Low temperature hydrogen generator

Information

  • Patent Grant
  • 7455829
  • Patent Number
    7,455,829
  • Date Filed
    Monday, August 22, 2005
    18 years ago
  • Date Issued
    Tuesday, November 25, 2008
    15 years ago
Abstract
A hydrogen generator having a hydrogen generating reaction between a chemical hydride and vapor from a liquid having a freezing point below 0° C. The liquid is selected from alcohols such as ethanol and methanol used pure or diluted with distilled water, and distilled water that has had a non-reactive salt such as calcium chloride or magnesium chloride dissolved therein.
Description
FIELD OF THE INVENTION

The present invention relates to hydrogen generators. More particularly, the invention relates to hydrogen generators that operate at low ambient temperatures, such as those below the freezing point of water.


BACKGROUND OF THE INVENTION

Hydrogen holds a substantial promise as a plentiful, clean-burning fuel that may even replace gasoline. The advantage of reducing the amount of greenhouse gas will become more important with time. The combustion of hydrogen produces water.


There are a number of systems for the generation of hydrogen for a variety of purposes. Estimates suggest that more than nine million tons of hydrogen is produced annually. Hydrogen is generated by a chemical reaction between a reactive metal fuel such as aluminum, magnesium, or lithium, and alloys or hydrides of these and similar reactants, with an “oxidizer” such as hydrogen peroxide, Freon, sulfur hexafluoride, water, and others. Molten metals are also used as one of the reactants. Hydrogen generating materials have been investigated including LiH, LiAlH4, NH3 Al, Mg, MgH2, and LiBH4. These materials are often reacted with water to generate hydrogen.


In many cases the most economical and efficient hydrogen generators are those that react water vapor from store liquid water with a chemical hydride. The water is stored at ambient temperature and converted to water vapor for the reaction with the chemical hydride. The main problem with these hydrogen generators is that they cannot operate below 0° Celsius with frozen water or ice, without disrupting operation or risking damage to the generator due to expansion as the liquid water changes to a solid.


It would be of advantage in the art if hydrogen generators that use liquid water converted to water vapor and a chemical hydride could operate where the water is stored at temperatures below 0° Celsius.


Yet another advantage would be if such a hydrogen generator would retain the advantages of stored liquid water producing water vapor for reaction with a chemical hydride reaction to generate hydrogen without the concern for colder temperatures.


Other advantages will appear hereinafter.


SUMMARY OF THE INVENTION

It has now been discovered that the above and other advantages of the present invention may be obtained in the following manner. Specifically, the present invention provides a low temperature hydrogen generator that produces hydrogen at temperatures below the freezing point of water.


In its simplest form the present invention comprises a the substitution of another liquid for water in the same hydrogen generator using the same hydride chemical reaction. The substitute liquid is selected from alcohols such as ethanol and methanol used pure or diluted with distilled water, and distilled water that has had a non-reactive salt such as calcium chloride or magnesium chloride dissolved therein. The stored liquid produces a gas vapor in the same manner as when pure distilled water is used.





BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the invention, reference is hereby made to the drawings, in which:


The Figure is a side elevational view in cross section of a hydrogen generator of the type in which the present invention may be used.





DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention improves the operating range of hydrogen generators that use a chemical hydride and water vapor from stored distilled water reaction to produce hydrogen. The distilled water is replaced with a liquid that has a freezing point below 0° C., and preferably below 15° C. and more preferably below 30° C. The liquid is preferably an alcohol or distilled water having a non-hydride reacting salt dissolved therein.


The Figure illustrates a conventional hydrogen generator 10, with water chambers 11, a diaphragm 13, valve disc 15, powder chamber 17 and fuel cell assembly 19. In use, the water chamber 11 is exposed to ambient conditions and when the temperature drops below 0° C., the water will freeze, and thus it won't flow into the fuel cell assembly 19 for conversion into water vapor. The hydrogen generator also includes a membrane 21, made from Gore-Tex or another material that is impermeable to water but permeable to water vapor. Membrane 21 separates the water chamber 11 and the valve 15. Water is vaporized at the interface of membrane 21 and the dry hydrogen inside the valve 15.


Examples of chemical hydrides are LiH, LiAlH4, NH3 MgH2, and LiBH4, but other hydrides used in conventional hydrogen generators are also intended for use in the present invention. The term “chemical hydride” is broadly intended to be any hydride capable of reacting with a liquid to produce hydrogen.


