JP2007007565A - Reinforcing structure for hydrogen-permeable film, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reinforcing structure for a hydrogen-permeable film which, itself has a simple structure, has airtightness and adhesiveness, and has an excellent handling performance of the hydrogen-permeable film in manufacturing, and to provide its manufacturing method. <P>SOLUTION: The reinforcing structure for the hydrogen-permeable film and its manufacturing method is characterized in that the reinforcing structure for the hydrogen-permeable film is disposed with a hydrogen-permeable foil film on one side surface of a metal frame body having a vertically penetrating opening. On the one side surface of the metal frame body is sequentially provided with a diffusion prevention layer and an intermediate layer, thereafter the hydrogen-permeable foil film is joined to the intermediate layer. Then selective etching is performed from the metal plate side to expose the hydrogen-permeable foil film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hydrogen permeable membrane reinforcing structure and a method for manufacturing the same, and more specifically, a hydrogen permeable foil membrane such as Pd or Pd alloy is disposed on one surface of a metal frame having an opening penetrating vertically. The present invention relates to a hydrogen permeable membrane reinforcing structure and a manufacturing method thereof.

For example, the reformed gas obtained by the steam reforming method of hydrocarbons, which is one of the methods for producing hydrogen, contains by-products such as CO and CO ₂ and surplus H ₂ O in addition to hydrogen as the main component. It is. For this reason, if the reformed gas is used as it is, for example, as fuel for a fuel cell, the cell performance is impaired. Of the fuel cells, CO in hydrogen gas used in PAFC is limited to 1 vol%, and PEFC is limited to 100 vol ppm. For this reason, these by-products and surplus H ₂ O must be removed before being introduced into the fuel cell.

  One hydrogen purification method for obtaining such high-purity hydrogen is a hydrogen permeable membrane method. In the hydrogen permeable membrane method, a hydrogen permeable foil membrane such as Pd or Pd alloy, that is, a hydrogen permeable membrane does not permeate gases other than hydrogen, but utilizes a characteristic of selectively permeating only hydrogen. By passing the hydrogen-containing gas through the hydrogen permeable membrane, hydrogen is selectively permeated and separated and purified. In this case, since the film thickness of the hydrogen permeable membrane is an extremely thin sheet (foil) such as about 0.5 to 20 μm, a frame for supporting the hydrogen permeable membrane is necessary.

  9 to 10 are figures disclosed in Japanese Patent Laid-Open No. 2001-276558 (hereinafter referred to as 558), FIG. 9 is an exploded perspective view for explaining the structure of the hydrogen gas separation unit, and FIG. It is a schematic perspective view of the hydrogen gas separator incorporating the unit. In FIG. 9, reference numeral 31 denotes an extension frame (frame body), which is made of stainless steel or the like. The stretch frame 31 is formed by masking the portions to be the peripheral portion 101 and the central portion 102 of the clad cut plate, etching the portion to be the opening S, and leaving the peripheral portion 101 and the central portion 102. 32 is a hydrogen gas separating material (hydrogen permeable foil film) such as Pd alloy foil, 33 is a metal support plate, and b is a pore. As shown in FIG. 10, the hydrogen gas separation unit configured in this manner is fixed to the case 34 by laser welding or the like so that the surface of the metal support plate 33 is on the inside to form a hydrogen gas separator. Reference numeral 35 denotes a purified hydrogen take-out pipe.

  In Japanese Patent Application Laid-Open No. 2004-142355 (hereinafter referred to as “355”), a hydrogen gas separation unit such as 558 may impair the separation function on a hydrogen-permeable layer such as a Pd alloy membrane. In order to solve the problem such as the occurrence of pinholes that are not present, a laminate in which a support layer, an intermediate layer such as Ag, and a transmission layer are laminated so as not to adversely affect the hydrogen transmission layer during etching processing There has been proposed a method of manufacturing an opening laminate that is etched using a metal. FIG. 11 is a diagram disclosed in Japanese Patent No. 355.

  In FIG. 11, the surface to be bonded to the intermediate layer 48 in the support layer 46 is activated, and the surface to be bonded to the support layer 46 in the intermediate layer 48 is activated. Then, both layers are laminated. FIG. 11A shows this two-layer laminate. A hydrogen permeable layer 44 is laminated on the surface of the laminated body on the intermediate layer 48 side. FIG. 11B shows this three-layer laminate. Next, the three-layer laminate is etched to leave a peripheral portion of the three-layer laminate, and an opening is formed in the central portion. In the etching process, the intermediate layer 48 functions as an etching stop by appropriately selecting the material of the support layer 46, the material of the intermediate layer 48, the etching solution, and the like. FIG. 11C shows this state. Further, the intermediate layer 48 is etched to obtain the state shown in FIG. The support layer 46 becomes a frame that supports the transmission layer 44 after the etching process.

