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GB1577830A - Titanium chromium hydrides - Google Patents

Titanium chromium hydrides Download PDF

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Publication number
GB1577830A
GB1577830A GB18151/78A GB1815178A GB1577830A GB 1577830 A GB1577830 A GB 1577830A GB 18151/78 A GB18151/78 A GB 18151/78A GB 1815178 A GB1815178 A GB 1815178A GB 1577830 A GB1577830 A GB 1577830A
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Prior art keywords
hydride
pressure
reactor
hydrides
range
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GB18151/78A
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US Department of Energy
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US Department of Energy
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/24Hydrides containing at least two metals; Addition complexes thereof
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Description

(54) TITANIUM CHROMIUM HYDRIDES (71) We, UNITED STATES DEPARTMENT of ENERGY, Washington, District of Columbia 20545, United States of America, a duly constituted department of the Government of the United States of America, established by the Department of Energy Organization Act of 1977 (Public Law 95-91), do hereby declare the invention, for which we pray that patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: 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. A variety of metal alloys have been developed which are capable of storing and releasing hydrogen under controlled conditions, such as iron-titanium alloys disclosed in U.S. Patent Nos. 3,508,414 and 3,516,263. U.S. Patent No. 3,922,872 describes a ternary alloy of iron, titanium, and manganese which is capable of storing even greater amounts of hydrogen.
There has been increasing interest in the possible application of hydrides for auto mobile use, it being well known that hydrogen either alone or in combination with hydrocarbon fuels could be employed in internal combustion engines.
One drawback in the possible use of hydrides heretofore known in automobile use is in the wide range of temperatures that the car is subject to so that a hydride must be capable of releasing, for example, its hydrogen at a controlled rate at temp eratures below zero degrees C.
It has been discovered that certain alloys will form hydrides having the unusual characteristics of being able to release hydrogen under high pressure at relatively very low temperatures, even below zero degrees C. In other words, such a hydride is potentially useful for use in an automobile as a source of fuel in view of the low starting temperatures frequently encountered.
Other possible uses for hydrides having the characteristics described above include thermal storage as part of a home heating and cooling heat pump system where the storage medium can be stored outside. In such a system where hydrogen can be absorbed at zero "C and de sorbed at a higher temperature, such as 50"C, it can be readily seen that integration with a solar source of heat is entirely possible.
In accordance with one embodiment of this invention there is provided a hydride having the chemical composition TiCr2 Hx where x is in the range of from 0.6 to 4.0.
A hydride produced in accordance with the principles of this invention is capable of sorbing or desorbing hydrogen at temperatures as low as -78 C, an obvious advantage in certain situations where previously known hydrides could not function.
In an alternative embodiment of the invention some of the chromium is replaced by manganese to produce a more stable hydride having a lower decomposition pressure. Such a hydride has the chemical composition TiCr2 y Mny Hz where y is a number in the range of from 0.5 to 1.5 and z is in the range of from 0.6 to 4.0.
In the accompanying drawing: Figure 1 shows pressure composition isotherms for specific hydrides covered by this invention.
Figure 2 shows a comparison of such isotherms for a hydride in which some of the chromium is replaced by manganese with a hydride without such replacement.
A hydride in accordance with this invention may be prepared by melting granules of Ti and Cr in the proper weight ratio in an arc furnace forming an intermetallic compound. The compound is then cooled to solidification and to ambient temperature and then is broken up into granules. The granules are put into a reactor which is then outgassed and heated to a temperature below melting to remove or reduce the presence of unwanted gases. The reactor is then exposed to hydrogen gas at a high pressure followed by cooling the reactor to a desired low temperature while maintaining the high pressure with H2. This condition is maintained until the desired degree of hydriding is obtained.
To dehydride the hydride, the reactor is vented while maintaining the low temperature.
EXAMPLES Ten grams consisting of about one-third titanium and the remainder were melted together in an arc furnace. The intermetallic compound was cooled to solidification down to room temperature. It was then broken up into granular form.
The granulated compound was put into a reactor consisting of a stainless steel container and all gases reduced or removed by heating and outgassing. After cooling back to atmospheric pressure, the reactor was exposed to H2 at 60 atmospheres pressure.
The container was cooled to -78 C while maintaining the initial pressure by supplying hydrogen periodically. This procedure was followed until hydriding was complete by the constancy of H2 pressure.
The properties of the hydride formed are shown by the pressure composition isotherms in Figure 1.
One of the advantages of this hydride is evident from studying the isotherms. By raising the temperature from -780C to -40 C, for example, when the hydride composition corresponds to the plateau region the pressure increases from 2 to 15 atmos- pheres, in effect using the hydride as a pump to raise the pressure of the hydrogen.
It is also evident from the curves that the temperature-pressure relationships are in the range where, the hydride could be useful in a liquefaction or refrigeration system.
It has been found that the characteristics of these hydrides can be altered somewhat by replacing some of the chromium with manganese so that the chemical composition of the hydride takes the form TiCr2 yHz where y is in the range of 0.5 to 1.5 and typically about one and z is from 0.6 to 40. Additions of the manganese make the hydride more stable and lowers the equilibrium pressure.
The hydrides are prepared as previously described for the titanium chromium hydrides For comparison, typical isotherms for hydrides of TiCr2 and TiCrMn are shown in Figure 2, illustrating this alternation in characteristics.
WHAT WE CLAIM IS: 1. A hydride having the chemical composition TiCr2 Hx where x is in the range of from 0.6 to 4.0.
2. A hydride as claimed in claim 1, substantially as hereinbefore described, illustrated and exemplified.
3. A hydride having the chemical composition TiCr2 yMnyHz where y is a number in the range of from 0.5 to 1.5 and z is in the range of from 0.6 to 4.0.
4. A hydride as claimed in claim 3, in which y is about 1.0 5. A hydride as claimed in claim 3 or 4 substantially as hereinbefore described and illustrated.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (5)

