• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention provides a supported metal membrane containing a metal membrane on the support surface of the porous membrane support. The supported metal membrane can be obtained by applying a metal film to the support surface of the membrane support, wherein the pores in the membrane support are sealed at least in the support surface area before applying the metal film, and after the application of the metal film is removed by removing the auxiliary material. .
    公开号:KR20020013778A
    申请号:KR1020010048294
    申请日:2001-08-10
    公开日:2002-02-21
    发明作者:드로스트에른스트；쿤베르너；로스마이케；빌란트슈테판；켐프베른트
    申请人:빈더 폴커；데엠체체 데구사 메탈스 카탈리스츠 세르덱 아게；
    IPC主号:
    专利说明:

    A supported metal membrane, a process for its preparation and use
    [7] The present invention provides a supported metal membrane comprising a metal membrane on a porous membrane support, and methods of making and using the same. Supported metal membranes of this type are used for gas mixture separation, in particular for separating hydrogen from reformed gasoline gas in order to supply the fuel cell with the necessary fuel gas.
    [8] For this purpose, palladium or palladium alloy membranes, such as dense palladium or palladium alloy membranes, on porous or nonporous supports are usually used. Among them, a foil made of a hydrogen permeable metal is used as the nonporous support. The permeability of the membrane to hydrogen increases with temperature. Thus, typical operating temperatures are from 300 to 600 ° C.
    [9] TS Moss and RC Dye, Proc.-Natl. Hydrogen Assoc. Annu. US Hydrogen Meet., 8th (1997), 357-365, and T. Moss, NM Peachey, RC Snow and Al C. Dai, Int. J. Hydrogen Energy 23 (2) , (1998), 99-106. Uses are described. The thickness of the layer applied on both sides can vary, resulting in an asymmetric component (eg 0.1 μm Pd / 40 μm V / 0.5 μm Pd). Permeation test demonstrated 20 times higher hydrogen permeation than self-supported Pd membrane. Thus, the membranes described are suitable for PEM fuel electrical systems rather than typical catalytic gas purification steps (aqueous gas shift reaction and selective oxidation of CO).
    [10] GB 1 292 025 describes the use of iron, vanadium, tantalum, nickel, niobium or alloys thereof as a nonporous support for non-aggregating or porous palladium (alloy) layers. A palladium layer of about 0.6 mm in thickness is applied to the support having a thickness of 12.7 mm by compression, spraying or electrodeposition processes. Thereafter, the thickness of the laminate produced in this way is reduced to 0.04 to 0.01 mm by rolling.
    [11] According to DE 197 38 513 C1, in particular the hydrogen-separated thin film (layer thickness: less than 20 μm) alternately electrodeposits palladium and alloy metals of group 8 or group IB of the periodic table with metal supports not described in more detail. It can manufacture. In order to convert the alternating layer into a homogeneous alloy, a heat treatment suitable for the electrodeposition process may be performed.
    [12] Metallic or ceramic materials are suitable as porous supports for palladium (alloy) membranes. According to JP 05078810 (WPIDS 1993-140642), palladium can be applied to the porous support, for example by a plasma spray process.
    [13] Y. Lin, G. Lee and M. Rei, Catal. According to Today 44 (1998) 343-349 and J. of Hydrogen Energy 25 (2000) 211-219, a flawless palladium film (layer thickness: 20 to 25 μm) is transferred to 316L porous stainless steel in an electroless plating process. It can be prepared on the prepared tubular support and then combined as a component in a steam reforming reactor. At an operating temperature of 300 to 400 ° C., H 2 containing 95% by volume of purified reformed gasoline is obtained. However, while the optimum operating temperature is very limited because the palladium film begins to fracture due to the presence of hydrogen at less than 300 ° C., at 400 to 450 ° C., the alloying components in the stainless steel support diffuse into the palladium layer, impairing permeability.