JP 2001-276558 A JP 2004-142355 A

  By the way, in the technique described in 558 and 355, it is important to manufacture a hydrogen permeable membrane module using Pd alloy foil. Ensuring airtightness at the time of joining. In order to realize this, in Japanese Patent No. 558, a stainless steel plate and a hydrogen permeable foil film are clad-bonded to ensure airtightness between the stainless steel / hydrogen permeable foil film. Thereafter, a hydrogen permeable portion is provided by selective etching of stainless steel to obtain a stainless steel frame-Pd membrane assembly. Since this form is reinforced with a stainless steel frame, it is easy to handle as a membrane, and the airtightness between the stainless steel / hydrogen permeable foil membrane is ensured. Even in this bonding process, a high yield rate can be expected.

  However, when a joined body in which a stainless steel plate and a hydrogen permeable foil film are in direct contact with each other is used under a high temperature (500 to 700 ° C.) such as a hydrocarbon steam reforming condition, the components mutually diffuse and hydrogen permeation occurs. In order to alter the conductive foil film, there has been a problem that the film strength, gas tightness and hydrogen permeation performance are remarkably lowered. Further, as disclosed in Japanese Patent No. 558, even if Ag or the like is inserted as an intermediate layer, for example, when a Pd alloy-based film material is used, Ag itself is dissolved in the film component, and thereafter, Pd alloy It is expected that the film and the stainless steel plate will diffuse to each other, and the above problem cannot be solved.

  An object of the present invention is to provide a hydrogen permeable membrane reinforcing structure that does not have the above-described drawbacks, has a simple structure, and is easy to handle a hydrogen permeable foil membrane that is a hydrogen permeable membrane, and a method for manufacturing the same. Is.

  The present invention is (1) a hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is arranged on one side of a metal frame having an opening penetrating vertically. Then, after sequentially providing a diffusion preventing layer and an intermediate layer on one side of the metal plate, a hydrogen permeable foil membrane is bonded to the intermediate layer, and then selective etching is performed from the metal plate side to form a hydrogen permeable foil membrane. It is characterized by being exposed. Here, the one side of the metal frame means one side of the upper and lower surfaces of the metal frame, and the same applies in this respect.

  The present invention is (2) a method for producing a hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is disposed on one side of a metal frame having openings extending vertically. Then, after sequentially providing a diffusion preventing layer and an intermediate layer on one side of the metal plate, a hydrogen permeable foil membrane is bonded to the intermediate layer, and then selective etching is performed from the metal plate side to form a hydrogen permeable foil membrane. It is exposed. The present invention (2) corresponds to the method for producing the hydrogen permeable membrane reinforcing structure of the present invention (1).

  The present invention is (3) a hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is arranged on one side of a metal frame having openings that penetrate vertically. And after providing a 1st intermediate | middle layer, a diffusion prevention layer, and a 2nd intermediate | middle layer sequentially on the single side | surface of a metal plate body, a hydrogen-permeable foil film | membrane is joined to the 2nd intermediate | middle layer, and then a metal plate The hydrogen permeable foil film is exposed by selective etching from the body side.

  The present invention is (4) a method for producing a hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is disposed on one side of a metal frame having openings that penetrate vertically. Then, after sequentially providing a diffusion preventing layer and an intermediate layer on one side of the metal plate, a hydrogen permeable foil membrane is bonded to the intermediate layer, and then selective etching is performed from the metal plate side to form a hydrogen permeable foil membrane. It is exposed. The present invention (4) corresponds to the method for producing the hydrogen permeable membrane reinforcing structure of the present invention (3).

  In the prior art, as disclosed in Japanese Patent No. 558, a hydrogen-permeable foil film and a stainless steel plate (metal frame) are directly clad-bonded to ensure airtightness and film handling properties. Due to the diffusion, there is a problem that the hydrogen permeable foil film is greatly damaged. On the other hand, according to the present invention, by interposing a diffusion preventing layer and an intermediate layer between them, the mutual diffusion of each component is ensured while ensuring airtightness, adhesion, and handling during production. Can be prevented. In addition to the intermediate layer, the intermediate layer is interposed between the stainless steel plate (metal frame) and the diffusion prevention layer, thereby increasing the bonding strength between the metal frame and the diffusion prevention layer. Can do.