**WARNING** start of CLMS field may overlap end of DESC **. and then is broken up into granules. The granules are put into a reactor which is then outgassed and heated to a temperature below melting to remove or reduce the presence of unwanted gases. The reactor is then exposed to hydrogen gas at a high pressure followed by cooling the reactor to a desired low temperature while maintaining the high pressure with H2. This condition is maintained until the desired degree of hydriding is obtained. To dehydride the hydride, the reactor is vented while maintaining the low temperature. EXAMPLES Ten grams consisting of about one-third titanium and the remainder were melted together in an arc furnace. The intermetallic compound was cooled to solidification down to room temperature. It was then broken up into granular form. The granulated compound was put into a reactor consisting of a stainless steel container and all gases reduced or removed by heating and outgassing. After cooling back to atmospheric pressure, the reactor was exposed to H2 at 60 atmospheres pressure. The container was cooled to -78 C while maintaining the initial pressure by supplying hydrogen periodically. This procedure was followed until hydriding was complete by the constancy of H2 pressure. The properties of the hydride formed are shown by the pressure composition isotherms in Figure 1. One of the advantages of this hydride is evident from studying the isotherms. By raising the temperature from -780C to -40 C, for example, when the hydride composition corresponds to the plateau region the pressure increases from 2 to 15 atmos- pheres, in effect using the hydride as a pump to raise the pressure of the hydrogen. It is also evident from the curves that the temperature-pressure relationships are in the range where, the hydride could be useful in a liquefaction or refrigeration system. It has been found that the characteristics of these hydrides can be altered somewhat by replacing some of the chromium with manganese so that the chemical composition of the hydride takes the form TiCr2 yHz where y is in the range of 0.5 to 1.5 and typically about one and z is from 0.6 to 40. Additions of the manganese make the hydride more stable and lowers the equilibrium pressure. The hydrides are prepared as previously described for the titanium chromium hydrides For comparison, typical isotherms for hydrides of TiCr2 and TiCrMn are shown in Figure 2, illustrating this alternation in characteristics. WHAT WE CLAIM IS:
1. A hydride having the chemical composition TiCr2 Hx where x is in the range of from 0.6 to 4.0.
2. A hydride as claimed in claim 1, substantially as hereinbefore described, illustrated and exemplified.
3. A hydride having the chemical composition TiCr2 yMnyHz where y is a number in the range of from 0.5 to 1.5 and z is in the range of from 0.6 to 4.0.
4. A hydride as claimed in claim 3, in which y is about 1.0
5. A hydride as claimed in claim 3 or 4 substantially as hereinbefore described and illustrated.
GB18151/78A 1977-06-06 1978-05-08 Titanium chromium hydrides Expired GB1577830A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US80419977A 1977-06-06 1977-06-06

Publications (1)

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GB1577830A true GB1577830A (en) 1980-10-29

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GB18151/78A Expired GB1577830A (en) 1977-06-06 1978-05-08 Titanium chromium hydrides

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5100615A (en) * 1989-09-11 1992-03-31 Agency Of Industrial Science And Technology Alloys of Ti-Cr-Cu for occluding hydrogen
RU2208573C1 (en) * 2002-01-23 2003-07-20 Институт структурной макрокинетики и проблем материаловедения РАН Titanium hydride production process
US9376316B2 (en) 2011-12-15 2016-06-28 USW Commercial Services Ltd. Metal hydrides and their use in hydrogen storage applications
US9739423B2 (en) 2014-06-13 2017-08-22 University Of South Wales Commercial Services Ltd. Synthesis and hydrogen storage properties of novel metal hydrides
US9960441B2 (en) 2013-06-14 2018-05-01 University Of South Wales Commercial Services Ltd. Synthesis and hydrogen storage properties of novel manganese hydrides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5100615A (en) * 1989-09-11 1992-03-31 Agency Of Industrial Science And Technology Alloys of Ti-Cr-Cu for occluding hydrogen
RU2208573C1 (en) * 2002-01-23 2003-07-20 Институт структурной макрокинетики и проблем материаловедения РАН Titanium hydride production process
US9376316B2 (en) 2011-12-15 2016-06-28 USW Commercial Services Ltd. Metal hydrides and their use in hydrogen storage applications
US10974961B2 (en) 2011-12-15 2021-04-13 USW Commercial Services, Ltd. Metal hydrides and their use in hydrogen storage applications
US11851327B2 (en) 2011-12-15 2023-12-26 USW Commercial Services Ltd. Metal hydrides and their use in hydrogen storage applications
US9960441B2 (en) 2013-06-14 2018-05-01 University Of South Wales Commercial Services Ltd. Synthesis and hydrogen storage properties of novel manganese hydrides
US10622655B2 (en) 2013-06-14 2020-04-14 Usw Commercial Services Ltd Synthesis and hydrogen storage properties of novel manganese hydrides
US9739423B2 (en) 2014-06-13 2017-08-22 University Of South Wales Commercial Services Ltd. Synthesis and hydrogen storage properties of novel metal hydrides
US10465852B2 (en) 2014-06-13 2019-11-05 USW Commercial Services Ltd. Synthesis and hydrogen storage properties of novel metal hydrides
US11421826B2 (en) 2014-06-13 2022-08-23 USW Commercial Services, Ltd. Synthesis and hydrogen storage properties of novel metal hydrides

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