The alcohol may be methanol or ethanol or either of these alcohols diluted with some amount of distilled water. Pure methanol has a freezing point of −98° C. and pure ethanol has a freezing point of −114° C. Adding a quantity of distilled water, which freezes at 0° C., will raise the freezing point to any temperature between 0° C. and that of the pure alcohol.


The salt used to lower the freezing point of distilled water may be any salt that does not react with chemical hydrides. Examples are calcium chloride and magnesium chloride, although any salt that lowers the freezing point of distilled water and does not react with a chemical hydride is intended for use in the present invention. Calcium chloride reduces the freezing point of distilled water to −30° C. Magnesium chloride reduces the freezing point of distilled water to −15° C. It is preferred that the liquid used in the present invention have a freezing point at least at −15° C. and more preferably at least at −30° C.


One advantage of using a salt in distilled water is that while it will not react to produce hydrogen, it will remain in solution and maintain the lowered freezing point of the liquid. The use of an alcohol as the liquid to react with the chemical hydride will, as the alcohol is used up in the reaction, cause the freezing point to rise. However, since pure methanol, for example, has a freezing point so far below 0° C., namely −98° C., this is not a concern unless a lot of distilled water is also included in the reactant liquid.


While particular embodiments of the present invention have been illustrated and described, it is not intended to limit the invention, except as defined by the following claims.

Claims
  • 1. In a hydrogen generator system having a hydrogen generating reaction between water vapor from stored distilled water and a chemical hydride, the improvement comprising: said distilled water comprising a temperature lowering salt dissolved therein to provide a liquid having a freezing point less than 0° C. to produce a vapor for said reaction;whereby the hydrogen generating reaction continues to function at ambient temperatures below 0° C.
  • 2. The system of claim 1, wherein said temperature lowering salt comprises calcium chloride or magnesium chloride.
  • 3. The system of claim 1, wherein said liquid has a freezing point below −15° C.
  • 4. The system of claim 1, wherein said liquid has a freezing point below −30° C.
  • 5. A method of generating hydrogen comprising the steps of: charging a hydrogen generator with a chemical hydride;charging said generator with a liquid having a freezing point below 0° C., the liquid comprising water and a temperature lowering salt dissolved in the water; andreacting said chemical hydride and a vapor formed from said liquid to produce hydrogen when said liquid is stored at ambient temperatures lower than 9° C.
  • 6. The method of claim 5, wherein said temperature lowering salt comprises calcium chloride or magnesium chloride.
  • 7. The method of claim 5, wherein said liquid has a freezing point below −15° C.
  • 8. The method of claim 5, wherein said liquid has a freezing point below −30° C.
  • 9. A hydrogen generator system comprising: a reaction chamber;a chemical hydride reaction agent;a liquid having a freezing point less than 0° C. and capable of reacting with said chemical hydride when converted to vapor to produce hydrogen, the liquid comprising water and a temperature lowering salt dissolved in the water;whereby the hydrogen generating reaction continues to function when said liquid is stored at ambient temperatures below 0° C.
  • 10. The system of claim 9, wherein said temperature lowering salt comprises calcium chloride or magnesium chloride.
  • 11. The system of claim 9, wherein said liquid has a freezing point below −15° C.
  • 12. The system of claim 9, wherein said liquid has a freezing point below −30° C.
Parent Case Info

This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/698457, filed Jul. 12, 2005.

