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US20020028345A1 - Process for preparing a composite metal membrane, the composite metal membrane prepared therewith and its use - Google Patents

Process for preparing a composite metal membrane, the composite metal membrane prepared therewith and its use Download PDF

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Publication number
US20020028345A1
US20020028345A1 US09/927,775 US92777501A US2002028345A1 US 20020028345 A1 US20020028345 A1 US 20020028345A1 US 92777501 A US92777501 A US 92777501A US 2002028345 A1 US2002028345 A1 US 2002028345A1
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Prior art keywords
membrane
metal
composite
alloy
support
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English (en)
Inventor
Bernd Kempf
Werner Kuhn
Ernst Drost
Hans Beyer
Meike Roos
Stefan Wieland
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DMC2 Degussa Metals Catalysts Cerdec AG
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DMC2 Degussa Metals Catalysts Cerdec AG
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Assigned to DMC2 DEGUSSA METALS CATALYSTS CERDEC AG reassignment DMC2 DEGUSSA METALS CATALYSTS CERDEC AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROOS, MEIKE, BEYER, HANS HERMANN, DROST, ERNST, KEMPF, BERND, KUHN, WERNER, WIELAND, STEFAN
Publication of US20020028345A1 publication Critical patent/US20020028345A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
    • C01B3/505—Membranes containing palladium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0687—Reactant purification by the use of membranes or filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C01B2203/041—In-situ membrane purification during hydrogen production
    • 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
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12875—Platinum group metal-base component

Definitions

  • the present invention provides a process for preparing a composite metal membrane on a porous membrane support.
  • Composite metal membranes of this type are used for separating gas mixtures, in particular for separating hydrogen from a reformate gas for supplying fuel cells with the required fuel gas.
  • palladium or palladium alloy membranes on either porous or non-porous supports are normally used, such as compact palladium or palladium alloy membranes.
  • Foils made of hydrogen-permeable metals, inter alia, are used as non-porous supports
  • the permeability of the membranes for hydrogen increases with temperature. Typical operating temperatures are therefore between 300 and 600° C.
  • T. S. Moss and R. C. Dye [Proc.-Natl. Hydrogen Assoc. Annu. U.S. Hydrogen Meet., 8th (1997), 357-365] and T. S. Moss, N. M. Peachey, R. C. Snow and R. C. Dye [Int. J. Hydrogen Energy 23(2), (1998), 99-106 ISSN: 0360-3199] describe the preparation and use of a membrane which is obtained by applying Pd or PdAg by cathode atomization to both faces of a foil of a metal from group 5B.
  • the thickness of the layers applied to the two faces may be varied so that an asymmetric component is produced (for example: 0.1 ⁇ m Pd/40 ⁇ m V/0.5 ⁇ m Pd).
  • Permeation trials demonstrate twenty-fold higher hydrogen permeation as compared with self-supported Pd membranes. Accordingly, the membrane described is suitable for use in a PEM fuel cell system instead of the traditional catalytic gas purification steps (water gas shift reaction and preferential oxidation of CO).
  • GB 1 292 025 describes the use of iron, vanadium, tantalum, nickel, niobium or alloys thereof as a non-porous support for a non-coherent, or porous, palladium (alloy) layer.
  • the palladium layer is applied by a pressing, spraying or electrodeposition process in a thickness of about 0.6 mm to a support with a thickness of 12.7 mm. Then the thickness of the laminate produced in this way is reduced to 0.04 to 0.01 mm by rolling.
  • particularly thin hydrogen separation membranes can be prepared by alternate electrodeposition of palladium and an alloy metal from group 1B or 8 of the periodic system of elements to a metallic support which is not specified in any more detail.
  • appropriate thermal treatment may follow the electrodeposition process.
  • Either metallic or ceramic materials are suitable as porous supports for palladium (alloy) membranes.
  • palladium may be applied to a porous support by a plasma spray process for example.
  • a defect-free palladium membrane (thickness of layer 20-25 ⁇ m) can be prepared on a tubular support made of porous stainless steel 316L in a electrolyses plating process and integrated as a component in a steam reforming reactor.
  • a purified reformate containing 95 vol. % H 2 is obtained.
