|Publication number||US3922872 A|
|Publication date||Dec 2, 1975|
|Filing date||Feb 4, 1975|
|Priority date||Feb 4, 1975|
|Publication number||US 3922872 A, US 3922872A, US-A-3922872, US3922872 A, US3922872A|
|Inventors||James J Reilly, Jr Richard H Wiswall|
|Original Assignee||Us Energy|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Referenced by (37), Classifications (27)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Reilly et al.
Dec. 2, 1975 IRON TITANIUM MANGANASE ALLOY HYDROGEN STORAGE Inventors: James J. Reilly, Bellport; Richard H.
Wiswall, ,Ir., Brookhaven, both of N.Y.
Assignee: The United States of America as represented by the United States Energy Research and Development Administration, Washington, DC.
Filed: Feb. 4, 1975 Appl. No.: 547,073
US. Cl. 62/48; 75/134 F; 75/l75.5;
252/471; 423/248 Int. Cl. F17C 11/00 Field of Search 62/48; 75/1755, 134 F;
Primary Examirter-Will1am F. ODea Assistant ExaminerRonald C. Capossela Attorney, Agent, or Firm-Dean E. Carlson; Leonard Belkin  ABSTRACT A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe, Mn, where x is in the range of about 0.02 to 0.5 and the method of storing hydrogen using said alloy.
4 Claims, 2 Drawing Figures lllllll lllllll N I e 3 Lu 10: I D (D m uJ Q: CL
z Q 6 1.0: o I m 2 Q OJ 1 l l l ATOM RATIO, H/M
IRON TITANIUM MANGANASE ALLOY HYDROGEN STORAGE BACKGROUND OF THE INVENTION The invention described herein was made in the course of, or under a contract with the US Atomic Energy Commission.
Hydrogen is a potential fuel for various types of power sources, such as fuel cells, internal combustion 1O engines, gas turbines, etc. It has two great advantages over fossil fuels, it is essentially nonpolluting and it can be produced using several all but inexhaustible energy sources, i.e., solar, nuclear and geothermal. However, a major problem is the difficulty encountered in its storage and bulk transport. Conventional storage methods, i.e., compression and liquefaction, do not appear to be practical in this context.
A possible solution to the problem lies in the use of a metal hydride as a hydrogen storage medium. Several hydrides are of interest but the material most near to practical application is iron titanium hydride, which can be synthesized through the direct union of hydrogen with the intermetallic compound, FeTi.
Our US. Pat. Nos. 3,508,414 and 3,516,263 disclose methods and apparatus for utilizing iron-titanium alloys to store hydrogen by the formation of hydrides.
One difficulty which has been discovered in the use of iron-titanium alloys for hydrogen storage is the effect of the presence of oxygen in the alloys in small amounts. For example, it has been discovered that the presence of oxygen in the amount of 7000 ppm in commercially available iron-titanium reduced substantially the maximum hydrogen that could be stored and the equilibrium dissociation pressure was increased. This had the effect of increasing the costs involved in storing hydrogen by the use of these alloys.
SUMMARY OF THE INVENTION It has been discovered that the addition of manga nese to the intermetallic alloy FeTi in certain specific amounts not only increases the amount of H which can be stored and at a lower pressure but also has the effect of compensating to a significant extent for the presence of oxygen, permitting significant increases in the amounts of hydrogen which can be stored under more convenient and economical pressures.
In accordance with a preferred embodiment of this invention there is provided a three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe Mn where x is in the range of about 0.02 to 0.5.
There is also provided, in accordance with another preferred embodiment of this invention, a method of storing hydrogen comprising contacting gaseous hydrogen with a solid alloy of TiFe Mn, where x is in the range of about 0.02 to 0.5.
It is thus a principal object of this invention to provide an improved alloy for the chemical storage of hydrogen.
Another purpose is to provide an improved method for the storage of hydrogen.
Other objects and advantages of this invention will hereinafter become obvious from the following description of preferred embodiments of this invention.
BRIEF DESCRIPTION OF THE DRAWING FIGS. 1 and 2 show curves illustrating the H storage characteristics of alloys incorporating the principles of this invention and comparing them with similar alloys not incorporating this invention.
DESCRIPTION OF THE BACKGROUND EMBODIMENTS An alloy in accordance with this invention may be prepared by melting granules or small ingots of Fe, Ti, and Mn in an are or induction furnace within an inert atmosphere followed by cooling.
The cooled alloy, in order to be utilized for the storage of hydrogen is comminuted or granulated and then activated by outgassing at high temperature (300 C) and exposing to H for a short time followed by outgassing again and cooling under hydrogen with about 1 atmosphere pressure.
