WO2008095515A1 - Contenant pour stocker des compositions contenant de l'hydrogène - Google Patents

Contenant pour stocker des compositions contenant de l'hydrogène Download PDF

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Publication number
WO2008095515A1
WO2008095515A1 PCT/EP2007/002375 EP2007002375W WO2008095515A1 WO 2008095515 A1 WO2008095515 A1 WO 2008095515A1 EP 2007002375 W EP2007002375 W EP 2007002375W WO 2008095515 A1 WO2008095515 A1 WO 2008095515A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
container
hydride
metal
container according
Prior art date
Application number
PCT/EP2007/002375
Other languages
German (de)
English (en)
Inventor
Klaus Nohl
Original Assignee
Hydrodivide Ag
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 Hydrodivide Ag filed Critical Hydrodivide Ag
Publication of WO2008095515A1 publication Critical patent/WO2008095515A1/fr

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Classifications

    • 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
    • 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
    • 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 present invention relates to a container for storing hydrogen-containing compositions, in particular hydrogen.
  • Hydrogen-containing compositions in particular hydrogen-containing gases, are usually stored in so-called pressure gas containers of unalloyed steel or aluminum. These usually consist of a cylindrical part which is closed by two outwardly curved bottoms or flat bottoms, wherein on one side usually a screwed valve is provided.
  • Pressure vessels typically have one or more safety-related accessories to protect the vessel from inadmissible operating conditions (exceeding the design pressure or temperature).
  • Equipment with safety function are u. a .: o safety valve (pressure relief in the environment or in a
  • the following causes can lead to bursting of the pressure vessel: o manufacturing errors, such. B. defective execution of welded joints; o Material defects or use of unsuitable or incorrect materials; o poor execution of repairs; o extensive rusting of the container with the result of tearing the
  • Container wall under operating pressure o special forms of corrosion that significantly affect the material properties, such.
  • the present invention is therefore based on the object of demonstrating possibilities for better storage of hydrogen-containing compositions, especially of hydrogen.
  • the loss to the environment should be prevented or at least minimized and the safety during storage should be further increased.
  • the cost-effective Solutions are sought and particularly suitable application areas are shown.
  • the solution of the present invention allows a comparatively simple and cost-effective storage of hydrogen-containing compositions, in particular of hydrogen-containing gases and of hydrogen.
  • the present invention relates to a container, d. H. an object having in its interior a cavity which serves in particular the purpose of separating its contents from its environment.
  • the container may in principle be closed to receive a hydrogen-containing composition, in particular a compressed hydrogen-containing gas.
  • Hydrogen-containing compositions in the context of the present invention designate all compositions which are capable of releasing molecular hydrogen into the environment, in particular molecular hydrogen (H 2 ), physical gas mixtures containing molecular hydrogen, and compositions containing hydrogen in physically bound form Hydrogen, based on the total weight of the composition to be stored, is preferably at least 50%, preferably at least 75%, particularly preferably at least 90%, in particular at least 95%.
  • the structurally ideal shape for the container is the ball and it is particularly preferred for very high internal pressures or very large volume (gas tank) as a design. Most, however, the cylindrical shape is used.
  • the jacket is preferably closed on both sides by flat or curved bottoms (dished bottoms or basket bottom plates), wherein on one side preferably an inlet and outlet valve is screwed.
  • the construction and dimensioning of the container suitably meets the legal requirements, in particular the EC Directive 97/23 / EC, Article 1, paragraph 2.1.1 (Pressure Equipment Directive) and the 14th GPSGV, ⁇ 2, paragraph 1a (Pressure Equipment Ordinance).
  • the container is preferably made of a gas-tight material as possible.
  • the use of unalloyed steel and / or aluminum, in particular unalloyed steel has proven particularly useful in this context.
  • Very particular preference is given to iron-carbon alloys which, based on their total weight, contain less than 2.06% by weight of carbon and preferably less than 1.0% by weight, particularly preferably less than 0.5% by weight. , In particular, contain less than 0.1 wt .-% of other alloying constituents other than iron.
  • the inside of the container is coated with at least one hydride-forming metal, the coating covering as much as possible the entire surface which may come into contact with the composition to be stored.
  • Another advantage is the most complete possible coating of the valve parts that can come into contact with the stored composition. Conveniently, at least 99% of the total surface area to be stored with the Composition can come into contact, coated with the hydride-forming metal,
  • Hydride-forming metals are known per se and refer to metals capable of forming metal hydrides, i. H. Compounds of metals with hydrogen, to form.
  • metal hydrides resemble solutions of hydrogen in metals or alloys in which hydrogen molecules are first adsorbed on the surface of the metal and then incorporated into the metal grid as elemental hydrogen.
  • the incorporation of hydrogen into the metal grid is in principle reversible.
  • metals take up the hydrogen below a certain temperature and / or above a certain pressure and a metal hydride is formed, whereby the incorporation (absorption) of the hydrogen into the metal lattice is usually accompanied by a sharp change of the original metal lattice.
  • the metal hydride releases hydrogen (desorption) again as the temperature is raised and / or the pressure is reduced, with the release of hydrogen in turn associated with a change in the metal lattice. Due to the desorption of hydrogen, especially in repeated absorption-desorption processes (a-ß phase transitions), a fairly brittle metal hydride is formed in most metals, but it is insensitive to air and water. This effect is commonly known as "hydrogen embrittlement" and occurs with all prior art hydrogen storage devices.
