Hydrogen generation by hydrolysis of hydrides for undersea vehicle fuel cell energy systems

• US 5,372,617 A
• Filed: 05/28/1993
• Issued: 12/13/1994
• Est. Priority Date: 05/28/1993
• Status: Expired due to Fees

• Current Assignee: Charles Stark Draper Laboratory Incorporated
• Original Assignee: Charles Stark Draper Laboratory Incorporated
• Inventors: Kerrebrock, Peter A., Wayne, A. Steven
• Primary Examiner(s): Warden, Robert J.
• Assistant Examiner(s): Carpenter, Robert
• Application Number:
  US08/069,097
• Time in Patent Office: 564 Days
• Field of Search: 48/197 R, 48/204, 48/61, 48/101, 48/189.2, 48/189.5, 48/85.2, 422/144, 422/146, 422/140, 422/200, 422/225, 422/229, 422/305, 423/286, 423/646, 423/657, 423/658.2, 366/288, 366/169, 366/325, 366/310, 123/3
• US Class Current: 48/61
• CPC Class Codes: C01B 13/0211 Peroxy compounds
• CPC Class Codes: C01B 3/065 from a hydride
• CPC Class Codes: C01B 3/10 by reaction of water vapour with metals
• CPC Class Codes: C01D 15/02 Oxides; Hydroxides
• CPC Class Codes: H01M 8/065 by dissolution of metals or alloys; by dehydriding metallic substances
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A hydrogen generator for hydrolyzing hydrides substantially at stoichiometry to provide hydrogen on demand to a fuel cell is disclosed. The generator comprises a sealable, pressurizable, thermally insulated vessel into which a hydride in granular form is loaded. Water, most of which may be a byproduct from the fuel cell, is controllably introduced into the vessel for reaction with the hydride to generate hydrogen. The rate of introduction of the water is determined by the demand for hydrogen at the fuel cell. Heat transfer apparatus is disposed about the vessel to control the temperature of the reaction. A stirring mechanism is disposed in the vessel to prevent clumping of the hydride, to distribute the water to unreacted hydride, and to disperse the heat of the reaction throughout the hydride mass and thence to the heat transfer apparatus. An outlet from the vessel is provided for transfer of the generated hydrogen to the fuel cell. The system is particularly suitable for use in closed systems such as undersea vehicles.

Claims

1. A hydrogen generator for generation of hydrogen gas by a substantially stoichiometric hydrolysis reaction between water and a hydride, said generator comprising:

a vessel having a chamber therein for containing a hydride, said vessel having a sealable closure on at least one end;

heat transfer apparatus disposed about a surface of said vessel for controlling the temperature of a hydrolysis reaction within said chamber;

a stirring apparatus disposed within said vessel for stirring the hydride within said chamber;

water input ports, in communication with a water source, said water input ports disposed at spaced intervals within said chamber for introducing water into said chamber for reaction with the hydride, whereby the hydride reacts with the water in a vicinity of the water ports to generate hydrogen gas; and

an output port for removing hydrogen gas from the vessel.

2. The hydrogen generator of claim 1 wherein said heat transfer apparatus comprises at least one coil disposed about the vessel.

3. The hydrogen generator of claim 2 further comprising a heat transfer fluid in said at least one coil.

4. The hydrogen generator of claim 3, wherein the heat transfer fluid comprises sea water.

5. The hydrogen generator of claim 1, further comprising thermal insulation enclosing and surrounding said vessel.

6. The hydrogen generator of claim 1 wherein said water ports comprise apertures in said stirring apparatus.

7. The hydrogen generator of claim 1 wherein said water ports comprise injection nozzles.

8. The hydrogen generator of claim 7 wherein said injection nozzles are located in said stirring apparatus.

9. The hydrogen generator of claim 1 wherein said water ports comprise capillary tubes.

10. The hydrogen generator of claim 9 wherein said capillary tubes are located within said stirring apparatus.

11. The hydrogen generator of claim 1 wherein said stirring apparatus comprises a helical ribbon blender.

12. The hydrogen generator of claim 1 wherein said stirring apparatus comprises a paddle blender.

13. The hydrogen generator of claim 1 wherein said stirring apparatus comprises a central shaft mounted for rotation about a central axis of said vessel and paddles extending at spaced locations from said central shaft.

14. The hydrogen generator of claim 12, wherein said stirring apparatus has a diameter corresponding to the diameter of the vessel.

15. The hydrogen generator of claim 1, wherein said stirring apparatus comprises a central shaft mounted for rotation about a central axis of said vessel and an orbital shaft mounted for orbital rotation about and offset a distance from the central axis.

