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WO1987002022A1 - Materiau pulverulent a accumulation d'hydrogene et sa fabrication - Google Patents

Materiau pulverulent a accumulation d'hydrogene et sa fabrication Download PDF

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Publication number
WO1987002022A1
WO1987002022A1 PCT/EP1986/000567 EP8600567W WO8702022A1 WO 1987002022 A1 WO1987002022 A1 WO 1987002022A1 EP 8600567 W EP8600567 W EP 8600567W WO 8702022 A1 WO8702022 A1 WO 8702022A1
Authority
WO
WIPO (PCT)
Prior art keywords
storage material
metal
catalyst
powder
hydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1986/000567
Other languages
German (de)
English (en)
Inventor
Eckehard Fromm
Hans-Georg Wulz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Original Assignee
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Max Planck Gesellschaft zur Foerderung der Wissenschaften eV filed Critical Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Publication of WO1987002022A1 publication Critical patent/WO1987002022A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • 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
    • 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
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
    • 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

  • the invention relates to hydrogen storage materials with improved contact stability and a process for their production.
  • Hydrogen is a gas that is widely used in many technical processes and in the storage of energy. There is therefore great interest in storing hydrogen.
  • One of the possibilities for storing hydrogen is its reversible conversion into a metal hydride.
  • this compact and safe storage form as powdered hydrides has increased. With a storage volume of 10 kJ / cm 3, their energy density is roughly the same as that of liquid hydrogen and roughly ten times that of hydrogen in pressure bottles at around 200 bar.
  • hydrogen is first reversibly bound to the surface of a storage material and then dissolved in the storage material or excreted as a hydride.
  • the H 2 ⁇ uptake in the store depends on the time, the H 2 0_ pressure and the temperature at which the loading takes place. It takes place in the following steps:
  • the last sub-step takes place quickly in the case of powdered samples and is therefore not speed-determining.
  • the kinetics of the absorption and release of hydrogen is essentially determined by the dissociation of the H 2 molecules on the oxide layer or by a slow diffusion of the atomic hydrogen through this oxide layer.
  • the hydrogen uptake of activated samples is explained by the fact that the dissociation of the H 2 molecules on the metallic or suboxidic structures in the sorption layer can take place relatively easily.
  • DE-OS 32 47 360 describes improved activation conditions for magnesium hydride-Mg-hydrogen storage by doping magnesium hydride or metallic Mg in finely divided form by contact with a solution of a transition metal complex or a transition metal organic -Connection.
  • the respective transition metal is extremely - k -
  • magnesium hydride or magnesium particles finely distributed on the surface of the magnesium hydride or magnesium particles and thus takes on the role of a catalyst in the hydrogenation and dehydrogenation processes of the storage material.
  • these magnesium stores are so sensitive to air that all manipulations, even the distillation of the solvents, must be carried out under an argon atmosphere.
  • Boes and Züc ner describe a process in which reactive metals are coated with a Pd film. In this way, a material that can be handled in the air is obtained.
  • DE-PS 32 34 671 describes a further development of this method. In a two-step process, the oxide skin is first pickled on an FeTi storage material and then a thin Pd layer is applied to the reactivated surface by ion exchange.
  • the aim of the invention is to create a hydride storage material which does not have the disadvantages of the known storage materials described and in particular is easy to manufacture and which is not contaminated by air and thus inactivated.
  • a powdery hydride storage material which is characterized by a content of at least one powdered subgroup metal or metal oxide which acts as a hydride / dehydrogenation catalyst.
  • Storage material-powder mixtures according to the invention surprisingly not only retain their storage capacity after mild contamination under weakly oxidizing conditions, but are also so insensitive to oxidizing substances that they can be stored in air without further notice. This is particularly surprising because the sensitivity to oxidation could not be eliminated with the complex surface coating of the storage material particles according to DE-OS 32 47 360.
