Integrated oxygen generation and carbon dioxide absorption method apparatus and systems

• US 7,427,449 B2
• Filed: 10/22/2002
• Issued: 09/23/2008
• Est. Priority Date: 10/23/2001
• Status: Expired due to Fees

• Current Assignee: AC Capital Management, Inc.
• Original Assignee: General Dynamics Information Technology Incorporated (General Dynamics Corporation)
• Inventors: Elledge, Thomas H. Jr., Delaney, Michael E.
• Primary Examiner(s): Langel; Wayne A.
• Application Number:
  US10/493,481
• Publication Number:
  US 20050031522A1
• Time in Patent Office: 2,163 Days
• Field of Search: 423/419.1, 423/430, 423/579, 422/122, 422/211, 422/240, 422/241
• US Class Current: 429/500
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: C01B 13/0211 Peroxy compounds
• CPC Class Codes: C01B 13/0214 Hydrogen peroxide
• CPC Class Codes: C01B 2203/04 containing a purification step for the hydrogen or the synthesis gas
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: H01M 8/04089 of gaseous reactants
• CPC Class Codes: H01M 8/0612 from carbon-containing material
• CPC Class Codes: H01M 8/0662 Treatment of gaseous reactants or gaseous residues, e.g. cleaning
• CPC Class Codes: H01M 8/0668 Removal of carbon monoxide or carbon dioxide
• CPC Class Codes: H01M 8/0687 Reactant purification by the use of membranes or filters
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2
• CPC Class Codes: Y02P 30/00 Technologies relating to oil refining and petrochemical industry

Abstract

A method for producing oxygen and absorbing carbon dioxide in a single operation using a solution that contains an oxygen source and a redox partner that can react to form oxygen and a chemical species that can form an insoluble carbonate to precipitate and chemically store carbon dioxide. Carbon dioxide is introduced into the solution and the carbonate precipitates as the oxygen is generated. In particular, the invention uses an aqueous solution of permanganate and hydrogen peroxide that react in the presence of a catalyst to produce oxygen and manganese (II) ions. Carbon dioxide gas introduced into the solution reacts with the manganese (II) ions to precipitate manganese carbonate. Other cations capable of reacting with carbon dioxide to form an insoluble carbonate, for example calcium, barium and magnesium, may also be added to the solution to precipitate carbonate salts. Calcium permanganate may used as a source of both calcium and permanganate.

Claims

1. A method for producing oxygen and absorbing carbon dioxide in a single operation comprising

providing a solution comprising a chemical species capable of reacting with carbon dioxide to form an insoluble precipitate and an oxygen source and a redox partner, said oxygen source and said redox partner reactable to form oxygen;

introducing carbon dioxide into said solution;

contacting said carbon dioxide with said chemical species capable of reacting with carbon dioxide; and

precipitating said insoluble precipitate from said solution.

2. The method of claim 1, wherein said oxygen source and said redox partner comprise hydrogen peroxide and a permanganate salt and said chemical species capable of reacting with carbon dioxide comprises manganese (II) ion.

3. A method for producing oxygen and absorbing carbon dioxide in a single operation comprising:

providing a solution comprising a permanganate salt, water and hydrogen peroxide;

allowing said permanganate salt, water and hydrogen peroxide to react to produce manganese (II) ion and oxygen in the presence of a catalyst;

introducing carbon dioxide gas into said solution;

contacting said carbon dioxide with said manganese (II) ion; and

allowing manganese carbonate to precipitate.

4. The method of claim 3, said solution further comprising a cation capable of reacting with carbon dioxide to form an insoluble carbonate.

5. The method of claim 4, said cation selected from the group consisting of calcium, barium, magnesium, silver, strontium, cobalt, nickel, cadmium, copper, iron and lead.

6. The method of claim 3, said permanganate salt comprising calcium permanganate and further comprising contacting said carbon dioxide with calcium ion in solution and allowing calcium carbonate to precipitate.