  • the optimum working temperature is very restricted because below 300° C. the palladium membrane starts to become brittle due to the presence of hydrogen, whereas above 400 to 450° C. the alloying constituents in the stainless steel support diffuse into the palladium layer and lead to impairment of the permeation properties.
  • Electrolyses plating processes are preferably used for coating ceramic supports.
  • CVD coating of an asymmetric, porous ceramic with palladium is described by E. Kikuchi [Catal. Today 56 (2000) 97-101] and this is used in a methane steam reforming reactor for separating hydrogen from the reformate.
  • the minimum layer thickness is 4.5 ⁇ m. If the layers are thinner, the gas-tightness of the layer can no longer be guaranteed.
  • coating with palladium alloys is also possible, wherein the alloy with silver prevents embrittlement of the palladium membrane and increases the permeability to hydrogen.
  • membranes which are provided with a reactive layer in addition to the hydrogen separation layer are also described for applications in fuel cell systems.
  • the porous support for a palladium (alloy) membrane may be covered, for example on the face which is not coated with Pd, with a combustion catalyst. The heat released during combustion at the reactive face is then simultaneously used to maintain the operating temperature of the hydrogen separation membrane (EP 0924162 A1).
  • Such a component may then be integrated in the reforming process downstream of a reformer or incorporated directly in the reformer (EP 0924161 A1, EP 0924163 A1).
  • EP 0945174 A1 discloses a design for the use of universally constructed layered membranes which may contain both fine-pore, separation-selective plastics and/or several ceramic layers and/or layers made of a separation-selective metal (preferably from groups 4B, 5B or 8), wherein these layers are applied to a porous support (glass, ceramic, expanded metal, carbon or porous plastics).
  • the objective of developing metal membranes for the separation of hydrogen from gas mixtures is to obtain high rates of permeation for the hydrogen.
  • the metal membrane must be designed to be as thin as possible while avoiding the occurrence of leakiness in the form of holes.
  • Such membranes can be processed only in a supported form.
  • the membrane support In order for the membrane support to have as little effect as possible on the permeation of hydrogen, it must have a high porosity.
  • the difficulty in the case of known processes for preparing supported membranes, of depositing a defect-free membrane on a porous support. There are two problems involved here.
  • the methods described for depositing for example palladium or a palladium alloy can guarantee a relatively defect-free membrane layer only above a certain thickness of the layer.
  • This minimum layer thickness is about 4 to 5 ⁇ m.
  • the coating techniques used for applying the membrane layer to the porous membrane support means that the average pore diameter of the membrane support ought not exceed a certain value because otherwise it would be impossible to apply coherent and defect-free coatings.
  • the maximum pore sizes of known membrane support materials, such as porous ceramics or porous metal supports, are therefore less than 0.1 ⁇ m. This means that the resistance to flow of the gas through the pores cannot be reduced to a desirable extent.
  • WO 89/04556 describes an electrochemical process for preparing a pore-free membrane based on palladium supported by a porous metal structure.
  • a pore-free palladium(-silver) membrane on a porous, metallic support is produced by coating one face of a metal alloy foil (preferably brass) with palladium or palladium/silver (thickness of palladium layer: about 1 ⁇ m) using an electrodeposition process.
  • the porosity of the support is produced later by dissolving the base metal components out of the brass foil.
  • Dissolution is performed electrochemically, wherein, in a cyclic process, both metal support components are first taken into solution but the more base metal component is redeposited directly onto the palladium layer (electrochemical recrystallisation).
  • the less base metal component in the foil-shaped alloy thus goes virtually quantitatively into solution so that a porous metal structure, preferably a porous copper structure, remains as a support for the palladium/silver membrane.
  • An object of the present invention is to provide a simple and cost-effective process for the preparation of a composite metal membrane for separating hydrogen from gas mixtures.
  • Another object of the invention is to obtain composite metal membranes, the membrane supports for which have a hitherto unrealizable, high porosity (average pore sizes and pore volumes).
  • a further object of the present invention is to obtain composite metal membranes in which the average pore size of the membrane support is greater than the thickness of the metal membranes.
  • the above and other objects of the invention can be achieved by a process for preparing a composite metal membrane which contains a thin metal membrane with a desired thickness and a metallic membrane support with a porous structure, wherein the metal membrane and the membrane support comprises two different metals or metal alloys.
