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Publication numberUS3315479 A
Publication typeGrant
Publication dateApr 25, 1967
Filing dateJun 15, 1966
Priority dateJun 15, 1966
Publication numberUS 3315479 A, US 3315479A, US-A-3315479, US3315479 A, US3315479A
InventorsJr James J Reilly, Jr Richard H Wiswall
Original AssigneeJr James J Reilly, Jr Richard H Wiswall
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Storing hydrogen
US 3315479 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,315,479 STORING HYDROGEN Richard H. Wiswall, Jr., Brookhaven, and James J. Reilly,

Jr., Bellport, N.Y., assignors to the United States of America as represented by the United States Atomic Energy Commission No Drawing. Filed June 15, 1966, Ser. No. 558,220

4 Claims. (Cl. 62-48) ABSTRACT OF THE DISCLOSURE A method for storing hydrogen whereby gaseous hydrogen is adsorbed by nickel-magnesium alloys at temperatures above 250 C. and pressures above 18 pounds per square inch.

. The invention described herein was made in the course of, or under a contract with the US. Atomic Energy Commission.

Prior art It is an object of this invention to provide those skilled in the art with a simple, economical, safe method of storing hydrogen.

Description of the invention We have discovered a novel method for storing hydrogen by forming a hydrogen metal alloy complex, wherein hydrogen gas is absorbed into a metal alloy, comprising contacting gaseous hydrogen with a solid nickel-magnesium alloy, said alloy containing from about 40 weight percent to about 80 weight percent nickel based upon the total weight of the nickel-magnesium alloy and from about 20 weight to about 60 weight percent magnesium based upon the total weight of the nickel-magnesium alloy, while maintaining said hydrogen and said alloy at a pressure of at least about 18 pounds per square inch and at a temperature of at least about 250 C. until said alloy has absorbed up to about 5 weight percent hydrogen based upon the total weight of the nickel-magnesium alloy. The product formed by our method is a hydrogen-nickelmagnesium complex, whose exact physical and chemical structure is not known at this time.

The hydrogen-mickel-magnesiurn complexes produced by the practice of our invention are stable at temperatures below 250 C. and the complexes need not be stored in pressure vessels. Thus, hydrogen can be readily stored by forming the complex in accordance with the method disclosed by our invention and thereafter cooling the complexes and maintaining them at normal atmospheric pressures until it is desired to release the hydrogen contained therein. To release the hydrogen from the complex, all that is required to be done is to heat the hydrogen containing complex to a temperature above 250 C. and to allow the hydrogen to escape.

A unique feature of our novel complexes is the fact that hydrogen is released at a constant rate from a complex when the complex is maintained at a specific temperature at or above 250 C. until the complex contains less than one weight percent of hydrogen based on the total weight of nickel-magnesium alloy contained in the complex. For example, a hydrogen-nickel-magnesium complex contain- 3,3 15,479 Patented Apr. 25, 1967 ing 5 weight percent hydrogen based upon the weight of the nickel-magnesium alloy upon being heated at-a constant temperature of 250 C. will maintain a constant hydrogen pressure of 18 lbs. per square inch above the alloy until about one weight percent of hydrogen remains in the complex. This feature provides those skilled in the art with a simple hydrogen source in which the rate of release can be carefully controlled by simply controlling the temperature of the complex during the release. Thus, it will be apparent to those skilled in the art that our invention can be readily adapted to conventional techniques to provide a safe dependable source of hydrogen for a multitude of uses such as rockets, fuel cells, etc.

In the preferred embodiment of our invention, the nickel-magnesium alloy contains 53 Weight percent nickel and 47 weight percent magnesium based on the total weight of the alloy. The alloys found useable in our invention can be produced by any conventional alloying technique. They can be produced by simply heating the proper amounts of nickel and magnesium under an inert or hydrogen atmosphere with an induction heater until a melt is formed, intimately mixing the ingredients of the melt and thereafter cooling the melt until a solid alloy is formed. Liquid metal alloys are not desirable for use in the practice of our invention because the pressure requirements required to form the desired hydrogen-alloy complex would be too great. The presence of oxygen in the nickel-magnesium alloy is to be avoided as oxygen tends to inhibit the rate of formation of the complex. We have found it preferable to use a powdered nickel-magnesium alloy in the practice of our invention because the increased surface area provided by the powder increases the rate of absorpition of the hydrogen by the alloy. However, our invention is not limited to any particular physical shape of the alloy and blocks and meshes of the alloy can be employed and indeed in certain applications such shapes may be desirable. Conventional pressure vessels and heating devices may be employed in the practice of our invention.

In the preferred embodiment of our invention the hydrogen and the nickel-magnesium alloy are heated to a temperature of 300 C. and maintained under a pressure of pounds per square inch absolute. The pressure can be maintained by adding additional increments of hydrogen to the system to counterbalance the increments taken up by the alloy during the absorption phase of the process.

We have found that one atom of hydrogen will be adsorbed per atom of metal contained in the alloy. One mol of an alloy having the formula Mg Ni will absorb up to 4.5 mols of hydrogen during the practice of our invention. Thus the alloys found useable in our invention will absorb roughly 5 weight percent hydrogen based on the total alloy weight.

Example I A pparatus.-An upright reactor vessel consisting of a stainless steel tube flanged on both ends and having an inside diameter of inch and a length of about 13 inches was fitted with a thermocouple well through the top flanged end of the vessel and extended therein for about 7 inches. A small crucible made of aluminum oxide was attached to the bottom of the thermocuple to hold the samples to be treated at about the middle of the vessel. The bottom end of the vessel was sealed and a connection was fitted to the side of the vessel to permit gas to be withdrawn and introduced in the vessel. The vessel was inserted into an electrically heated furnace.

