USRE30083E - Iron titanium manganase alloy hydrogen storage - Google Patents

Iron titanium manganase alloy hydrogen storage Download PDF

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Publication number
USRE30083E
USRE30083E US05/849,569 US84956977A USRE30083E US RE30083 E USRE30083 E US RE30083E US 84956977 A US84956977 A US 84956977A US RE30083 E USRE30083 E US RE30083E
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alloy
hydrogen
pressure
manganase
hydrogen storage
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US05/849,569
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James J. Reilly
Richard H. Wiswall, Jr.
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US Department of Energy
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US Department of Energy
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • Hydrogen is a potential fuel for various types of power sources, such as fuel cells, internal combustion 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 three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe 1-x Mn x where x is in the range of about 0.02 to 0.5.
  • a method of storing hydrogen comprising contacting gaseous hydrogen with a solid alloy of TiFe 1-x Mn x where x is in the range of about 0.02 to 0.5.
  • Another purpose is to provide an improved method for the storage of hydrogen.
  • FIGS. 1 and 2 show curves illustrating the H 2 storage characteristics of alloys incorporating the principles of this invention and comparing them with similar alloys not incorporating this invention.
  • An alloy in accordance with this invention may be prepared by melting granules or small ingots of Fe, Ti, and Mn in an arc 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 2 for a short time followed by outgassing again and cooling under hydrogen with about 1 atmosphere pressure.
  • the activated alloy is exposed to H 2 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.
  • 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 2 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 2 concentration.
  • a similar alloy (B) was prepared in which some of the iron was displaced by Mn and had the formula TiFe 0 .7 Mn 0 .3.
  • 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 2 as in alloy (A).
  • the atom ratio, H/M is defined as the ratio of atoms of hydrogen to total atoms of metal.
  • Curves C in FIG. 2 shows isotherms for a FeTi alloy at 55° and 70° C. while curve D shows the isotherm at 61° C. for the composition TiFe 0 .8 Mn 0 .2. Not only does alloy D have a lower dissociation pressure but in addition H 2 storage capacity was increased by about 10 percent by weight. This is shown by the upper limits of the curve.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe1-x Mnx where x is in the range of about 0.02 to 0.5 and the method of storing hydrogen using said alloy.

Description

BACKGROUND OF THE INVENTION
The invention described herein was made in the course of, or under a contract with the U.S. Atomic Energy Commission.
Hydrogen is a potential fuel for various types of power sources, such as fuel cells, internal combustion 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 U.S. 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 manganese to the intermetallic alloy FeTi in certain specific amounts not only increases the amount of H2 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 TiFe1-x Mnx 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 TiFe1-x Mnx 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 H2 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 arc 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 H2 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 H2 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 H2 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 H2 concentration. A similar alloy (B) was prepared in which some of the iron was displaced by Mn and had the formula TiFe0.7 Mn0.3. 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 H2 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 H2 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 70° C. while curve D shows the isotherm at 61° C. for the composition TiFe0.8 Mn0.2. Not only does alloy D have a lower dissociation pressure but in addition H2 storage capacity was increased by about 10 percent by weight. This is shown by the upper limits of the curve.

Claims (5)

What is claimed is:
1. A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe1-x Mnx 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 TiFe1-x Mnx where x is in the range of about 0.02 to 0.5 with gaseous H2 at a pressure above the dissociation pressure of the hydride.
3. The method of claim 2 in which the pressure of H2 during contacting is at least twice the dissociation pressure of the hydride for the temperature during contacting.
4. The method of claim 3 in which the pressure of H2 during contacting is about ten times the dissociation pressure of the hydride for the temperature during contacting. .Iadd.
5. The product of the method of claim 2. .Iaddend.
US05/849,569 1975-02-04 1977-11-08 Iron titanium manganase alloy hydrogen storage Expired - Lifetime USRE30083E (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4546093A (en) 1984-07-05 1985-10-08 China Petrochemical Development Corp. Preparation of catalyst system for the synthesis of 2-6-xylenol
US20110119992A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Company Oxidation resistant interstitial metal hydride catalysts and associated processes
US20110119993A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Company High severity hydroprocessing interstitial metal hydride catalysts and associated processes
US20110119990A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Companhy Group 13-15 interstitial metal hydride catalysts and associated processes
US20110119991A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Company Interstitial metal hydride catalyst activity regeneration and hydroprocessing processes
US8598067B2 (en) 2010-11-09 2013-12-03 Exxonmobil Research And Engineering Company Interstitial metal hydride catalyst systems and associated processes
US8637424B2 (en) 2010-11-09 2014-01-28 Exxonmobil Research And Engineering Company Integrated interstitial metal hydride catalyst support systems and associated processes
US8765628B2 (en) 2010-11-09 2014-07-01 Exxonmobil Research And Engineering Company Poison resistant catalyst systems and associated processes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798806A (en) * 1952-08-19 1957-07-09 Rem Cru Titanium Inc Titanium alloy
US3508414A (en) * 1968-03-05 1970-04-28 Atomic Energy Commission Method of storing hydrogen
US3516263A (en) * 1969-03-25 1970-06-23 Atomic Energy Commission Method of storing hydrogen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798806A (en) * 1952-08-19 1957-07-09 Rem Cru Titanium Inc Titanium alloy
US3508414A (en) * 1968-03-05 1970-04-28 Atomic Energy Commission Method of storing hydrogen
US3516263A (en) * 1969-03-25 1970-06-23 Atomic Energy Commission Method of storing hydrogen

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
An Engineering Scale Energy Storable Reservoir of Iron Titanium Hydride: G. Strickland et al., Mar. 18-20, 1974. *
Iron Titanium Hydride as a Source of Hydrogen Fuel for Stationary and Automotive Applications: J. J. Reilly et al., May 1974. *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4546093A (en) 1984-07-05 1985-10-08 China Petrochemical Development Corp. Preparation of catalyst system for the synthesis of 2-6-xylenol
US20110119992A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Company Oxidation resistant interstitial metal hydride catalysts and associated processes
US20110119993A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Company High severity hydroprocessing interstitial metal hydride catalysts and associated processes
US20110119990A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Companhy Group 13-15 interstitial metal hydride catalysts and associated processes
US20110119991A1 (en) * 2009-11-24 2011-05-26 Exxonmobil Research And Engineering Company Interstitial metal hydride catalyst activity regeneration and hydroprocessing processes
WO2011066208A1 (en) * 2009-11-24 2011-06-03 Exxonmobil Research And Engineering Company Oxidation resistant interstitial metal hydride catalysts and associated processes
US8618010B2 (en) 2009-11-24 2013-12-31 Exxonmobil Research And Engineering Company Interstitial metal hydride catalyst activity regeneration process
US9663728B2 (en) 2009-11-24 2017-05-30 Exxonmobile Research And Engineering Company Group 13-15 interstitial metal hydride catalysts and associated processes
US8598067B2 (en) 2010-11-09 2013-12-03 Exxonmobil Research And Engineering Company Interstitial metal hydride catalyst systems and associated processes
US8637424B2 (en) 2010-11-09 2014-01-28 Exxonmobil Research And Engineering Company Integrated interstitial metal hydride catalyst support systems and associated processes
US8765628B2 (en) 2010-11-09 2014-07-01 Exxonmobil Research And Engineering Company Poison resistant catalyst systems and associated processes
US8932455B2 (en) 2010-11-09 2015-01-13 Exxonmobil Research And Engineering Company Interstitial metal hydride catalyst systems and associated processes

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