  • the elements of the I and VIII subgroup and in particular the Pt metals are preferred. Pd is very particularly preferred.
  • palladium powder instead of palladium powder as a catalyst, other metals, such as. B. the aforementioned metals of the subgroup elements can be used.
  • all metals and metal alloys which can be used as catalysts for hydrogenation and dehydrogenation processes are suitable according to the invention.
  • the amount of catalyst is expediently at least 0.01% by weight and can generally be between about 0.5 to 20% by weight, preferably between about 2 and 15% by weight, based on the sum of the storage material and catalyst additive.
  • the optimal amount can easily be determined by preliminary tests, and in special cases the above-mentioned limit conditions can also be exceeded or fallen short of, e.g. B. when the catalyst metal is only present as a coating of a support material.
  • the lower limits given apply to the catalysts as such, the upper limits rather to catalysts containing a support.
  • Hydrogen storage materials are intermetallic compounds. They can be divided into four basic binary types with the general formulas AB (e.g. FeTi), AB g (e.g. LaNi 5 , CaNi 5 ), AB 2 (e.g. ZrMn 2 , TiMn 2 ), A " Classify B (Mg 2 Ni). Alloys in which A or B are wholly or partly replaced by similar metals can also be derived from this. These include alloys such as Fe Q ⁇ 5 Mn Q / 15 Ti, Co Q / 5 Mn Q ⁇ Ti, La i ⁇ Al ⁇ ,
  • this also includes alloys with Ce and rare earths (mixed metal, Mm), such as MmNi 5 , i 4 - AI- 5 , Mm i 5 Cr Mn, CaMmNi .. (see GD Sandrock, Proc. Of Hydrogen Energy Symposium, Swiss, Sweden, May 21, 1981; J. Osumi, H. Suzuki, A. Kato, K. Oguro, M. Nakae, J. Less-Comm. Met. 79 (1981) 207). All of these types of storage materials can be used in the practice of the invention. FeTi, mixed metal Ni 5 and TiVMn alloys have preferably been tested.
  • a metal powder which has a better thermal conductivity than the storage material is also mixed with the storage material / catalyst mixture according to the invention in order to improve the thermal conductivity.
  • the storage material is mixed with a copper powder for this purpose, which is provided with a layer of one of the aforementioned hydrogenation catalysts, in particular palladium.
  • the storage materials according to the invention are produced simply by mixing the powdery storage material with the catalyst powder. After the usual activation, the homogeneous storage material-catalyst mixture is preferably subjected to a pre-oxidation at least once for 1 minute. Such a pre-oxidation is best carried out several times in succession. The total duration of the oxidation should not exceed 10 minutes. This oxidation can simply be carried out directly with air at a reduced pressure of at least 10 * bar to at most 10 ⁇ bar. The storage material is preferably exposed to air 3 to 4 times for 1 to 3 minutes at about 10 bar However, pre-oxidation strongly depends on the storage material used and can vary considerably depending on its composition. The invention is illustrated by the following examples in conjunction with the drawing.
  • Example 1 is a graphical representation of the hydrogen storage device of Example 3 which was not pretreated according to the invention. Treatment with air leads here to a drastic loss of storage capacity.
  • Fig. 2 is a graphical representation analogous to Fig. 1 for a hydrogen storage device according to the invention. Treatment with air does not lead to any change in the storage capacity.
  • the ordinate shows the hydrogen uptake as the atomic ratio of hydrogen to metal atoms of the charged storage material after 100 seconds in 32 bar H 2 .
  • An active storage powder made of FeTi with 5% Pd powder is passivated with air for 30 minutes. After the sample has been standing at room temperature and 32 bar of hydrogen for an hour, the storage material is reactivated, as can be achieved with the storage powder only by activation annealing at 400 ° C.
  • a powdery TiVMn alloy is mixed with 10% by weight of palladium powder until homogeneous and activated at 250 ° C. and 32 bar H 2 . After the third hydrogenation cycle, the amount of hydrogen absorbed was 1.75 times that of the storage material. A three times
  • the powdery TiVMn alloy of Example 2 is activated without Pd powder addition, as described there, and with 3 times aeration for 2 min at 10 -2 bar
  • _2 is oxidized with 10 bar air for 2, 4 and 2 minutes.
  • a powdered mixed metal Ni. - A1 Q - storage alloy is mixed with 10 wt.% Pd (Al 2 0 3 ) hydrogenation catalyst powder until homogeneous and at 18 hours

