WO1992002935A1 - Production d'hydrogene controlee a partir de materiau pulverulent - Google Patents

Production d'hydrogene controlee a partir de materiau pulverulent Download PDF

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Publication number
WO1992002935A1
WO1992002935A1 PCT/GB1991/001332 GB9101332W WO9202935A1 WO 1992002935 A1 WO1992002935 A1 WO 1992002935A1 GB 9101332 W GB9101332 W GB 9101332W WO 9202935 A1 WO9202935 A1 WO 9202935A1
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WO
WIPO (PCT)
Prior art keywords
aluminium
hydrogen
container
permeable
powders
Prior art date
Application number
PCT/GB1991/001332
Other languages
English (en)
Inventor
Christopher John Newton
Original Assignee
Alcan International Limited
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 Alcan International Limited filed Critical Alcan International Limited
Publication of WO1992002935A1 publication Critical patent/WO1992002935A1/fr

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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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/34—Disposal of solid waste
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention concerns a composite component which allows for the controlled evolution of hydrogen gas which has particular applications for the storage of nuclear fuel elements.
  • Nuclear fuel elements are transported and stored in water filled vessels during which time radiolysis occurs evolving oxygen and peroxides which can produce an explosive gas mixture within the vessel.
  • a neutron shielding material is used that is fabricated from aluminium metal matrix composite (MMC) .
  • MMC aluminium metal matrix composite
  • An unexpected, but essential, by-product of the use of this shielding material is that corrosion of the .MMC evolves hydrogen and consumes certain products of radiolysis, i.e. oxygen and peroxides, rendering the gas space in the vessels an unexplosive mixture of hydrogen and nitrogen.
  • the present commercially supplied material for this application is a laminate of aluminium and porous aluminium metal matrix containing 30% boron carbide; this material corrodes slowly and in an uncontrolled way that may compromise its r-eutron absorption capabilities.
  • This shielding material is being replaced with boron containing stainless steel but there is still need to maintain the safe gas composition in these vessels from controlled aluminium corrosion.
  • Aluminium is corroded by water, the reaction evolves hydrogen and forms aluminium oxides, mainly aluminium hydroxide. It has been proposed that this reaction can be used to generate hydrogen for use in fuel cells for hydrogen powered vehicles or the like.
  • GB 2217512 proposes preventing oxygen accumulation in storage vessels by making the solution caustic, pH12 or greater, and introducing aluminium rods which are then corroded by the caustic solution and evolve hydrogen. To control corrosion the rods are partially coated with a corrosion resistant ceramic layer.
  • the present invention provides a composite component for the controlled release of hydrogen which comprises a metal alloy powder or a mixture of two or more metal powders within a permeable container.
  • the present invention further provides a method of generating hydrogen which method comprises contacting a permeable container containing a metal alloy powder, or a mixture of metal powders, with water.
  • the metal alloy is most preferably an aluminium alloy, or alteratively one of the metal powders is aluminium.
  • the aluminium alloy powder may be a mixture of one or more alloys.
  • the aluminium alloy powder is conveniently produced by a spray process; the overspray powder produced during spray deposition processes can be used.
  • the aluminium alloy powder may also be mixed with other components such as ceramics, e.g. graphite, boron carbide or silicon carbide.
  • the inventors have found that it is necessary to use an alloy, preferably an aluminium alloy or an aluminium metal matrix composite, rather than aluminium itself in order to ensure the necessary evolution of hydrogen over a long time period and provide controlled hydrogen evolution.
  • the present invention relies on the use of an aluminium alloy.
  • the object of the present invention may also be achieved by the use of an intimate mix of aluminium powder with one or more other powdered metals such as Mg, Cu, Fe etc. which might otherwise be conventionally alloyed with aluminium, the term "alloy" as used herein should be taken to include such a mix of metal powders, although this mode is not preferred.
  • Aluminium-lithium alloys generate hydrogen very rapidly.
  • alloys such as 2618 (Al-Cu-Mg) and 7075 (Al-Zu-Mg-Cu) exhibit an induction period before hydrogen evolution occurs.
  • Addition of other components which stimulate galvanic corrosion e.g. ceramics such as B 4 C.,, SiC or C may also be added to increase hydrogen evolution rate. These components may be added separately in powder form to the aluminium alloy powder. It is possible to tailor the hydrogen evolution profile by combining one or more alloys or metal matrix composite powders.