7. The method of claim 3, further comprising providing a diffusor or atomiser for introducing said carbon dioxide.

8. The method of claim 3, further comprising removing said oxygen from said solution.

9. The method of claim 3, said catalyst selected from the group consisting of iron, copper, platinum, nickel and combinations thereof.

10. The method of claim 3, wherein said catalyst is in or on a solid or perforated plate in said solution.

11. The method of claim 3, said carbon dioxide introduced as an admixture with hydrogen gas.

12. The method of claim 11, further comprising

providing a tank separated into a first chamber and a second chamber, said first chamber fluidly coupled to said second chamber, said second chamber further comprising a hydrogen gas outlet, said tank containing said solution, and said oxygen produced in said first chamber;

and

the method further comprising introducing said carbon dioxide into second chamber; and

removing said hydrogen through said hydrogen gas outlet.

13. The method of claim 11, wherein the source of at least a portion of said admixture is the reformation of hydrocarbon fuel.

14. The method of claim 11, wherein said hydrogen gas does not undergo a chemical reaction in said solution.

15. The method of claim 3, further comprising removing unreacted carbon dioxide gas from said solution.

16. The method of claim 15, further comprising storing said unreacted carbon dioxide as a gas.

17. The method of claim 16, further comprising chemically storing said unreacted carbon dioxide as an insoluble carbonate salt.

18. The method of claim 3, further comprising providing sulfur to said solution, contacting said sulfur with said manganese (II) ion and allowing a sulfur containing manganese compound to precipitate.

19. The method of claim 3, said solution further comprising cations capable of forming insoluble sulfur salts and the method further comprising contacting said cations with sulfur and allowing said insoluble sulfur salts to precipitate.

20. The method of claim 19, wherein said sulfur is in a form the group consisting of selected from sulfide, sulfate and sulfite.

21. An apparatus for producing oxygen and absorbing carbon dioxide comprising:

a tank containing an aqueous solution comprising a chemical species capable of reacting with carbon dioxide to form an insoluble precipitate, an oxygen source and a redox partner, said oxygen source and said redox partner reactable to form oxygen, and said tank comprising a material that does not catalyze the reaction of said oxygen source and said redox partner;

a catalyst for catalyzing the reaction of said oxygen source and said redox partner positioned in said tank to contact the aqueous solution;

a carbon dioxide inlet in said tank positioned to introduce carbon dioxide into the solution; and

an oxygen outlet in said tank positioned to allow oxygen gas to escape.

22. The apparatus of claim 21, said carbon dioxide inlet comprising a diffuser.

23. The apparatus of claim 21, said catalyst selected from the group consisting of iron, copper, nickel and platinum.

24. The apparatus of claim 21, said material selected from the group consisting of polytetrafluoroethylene and carbon fiber.

25. The apparatus of claim 21 wherein said oxygen source and said redox partner comprise hydrogen peroxide and a permanganate salt and said chemical species capable of reacting with carbon dioxide comprises manganese (II) ion.

26. An apparatus for producing oxygen and absorbing carbon dioxide comprising:

a tank for receiving an aqueous solution, comprising a material that does not catalyze the reaction of permanganate ion with hydrogen peroxide;

a catalyst for reacting a permanganate salt with hydrogen peroxide to produce oxygen positioned in said tank to contact the aqueous solution when added to said tank;

a carbon dioxide inlet in said tank positioned to introduce carbon dioxide into the solution when added to said tank;

an oxygen outlet in said tank positioned to allow oxygen gas to escape; and

at least one plate separating said tank into at least a first and a second fluidly coupled chamber, said first chamber comprising said carbon dioxide inlet and a hydrogen gas outlet and said second chamber comprising said oxygen outlet.