  • the process is characterized in that a precursor of the metal membrane is placed on a non-porous precursor of the membrane support, the metal composite is produced between the two precursors, the desired thickness of the metal membrane is obtained by mechanically working the metal composite and then the porous structure for the membrane support is produced.
  • FIG. 1 is a schematic cross section of an asymmetric composite metal membrane according to the invention
  • FIG. 2 is a schematic cross section of a composite metal membrane of the invention after electrochemical action
  • FIG. 3 is a schematic cross section of a composite metal membrane of the invention with a temporary covering membrane
  • FIG. 4 is a schematic cross section of a symmetric composite metal membrane of the invention before dissolution
  • FIG. 5 is a schematic cross section of a completed composite metal membrane of the invention.
  • FIG. 6 is an electron micrograph of the composite metal membrane of the invention.
  • FIG. 7 is an enlarged view of the cross section of FIG. 6.
  • FIGS. 1 and 2 illustrate the production of an asymmetric composite metal membrane ( 1 ) as described in example 2.
  • the composite metal membrane ( 1 ) comprises a metal membrane ( 2 ) (e.g. made from PdAg23) and a membrane support ( 3 ) comprising an eutectic alloy (e.g. AgCu28).
  • the eutectic alloy comprises two phase regions ( 5 ) and ( 6 ).
  • Phase regions ( 5 ) are the more noble regions which are destined for forming the membrane support after dissolution of the more electronegative material from phase regions ( 6 ).
  • Phase regions ( 5 ) are of less electronegative phase, e.g. the Ag-rich phase of AgCu28 Phase regions (c) are of more electronegative phase, e.g. the Cu-rich phase of AgCu28.
  • FIG. 1 shows the situation after metal working (e.g. rolling) the laminate down to the desired thickness but before dissolution of the material from phase regions ( 6 ).
  • FIG. 2 shows the cross-section of FIG. 1 after electrochemical dissolution of the more electronegative material from phase regions ( 6 ). Due to this electrochemical dissolution, the phase regions ( 6 ) are transformed into the pores of the completed membrane support. The resulting pore structure is an open pore structure providing unobstructed flow paths for the gases from the interface ( 4 ) to the opposite face of the membrane support ( 3 ).
  • FIG. 3 shows a cross-section through a composite metal membrane ( 1 ) with a temporary covering membrane ( 10 ) (e.g. made of copper) before the temporary membrane and the phase regions ( 6 ) have been dissolved. There is an interface between temporary covering membrane ( 10 ) and the metal membrane ( 2 ). After dissolution of the more electronegative material from phase regions ( 6 ) and of the temporary covering membrane ( 10 ) the same composite metal membrane as shown in FIG. 2 results.
  • a temporary covering membrane e.g. made of copper
  • This method is used in example 2 to produce an asymmetric composite metal membrane.
  • FIGS. 4 and 5 illustrate the production of a symmetric composite metal membrane.
  • FIG. 4 shows the situation before dissolution of the more electronegative material from phase regions ( 6 ) while
  • FIG. 5 shows the completed composite metal membrane after dissolution of the more electronegative material.
  • the second membrane support ( 11 ) is comprised of a eutectic alloy of two phase regions ( 5 ) and ( 6 ).
  • the eutectic alloy can be AgCu28.
  • FIGS. 6 and 7 show experimentally obtained composite metal membranes of the symmetric type. These cross sections were taken with a scanning electron microscope.
  • FIG. 7 is an enlarged view of the cross section of FIG. 6.
  • the pore structure of the membrane support can clearly be seen.
  • the thickness of the membrane is approximately 5 ⁇ m as can be derived by comparing with the ruler in the lower region of the photographs.
  • solid, pore-free metal foils are initially used to produce the composite metal membrane.
  • a metal foil with a thickness from 50 to 100 ⁇ m is used as precursor.
  • a foil of this thickness can be produced virtually pore-free in outstanding quality via a metal-processing route.
  • This foil is placed on a thicker metal foil (or sheet) which later forms the membrane support.
  • the composite is formed between the two metal foils. This is preferably achieved by roll-bonding, explosive plating or diffusion welding. The result is a two-layered composite. Before bonding the metal foils, it is recommended that the contact areas be carefully cleaned and roughened in a known manner.