  • the powder may be loose or compacted. By careful sizing of the component and the particles the gas can escape through the porosity inherent in the powder. It is preferred to only partially fill the permeable container with the powder. On contact with water the powder reacts and to some degree expands and forms a highly porous solid mass within the container, through which water and hydrogen are able to move quite freely.
  • the hydrogen evolution profile and corrosion characteristics can be varied by choice of particle size and packing. A larger initial void volume in the container causes a longer delay before gas evolution. The more closely packed the less porous the solid powder mass formed is which results in a slower reaction rate. Size of powder particles is not critical. Typically, they will be in the range 10-100 microns. Smaller particles show a higher reaction rate, presumably due to their greater surface area to volume ratio.
  • the container which holds the powder is permeable to water and hydrogen but impermeable to the reaction products.
  • the container may be constructed entirely from a permeable material or be provided with a permeable portion.
  • a preferred permeable material is a porous membrane.
  • Particularly preferred is a porous membrane in the form of a ceramic coated fine wire mesh.
  • Such a membrane is available under the name Ceramesh.
  • the membrane allows water into the powder but retains gelatinous aluminium hydroxide corrosion products.
  • the mesh acts to retain dimensional stability of the component as it corrodes.
  • the use of this form of membrane also has the advantage that all shape fabrication can be contained in the mesh used to house the powder.
  • the technology to handle both simple and complex hollow shapes in wire mesh is available and removes the need for complex processing of the powders.
  • the component can be fabricated to any desired size and shape to fit a particular application.
  • the container comprises a corrosion resistant tube, e.g. stainless steel, containing the alloy powder and closed at each end by a permeable membrane.
  • a corrosion resistant tube e.g. stainless steel
  • This construction has the advantage of being more robust.
  • the packaging of the alloy powder within permeable containers has the advantage that once spent, the unit may be removed as a whole for easy disposal and also lends itself to automated or remote handling. This can be particularly important if the unit is contaminated with radioactivity.
  • any permeable material which allows passage of water and hydrogen but retains the reaction product is suitable for use in the present invention.
  • the permeable material should not be polymer based due to possible degradation by radiation.
  • the hydrogen evolution profile may also be altered by changing the relative permeability e.g. pore size of the unit. A smaller pore/mesh size tends to reduce the rate of hydrogen evolution.
  • the aluminium alloy powder When placed in an aqueous environment the aluminium alloy powder will corrode releasing hydrogen at a rate dependent on its composition, particle size fractions and the proportions of galvanic couples available (these can be balanced using graphite or carbide containing particles to act as local cathodes) .
  • the powdered aluminium alloy is found to be an extremely active oxygen getter, reacting with oxygen or peroxides dissolved in the water to form aluminium oxides.
  • the component When used inside radioactive fuel storage vessels the component will corrode and consume, certain products of radiolysis e.g. oxygen and peroxides, changing the gas space in the vessels to an unexplosive mixture of hydrogen and nitrogen. Initially, the oxygen in the space above the fuel elements dissolves in the water, reacts with the aluminium alloy and is replaced with hydrogen.
  • the present invention also provides long term protection against oxygen or peroxides accumulation resulting from hydrolysis which are removed from solution as they are formed.
  • the present invention also has the advantage of being responsive to the oxygen level in the storage vessel in that the presence of oxygen promotes corrosion of the component and corrosion slows when oxygen levels are reduced.
  • the present invention provides a method of storing irradiated nuclear material in a vessel containing water which comprises introducing into said vessel a permeable container containing metal alloy powder or a mixture of metal powders.
  • the present invention could be applied to any situation where it is desired to remove oxygen from an aqueous solution, of from a gas in contact with such a solution. Accordingly the present invention further provides a method of removing oxygen from an aqueous solution or from gas in contact with such a solution which method comprises introducing into said solution a permeable container containing a metal alloy powder o a mixture of one or more metal powders.
  • the present invention provides a component for safe control of gas chemistry during nuclear fuel storage and transport.
  • the component can be produced with minimum fabrication. It allows a controlled rate of corrosion of aluminium during nuclear fuel storage.