  • the hydride-forming metal coating of the invention is characterized by a hydrogen desorption temperature of greater than 6O 0 C, preferably greater than 12O 0 C, in particular of greater than 200 ° C from.
  • the hydrogen desorption temperature denotes the temperature at which a metal laden with hydrogen begins to release the hydrogen back to the environment.
  • the measurement of the desorption temperature is preferably carried out under atmospheric pressure (1033 mbar) under a nitrogen atmosphere.
  • a pressure vessel according to the prior art is internally coated with, for example, a LaMg 2 Ni alloy.
  • the LaMg 2 Ni alloy has a strictly ordered crystal structure, which is retained even after hydrogen uptake.
  • the hydrogen atoms penetrate into the metal lattice via the regular interstices and in each case acquire one of the electrons which are freely mobile in the alloy. In this way, the hydrogen atoms combine chemically with the nickel atoms: This results in insulating NiH 4 molecules. This process is reversible only at temperatures above 200 0 C. As a result, the LaMg 2 Ni- hydride does not embrittle and protects the underlying container material as a hydrogen barrier. It should be noted that not every metal is suitable for forming such a hydrogen barrier. Rather, it is important that the desorption of the metal meets the criterion of the invention.
  • hydride-forming metals include hydride-forming metallic elements, such as. As palladium or magnesium, hydride-forming intermetallic compounds, such as ZrMn 2 , LaNi 5 or Mg 2 Ni, and hydride-forming alloys, such as. B. LaMg 2 Ni, TiNi-Ti 2 Ni or Mg-Mg 2 Ni. Furthermore, hydride-forming alkali aluminum compounds which can form so-called. Alanates are particularly advantageous.
  • the thickness of the hydride-forming metal layer is preferably less than 1 mm, preferably less than 50 .mu.m, very particularly preferably less than 1 .mu.m, in particular less than 50 nm.
  • the thickness of 10 nm should preferably not be undershot.
  • layer thicknesses greater than 1 mm there may be problematic stresses due to different thermal expansion coefficients.
  • the metal is first applied to the inside of the container, preferably by vapor deposition, coating from the liquid phase, in particular by chemical deposition or physical Deposition (hot dip of metal), electrochemical coating (deposition of metals from solutions of their salts at the cathode), vapor deposition, in particular by chemical vapor deposition (CVD) or physical vapor deposition (PVD) Film formation by solids or gases), sputtering, plating, thermal spraying (melting of powdered metals in a burner into droplets that strike and form a layer at high speed on the material to be coated) or electron beam evaporation.
  • vapor deposition coating from the liquid phase
  • electrochemical coating deposition of metals from solutions of their salts at the cathode
  • vapor deposition in particular by chemical vapor deposition (CVD) or physical vapor deposition (PVD) Film formation by solids or gases
  • sputtering plating
  • thermal spraying melting of powdered metals in a burner into droplets that strike and form
  • the layer thus applied settles in the first filling of the container with a hydrogen-containing composition in metal hydride.
  • the so-called ⁇ -phase catalytically split hydrogen molecules, that is to say hydrogen atoms, are dissolved into the metal lattice as interstitial or interstitial atoms on the metal surface. If the pressure in the pressure vessel now increases, the hydrogen concentration in the metal grid or in the intermetallic bond also increases. When saturation of the ⁇ phase is reached, the metal hydride forms. This is called the beta phase. Since this reaction is exothermic, the heat of reaction should be dissipated with thicker layers in order to avoid a standstill of the reaction.
  • This yff phase is in the case of the metal hydride coating according to the invention with a desorption temperature greater than 6O 0 C, z. B. a LaMg2Ni alloy, stable up to this desorption temperature. Pressure and temperature fluctuations below the desorption temperature do not harm the hydrogen barrier.
  • a leveling layer may be provided below the hydride-forming metal layer to compensate for any differences in thermal expansion coefficient between the vessel and the hydride-forming metal layer and / or the metal hydride to be formed.
  • the thermal expansion coefficient of the compensation layer preferably between that of the metal hydride to be formed and that of the container material.
  • the hydride-forming metal layer can be coated with a polymer or metal layer.
  • the application of the polymer or metal layer is carried out by methods of the prior art.
  • the container of the present invention preferably includes one or more safety-related accessories to protect the container from improper operating conditions (exceeding the design pressure or temperature).
  • suitable safety accessories are known per se and include in particular the aforementioned parts.
  • the filling of the container can be done in a known per se.
  • the container according to the invention is particularly suitable as a pressure vessel for the storage of compressed hydrogen-containing gases. Furthermore, it can also be used as a so-called "metal hydride reservoir.” A metal or a metal alloy is introduced into the container according to the invention and the hydrogen is dissolved in this metal or metal alloy Metal hydride: The metal or metal alloy is loaded with hydrogen by pressure, which can be expelled again by reducing the pressure and applying light heat.
  • the desorption temperature of the hydrogen storage material is suitably smaller than the desorption temperature of the hydride-forming coating according to the invention and is preferably less than 12O 0 C, more preferably less than 100 0 C, in particular smaller 8O 0 C. It is conveniently also determined at atmospheric pressure (1033 mbar) under a nitrogen atmosphere.
  • the storage of the container according to the invention provided with a metal hydride layer is not particularly limited. Conveniently, however, during the useful life of the container, the intended or unintentional heating of the metal hydride, which has formed from the hydride-forming metal coating, to a temperature above the hydrogen desorption temperature of the metal hydride avoided as possible.
  • the hydrogen containers according to the invention are so dense that they could be sent by post and the storage of hydrogen-powered vehicles in garages could be allowed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