US Referenced Citations (95)
Number Name Date Kind
2935382 Osborn et al. May 1960 A
3133837 Eidensohn May 1964 A
3931395 Beckert et al. Jan 1976 A
4048385 Regnaut Sep 1977 A
4476196 Poeppel et al. Oct 1984 A
4476197 Herceg Oct 1984 A
4596748 Katz et al. Jun 1986 A
4659559 Struthers Apr 1987 A
4826741 Aldhart et al. May 1989 A
4857420 Maricle et al. Aug 1989 A
4876163 Reichner Oct 1989 A
4910100 Nakanishi et al. Mar 1990 A
5248125 Fritch et al. Sep 1993 A
5298341 Khandkar et al. Mar 1994 A
5372617 Kerrebrock et al. Dec 1994 A
5449697 Noaki et al. Sep 1995 A
5789100 Burroughs et al. Aug 1998 A
5804329 Amendola Sep 1998 A
5836750 Cabuz Nov 1998 A
5849046 Bailey Dec 1998 A
5851689 Chen Dec 1998 A
5861221 Ledjeff et al. Jan 1999 A
5948558 Amendola Sep 1999 A
5974235 Nunally et al. Oct 1999 A
6052124 Stein et al. Apr 2000 A
6054234 Weiss et al. Apr 2000 A
6093501 Werth Jul 2000 A
6250078 Amendola et al. Jun 2001 B1
6280869 Chen Aug 2001 B1
6307605 Bailey Oct 2001 B1
6326097 Hockaday Dec 2001 B1
6428680 Kriechauf Aug 2002 B1
6433129 Amendola et al. Aug 2002 B1
6434278 Hashimoto Aug 2002 B1
6468694 Amendola Oct 2002 B1
6483275 Nebrigic et al. Nov 2002 B1
6497973 Amendola Dec 2002 B1
6506510 Sioui et al. Jan 2003 B1
6524542 Amendola et al. Feb 2003 B2
6534033 Amendola et al. Mar 2003 B1
6541149 Maynard et al. Apr 2003 B1
6544679 Petillo et al. Apr 2003 B1
6586563 Ortega et al. Jul 2003 B1
6620542 Pan Sep 2003 B2
6670444 Amendola et al. Dec 2003 B2
6683025 Amendola et al. Jan 2004 B2
6706909 Snover et al. Mar 2004 B1
6728422 Weiss Apr 2004 B1
6760488 Moura et al. Jul 2004 B1
6932847 Amendola et al. Aug 2005 B2
6939529 Strizki et al. Sep 2005 B2
6950030 Kovarik et al. Sep 2005 B2
6977123 Burroughs et al. Dec 2005 B1
7001681 Wood Feb 2006 B2
7019105 Amendola et al. Mar 2006 B2
7073368 Wood et al. Jul 2006 B2
7083657 Mohring et al. Aug 2006 B2
7105033 Strizki et al. Sep 2006 B2
7108777 Xu et al. Sep 2006 B2
20010012494 Kreichauf Aug 2001 A1
20010028973 Ong et al. Oct 2001 A1
20020068213 Kaiser et al. Jun 2002 A1
20020177031 Doshi et al. Nov 2002 A1
20030009942 Amendola et al. Jan 2003 A1
20030044656 Wood Mar 2003 A1
20030054215 Doshi et al. Mar 2003 A1
20030091877 Chen et al. May 2003 A1
20030157018 Zaluski et al. Aug 2003 A1
20040009379 Amendola et al. Jan 2004 A1
20040009392 Petillo et al. Jan 2004 A1
20040011662 Xu et al. Jan 2004 A1
20040033194 Amendola et al. Feb 2004 A1
20040035054 Mohring et al. Feb 2004 A1
20040047801 Petillo et al. Mar 2004 A1
20040081615 Brinkley, III Apr 2004 A1
20040120889 Shah et al. Jun 2004 A1
20040148857 Strizki et al. Aug 2004 A1
20040161646 Rezachek et al. Aug 2004 A1
20040191152 Amendola et al. Sep 2004 A1
20050132640 Kelly et al. Jun 2005 A1
20050135996 Ortega et al. Jun 2005 A1
20050142410 Higashi et al. Jun 2005 A1
20050181245 Bonne et al. Aug 2005 A1
20050238573 Zhang et al. Oct 2005 A1
20050260461 Wood et al. Nov 2005 A1
20050262924 Wood et al. Dec 2005 A1
20050268555 Amendola et al. Dec 2005 A1
20050276746 Zhang et al. Dec 2005 A1
20060014059 Wood Jan 2006 A1
20060021279 Mohring et al. Feb 2006 A1
20060040152 Wood Feb 2006 A1
20060102489 Kelly May 2006 A1
20060102491 Kelly et al. May 2006 A1
20060144701 Kelly Jul 2006 A1
20070217994 Amendola et al. Sep 2007 A1
Foreign Referenced Citations (14)
Number Date Country
19734259 Feb 1999 DE
1351329 Oct 2003 EP
1496561 Jan 2005 EP
723180 Feb 1955 GB
57138782 Aug 1982 JP
60000066 Jan 1985 JP
4342439 Nov 1992 JP
9326259 Dec 1997 JP
0035032 Jun 2000 WO
0045457 Aug 2000 WO
0185606 Nov 2001 WO
03084866 Oct 2003 WO
2004025750 Mar 2004 WO
2004075375 Sep 2004 WO
Related Publications (1)
Number Date Country
20070041897 A1 Feb 2007 US
Provisional Applications (1)
Number Date Country
60698457 Jul 2005 US