In order to form the hydride the activated alloy is exposed to H at a pressure usually 10 atmospheres above dissociation pressure at that temperature, due to hysteresis type effects. The hydriding pressure should for best results be at least twice the dissociation pressure because of the already mentioned hysteresis effect.
EXAMPLES An alloy was prepared with the composition (A) of FeTi and the dissociation pressure-composition isotherms for this alloy are shown in FIG. 1. The H dissociation pressure of this alloy can be seen from the curve at 40 C to be at least 7.2 atmospheres and reaches 25 atmospheres at the maximum H concentration. A similar alloy (B) was prepared in which some of the iron was displaced by Mn and had the formula TiFe Mn The dissociation pressures for this alloy at the same temperature, as shown in FIG. 1, range from 0.42 to 9 atmospheres for the same amount of stored H as in alloy (A). In the drawing, the atom ratio, H/M is defined as the ratio of atoms of hydrogen to total atoms of metal.
It was found that for other temperature conditions the presence of Mn displacing some of the iron additionally made it possible to increase the amount of H which could be stored as well as reducing the dissociation pressure. Curves C in FIG. 2 shows isotherms for a FeTi alloy at 55 and C'while curve D shows the isotherm at 61 C for the composition TiFe Mn Not only does alloy D have a lower dissociation pressure but in addition H storage capacity was increased by about 10 percent by weight. This is shown by the upper limits of the curve.
What is claimed is:
1. A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe Mn, where x is in the range of about 0.02 to 0.5.
2. The method of storing hydrogen comprising contacting a solid alloy of TiFe Mn, where x is in the range of about 0.02 to 0.5 with gaseous H at a pressure above the dissociation pressure of the hydride.
3. The method of claim 2 in which the pressure of H during contacting is at least twice the dissociation pressure of the hydride for the temperature during contactmg.
4. The method of claim 3 in which the pressure of H during contacting is about ten times the dissociation pressure of the hydride for the temperature during contacting.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2798806 *||Aug 19, 1952||Jul 9, 1957||Rem Cru Titanium Inc||Titanium alloy|
|US3508414 *||Mar 5, 1968||Apr 28, 1970||Atomic Energy Commission||Method of storing hydrogen|
|US3516263 *||Mar 25, 1969||Jun 23, 1970||Atomic Energy Commission||Method of storing hydrogen|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4079523 *||Nov 8, 1976||Mar 21, 1978||The International Nickel Company, Inc.||Iron-titanium-mischmetal alloys for hydrogen storage|
|US4111689 *||Feb 9, 1976||Sep 5, 1978||Franklin Baumgartner||Method of storing hydrogen|
|US4133426 *||Feb 24, 1978||Jan 9, 1979||The International Nickel Company, Inc.||Hydride container|
|US4134490 *||Feb 24, 1978||Jan 16, 1979||The International Nickel Company, Inc.||Gas storage containment|
|US4134491 *||Feb 24, 1978||Jan 16, 1979||The International Nickel Company, Inc.||Hydride storage containment|
|US4135621 *||Feb 24, 1978||Jan 23, 1979||The International Nickel Company, Inc.||Hydrogen storage module|
|US4153484 *||Jan 18, 1977||May 8, 1979||Matsushita Electric Industrial Co., Ltd.||Hydrogen storage material|
|US4154364 *||Dec 23, 1976||May 15, 1979||Shin-Etsu Chemical Co., Ltd.||Thermally insulating containers for liquefied gases|
|US4160014 *||May 10, 1978||Jul 3, 1979||Matsushita Electric Industrial Co., Ltd.||Hydrogen storage material|
|US4163666 *||Jan 31, 1978||Aug 7, 1979||Dan Davidov||Hydrogen charged alloys of Zr(A1-x Bx)2 and method of hydrogen storage|
|US4178987 *||Jul 12, 1978||Dec 18, 1979||Standard Oil Company, A Corporation Of Indiana||Moving bed hydride/dehydride systems|
|US4183369 *||Nov 4, 1977||Jan 15, 1980||Thomas Robert E||Method of transmitting hydrogen|