16. The hydrogen generator of claim 15, wherein said stirring apparatus further comprises a helical ribbon blender mounted for rotation about said orbital shaft.

17. The hydrogen generator of claim 16, wherein said stirring apparatus further comprises paddles extending at spaced locations from said central shaft.

18. The hydrogen generator of claim 1 wherein said stirring apparatus is mounted within said vessel to run sufficiently close to a wall of said vessel to scrape accumulated reaction product off of said stirring apparatus by contact with the wall of said vessel.

19. The hydrogen generator of claim 1 further comprising a motor mounted to drive said stirring apparatus.

20. The hydrogen generator of claim 1, further comprising a controller in communication with a water source for introducing water at a controlled rate to said water ports.

21. The hydrogen generator of claim 20, wherein said controller is in further communication with said heat transfer apparatus for conducting heat at a controlled rate via said heat transfer apparatus to maintain the temperature within said chamber within a predetermined range.

22. The hydrogen generator of claim 21, further comprising a temperature gage within said vessel, said temperature gage in communication with said controller for monitoring the temperature within said chamber.

23. The hydrogen generator of claim 20, wherein said controller is further in communication with said stirring apparatus for controlling the stirring apparatus.

24. The hydrogen generator of claim 1, wherein said vessel comprises a cylindrical enclosure having dome-shaped ends.

25. The hydrogen generator of claim 1, further comprising at least one hydride substantially filling said vessel, whereby the rate of reaction is controlled by the rate of introduction of the water into the vessel.

26. The hydrogen generator of claim 25, wherein said at least one hydride comprises at least one of lithium borohydride, calcium hydride, or lithium hydride.

27. The hydrogen generator of claim 25, wherein said at least one hydride comprises a blend of calcium hydride and lithium borohydride.

28. The hydrogen generator of claim 27, wherein said calcium hydride comprises at least 8 percent by weight of said blend.

29. The hydrogen generator of claim 1, wherein:

said chamber further comprises a storage chamber and a reaction chamber;

said stirring apparatus comprises a feed apparatus for transferring the hydride from said storage chamber to said reaction chamber; and

said water ports are disposed in said reaction chamber.

30. The hydrogen generator of claim 29, wherein said stirring apparatus further comprises a stirrer in said reaction chamber.

31. The hydrogen generator of claim 30, wherein said water ports are disposed in said stirrer in said reaction chamber.

32. The hydrogen generator of claim 1, further comprising a sealed joint for maintaining said closure in sealing engagement on said vessel.

68. The hydrogen generator of claim 2 further comprising a pump for pumping a heat transfer fluid through said at least one coil.

33. A hydrogen generator for generation of hydrogen gas by a substantially stoichiometric hydrolysis reaction between water and hydride for use with a fuel cell, said generator comprising:

a vessel having a chamber therein, said vessel having a sealable closure on at least one end;

a hydride in a granular form disposed within said chamber;

heat transfer apparatus disposed about a surface of said vessel for controlling the temperature of a hydrolysis reaction within said chamber;

a stirring apparatus disposed within said vessel for stirring said hydride within said chamber;

water input ports disposed at spaced intervals within said chamber for introducing water into said chamber for reaction with said hydride, whereby said hydride reacts with the water in a vicinity of the water ports to generate hydrogen gas;

a water source in fluid communication with said water ports for supplying water to said water ports;

an output port for removing hydrogen gas from said vessel; and

a controller in communication with said heat transfer apparatus, said stirring apparatus, and said water source for introducing water at a controlled rate into said chamber for reaction with said hydride within a predetermined temperature range, whereby the rate of the hydrolysis reaction is controlled by the rate of introduction of the water into said chamber.

34. The hydrogen generator of claim 33, wherein said water ports are disposed in said stirring apparatus.

35. The hydrogen generator of claim 33, wherein said hydride comprises at least one of lithium borohydride, calcium hydride, or lithium hydride.

36. The hydrogen generator of claim 33, wherein said hydride comprises a blend of calcium hydride and lithium borohydride.

37. The hydrogen generator of claim 36, wherein, said blend comprises at least 8 percent by weight calcium hydride.

38. The hydrogen generator of claim 33, wherein said hydride has a particle size smaller than a 40 mesh sieve.

39. The hydrogen generator of claim 33, wherein said hydride substantially fills said chamber.

40. The hydrogen generator of claim 33, wherein said controller is in communication with said heat transfer apparatus to maintain the temperature within said vessel above the dehydration temperature of said hydride within said chamber.

41. The hydrogen generator of claim 33, wherein said controller is in communication with said heat transfer apparatus to maintain the temperature within said vessel below the melt temperature of said hydride within said chamber.