L'invention concerne un contenant pour le stockage de compositions contenant de l'hydrogène, dont la face intérieure est revêtue d'au moins un métal qui forme des hydrures et qui présente une température de désorption de l'hydrogène supérieure à 60 °C. Le contenant selon l'invention peut être qualifié d'étanche à l'hydrogène et convient notamment pour le stockage de gaz contenant de l'hydrogène, d'hydrures métalliques, de nanotubes chargés en hydrogène, de nanocubes poreux chargés en hydrogène et de polymères dopés avec des métaux et chargés en hydrogène.
PCT/EP2007/002375 2007-02-05 2007-03-17 Contenant pour stocker des compositions contenant de l'hydrogène WO2008095515A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007006416.2 2007-02-05
DE102007006416A DE102007006416A1 (de) 2007-02-05 2007-02-05 Behälter zur Lagerung von wasserstoffhaltigen Zusammensetzungen

Publications (1)

Publication Number Publication Date
WO2008095515A1 true WO2008095515A1 (fr) 2008-08-14

Family

ID=38792516

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/002375 WO2008095515A1 (fr) 2007-02-05 2007-03-17 Contenant pour stocker des compositions contenant de l'hydrogène

Country Status (2)

Country Link
DE (1) DE102007006416A1 (fr)
WO (1) WO2008095515A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018131465A1 (de) * 2018-12-07 2020-06-10 Volkswagen Aktiengesellschaft Wasserstoffspeichertank und Brennstoffzellensystem sowie Kraftfahrzeug mit einem solchen

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2291446A1 (fr) * 1974-11-15 1976-06-11 Fulmer Res Inst Ltd Bouteille a gaz
DE3150133A1 (de) * 1981-12-18 1983-07-07 Daimler-Benz Ag, 7000 Stuttgart Verfahren zum schutz der behaelterwaende eines metallhydridspeichers vor deformation
FR2733296A1 (fr) * 1995-04-19 1996-10-25 Sardou Max Reservoir sous pression a renfort composite a permeation reduite
DE19826681A1 (de) * 1998-06-16 1999-12-23 Niels Marquardt Getter-Werkstoffe in Form dünner Schichten auf der Basis gassorbierender Metalle oder fullerenartiger Kohlenstoff-Nanostrukturen, Verfahren zur Herstellung dieser Schichten und Verwendung derselben zur Hochvakuumerzeugung und Gasspeicherung
WO2002088593A1 (fr) * 2001-04-25 2002-11-07 Eva Maria Moser Contenant etanche au gaz
US20050061685A1 (en) * 2003-09-18 2005-03-24 Struthers Ralph C. Storage device and method for sorption and desorption of molecular gas contained by storage sites of nano-filament laded reticulated aerogel

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2291446A1 (fr) * 1974-11-15 1976-06-11 Fulmer Res Inst Ltd Bouteille a gaz
DE3150133A1 (de) * 1981-12-18 1983-07-07 Daimler-Benz Ag, 7000 Stuttgart Verfahren zum schutz der behaelterwaende eines metallhydridspeichers vor deformation
FR2733296A1 (fr) * 1995-04-19 1996-10-25 Sardou Max Reservoir sous pression a renfort composite a permeation reduite
DE19826681A1 (de) * 1998-06-16 1999-12-23 Niels Marquardt Getter-Werkstoffe in Form dünner Schichten auf der Basis gassorbierender Metalle oder fullerenartiger Kohlenstoff-Nanostrukturen, Verfahren zur Herstellung dieser Schichten und Verwendung derselben zur Hochvakuumerzeugung und Gasspeicherung
WO2002088593A1 (fr) * 2001-04-25 2002-11-07 Eva Maria Moser Contenant etanche au gaz
US20050061685A1 (en) * 2003-09-18 2005-03-24 Struthers Ralph C. Storage device and method for sorption and desorption of molecular gas contained by storage sites of nano-filament laded reticulated aerogel

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Publication number Publication date
DE102007006416A1 (de) 2008-08-07

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