<Aspects of the present invention (1) to (2)>
In the present invention (1) to (2), a diffusion preventing layer and an intermediate layer are provided between the metal frame and the hydrogen permeable foil film. 1 and 2 are diagrams for explaining this aspect. 1A to 1G are diagrams for explaining the manufacturing process, and FIGS. 2A to 2B are perspective views of FIGS. 1F to 1G in the manufacturing process. 1-2, 1 is a metal plate body, 2 is a diffusion preventing layer, 3 is an intermediate layer, and 4 is a hydrogen permeable foil film, that is, a hydrogen permeable film. The hydrogen permeable foil membrane selectively separates and purifies hydrogen by selectively permeating hydrogen from the hydrogen-containing gas.

  FIG. 1A shows a metal plate 1. The constituent material of the metal plate 1 can be etched, and can sufficiently support the members formed on the frame surface after the etching process, that is, the diffusion preventing layer 2, the intermediate layer 3, and the hydrogen permeable foil film 4. Any metal having strength and the like may be used, and examples thereof include stainless steel, nickel, nickel-base alloy, copper alloy, iron-base alloy (iron-nickel alloy, etc.), and the like.

  Since the metal plate body 1 becomes the metal frame body 1 having an opening penetrating vertically after the selective etching process described later, the constituent material of the metal plate body 1 becomes the constituent material of the metal frame body 1 as it is.

  A diffusion prevention layer 2 is provided on one side of the metal plate 1. FIG. 1B shows this state. The diffusion preventing layer 2 can be formed by dip coating, spraying, printing, arc ion plating, vapor deposition, or the like. Among these, the printing method is particularly useful because the metal plate 1 is a flat plate. The thickness of the diffusion preventing layer 2 can be appropriately selected within the range where the purpose, that is, the mutual diffusion prevention between the components of the metal frame 1 and the intermediate layer 3 and the hydrogen permeable foil film 4 can be achieved. The range is preferably 0.05 to 1 μm.

A refractory metal or ceramic is used as a constituent material of the diffusion preventing layer 2. Among them, the high melting point metal is a metal having a melting point of 1800 ° C. or higher, and examples thereof include Zr, Mo, Ta, W, Cr, Hf, Nb, Ru, and the like. The ceramic is composed of one or more elements selected from the group of Ti, Si, Al, Mg, Ca, Y, Zr, and Hf and one or more elements selected from the group of N, C, O, and B. Examples thereof are TiN, TiC, TiO ₂ , TiB, Si ₃ N ₄ , SiC, SiO ₂ , AlN, Al ₂ O ₃ , MgO, CaO, AlSiO _X , Y ₂ O ₃ , ZrO ₂ , TiAlN, MgO.Al ₂ O ₃ , 2MgO.SiO _{2 and the} like can be mentioned. These ceramics may be used as a diffusion prevention layer as a single layer or as a diffusion prevention layer by laminating a plurality of layers such as an Al ₂ O ₃ layer and a ZrO ₂ layer.

  Next, the intermediate layer 3 is disposed on the surface of the diffusion preventing layer 2 to form a three-layer laminate. FIG. 1C shows this state. The intermediate layer 3 is a layer for increasing the bonding strength between the diffusion preventing layer 2 and the hydrogen permeable film 4. The surface of the diffusion preventing layer 2 is plated, vapor deposited, arc ion plating, etc. It can carry out by apply | coating to layer form by an appropriate method.

  As the constituent material of the intermediate layer 3, Au, Ag, Cu, Al, Ti, Ni, Co, Pt, Pd, Rh, Ru, or the like is used. Two or more of these metals may be combined. The thickness of the intermediate layer 3 can be appropriately selected as long as the adhesion between the diffusion preventing layer 2 and the hydrogen permeable foil film 4 can be secured. The range is 0.05 to 20 μm, preferably 0.1 to 10 μm.

  And as shown in FIG.1 (e), the hydrogen permeable foil film | membrane 4 is arrange | positioned and joined to the surface at the side of the intermediate | middle layer 3 of this three-layer laminated body. Since this arrangement | positioning operation only needs to stick a hydrogen-permeable foil film on the whole surface by the side of the intermediate | middle layer 3 of a three-layer laminated body, it can arrange | position easily.