  • the metal composite When producing the metal composite by this process, a certain reduction in thickness takes place. After this, further mechanical working procedures by means of rolling, pressing, flow moulding, deep-drawing or combinations of these forming techniques take place until the desired thickness of the metal membrane is achieved.
  • the measures required for this such as, for example, thermal treatments between the individual forming steps, are known to a person skilled in the art of metals.
  • the shape of the final composite metal membrane is not restricted to flat membranes. Rather, the composite metal membrane may be shaped to give various types of geometric structures which also have the advantage that their mechanical stability is substantially better than that of a flat membrane with the same wall thickness.
  • the techniques which can be used for this are, for example, rolling, pressing, flow moulding or deepdrawing. Mechanical working the composite metal membrane to give thin tubules by means of a drawing process is mentioned in particular here.
  • the ratio of thicknesses between metal membrane and membrane support in the final composite metal membrane is preferably between 1:5 and 1:20 and corresponds to the ratio of the thicknesses of the initial foils before metal-processing has been performed.
  • the metal-processing production of the metal membrane described has the essential advantage over known coating processes that a pore-free metal foil of high quality can be used initially and its freedom from pores can also be guaranteed after the reforming procedures.
  • the porous structure of the support foil produced only after completing the reforming procedures.
  • the porous structure may be either a regular perforated structure, which can be produced, for example, by chemical, electrochemical or physical etching processes, or else an open-pore structure with a statistical distribution of pore sizes and pore arrangements.
  • the latter structure is preferably used. It can be produced when the precursor for the membrane support contains a two-phase or multi-phase metal alloy and, after producing and reforming the metal composite, one or more alloy phases are electrochemically dissolved out of the membrane support.
  • the membrane support preferably contains a eutectic alloy, wherein the porous structure is formed by electrochemical dissolution of the more base (more electronegative) phase.
  • the eutectic alloy AgCu which contains an Ag-rich and a Cu-rich phase, for example, is especially suitable.
  • the Cu-rich phase can be very easily dissolved out via an electrochemical route.
  • the Ag-rich phase then remains almost untouched.
  • the membrane support in accordance with WO 89/04556 is completely dissolved and then rebuilt, a rigid structure consisting of the Ag-rich alloy phase is retained in accordance with the present process, with corresponding positive effects on the stability of the membrane support.
  • Another advantage of the process according to the invention comprises the fact that the domain structure of the two-phase or multi-phase metallic membrane support can be altered or adjusted within certain limits by choosing the alloy composition and by thermal treatment so that deliberate control of the porosity of the membrane support is possible.
  • the pore diameter can be varied by the present process to a much greater extent than when using the traditional process.
  • the average pore diameter in the membrane support can be greater than the thickness of the metal membrane. Average pore diameters in the membrane support greater than 0.5 and less than 10 ⁇ m are preferably striven for.
  • the copper content of the eutectic alloy is preferably between 20 and 80 wt. %, with respect to the total weight of alloy.
  • the composite metal membrane is subjected to a thermal treatment at 400 to 750° C. On the one hand this reverses any structural changes resulting from the metal working process and on the other hand affects the structural characteristics of the membrane support, and thus its subsequent porosity in a desirable manner.
  • the proposed process is suitable for the preparation of supported metal membranes from a variety of materials.
  • the metal membranes preferably contain palladium or palladium alloys which have especially advantageous properties as gas separation membranes.
  • Suitable palladium alloys are, for example, PdAg23, PdCu40 or a PdY alloy.
  • Another characteristic of the process is the fact that the structure of the boundary surface of the metal membrane is provided by the surface structure of the metal foil used in the preparation and thus can be relatively smooth. Subsequent production of porosity in the membrane support affects the surface structure of the metal membrane to only an insubstantial extent. The final metal membrane therefore has a very uniform thickness and is substantially smooth.
  • the porous, metallic membrane support is used to support the thin metal membrane, wherein the membrane support should impair the permeability of the laminated membrane as little as possible, as compared with a freely suspended metal membrane of the same thickness.
  • a certain minimum thickness of membrane support is required in order to ensure the requisite mechanical stability of the laminated membrane.
  • the thickness of the membrane support should therefore be less than 100 ⁇ m and should not be less than 20 ⁇ m. Membrane support thicknesses between 50 and 20 ⁇ m are preferably striven for.