    [14] Electroless plating processes are preferably used for the coated ceramic support. Thus, CVD coatings of asymmetric porous ceramics using palladium are described in E. Kikuchi, Catal. Today 56 (2000) 97-101, which is used in a methane steam reforming reactor for separating hydrogen from reforming gasoline. The minimum layer thickness is 4.5 μm. If the layer is thick, the airtightness of the layer can no longer be assured. Apart from CVD coatings with pure Pd, coatings with palladium alloys are also possible, where the use of silver in the alloys prevents the embrittlement of the palladium film and increases its permeability to hydrogen.
    [15] In addition to pure hydrogen separation membranes, membranes comprising reactive layers in addition to hydrogen separation layers (palladium) have also been described for application in fuel cell systems. Thus, the porous support for the palladium (alloy) membrane can be coated with a combustion catalyst, for example, on the side which is not coated with Pd. The heat released during combustion at the reaction surface is used to simultaneously maintain the operating temperature of the hydrogen separation membrane (EP 0924162 A1). These components can then be combined in the reforming process downstream of the modifier or incorporated directly into the modifier (EP 0924161 A1 and EP 0924163 A1).
    [16] Also, not only palladium membranes can be used for hydrogen separation in the fuel cell region. EP 0945174 A1 contains layers which can be made of both microporous separation-selective plastics and / or multiple ceramic layers and / or separation-selective metals (preferably Groups 4B, 5B or 8). Designs for use in commonly constructed laminated membranes are described, where these layers are applied to porous supports (glass, ceramic, expanded metal, carbon or porous plastics).
    [17] The purpose of developing a metal membrane for hydrogen separation from a gas mixture is to obtain a high permeability for hydrogen. For this purpose, the metal film should be designed as thin as possible while preventing leakage from occurring in the form of holes. Such membranes can only be processed into supported forms. In order for the membrane support to not affect the permeation of hydrogen as much as possible, the membrane support must have high porosity. Thus, for known methods of preparing supported membranes, defect-free membranes are difficult to deposit on porous supports. Two problems are related to this. On the other hand, for example, the method described for palladium or palladium alloy deposition can assure a relatively flawless film layer only in layers above a certain thickness. This minimum thickness is about 4-5 μm. On the other hand, the coating technique used to apply the membrane layer to the porous membrane support means that the average pore diameter of the membrane support should not exceed a certain value, because otherwise it is impossible to apply a coating without cohesive and flawless. Thus, the pore size of known membrane support materials such as porous ceramics or porous metal supports is less than 0.1 μm. This means that the flow resistance of the gas passing through the pores cannot be reduced to the desired degree.
    [18] WO 89/04556 describes an electrochemical process for producing a palladium-based pore-free membrane supported by a porous metal structure. According to this process, the pore-free palladium (-negative) membrane on the porous metallic support has a palladium or palladium / silver (palladium layer thickness of about 1) using an electrodeposition process on one side of a metal alloy foil (preferably brass chain). It is prepared by coating with [micro] m). The porosity of the support is created later by dissolving the base component in the brass chain foil. In the electrochemical dissolution and in the circulation process, both components are first introduced into the solution, but more basic components are deposited directly onto the palladium layer (electrochemical recrystallization). Thus, the less basic component in the foil type alloy migrates into solution substantially quantitatively such that the porous metal structure, preferably the porous copper structure, is maintained as a support for the palladium / silver membrane.
    [19] The process according to WO 89/04556 has the disadvantage that the brass foil used as the support is substantially completely dissolved and formed again by electrochemical recrystallization. This means that the composite or laminate formed between the palladium layer and the support foil is broken. The mechanical strength of the recrystallized foil is low and its porosity is not limited.
    [20] It is an object of the present invention to provide a supported metal membrane for hydrogen separation from a gas mixture, which can be produced in a simple and cost effective manner. Another object of the present invention is a supported metal membrane which is of high porosity (average pore size and pore volume) which membrane supports are not feasible so far. A further object of the present invention is a large complex metal membrane in which the average pore size of the membrane support exceeds the thickness of the metal membrane.