|US4195989 *||Oct 25, 1978||Apr 1, 1980||Matsushita Electric Industrial Co., Ltd.||Hydrogen storage material|
|US4196525 *||Aug 1, 1977||Apr 8, 1980||Johnson, Matthey & Co., Limited||Storage of gas|
|US4200623 *||Oct 25, 1978||Apr 29, 1980||Compagnie Francaise De Raffinage||Process for the preparation of a hydrogen reserve|
|US4200624 *||Oct 25, 1978||Apr 29, 1980||Compagnie Francaise De Raffinage||Combined hydrogen storage and production process|
|US4214699 *||Apr 10, 1978||Jul 29, 1980||Daimler-Benz Aktiengesellschaft||Parking heater and method using hydrides in motor vehicles powered by hydrogen|
|US4215008 *||Jun 27, 1978||Jul 29, 1980||Shin-Etsu Chemical Co. Ltd.||Rare earth-containing alloys and method for purification of hydrogen gas therewith|
|US4262739 *||Jan 3, 1979||Apr 21, 1981||The United States Of America As Represented By The Department Of Energy||System for thermal energy storage, space heating and cooling and power conversion|
|US4278466 *||Nov 9, 1979||Jul 14, 1981||Battelle Memorial Institute||Titanium alloy composition and method for the storage of hydrogen|
|US4283226 *||Nov 8, 1976||Aug 11, 1981||U.S. Philips Corporation||Method of preparing titanium iron-containing material for hydrogen storage|
|US4305725 *||Oct 20, 1980||Dec 15, 1981||Rca Corporation||Method of and apparatus for outgassing raw material used to grow crystals|
|US4311232 *||Sep 11, 1979||Jan 19, 1982||Kernforschungsanlage Julich Gmbh||FeTiMn Alloy granulate in a pressure container for storage of hydrogen and deuterium|
|US4350673 *||Feb 2, 1979||Sep 21, 1982||Matsushita Electric Industrial Company, Limited||Method of storing hydrogen|
|US4358316 *||Dec 29, 1980||Nov 9, 1982||University Patents, Inc.||Alloys for hydrogen storage|
|US4360445 *||Jun 16, 1981||Nov 23, 1982||The United States Of America As Represented By The United States Department Of Energy||Oxygen stabilized zirconium-vanadium-iron alloy|
|US4370163 *||Sep 4, 1980||Jan 25, 1983||Matsushita Electric Industrial Company, Limited||Hydrogen storage alloy and process for making same|
|US4440736 *||May 2, 1983||Apr 3, 1984||Allied Corporation||Titanium-based body-centered cubic phase alloy compositions and room temperature hydride-forming reactions of same|
|US4444727 *||Jun 21, 1982||Apr 24, 1984||Matsushita Electric Industrial Co. Ltd.||Hydrogen gas purification apparatus|
|US4546093 *||Jul 5, 1984||Oct 8, 1985||China Petrochemical Development Corp.||Preparation of catalyst system for the synthesis of 2-6-xylenol|
|US6068683 *||Aug 3, 1994||May 30, 2000||The Regents Of The University Of California||Apparatus for separating and collecting hydrogen gas|
|US6274532 *||Jul 23, 1997||Aug 14, 2001||Krupp Vdm Gmbh||Method of making a completely-metallic oxidation catalyst|
|US6378601 *||May 12, 2000||Apr 30, 2002||Energy Conversion Devices, Inc.||Hydrogen cooled hydrogen storage unit having a high packing density of storage alloy and encapsulation|
|US6591616 *||Jul 10, 2001||Jul 15, 2003||Energy Conversion Devices, Inc.||Hydrogen infrastructure, a combined bulk hydrogen storage/single stage metal hydride hydrogen compressor therefor and alloys for use therein|
|EP0009646A1 *||Sep 5, 1979||Apr 16, 1980||Forschungszentrum Jülich Gmbh||Granulate from a FeTiMn alloy for the storage of hydrogen and/or deuterium in pressure vessels and apparatus for the storage thereof|
|EP0011602A1 *||Nov 5, 1979||May 28, 1980||Battelle Memorial Institute||Alloy based on titanium and iron for the storage of hydrogen|
|WO1982002214A1 *||Dec 23, 1981||Jul 8, 1982||Patents Inc University||Alloys for hydrogen storage|
|U.S. Classification||34/416, 62/46.2, 148/DIG.153, 502/324, 423/644, 420/900, 423/248, 376/151, 420/581, 95/116|
|International Classification||C22C14/00, F17C11/00, C01B3/00, H01M4/38|
|Cooperative Classification||Y02E60/327, Y10S420/90, Y10S148/153, H01M4/383, C22C14/00, Y02E60/321, F17C11/005, Y02E60/12, C01B3/0031|
|European Classification||H01M4/38B, F17C11/00D, C22C14/00, C01B3/00D2F|