27. The apparatus of claim 26, said carbon dioxide inlet comprising a diffuser.

28. The apparatus of claim 26, said catalyst selected from the group consisting of iron, copper, nickel and platinum.

29. The apparatus of claim 26, said oxygen outlet comprising a membrane selectively permeable to oxygen.

30. The apparatus of claim 26, said hydrogen gas outlet comprising a membrane selectively permeable to hydrogen.

31. The apparatus of claim 26, said material selected from the group consisting of polytetrafluoroethylene and carbon fiber.

32. A system for generating power comprising:

a power generator for generating power or electricity, and

an integrated oxygen generator/carbon dioxide absorber, said integrated oxygen generator/carbon dioxide absorber providing oxygen to said power generator and absorbing waste carbon dioxide from said power generator;

said integrated oxygen generator/carbon dioxide absorber comprising;

a tank comprising a material that does not catalyze the reaction of permanganate ion with hydrogen peroxide,

an aqueous solution comprising a permanganate salt and hydrogen peroxide contained in said tank,

a catalyst in contact with said aqueous solution for catalyzing the reaction of said permanganate salt with said hydrogen peroxide to produce oxygen,

a carbon dioxide inlet in said tank positioned to introduce carbon dioxide into said aqueous solution and

an oxygen outlet in said tank positioned to allow oxygen gas to escape from said tank.

33. The system of claim 32, said power generator comprising an apparatus selected from the group consisting of a turbine, a fuel cell, an internal combustion engine and a heat powered engine.

34. The system of claim 33, said heat powered engine comprising a Brayton cycle engine or Sterling engine.

35. The system of claim 32, said power generator comprising a fuel cell and a reformer operative to convert a hydrocarbon into hydrogen and carbon dioxide;

said reformer coupled to said CO₂ inlet;

said fuel cell utilizing hydrogen and oxygen as an energy source; and

said oxygen generator/carbon dioxide absorber further comprising a hydrogen outlet and a partition separating said tank into two or more fluidly coupled chambers wherein said carbon dioxide inlet and said hydrogen outlet are in the same chamber and said hydrogen outlet and said oxygen outlet are in different chambers;

said hydrogen outlet comprising a membrane selectively permeable to hydrogen;

said oxygen outlet comprising a membrane selectively permeable to oxygen;

said hydrogen outlet fluidly connected to said fuel cell for allowing hydrogen to flow from said oxygen generator/carbon dioxide absorber to said fuel cell; and

said oxygen outlet fluidly connected to said fuel cell for allowing oxygen to flow from the oxygen generator/carbon dioxide absorber to the fuel cell.

36. The system of claim 35, wherein said reformer is fluidly connected to said carbon dioxide inlet for allowing carbon dioxide and hydrogen to flow from said reformer to said oxygen generator/carbon dioxide absorber.

37. The system of claim 35, said fuel cell comprising a PEM fuel cell,

said oxygen outlet fluidly coupled to the cathode of said PEM fuel cell and

said hydrogen outlet fluidly coupled to the anode of said PEM fuel cell.

38. The system of claim 35, said hydrocarbon selected from the group consisting of diesel fuel, methanol, fuel oil, ethanol and gasoline.

39. The system of claim 32, wherein said power generator comprises a hydrocarbon direct fuel cell comprising a waste outlet, and

said waste outlet fluidly coupled to said carbon dioxide inlet.

40. The system of claim 39, said hydrocarbon selected from the group consisting of methanol, ethanol, diesel fuel and gasoline.

41. The system of claim 32, wherein said power generator comprises a turbine powered by combustion of a hydrocarbon fuel, said turbine comprising an exhaust outlet for exporting waste from combustion of said hydrocarbon fuel,

said exhaust outlet fluidly coupled to said carbon dioxide inlet.

42. The system of claim 32, said power generator comprising a heat powered engine heated by combustion of hydrocarbon fuel and comprising an exhaust outlet for exporting waste from combustion of said hydrocarbon fuel, said exhaust outlet fluidly coupled to said carbon dioxide inlet.

43. The system of claim 42, said heat powered engine selected from the group consisting of a Brayton cycle engine and a Sterling engine.