    [21] This object is achieved by a supported metal membrane comprising a metal membrane on the support surface of the porous membrane support. The supported metal membrane is applied by applying a metal film to the support surface of the membrane support, wherein the pores in the membrane support are sealed by the auxiliary material at least in the support surface area before applying the metal film, and then open by removing the auxiliary material after applying the metal film. Can be achieved.
    [22] In the context of the present invention, the support surface of the membrane support and the contact surface thereof are distinguished. The support surface includes the entire surface area useful for coating with the metal film, namely the surface of the pores contained in the surface of the support surface, sealed with the auxiliary material, and the direct contact surface of the membrane support with the metal film after removal of the auxiliary material.
    [23] Metal membranes according to the invention can be obtained, for example, by selecting a porous membrane support in which the pores are completely sealed with the auxiliary material or only in the region of the intended support surface. The membrane support preferably consists of a porous metal, metal alloy, sintered metal, sintered steel, glass or ceramic. The pores in these materials are sealed before applying the metal film to, for example, chemically easily removable metals, salts, graphite, polymers or high molecular weight organic compounds.
    [24] Before applying the metal film, it is recommended to smooth the support surface of the membrane support by a suitable method (eg grinding and polishing), in particular to expose and clean the subsequent contact surface with the metal film. The high quality surface produced in this way is transferred to the applied metal film and maintained even after removing the auxiliary material, so that the finally supported metal film has a very flat structure with a uniform layer thickness.
    [25] Depending on the nature of the auxiliary material and the membrane support, the auxiliary material may be removed from the pores of the membrane support in a variety of ways such as, for example, melting, burning, dissolving, chemical dissolving and electrochemical dissolving.
    [26] Electrochemical deposition, or PVD or CVD processes, are suitable for applying metal films to membrane supports. A preferred PVD process for depositing a metal film on a film support is cathode sputtering. This process generally produces very dense layers with low porosity, ie high packing density.
    [1] 1 shows an ideal cross-sectional view of a supported metal membrane according to the invention before the auxiliary material is removed from the pores of the membrane support.
    [2] 2 shows an ideal cross-sectional view of a supported metal membrane according to the invention after the auxiliary material has been removed from the pores of the membrane support.
    [3] 3 shows an ideal cross-sectional view of a supported metal film according to the invention with a diffusion barrier layer between the metal film and the membrane support.
    [4] 4 shows an ideal cross-sectional view of a supported metal membrane according to the invention having a diffusion barrier layer between the metal membrane and the membrane support and having a catalyst coating on the surface of the membrane support opposite the metal membrane.
    [5] 5 shows a cross section of an experimental PdAg-membrane on an AgCu-membrane support with a raster electron microscope.
    [6] FIG. 6 shows the porous structure of a membrane support consisting of a post AgZu-alloy after decomposition of a copper rich phase.
    [27] The process for preparing a supported metal film according to the invention described includes the following steps:
    [28] Filling the pores of the porous membrane support with an auxiliary material (a),
    [29] (B) smoothing and cleaning the support surface,
    [30] (C) applying a metal film to the support surface; and
    [31] (D) removing the auxiliary material from the pores of the membrane support.
    [32] Another possibility of making supported membranes includes initially selecting a nonporous membrane support having potential porosity. The term "potential porosity" means that the membrane support is a non-uniform structure, where subsequent pores are filled with auxiliary material which is removed only after applying the metal membrane to the support surface of the membrane support.