  • the present composite material used for this application corrodes slowly and is difficult and costly to fabricate. For suitable control of gas within a storage vessel using presently
  • the present invention has been illustrated with particular reference to evolution of hydrogen and control of gas composition within a sealed container such as might be used to transport radioactive fuel and waste material.
  • the component of the present invention could also be used to allow controlled hydrogen gas generation in other applications such as fuel cells, utilising aluminium scrap, powders and swarf etc.
  • the present invention is described with reference particularly to aluminium it is also possible to use other metals including zinc and magnesium particulates alone or in combination with aluminium.
  • the present invention is exemplifed using overspray powder produced during conventional spray deposition processes and conventional aluminium alloys, chosen for their structural performance, are used. It is of course possible to deliberately spray a powder rather than just use overspray waste but it is also possible to produce alloys specifically chosen for their hydrogen generating or oxygen getting capabilities. For example, use of lithium produces a highly active hydrogen generating alloy powder. Other elements such as Cd, Sn, Bi, Sb, In, Ge, B, Se, Te, P, As, C, Re, Pd, Nb, Si and Zn may also be alloyed or mixed with aluminium to give an enhanced rate of hydrogen generation.
  • the containers of alloy powder could be used to generate hydrogen for fuel cells in a controlled manner since the hydrogen evolution profile can be reliably controlled and predicted. For example, it may be desired to produce an initial rapid burst of hydrogen followed by a more steady release e.g. when initially starting a hydrogen powered unit or as an emergency back up source in which case a unit containing Al-Li powder or a mixture with other alloys, could be introduced. Hydrogen can also be used in control of generator fires and strategically placed units could be easily stored but ready so that they can be contacted with water to provide a ready source of hydrogen.
  • the packaging of the alloy powder within permeable containers and the ability to tailor the hydrogen evolution profile mean that this invention is applicable to any situation where hydrogen generation is required. The invention will now be illustrated by reference to the following examples Example 1.
  • Aluminium 8090 alloy powder obtained as overspray material from a spray deposition process was placed in tubing fabricated from ZrO- coated fine wire mesh.
  • the tubes containing the powder were immersed in water and the volume of hydrogen evolved determined.
  • Figure 1 shows the results obtained as volume of hydrogen evolved per gram of aluminium with respect to time.
  • Al-Li-Mg-Cu 8090 and a Al-4.5% Li binary alloy are shown in Figures 3 and 4 as a function of time. Also shown are data for a 50%:50% mixtures of 8090/7075 monolithic and SiC MMC powders. It was evident from these results that the rate of hydrogen evolution changes with time and that it depends on powder composition. The presence of SiC stimulated an increase in gas evolution rate when 8090 SiC MMC was compared to 8090 monolithic powder. The Al-Li alloy powder was violently reactive with water, this alloy powder generates a large volume of hydrogen rapidly and could be useful for applications where a rapid, high output of hydrogen is required. Alloy powders 2618 and 7075 showed a characteristic induction period prior to release of hydrogen.
  • Tests were performed to determine if the overspray powder was capable of reducing the oxygen concentration in an enclosed vessel part-filled with water. This is a simple simulation of a radioactive fuel storage vessel.
  • the vessels were held at temperature in a calibrated water bath.
  • Measuring cylinders were prepared according to the method described above and sequential gas samples were taken from the same sealed measuring cylinder at 25°C, at regular time intervals. This approach incurred the penalty that the enclosed gas space was altered by the action of extracting a sample. However, this error was compensated for by employing the nitrogen response of the gas sample as a control reference. An additional source of error was contamination of the test gas with air through the punctured septum. If this had occurred the oxygen concentration should not have decreased. Two tests of this type were attempted but only one remained pressurised throughout the planned test period of 15 days.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention se rapporte à un constituant servant à la production contrôlée d'hydrogène et à la suppression d'oxygène et utilisant une poudre d'alliage d'aluminium. Ce constituant s'adresse particulièrement au contrôle de l'oxygène à l'intérieur d'un réservoir scellé tel qu'un conteneur de combustible radioactif.
PCT/GB1991/001332 1990-08-03 1991-08-05 Production d'hydrogene controlee a partir de materiau pulverulent WO1992002935A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9017038.2 1990-08-03
GB909017038A GB9017038D0 (en) 1990-08-03 1990-08-03 Controlled hydrogen generation from composite powder material