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Catalysts (AREA)

Abstract

Matériau pulvérulent à accumulation d'hydrides contenant au moins un métal ou oxyde métallique pulvérulent de groupes associés, servant de catalyseur d'hydrogénation/déshydrogénation, comme par exemple le palladium, Pd(Al2O3) et/ou du cuivre enrobé de Pd dans le matériau d'accumulation.
PCT/EP1986/000567 1985-10-03 1986-10-03 Materiau pulverulent a accumulation d'hydrogene et sa fabrication Ceased WO1987002022A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853535378 DE3535378A1 (de) 1985-10-03 1985-10-03 Pulverfoermiger wasserstoff-speicherwerkstoff und seine herstellung
DEP3535378.3 1985-10-03

Publications (1)

Publication Number Publication Date
WO1987002022A1 true WO1987002022A1 (fr) 1987-04-09

Family

ID=6282704

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1986/000567 Ceased WO1987002022A1 (fr) 1985-10-03 1986-10-03 Materiau pulverulent a accumulation d'hydrogene et sa fabrication

Country Status (3)

Country Link
EP (1) EP0239628A1 (fr)
DE (1) DE3535378A1 (fr)
WO (1) WO1987002022A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117505850A (zh) * 2023-10-23 2024-02-06 浙江大学 具有抗氧气毒化性和长效循环稳定性的钯包覆ZrCo储氢合金及其制备和应用

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4121711B2 (ja) * 1999-03-26 2008-07-23 ゲーカーエスエス フオルシユングスツエントルーム ゲーエストハフト ゲーエムベーハー 水素吸蔵金属含有材料及びその製造方法
DE19915142B4 (de) * 1999-03-26 2006-05-04 Gkss-Forschungszentrum Geesthacht Gmbh Metallhaltiger Elektrodenwerkstoff für Primär- und Sekundärelemente
DE19913714A1 (de) * 1999-03-26 2000-09-28 Geesthacht Gkss Forschung Metallhaltiger Werkstoff und Verfahren zu seiner Herstellung
DE10337970B4 (de) * 2003-08-19 2009-04-23 Gkss-Forschungszentrum Geesthacht Gmbh Metallhaltiger, wasserstoffspeichernder Werkstoff und Verfahren zu seiner Herstellung
DE10339198B4 (de) * 2003-08-22 2009-04-23 Gkss-Forschungszentrum Geesthacht Gmbh Metallhaltiger, wasserstoffspeichernder Werkstoff und Verfahren zu seiner Herstellung
WO2005032709A2 (fr) * 2003-09-30 2005-04-14 General Electric Company Compositions de stockage d'hydrogene et procedes de production associes
US7175826B2 (en) * 2003-12-29 2007-02-13 General Electric Company Compositions and methods for hydrogen storage and recovery
US7029517B2 (en) 2003-11-06 2006-04-18 General Electric Company Devices and methods for hydrogen storage and generation
DE102004002120A1 (de) * 2004-01-14 2005-08-18 Gkss-Forschungszentrum Geesthacht Gmbh Metallhaltiger, wasserstoffspeichernder Werkstoff und Verfahren zu seiner Herstellung
FR2881733B1 (fr) * 2005-02-07 2008-02-08 Inst Francais Du Petrole Nouveau materiau pour le stockage de l'hydrogene comprenant un systeme equilibre entre un alliage de magnesium et d'azote et l'hydrure correspondant
DE102008063895B3 (de) * 2008-12-19 2010-06-10 Gkss-Forschungszentrum Geesthacht Gmbh Verfahren zur Aktivierung oder Regeneration eines Wasserstoffspeichermaterials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1328825A (fr) * 1962-07-13 1963-05-31 Accumulatoren Fabrik Ag Procédé pour l'accumulation d'hydrogène et dispositif pour sa mise en oeuvre
US4134490A (en) * 1978-02-24 1979-01-16 The International Nickel Company, Inc. Gas storage containment
FR2441652A1 (fr) * 1978-11-14 1980-06-13 Battelle Memorial Institute Composition a base de magnesium pour le stockage de l'hydrogene et procede de preparation de cette composition
EP0069555A1 (fr) * 1981-07-02 1983-01-12 Inco Selective Surfaces, Inc. Granules aptes à former des hydrures
EP0094136A1 (fr) * 1982-05-07 1983-11-16 Stamicarbon B.V. Procédé pour la séparation de l'hydrogène d'un mélange de gaz

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4389326A (en) * 1979-08-27 1983-06-21 Agence Nationale De Valorization De La Recherche Method of storing hydrogen in intimate mixtures of hydrides of magnesium and other metals or alloys
US4489049A (en) * 1982-06-09 1984-12-18 The United States Of America As Represented By The Secretary Of The Navy Solid state hydrogen pumping and storage material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1328825A (fr) * 1962-07-13 1963-05-31 Accumulatoren Fabrik Ag Procédé pour l'accumulation d'hydrogène et dispositif pour sa mise en oeuvre
US4134490A (en) * 1978-02-24 1979-01-16 The International Nickel Company, Inc. Gas storage containment
FR2441652A1 (fr) * 1978-11-14 1980-06-13 Battelle Memorial Institute Composition a base de magnesium pour le stockage de l'hydrogene et procede de preparation de cette composition
EP0069555A1 (fr) * 1981-07-02 1983-01-12 Inco Selective Surfaces, Inc. Granules aptes à former des hydrures
EP0094136A1 (fr) * 1982-05-07 1983-11-16 Stamicarbon B.V. Procédé pour la séparation de l'hydrogène d'un mélange de gaz

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117505850A (zh) * 2023-10-23 2024-02-06 浙江大学 具有抗氧气毒化性和长效循环稳定性的钯包覆ZrCo储氢合金及其制备和应用

Also Published As

Publication number Publication date
EP0239628A1 (fr) 1987-10-07
DE3535378A1 (de) 1987-04-16

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