    [33] The supported metal film is formed by a membrane support made of a multiphase eutectic alloy and a more basic (more negative) phase arranged in an anomalous region of the auxiliary material, and is electrochemically dissolved with the product of the pores after applying the metal film. Can be achieved in a simple way. The eutectic alloy AgCu, consisting of a Cu rich alloy phase and an Ag rich alloy phase, is particularly suitable for this purpose. The Cu-rich phase is more negative electronegative, and electrochemical pathways can be used to selectively dissolve the membrane support with the desired porosity product. Thereafter, the Ag-rich phase is hardly damaged. On the other hand, according to WO 89/04556, the membrane support is completely dissolved and reformed, and according to the invention, a hard structure on the Ag-rich alloy phase is maintained which has a practical effect corresponding to the stability of the membrane support.
    [34] The copper content of the eutectic alloy is preferably 20 to 80% by weight based on the total weight of the alloy. By suitable heat treatment of the support at 400 to 750 ° C. before or after applying the metal film, the overall structure of the support and thus its subsequent porosity can be influenced in an advantageous manner.
    [35] In summary, the process for producing a supported metal film according to the present invention using a membrane support made from a process alloy as described above comprises the following process steps:
    [36] (A) cleaning the support surface of the membrane support,
    [37] Applying a metal film to the support surface (b),
    [38] (C) treating the stack of metal film and membrane support at a temperature of 300 to 700 ° C. and
    [39] (D) electrochemically dissolving the more basic phase in the membrane support.
    [40] The supported metal membrane according to the invention is preferably used as a gas separation membrane for separating hydrogen from the gas mixture. In this case, the metal film is preferably made from a palladium or a palladium alloy, for example PdAg23, PdCu40 or PdY10.
    [41] Small thickness metal membranes are needed for use as gas separation membranes to ensure the best possible permeability to the desired gas. Gas separation membranes of palladium or palladium alloys having a thickness of 20 μm or more are only slightly interesting for the separation of hydrogen from the gas mixture, because the precious metals are expensive and the transmittance is low. Films less than 0.3 μm thick may have a number of drawbacks. In addition, the transmittance for undesired gases increases at a small thickness. As a result of these two effects, the resolution of membranes with a membrane thickness of less than 0.3 μm is reduced to values that can no longer be tolerated. Therefore, the metal film preferably has a thickness of 0.3 to 5 mu m, preferably 0.5 to 3 mu m.
    [42] Porous metal membrane supports are used to support thin metal films, where the membrane supports will hardly impair the permeability of the metal membrane as compared to free floating metal membranes of the same thickness. On the other hand, a certain minimum thickness is necessary to ensure the necessary mechanical stability of the supported membrane. Therefore, the thickness of the membrane support should be 20 µm or more and less than 100 µm. It is desirable to try to obtain a membrane support thickness of 50-20 μm.
    [43] When supported metal membranes are used as gas separation membranes for hydrogen containing gas mixtures, they well withstand operating conditions that are drastically variable over time. This temporarily changes the membrane volume and dimensions as a result of incorporation, releases hydrogen, and changes temperature. The change in membrane dimension is comparable with the dimension of the membrane support to avoid rupture of the supported metal membrane. Thus, metal composite films (metal films on metal film supports) are preferred for non-uniform metal-ceramic-composites (metal films on ceramic supports) when volume or dimensional changes due to temperature changes are a problem. It is shown that the coefficients of thermal expansion of the two metals are the same as those of the metal and the ceramic.
    [44] From the film materials PdAg23, PdCu40 and PdY10 described above, alloy PdAg23 undergoes a significantly stronger change in dimensions and volume than alloy PdCu40 due to hydrogen incorporation. Therefore, a metal film made of PdCu40 on an AgCu-based film support is preferable as a metal composite film for hydrogen purification.
