priority Date: 06/11/2003
• Status: Active Grant

• Current Assignee: Steven Amendola
• Original Assignee: Steven Amendola
• Inventors: Amendola, Steven
• Granted Patent: US 7,799,315 B2
• Time in Patent Office: Days
• US Class Current: 423/658.200
• CPC Class Codes: B01J 19/127 Sunlight; Visible light
• CPC Class Codes: B01J 19/1818 in series
• CPC Class Codes: B01J 19/20 in the form of helices, e.g. screw reactors
• CPC Class Codes: B01J 2208/00212 Plates; Jackets; Cylinders
• CPC Class Codes: B01J 2219/00006 Large-scale industrial plants
• CPC Class Codes: B01J 2219/00029 Batch processes
• CPC Class Codes: B01J 2219/00033 Continuous processes
• CPC Class Codes: B01J 2219/0004 Processes in series
• CPC Class Codes: B01J 2219/187 inclined at an angle to the horizontal or to the vertical plane
• CPC Class Codes: B01J 7/02 by wet methods
• CPC Class Codes: B01J 8/0442 the beds being placed in separate reactors
• CPC Class Codes: B01J 8/0457 the beds being placed in separate reactors
• CPC Class Codes: B01J 8/0496 Heating or cooling the reactor
• CPC Class Codes: B01J 8/10 moved by stirrers or by rotary drums or rotary receptacles or endless belts
• CPC Class Codes: C01B 13/0207 Water
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• CPC Class Codes: C01B 2203/0465 Composition of the impurity
• CPC Class Codes: C01B 2203/0485 the impurity being a sulfur compound
• CPC Class Codes: C01B 3/06 by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by electrolysis of water C25B1/04
• CPC Class Codes: C01B 3/52 by contacting with liquids; Regeneration of used liquids C01B3/508 takes precedence
• CPC Class Codes: C01B 7/01 : Chlorine; Hydrogen chloride
• CPC Class Codes: C01B 7/03 : Preparation from chlorides
• CPC Class Codes: C01B 7/04 : Preparation of chlorine from hydrogen chloride
• CPC Class Codes: Y02E 20/18 : Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight

Abstract

A thermochemical water-splitting process all reactions of which operate at relatively low temperatures and high efficiencies, and in which relatively inexpensive materials and processing methods are made possible. This invention involves the decomposition of a metal halide compound, i.e., one which is capable of being reduced from a higher oxidation state to lower oxidation state, e.g. vanadium chloride III→vanadium dichloride. The process is cyclic and regenerative, and the only net inputs are water and heat; and the only net outputs are hydrogen and oxygen. The process makes it possible to utilize a wide variety of available heat, including solar, sources for the energy input.

Claims

1. A process for producing hydrogen comprising reacting a suitable metal halide compound MX using heat so as to reduce compound MX from an initial valence state to a lower valence state;

wherein a gas is formed, which thereafter is reacted with water in the presence of an acid-absorbing material to form oxygen and an acidic compound formed by an acid and the acid absorbing material;

separating the oxygen;

separating the acid from the acid-absorbing material; and

reacting the acid and the reduced metal halide to produce hydrogen and the compound MX.

2. A process according to claim 1 wherein the process is a dry process.

3. The process according to claim 1 wherein at least one of the reactions is a wet reaction.

4. The process according to claim 1 wherein M is selected from the group consisting of vanadium, chromium, niobium, titanium, molybdenum, manganese and iron.

5. The process according to claim 1 wherein M is vanadium.

6. The process according to claim 1 wherein X is selected from the group consisting of chlorine, bromine and iodine.

7. The process according to claim 1 wherein X is chlorine.

8. The process according to claim 1 wherein MX is vanadium trichloride.

9. The process according to claim 1 wherein MX is in the form of a double salt.

10. The process according to claim 9 wherein a first portion of the double salt is selected from the group consisting of sodium, potassium, vanadium, chromium, niobium, titanium, molybdenum, manganese, iron and is different than M;

and wherein a second portion of the double salt is selected from the group consisting of chlorine, bromide and iodine and is the same as X.

11. The process according to claim 1 wherein MX is reacted in the presence of a catalyst.

12. The process according to claim 9 wherein the double salt is reacted in the presence of a catalyst.

13. The process according to claims 11 and 12 wherein the catalyst is selected from the group consisting of PbX, SbX, CrX, MnX, KNiX, NiX, BiX, FeX, CuX wherein X is a chloride, bromide or iodine.