The hydrogen permeable foil film 4 is not particularly limited as long as it is a foil film made of a material having a function of selectively transmitting hydrogen, and examples thereof include the following (1) to (6).
(1) Pd film (2) Pd alloy film (3) Alloy film of Group 5 metal (V, Nb or Ta) and Group 6 metal (Cr, Mo, W) or other metals (4) Multilayer of Pd alloy film Film (ie, multilayer film of Pd alloy film itself)
(5) Multi-layer film of Pd film, alloy film of Group 5 metal (V, Nb or Ta) and Group 6 metal (Cr, Mo, W) or other metal (6) Pd alloy film and Group 5 Multilayer film of metal (V, Nb or Ta) and group 6 metal (Cr, Mo, W) or other metal alloy film Among them, (2) Pd alloy film is an alloy film of Pd and other metal Examples of the metal alloyed with Pd include Au, Ag, Cu, Pt, Rh, Ru, Ir, Ce, Sm, Tb, Dy, Ho, Er, Yb, Y, and Gd. Two or more of these metals may be combined and alloyed with Pd.
A foil film made of these materials is produced by various methods such as a rolling method, an ion plating method, and a plating method.

  The hydrogen permeable foil film needs to be a dense film having no holes, but since the diffusion preventing layer 2 is interposed in the present invention, the hydrogen permeable foil film itself can be thinned. The thickness can be selected in the range of 1 to 100 μm, preferably in the range of 5 to 50 μm, more preferably in the range of 5 to 30 μm. For example, Pd and Pd alloys are expensive, but the cost can be reduced and the hydrogen permeation rate can be improved by reducing the film thickness. Since the hydrogen permeable foil membrane is such an extremely thin film, it is very difficult to handle, but according to the present invention, such a hydrogen permeable foil membrane is disposed on the entire surface of the intermediate layer 3. Therefore, it can arrange | position easily and can join easily by a cold rolling method, a hot rolling method, a diffusion bonding method, etc.

  Masking is performed on the peripheral upper surface of the metal plate 1, that is, the portion that serves as a frame for supporting the hydrogen permeable membrane 4 in the laminate obtained by integrating the three-layer laminate and the hydrogen permeable foil membrane thus formed. Masking is performed by applying a resist solution such as a PVA-bichromic acid aqueous solution to the peripheral upper surface of the metal plate 1 and drying it. For the application of the resist solution, a roll coating method, a spin coating method, a dip pulling method, or the like can be applied. The thickness of the resist film only needs to be a thickness that can protect the upper surface of the peripheral edge during the etching process, and is, for example, about 5 to 10 μm. FIG. 1 (f) shows a state where masking is performed in this manner, and FIG. 2 (a) shows the state as a perspective view.

  Then, selective etching, that is, a portion excluding the masking portion is etched. As an etching solution in the etching process, a ferric chloride aqueous solution or the like is used. In this process, the exposed portion of the metal plate 1 that is not masked is selectively etched into the diffusion preventing layer 2 and the intermediate layer 3 to form a recess, that is, an opening as indicated by S in FIG. . FIG. 2B is a perspective view showing a state in which the concave portion S is formed, and a sectional view taken along line AA in FIG. 2B corresponds to FIG. The metal plate 1 becomes the metal frame 1 after the selective etching.

  The laminate having the opening S corresponds to the hydrogen permeable membrane reinforcing structure of the present invention (1), and the manufacturing process thereof corresponds to the present invention (2). As shown in FIGS. 1 (g) and 2 (b), this hydrogen permeable membrane reinforcing structure has one side of a metal frame 1 having an opening S penetrating vertically (FIGS. 1 (g) and 2 (b)). The diffusion preventing layer 2 and the intermediate layer 3 are interposed between the lower surface] and the peripheral upper surface of the hydrogen permeable foil film 4 corresponding to this surface, and the hydrogen permeable foil film 4 at the bottom of the opening S. Is exposed.

<Aspects of the present invention (3) to (4)>
In the present invention (3) to (4), an intermediate layer is provided between the metal frame and the diffusion preventing layer, and an intermediate layer is provided between the diffusion intermediate layer and the hydrogen permeable membrane. FIG. 3 is a diagram for explaining this aspect. The hydrogen permeable membrane reinforcing structure is formed in the order shown in FIGS. 3A to 3H to obtain the structure shown in FIG. In FIG. 3, 21 is a metal plate, 22 is an intermediate layer, 23 is a diffusion prevention layer, 24 is an intermediate layer, and 25 is a hydrogen permeable foil film. In this embodiment, the intermediate layer 22 is referred to as a first intermediate layer, and the intermediate layer 24 is referred to as a second intermediate layer.