  • the process described so far produces the composite metal membrane by metal working of a two-layered arrangement of a precursor of the metal membrane and a precursor of the membrane support.
  • a temporary covering membrane for the metal membrane in order to improve the processability during the metal working process.
  • the covering membrane may be removed before, at the same time as or after the production of porosity in the membrane support.
  • a second membrane support is used instead of the temporary covering membrane.
  • the metal membrane is located between two membrane supports.
  • the second membrane support advantageously consists of the same material as the first membrane support.
  • the process products of this process variant are thus symmetric, three-layered composite metal membranes, wherein both faces of the gas separation membrane are covered by porous metallic membrane supports.
  • this process variant also has better processability during the metal working process than is the case when preparing the two-layered composite metal membrane.
  • the specifications already mentioned with regard to the choice of materials for the metal membrane and the membrane support and also for their thicknesses in the final metal composite and for the porosity of the membrane support also still apply.
  • the composite metal membranes prepared by the process according to the invention are preferably used for the separation of hydrogen from gas mixtures, in particular from reformate gas.
  • the various process variants enable the preparation of composite metal membranes in which the membrane supports have a previously unrealisable, high, porosity (average pore sizes and pore volumes). With thicknesses of gas separation membrane of 1 to 20, preferably 1 to 5 ⁇ m, the membrane support(s) have an average pore size greater than 0.5 and less than 10 ⁇ m. Thus, it is possible for the first time, using the process described above, to produce composite metal membranes in which the average pore size in the membrane support(s) is greater than the thickness of the gas separation membrane. These composite metal membranes therefore have outstanding hydrogen permeability.
  • a foil of PdAg23 (dimensions: 30 ⁇ 0.07 ⁇ 500 mm) was placed between two foils of AgCu28 (dimensions: 30 ⁇ 1.0 ⁇ 500 mm). The contact areas were carefully cleaned and mechanically roughened beforehand. The three foils were welded together at a front face and then bonded to each other by metal-processing in a hot roll-bonding procedure. For this purpose, the foils were annealed in a tubular furnace at 600° C. for a period of 20 min under an inert gas (argon) and then rolled out on preheated roll faces (200° C.) with a deformation aspect of 45% to form one composite foil.
  • argon inert gas
  • the composite metal foil was subjected to thermal treatment under an inert gas (argon) at 600° C. for a period of 30 min and cleaned by cathodic degreasing.
  • the Cu-rich phase in the AgCu28 alloy was then anodically dissolved out in a sulfuric acid electrolyte with 10% strength sulfuric acid operated potentiostatically at 40° C. and with a constant bath voltage of 220 mV over the course of 16 hours. This produced an open-pore structure in the membrane support foils.
  • a foil of PdAg23 (dimensions 30 ⁇ 0.07 ⁇ 500 mm) was placed on a foil of AgCu28 (dimensions 30 ⁇ 1.0 ⁇ 500 mm). The two foils were welded together at a front face. The contact areas of the foils had been cleaned and roughened beforehand, as described in example 1.
  • the metal laminate was produced by hot roll-bonding as in example 1. Further processing was also performed as described in example 1.
  • a gas separation membrane supported on one face was also prepared.
  • the foil of PdAg23 (dimensions: 30 ⁇ 0.07 ⁇ 500 mm) was placed between two strips, one of which consisted of an AgCu28 alloy and subsequently formed the membrane support, whereas the second foil consisted of copper.
  • the copper foil was used only as a temporary support foil and was completely removed during the electrolytic treatment to form the pores in the membrane support foil.
  • a round plate of PdAg23 (diameter 60 mm; thickness 1 mm) was placed between a lower round plate of AgCu28 (diameter 60 mm; thickness 12 mm) and an upper round plate of copper (diameter 60 mm, thickness 8 mm).
  • the contact areas had been carefully cleaned and mechanically roughened beforehand.
  • the round plates were inserted in a hydraulic press and pressed together with a compression force of 2000 kg/cm 2 to produce the metal composite. This produced a reduction in thickness of about 10%.
  • Cylindrical pellets with a diameter of 12 mm were cut out of the laminated plate produced in this way and moulded into tubular blanks, the walls of which consisted, from the inside to the outside, of a layer of copper, a layer of PdAg23 and a layer of AgCu28, in an inverted flow-moulding process using a hydraulic press.