Publications (1)

Publication Number Publication Date
WO1992002935A1 true WO1992002935A1 (fr) 1992-02-20

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PCT/GB1991/001332 WO1992002935A1 (fr) 1990-08-03 1991-08-05 Production d'hydrogene controlee a partir de materiau pulverulent

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AU (1) AU8308591A (fr)
GB (1) GB9017038D0 (fr)
WO (1) WO1992002935A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1829820A1 (fr) * 2006-02-16 2007-09-05 Sociedad española de carburos metalicos, S.A. Méthode pour l'obtention d'hydrogène

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1048642B (de) * 1959-01-15 München Bernhard Philbert Einrichtung zur Beseitigung 'von Abfallsubstanzen, insbesondere von radioaktiven Abfallsubstanzen und radioaktiv oder sonstwie verseuchten Gegenständen
GB2077026A (en) * 1980-05-16 1981-12-09 Nukem Gmbh A process for the safe storage of tritium
US4424903A (en) * 1980-03-26 1984-01-10 Kernforschungsanlage Julich Gmbh Apparatus for storing tritium, especially tritium wastes from nuclear power plants
GB2217512A (en) * 1988-04-21 1989-10-25 British Nuclear Fuels Plc Storage of nuclear fuel
US4943394A (en) * 1988-01-30 1990-07-24 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method of storing radioactive waste without risk of hydrogen escape
FR2642220A1 (fr) * 1989-01-26 1990-07-27 British Nuclear Fuels Plc Recipient pour matiere radioactive, comportant un dispositif pour catalyser la recombinaison de l'hydrogene et de l'oxygene gazeux du recipient pour donner de l'eau

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1048642B (de) * 1959-01-15 München Bernhard Philbert Einrichtung zur Beseitigung 'von Abfallsubstanzen, insbesondere von radioaktiven Abfallsubstanzen und radioaktiv oder sonstwie verseuchten Gegenständen
US4424903A (en) * 1980-03-26 1984-01-10 Kernforschungsanlage Julich Gmbh Apparatus for storing tritium, especially tritium wastes from nuclear power plants
GB2077026A (en) * 1980-05-16 1981-12-09 Nukem Gmbh A process for the safe storage of tritium
US4943394A (en) * 1988-01-30 1990-07-24 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method of storing radioactive waste without risk of hydrogen escape
GB2217512A (en) * 1988-04-21 1989-10-25 British Nuclear Fuels Plc Storage of nuclear fuel
FR2642220A1 (fr) * 1989-01-26 1990-07-27 British Nuclear Fuels Plc Recipient pour matiere radioactive, comportant un dispositif pour catalyser la recombinaison de l'hydrogene et de l'oxygene gazeux du recipient pour donner de l'eau

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1829820A1 (fr) * 2006-02-16 2007-09-05 Sociedad española de carburos metalicos, S.A. Méthode pour l'obtention d'hydrogène

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GB9017038D0 (en) 1990-09-19
AU8308591A (en) 1992-03-02

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