    [45] It is often advantageous to form the metal film as a multilayer structure. In this case, the first layer located directly on the membrane support can be designed as a diffusion barrier. The diffusion barrier must prevent any change in the alloy composition in the metal film due to the diffusion of the film, which occurs especially when the metal film is diffused or supported into the film of the alloying component with respect to the metal film support. Changes in this type of alloy composition will have a significant impact on the permeability of the metal film. Ceramic oxides such as aluminum oxide, titanium oxide and cerium oxide are suitable as diffusion barriers. As an alternative to diffusion barriers from oxidizing materials, metal layers from vanadium, tantalum or niobium can be used. These metals have a good transmittance for hydrogen. The thickness of these diffusion barrier layers should be less than 0.5 μm for the oxide layer and less than 2 μm for the metal barrier. The thickness of the barrier layer is preferably less than 0.1 μm in both cases.
    [46] If a supported metal membrane is used to purify the reformed gasoline gas, it may be convenient to combine the supported metal membrane with the catalyst. For this reason, a catalytically active coating is applied to the surface of the porous membrane support opposite the metal membrane. In addition, a functional layer for removing impurities and harmful substances may be applied instead of a catalytically active coating.
    [47] The supported membranes according to the invention are preferably used for separating hydrogen from gas mixtures, especially reformed gasoline gas. The present invention makes it possible to produce supported metal membranes whose membrane support is so far non-present high porosity (average pore size and pore volume). Since the thickness of the gas separation membrane is 0.3 to 5 mu m, preferably 0.5 to 3 mu m, the average pore size of the membrane support is more than 0.5 mu m and less than 10 mu m. Thus, firstly, the supported metal membrane is described herein that the average pore size of the membrane support exceeds the thickness of the metal membrane. Therefore, it has remarkable hydrogen permeability.
    [48] In general, the supported metal film will be used in the form of a flat foil. However, metal films can also be made in the form of variable geometries with the added advantage of improved mechanical stability over flat foils of the same thickness. In particular, the supported metal film can be made into a thin tubular shape.
    [49] The invention is illustrated in more detail by figures 1 to 6 and the following examples.
    [50] 1 shows an ideal cross-sectional view of a supported metal membrane according to the invention before removing the auxiliary material from the pores of the membrane support. Reference numeral 1 denotes a composite metal film, that is, a composite comprising a metal film 2 and a film support 3. The surface area of the membrane support at the interface between the metal film and the membrane support is the support surface 4 previously defined. The support surface consists of a different surface region comprising a region 7 formed of membrane support material 5 and a region 8 formed of pores 6 filled with auxiliary material in the plane of the support surface 4. Region 8 was previously defined as a contact surface.
    [51] FIG. 2 shows the same cross section as in FIG. 1 after removal of the auxiliary material from the pores of the membrane support.
    [52] During operation of the metal membrane supported as a gas separation membrane for cleaning hydrogen, the material of the membrane support diffuses into the metal membrane 2, thereby inadvertently decreasing the hydrogen permeability of the metal membrane. To reduce this diffusion, a diffusion suppression barrier 9 can be introduced between the metal film 2 and the membrane support 3. 3 shows a cross section of a composite membrane according to the invention with this diffusion barrier between the membrane and the support. Suitable materials for the diffusion barrier are aluminum oxide, titanium oxide and cerium oxide, and the metal layer is made from vanadium, tantalum or niobium as already described above.
    [53] 4 shows an embodiment of a supported metal film according to the invention with a functional layer 10 deposited on the surface of the membrane support opposite the metal film. The functional layer may be a catalyst layer for oxidizing carbon dioxide to carbon monoxide by an aqueous gas shift reaction or may be an absorbing layer for absorbing sulfur components such as hydrogen sulfide.
    [54] Example 1:
    [55] Thin Pd layers with layer thicknesses of 0.1 μm, 0.5 μm and 2 μm are prepared on AgCu28 foil by electrodeposition. The AgCu28 foil has a thickness of 50 μm.
    [56] After the coated foil is heat treated at 600 ° C. for 30 minutes under protective gas (argon), the Cu rich phase dissolves the AgCu28 alloy material in the membrane support. It is bipolarly dissolved at a constant bath voltage of 230 mV over 20 hours in a sulfuric acid electrolyte with 10% sulfuric acid operating at a potentiostatic potential at 40 ° C. This creates a structure of open pores in the membrane support foil.