Procedure A 2 gm. sample of an alloy consisting of 45% by weight Mg and 55% by weight Ni (Mg Ni) was weighed out in a dry box. The sample was pulverized so that it could through a mesh screen, reweighed and introduced of 275 C. H was admitted to the reactor until a pres-..

sure of 125 p.s.i.a. was reached at which point the vessel was sealed. The reactor vessel was then heated to about 300 C. The rate at which the sample absorbed H could be determined by the pressure decrease in the system over a period of time. When absorption was essentially complete, the reactor was cooled to room temperature and gaseous H was vented from the system until a predeter-. mined pressure of p.s.i.a. was reached. The sample was reheated to about 300 C. and allowed to come to equilibrium and the pressure recorded. At equilibrium some gaseous H was removed from the system after which a new equilibrium was reached. When no further H evolved from the sample upon removing gaseous H the entire cycle was repeated by readimitting H into the system and reabsorbing H in the alloy.

Results A hydrogen content of over 4 wt. percent has been repeatedly obtained by absorption in an alloy with the starting composition of wt. percent Mg, wt. percent Ni (Mg Ni). The fact that the sorption-desorption cycle can be repeated indefinitely is of practical significance for it allows for economic use of the alloys to effectuate H storage.

We have also prepared samples of the alloy which were cooled to room temperature afterthey had sorbed about 4 weight percent hydrogen based upon the weight of the nickel-magnesium alloy. These samples did not lose their hydrogen upon exposure to the atmospheric conditions found in our laboratory. Further, they were not damaged when they were recycled through the procedure described in this example.

We claim:

1. The method of storing hydrogen comprising contacting gaseous hydrogen with a solid nickel-magnesium alloy, said alloy being composed of from about 40 weight percent to about 80 weight percent nickel based on the total Weight of the nickel-magnesium alloy and from about 20 weight percent to about weight percent magnesium based upon the total weight of the nickelmagnesium alloy, while maintaining said hydrogen and said alloy at a pressure of at least about 18 pounds per square inch and at a temperature of at least about 250 C. until said alloy has absorbed .up to about 5 weight percent hydrogen based on the total weight of the nickel- .magnesium alloy.

References Cited by the Examiner UNITED STATES PATENTS 2,356,334 8/1944 Maude et al. 6248 2,663,626 12/1953 Spangler 62-48 2,712,730 7/1955 Spangler 6248 3,151,467 10/1965 Cohen et a1. 62-48 LLOYD L. KING, Primary Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2356334 *Dec 18, 1941Aug 22, 1944Hooker Electrochemical CoMeans for storing and concentrating anhydrous hydrogen chloride
US2663626 *May 14, 1949Dec 22, 1953Pritchard & Co J FMethod of storing gases
US2712730 *Oct 11, 1951Jul 12, 1955Pritchard & Co J FMethod of and apparatus for storing gases
US3151467 *Dec 4, 1961Oct 6, 1964Union Carbide CorpProcess and apparatus for the filling, transportation and dispensing of hazardous fluids
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3375676 *May 23, 1967Apr 2, 1968Atomic Energy Commission UsaMethod of storing hydrogen
US3508414 *Mar 5, 1968Apr 28, 1970Atomic Energy CommissionMethod of storing hydrogen
US3516263 *Mar 25, 1969Jun 23, 1970Atomic Energy CommissionMethod of storing hydrogen
US3943719 *Feb 26, 1975Mar 16, 1976Terry Lynn EHydride-dehydride power system and methods
US3967465 *Jun 27, 1974Jul 6, 1976U.S. Philips CorporationContainer for storing and transporting a liquefied gas
US4133426 *Feb 24, 1978Jan 9, 1979The International Nickel Company, Inc.Hydride container
US4134490 *Feb 24, 1978Jan 16, 1979The International Nickel Company, Inc.Gas storage containment
US4134491 *Feb 24, 1978Jan 16, 1979The International Nickel Company, Inc.Hydride storage containment
US4215008 *Jun 27, 1978Jul 29, 1980Shin-Etsu Chemical Co. Ltd.Rare earth-containing alloys and method for purification of hydrogen gas therewith
US4242315 *Apr 10, 1978Dec 30, 1980U.S. Philips CorporationHydrides of the formula ABn Hm
US4249654 *Sep 25, 1979Feb 10, 1981Helversen Frederick DHydrogen storage apparatus
US4375257 *Aug 1, 1980Mar 1, 1983U.S. Philips CorporationHydrogen storage and supply device
US4389326 *Jun 12, 1981Jun 21, 1983Agence Nationale De Valorization De La RechercheMethod of storing hydrogen in intimate mixtures of hydrides of magnesium and other metals or alloys
US4499864 *Feb 10, 1983Feb 19, 1985Conoco Inc.Hydride cold start container in fuel treatment and distribution apparatus and method
US6378601 *May 12, 2000Apr 30, 2002Energy Conversion Devices, Inc.Hydrogen cooled hydrogen storage unit having a high packing density of storage alloy and encapsulation
US6591616 *Jul 10, 2001Jul 15, 2003Energy Conversion Devices, Inc.Hydrogen infrastructure, a combined bulk hydrogen storage/single stage metal hydride hydrogen compressor therefor and alloys for use therein
DE2820671A1 *May 11, 1978Dec 14, 1978Standard Oil CoHydrid-waermepumpe
EP0007840A1 *Jul 6, 1979Feb 6, 1980ANVAR Agence Nationale de Valorisation de la RechercheProcess for storing and utilizing hydrogen, notably in engines
Classifications
U.S. Classification62/46.2, 62/112
International ClassificationF17C11/00, C01B3/00
Cooperative ClassificationC01B3/0042, Y02E60/321, F17C11/005, Y02E60/327
European ClassificationC01B3/00D2F4, F17C11/00D