  • the tubular blanks were drawn out by conventional tube drawing, after thermal treatment at 600° C.
  • Example 4 was repeated, but this time the round plate of copper used only for temporary support purposes was omitted so that the PdAg surface was present directly on the internal face of the tubes prior to the final electrochemical treatment. As a result, difficult dissolution of the internal coating, in particular in the case of small tube diameters, was not required.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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US09/927,775 2000-08-12 2001-08-13 Process for preparing a composite metal membrane, the composite metal membrane prepared therewith and its use Abandoned US20020028345A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10039595.3 2000-08-12
DE10039595A DE10039595B4 (de) 2000-08-12 2000-08-12 Verfahren zur Herstellung einer Metallverbundmembran, damit hergestellte Metallverbundmembran und deren Verwendung

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US20020020298A1 (en) * 2000-08-12 2002-02-21 Ernst Drost Supported metal membrane, a process for its preparation and use
US20030233940A1 (en) * 2002-06-07 2003-12-25 Hideaki Takatani Hydrogen separation membrane, hydrogen separation unit, and manufacturing method for hydrogen separation membrane
US20040040416A1 (en) * 2002-08-27 2004-03-04 Jonah Erlebacher Method of forming nanoporous membranes
US20040245191A1 (en) * 2002-07-25 2004-12-09 Hiroshi Yagi Thin film supporting substrate for used in filter for hydrogen production filter and method for manufacturing filter for hydrogen production
US20050242022A1 (en) * 2004-03-30 2005-11-03 Sangkyun Kang Gas/ion species selective membrane supported by multi-stage nano-hole array metal structure
US20140151287A1 (en) * 2012-12-03 2014-06-05 Omar H. Balcazar Screen and method of making the same
US20150342469A1 (en) * 2012-12-21 2015-12-03 Heraeus Deutschland GmbH & Co. KG Thin metal membrane with support
US20170014754A1 (en) * 2014-03-31 2017-01-19 Fujifilm Corporation Gas separation composite and method of producing same
CN113560708A (zh) * 2021-07-29 2021-10-29 西安天力金属复合材料股份有限公司 一种钯基合金薄膜和多孔不锈钢载体的连接方法
CN116196771A (zh) * 2023-04-28 2023-06-02 成都华之煜新材料有限公司 一种高孔隙率非对称多孔金属膜制备方法

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JP2005243416A (ja) * 2004-02-26 2005-09-08 Toyota Motor Corp 燃料電池システム
EP2552571B1 (de) * 2010-03-26 2018-12-26 Shell Oil Company Verfahren zur herstellung einer geträgerten gastrennmembran
JP5825465B2 (ja) * 2011-01-27 2015-12-02 国立研究開発法人産業技術総合研究所 水素分離膜、その製造方法及び水素分離方法
KR101284115B1 (ko) * 2011-08-18 2013-07-10 한국에너지기술연구원 이트리움으로 도핑된 바나듐 기재 합금 수소 분리막과 이를 이용한 수소 분리방법
CN103998119B (zh) * 2011-12-20 2016-10-19 国际壳牌研究有限公司 制造复合金属气体分离膜的方法
CN105854629B (zh) * 2016-03-23 2019-10-08 成都易态科技有限公司 多孔薄膜及其制备方法
WO2021106203A1 (ja) * 2019-11-29 2021-06-03 国立大学法人東海国立大学機構 水素透過装置、水素透過金属膜、水素透過金属膜の製造方法、ガスケット、及びガスケットの製造方法
CN111804921A (zh) * 2020-07-17 2020-10-23 江苏云才材料有限公司 一种梯度金属多孔材料的制备方法

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US6649559B2 (en) * 2000-08-12 2003-11-18 Dmc2 Degussa Metals Catalysts Cerdec Ag Supported metal membrane, a process for its preparation and use
US20020020298A1 (en) * 2000-08-12 2002-02-21 Ernst Drost Supported metal membrane, a process for its preparation and use
EP1375421A3 (de) * 2002-06-07 2005-04-20 Mitsubishi Heavy Industries, Ltd. Membran zur Trennung von Wasserstoff, Wasserstofftrenneinheit und Verfahren zur Herstellung einer Membran zur Trennung von Wasserstoff