    [57] The metallographic examinations and images presented by scanning electron microscopy on the cross section of the resulting supported metal membranes show a dense Pd membrane that has open porosity and is firmly deposited on a porous AgCu support layer having a pore size of 1 to 5 μm.
    [58] Example 2:
    [59] Using PdAg23, a target PdAg23 layer 2 μm thick is deposited on the foil of AgCu28 by cathode sputtering.
    [60] After the coated foil is heat treated at 600 ° C. for 30 minutes under protective gas (argon), the Cu rich phase dissolves the AgCu28 alloy material in the membrane support. It is bipolarly dissolved at a constant bath voltage of 230 mV over 20 hours in a sulfuric acid electrolyte with 10% sulfuric acid operating at a potentiostatic potential at 40 ° C. This creates a structure of open pores in the membrane support foil.
    [61] FIG. 5 shows the cross section of the metal composite film thus produced after dissolving the copper rich phase of the membrane support with a scanning electron microscope. 5, the large pore structure of the membrane support can be clearly seen. The average pore size is greater than the thickness of the metal film. The metal membrane is unachievably flat when the metal membrane is deposited on the porous membrane support. As shown in FIG. 5, the average pore diameter increases with increasing distance from the metal film and is largest at the surface of the membrane support opposite the metal film. This inclined pore structure is due to the negative dissolution of the Cu-rich phase of the membrane support as described above.
    [62] Example 3:
    [63] Additional membrane support foils of AgCu28 are used to investigate the effect of heat treatment on the formation of pore structures. The Cu-rich phase dissolves the foil as described in Examples 1 and 2.
    [64] 6 shows a cross section of the membrane support foil after dissolving the Cu-rich phase. The foil is heat treated differently from the foil of the above embodiment. The average pore diameter of the pore structures is much smaller than the diameter of FIG. 5, indicating that the porosity and its structure are affected by the heat treatment of the process membrane support during the preparation of the membrane support foil.
    [65] In order to obtain the desired foil thickness and the second heat treatment, the thermomechanical formation of the AgCu28 alloy during rolling measures the pore structure of the final membrane support. Rapid cooling of the AuCu28 alloy during manufacture results in a smaller phase region, resulting in a smaller average pore diameter after dissolution of the Cu-rich phase. The second heat treatment extended after thermomechanical formation initiates recrystallization of the molten alloy, increasing the size of the phase region and increasing the average pore size of the complete membrane support as described in Example 2. In addition, the size of the phase region can be affected by changing all the compositions of the alloy.
    [66] In this embodiment, only process AgCu28 alloy-based membrane supports are used, but the present invention is not limited to the use of such process alloys as membrane support materials. As already mentioned above, it is possible to use a porous membrane support in which the pores are filled with an auxiliary material before the deposition of the metal membrane, and after the application of the metal membrane the auxiliary material is removed from the pores.
    [67] According to the present invention, a supported metal membrane for hydrogen separation from a gas mixture is produced in a simple and cost effective manner.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] As the pores of the membrane support are obtained by applying a metal film to the support surface of the membrane support which is sealed by the auxiliary material at least in the support surface area before applying the metal film and by removing the auxiliary material after applying the metal film, A supported metal membrane containing a metal membrane on the support surface of the porous membrane support.
    [2" claim-type="Currently amended] The metal, salt, graphite, polymer or high molecular weight organic compound of claim 1, wherein the membrane support is made from a porous metal, a metal alloy, a sintered metal, a sintered steel, glass or ceramic, and the auxiliary material is chemically easily removable. Supported metal membrane.
    [3" claim-type="Currently amended] The method of claim 1, wherein the support is made of a multiphase process alloy, and the auxiliary material is electrochemically formed by forming a more basic (more negative) phase arranged in the phase region and generating pores after applying the metal film. A supported metal membrane characterized by dissolving.