14. The process according to claim 1 operated as a batch process.

15. The process according to claim 1 operated as a continuous process.

16. The process according to claim 1 wherein the heat used in all reactions is at a temperature equal to or lower than the temperature of the heat used in reducing MX to a lower valence state.

17. The process according to claim 16 wherein the heat used in all reactions is about 600°

C. and below.

18. The process according to claim 16 wherein the heat used in reducing MX to a lower valence state is about 400°

C. and below.

19. The process according to claim 9 wherein the heat used in all reactions is at a temperature lower than the temperature of the heat used in reducing the double salt to a lower valence state.

20. The process according to claim 1 wherein the acid-absorbing material is any suitable material that will absorb acidic gases so as to shift the reaction'"'"'s equilibrium to a production of oxygen.

21. The process according to claim 20, wherein the acid-absorbing material is capable of being regenerated by heat.

22. The process according to claim 21 wherein the acid-absorbing material is selected from the group consisting of a polymer having an active amine group, amines, and compounds that form a hydrogen halide salt.

23. The process according to claim 20 wherein the acid-absorbing material is selected from the group consisting of monoethanolamine, diethanolamne, triethonolamine, melamine, zeolites, charcoals, silicas, alumina, magnesia and compounds that have any functionality than can be reversibly absorban acid gas.

24. The process according to claim 1 wherein a catalyst is used in reacting the gas with water and acid-absorbing material.

25. The process according to claim 24 wherein the catalyst is selected from the group consisting of a cobalt catalyst and a copper catalyst.

28. The process according to claim 1, wherein solar power is used as a source of heat for at least one of the reactions.

29. The process according to claim 1, wherein a source of heat for at least one of the reactions is selected from the group consisting of exhaust from a gas turbine, flue gases, waste heat from any chemical reactions where heat is available, foundry cooling processes, burning of off-gases from a refinery, and oil and natural gas well, intentional burning of lower BTU gases which produce a lower flame temperature than pure fuels, and the burning of any fuels for the purpose of generating hydrogen and oxygen.

30. The process according to claim 1, used in an integrated gas combination cycle.

31. The process according to claim 1 used in conjunction with a gas turbine to generate electricity.

32. The process according to claim 1 used in the generation of natural gas from coal.

33. The process according to claim 1 used in the processing of crude oil.

26. A process for producing hydrogen comprising reacting vanadium tricholoride with FeCl₃ as a catalyst using heat having a temperature of about 600°

C. or below to effect the reduction of vanadium trichloride to vanadium dichloride and chlorine gas;

thereafter reacting the chlorine gas with steam and melamine in the presence of a cobalt catalyst using heat having a temperature of about 600°

C. or below to produce a melamine-hydrogen chloride compound and oxygen;

thereafter separating the oxygen from the melamine-hydrogen chloride compound which is thereafter heated to a temperature of about 600°

C. or below to separate hydrogen chloride and the melamine; and

reacting the hydrogen chloride and vanadium dichloride to produce vanadium trichloride.

27. The process according to claim 26 which is continuous.

34. A process for the thermochemical decomposition of a hydrogen halide comprising reacting a starting metal halide using heat to form a halogen gas and the metal halide reduced to a lower valence state;

reacting said reduced metal halide with the halogen halide using heat to form hydrogen and wherein the starting metal halide is capable of being reformed by reacting the reduced metal halide with the hydrogen halide.

35. The process according to claim 34 wherein a metal component of the starting metal halide is selected from the group consisting of vanadium, chromium, niobium, titanium, manganese, iron, lead antimony, nickel, potassium, cobalt, bismuth, and molybdenum.

36. The process according to claim 34 wherein the halide component of the starting metal halide is selected from the group consisting of chlorine, bromine and iodine.

37. The process according to claim 34 wherein the starting metal halide is a double salt.

38. The process according to claim 34 and 37 wherein reaction of the starting metal halide is catalyzed with a suitable catalyst.

39. The process according to claim 34 and 37 wherein the heat used in all reactions is at a temperature of about 600°

C. and below.

40. The process according to claim 34 and 37 wherein the heat used in reacting the starting metal halide is at a temperature of about 400°

C. and below.

41. The process according to claim 34 wherein the metal halide is vanadium halide.

42. A process for the thermochemical decomposition of hydrogen chloride comprising reacting vanadium trichloride using heat and iron trichloride as a catalyst to form chlorine gas and vanadium dichloride;

reacting the vanadium dichloride with hydrogen chloride using heat to form hydrogen and chlorine gas, wherein the vanadium trichloride is reformed by reacting the vanadium dichloride with the hydrogen chloride, and further wherein the heat used in all reactions is at a temperature of about 400°

C. and below.