US20030233940A1 (en) * 2002-06-07 2003-12-25 Hideaki Takatani Hydrogen separation membrane, hydrogen separation unit, and manufacturing method for hydrogen separation membrane
US7144444B2 (en) 2002-06-07 2006-12-05 Mitsubishi Heavy Industries, Ltd. Hydrogen separation membrane, hydrogen separation unit, and manufacturing method for hydrogen separation membrane
US7241396B2 (en) 2002-07-25 2007-07-10 Dai Nippon Insatsu Kabushiki Kaisha Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter
US20110100828A1 (en) * 2002-07-25 2011-05-05 Dai Nippon Insatsu Kabushiki Kaisha Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter
US8163157B2 (en) 2002-07-25 2012-04-24 Dai Nippon Insatsu Kabushiki Kaisha Method of producing a hydrogen production filter
EP1541221A4 (de) * 2002-07-25 2006-04-05 Dainippon Printing Co Ltd In einem filter zur wasserstofferzeugung verwendetes d nnfilmst tzsubstrat und verfahren zur herstellung eines filters zur wasserstofferzeugung
US20060180574A1 (en) * 2002-07-25 2006-08-17 Dai Nippon Printing Co., Ltd. Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter
US20040245191A1 (en) * 2002-07-25 2004-12-09 Hiroshi Yagi Thin film supporting substrate for used in filter for hydrogen production filter and method for manufacturing filter for hydrogen production
US7112287B2 (en) 2002-07-25 2006-09-26 Dai Nippon Insatsu Kabushiki Kaisha Thin film supporting substrate for used in filter for hydrogen production filter and method for manufacturing filter for hydrogen production
US20070175764A1 (en) * 2002-07-25 2007-08-02 Dai Nippon Insatsu Kabushiki Kaisha Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter
US7803263B2 (en) 2002-07-25 2010-09-28 Dai Nippon Insatsu Kabushiki Kaisha Thin film support substrate for use in hydrogen production filter and production method of hydrogen production filter
US6805972B2 (en) * 2002-08-27 2004-10-19 Johns Hopkins University Method of forming nanoporous membranes
WO2004020064A3 (en) * 2002-08-27 2004-07-15 Univ Johns Hopkins Method of forming nanoporous membranes
US20040040416A1 (en) * 2002-08-27 2004-03-04 Jonah Erlebacher Method of forming nanoporous membranes
US7108813B2 (en) 2004-03-30 2006-09-19 The Board Of Trustees Of The Leland Stanford Junior University Gas/ion species selective membrane supported by multi-stage nano-hole array metal structure
US20050242022A1 (en) * 2004-03-30 2005-11-03 Sangkyun Kang Gas/ion species selective membrane supported by multi-stage nano-hole array metal structure
US20140151287A1 (en) * 2012-12-03 2014-06-05 Omar H. Balcazar Screen and method of making the same
US20170175495A1 (en) * 2012-12-03 2017-06-22 Baker Hughes Incorporated Screen and method of making the same
US9945213B2 (en) * 2012-12-03 2018-04-17 Baker Hughes, A Ge Company, Llc Screen and method of making the same
US20150342469A1 (en) * 2012-12-21 2015-12-03 Heraeus Deutschland GmbH & Co. KG Thin metal membrane with support
US10973420B2 (en) 2012-12-21 2021-04-13 Heraeus Deutschland GmbH & Co. KG Thin metal membrane with support
US20170014754A1 (en) * 2014-03-31 2017-01-19 Fujifilm Corporation Gas separation composite and method of producing same
US10105640B2 (en) * 2014-03-31 2018-10-23 Fujifilm Corporation Gas separation composite and method of producing same
CN113560708A (zh) * 2021-07-29 2021-10-29 西安天力金属复合材料股份有限公司 一种钯基合金薄膜和多孔不锈钢载体的连接方法
CN116196771A (zh) * 2023-04-28 2023-06-02 成都华之煜新材料有限公司 一种高孔隙率非对称多孔金属膜制备方法

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CA2354920A1 (en) 2002-02-12
BR0103275A (pt) 2002-05-28
JP2002153737A (ja) 2002-05-28
EP1179361A1 (de) 2002-02-13
DE10039595B4 (de) 2006-06-01
KR20020013767A (ko) 2002-02-21

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