    [4" claim-type="Currently amended] 4. The supported metal membrane of claim 3, wherein the support is made of eutectic alloy AgCu, and the porosity is produced by electrochemical decomposition of a Cu-rich phase.
    [5" claim-type="Currently amended] 5. The supported metal film as claimed in claim 1, wherein the metal film is applied by electrochemical deposition or by a PVD or CVD process. 6.
    [6" claim-type="Currently amended] 6. The supported metal film according to claim 5, wherein the applied metal film is made of palladium or palladium alloy.
    [7" claim-type="Currently amended] 8. The supported metal film of claim 6, wherein the metal film contains PdAg23, PdCu40 or PdY10.
    [8" claim-type="Currently amended] 2. The supported metal film according to claim 1, wherein the metal film has a thickness of less than 5 μm, preferably 2 to 0.3 μm.
    [9" claim-type="Currently amended] The supported metal membrane according to claim 8, wherein the average pore size of the membrane support is greater than 0.5 μm and less than 10 μm.
    [10" claim-type="Currently amended] 10. The supported metal membrane of claim 9 wherein the average pore size of the membrane support exceeds the metal membrane thickness.
    [11" claim-type="Currently amended] 2. The supported metal film according to claim 1, wherein the metal film consists of a multilayered film.
    [12" claim-type="Currently amended] 12. The supported metal film of claim 11, wherein a layer serving as a diffusion barrier is arranged between the metal film and the film support.
    [13" claim-type="Currently amended] The supported metal membrane of claim 1, which is made of foil or tubule.
    [14" claim-type="Currently amended] The supported metal membrane of claim 1 wherein the membrane support is in a porous honeycomb structure.
    [15" claim-type="Currently amended] The supported metal membrane of claim 1, wherein a catalytically active coating is applied to the surface of the porous membrane support opposite the metal membrane.
    [16" claim-type="Currently amended] The supported metal membrane of claim 1, wherein a functional layer for removing impurities and harmful substances is applied to the surface of the porous membrane support opposite the metal membrane.
    [17" claim-type="Currently amended] Use of a supported metal membrane according to any one of claims 1 to 16 for separating hydrogen from a gas mixture.
    [18" claim-type="Currently amended] Filling the pores of the porous membrane support with an auxiliary material (a),
    (B) smoothing and cleaning the support surface,
    (C) applying a metal film to the support surface; and
    (D) removing the auxiliary material from the pores of the membrane support.
    [19" claim-type="Currently amended] (A) cleaning the support surface of the membrane support,
    Applying a metal film to the support surface (b),
    (C) treating the stack of metal film and membrane support at a temperature of 300 to 700 ° C. and
    A process for preparing a supported metal film according to claim 3, characterized by the step (d) of electrochemically dissolving the more basic phase in the membrane support.
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    同族专利:
    公开号 | 公开日
    US20020020298A1|2002-02-21|
    DE10039596C2|2003-03-27|
    US6649559B2|2003-11-18|
    EP1180392B1|2004-06-30|
    DE10039596A1|2002-02-28|
    JP2002126474A|2002-05-08|
    AT270140T|2004-07-15|
    CA2354952A1|2002-02-12|
    EP1180392A1|2002-02-20|
    DE50102717D1|2004-08-05|
    BR0103318A|2002-04-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-08-12|Priority to DE10039596.1
    2000-08-12|Priority to DE10039596A
    2001-08-10|Application filed by 빈더 폴커, 데엠체체 데구사 메탈스 카탈리스츠 세르덱 아게
    2002-02-21|Publication of KR20020013778A
    优先权:
    申请号 | 申请日 | 专利标题
    DE10039596.1|2000-08-12|
    DE10039596A|DE10039596C2|2000-08-12|2000-08-12|Supported metal membrane, process for its manufacture and use|
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