42. The hydrogen generator of claim 33, wherein said controller is in communication with said water source to introduce no more than a stoichiometric amount of water into said chamber for reaction with said hydride.

43. The hydrogen generator of claim 33, wherein said controller is in communication with said water source to introduce water into said chamber at a rate in response to a demand for hydrogen gas.

44. The hydrogen generator of claim 33, wherein said controller is in communication with said water source to introduce water into said chamber to maintain pressure within said chamber within a range of 150 to 250 psig.

45. An energy system for an undersea vehicle comprising:

a fuel cell for generating electrical power and water from hydrogen gas and oxygen gas;

a connection from a source of oxygen gas to the fuel cell;

a hydrogen generator operatively coupled to said fuel cell for generation of hydrogen gas by a substantially stoichiometric hydrolysis reaction between water and a hydride, said generator comprising;

a vessel having a chamber therein, said vessel having a sealable closure on at least one end;

a hydride in a granular form disposed within said chamber;

a stirring apparatus disposed within said vessel for stirring said hydride within said chamber;

water input ports disposed at spaced intervals within said chamber for introducing water into said chamber for reaction with said hydride in a vicinity of said water ports;

an output port in communication with said fuel cell for removing hydrogen gas from said vessel and directing said hydrogen gas to said fuel cell along a hydrogen gas flow path; and

a controller in communication with said fuel cell and said hydrogen generator for controllably introducing the water into said chamber through said water ports for reaction substantially at stoichiometry with said hydride.

46. The energy system of claim 45, wherein said hydrogen generator further comprises heat transfer apparatus disposed about a surface of said vessel for controlling the temperature of the hydrolysis reaction within said chamber.

47. The energy system of claim 46, further comprising a temperature gage in said vessel in communication with said controller for monitoring the temperature within said chamber, and wherein said controller is further operative to maintain the temperature above the dehydration temperature of said hydride.

48. The energy system of claim 47, wherein said controller is further operative to maintain the temperature below the melt temperature of said hydride.

49. The energy system of claim 45, wherein said controller is in communication with said fuel cell for determining demand for hydrogen gas at said fuel cell, and said controller is further operative to control the introduction of the water into said vessel through said water ports to control the rate of the hydrolysis reaction within said vessel to produce hydrogen gas to satisfy the demand at said fuel cell.

50. The energy system of claim 45, further comprising a water reservoir in fluid communication with said water ports for supplying water to said water ports.

51. The energy system of claim 45, further comprising a fluid path from said fuel cell to said water ports of said hydrogen generator, whereby the water produced by said fuel cell is introduced into said hydrogen generator for reaction with said hydride.

52. The energy system of claim 51, further comprising a heater disposed along said fluid path to heat the water to produce steam for introduction into said hydrogen generator.

53. The energy system of claim 45, wherein said heat transfer apparatus comprises at least one coil disposed about the vessel.

54. The energy system of claim 53, further comprising a heat transfer fluid in said at least one coil.

55. The energy system of claim 54, wherein the heat transfer fluid comprises sea water.

56. The energy system of claim 45, wherein said hydride comprises at least one of lithium borohydride, calcium hydride, or lithium hydride.

57. The energy system of claim 45, wherein said hydride comprises a blend of calcium hydride and lithium borohydride.

58. The energy system of claim 57, wherein said blend comprises at least 8 percent by weight calcium hydride.

59. The energy system of claim 45, wherein said hydride has a particle size smaller than a 40 mesh sieve.

60. The energy system of claim 45, further comprising thermal insulation enclosing and surrounding said vessel.

61. The energy system of claim 45, wherein said water ports are disposed in said stirring apparatus.

62. The energy system of claim 45, further comprising a pressure relief valve disposed in communication with said chamber.

63. The energy system of claim 45, further comprising a filter for removing particulates along the hydrogen flow path between said hydrogen generator and said fuel cell.

64. The energy system of claim 45, further comprising an ion scrubber along the hydrogen flow path between said hydrogen generator and said fuel cell.

65. The energy system of claim 45, further comprising a heat exchanger along the hydrogen flow path between said hydrogen generator and said fuel cell.

66. The energy system of claim 45, further comprising a pressure gage operatively connected to said vessel to indicate the pressure within said vessel, said pressure gage in communication with said controller for monitoring the pressure within said chamber.

67. The energy system of claim 66, wherein said controller is further operative to maintain the pressure within said chamber between 150 and 250 psig.

69. The energy system of claim 53, further comprising a pump for pumping a heat transfer fluid through said at least one coil.