  As shown in FIG. 3, a first intermediate layer 22 is provided between the metal plate 21 and the diffusion prevention layer 23, and a second intermediate layer 24 is provided between the diffusion prevention layer 23 and the hydrogen permeable foil film 25. Provide. Among these, the first intermediate layer 22 is a layer for increasing the bonding strength between the metal plate 21 and the diffusion preventing layer 23. The first intermediate layer 22 can be formed by coating the surface of the metal plate body 21 in a layered manner by a plating method, a vapor deposition method, an arc ion plating method, or other appropriate methods.

  As the constituent material of the first intermediate layer 22, Au, Ag, Cu, Ni, Co, Pt, Pd, Rh, and Ru are used. These metals may be used in the form of a combination of two or more, for example, as an alloy. The second intermediate layer 24 corresponds to the intermediate layer 3 in the above-described <Aspects of the present invention (1) to (2)>, and the same material as the intermediate layer 3 is used. Regarding the constituent materials of the metal frame 21, the diffusion preventing layer 23, and the hydrogen permeable foil film 25, the metal frame 1, the diffusion preventing layer 2, and the hydrogen in the above-described <aspects of the present invention (1) to (2)>. The same as the permeable foil film 4.

  And in the above-mentioned <mode of this invention (1)-(2)>, it is set as the structure of FIG.3 (h) similarly to having demonstrated based on FIGS. 1-2. That is, as shown in FIG. 3D, a four-layer laminate including the first intermediate layer 22 is formed. The four-layer laminate thus formed and the hydrogen permeable foil film 25 are integrated as shown in FIG. In this laminated body, masking is performed on the peripheral upper surface of the metal plate 21, that is, a portion that becomes a frame for supporting the hydrogen permeable film 25, and a portion other than the masking portion is etched. The metal plate body 21 becomes the metal frame body 21 after the selective etching. In this way, a recess, that is, an opening S is formed. This is a portion indicated as S in FIG.

  The laminated body having the opening S corresponds to the hydrogen permeable membrane reinforcing structure of the present invention (3), and the manufacturing process corresponds to the present invention (4). As shown in FIG. 3H, this hydrogen permeable membrane reinforcing structure corresponds to one surface (the lower surface in FIG. 3H) of the metal frame 21 having an opening S penetrating vertically, and this surface. The first intermediate layer 22, the diffusion preventing layer 23, and the second intermediate layer 24 are interposed between the peripheral upper surface of the hydrogen permeable foil film 4, and the hydrogen permeable foil film 4 is exposed at the bottom of the opening S. It has a shape.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, it cannot be overemphasized that this invention is not limited to an Example. In this example, a hydrogen permeable membrane reinforcing structure as a comparative example (hereinafter referred to as a “comparative example hydrogen permeable membrane reinforcing structure”) was prepared by the method disclosed in Japanese Patent No. 558, and FIG. A hydrogen permeable membrane reinforcing structure according to the present invention (hereinafter referred to as “Example hydrogen permeable membrane reinforcing structure”) according to the present invention was prepared as in (g), and a heating test was performed on each.

<Production of comparative example hydrogen permeable membrane reinforced structure>
It was fabricated by the process shown in FIG. A stainless steel plate (SUS430 series) having a thickness of 0.1 mm is used as the metal plate 1, and a hydrogen permeable foil film 4 of Pd—Ag alloy is pasted on one side thereof, and then pressed by a cold pressure welding method. A layer structure was obtained. Masking with a thickness of 10 μm was performed on the peripheral upper surface of the surface on the stainless steel plate side of the two-layer structure thus obtained. Masking was performed by applying a PVA-bichromic acid aqueous solution by a roll coating method and then drying. Next, etching was performed using a ferric chloride aqueous solution. By etching, the exposed portion of the stainless steel plate not masked on the stainless steel plate surface was etched to obtain an opening laminate having a recess S.

<Preparation of Example Hydrogen Permeation Membrane Reinforced Structure>
A stainless steel plate (SUS430) having a thickness of 0.05 mm is used as the metal plate 1, alumina (Al ₂ O ₃ ) is used as the diffusion prevention layer 2, Ag is used as the intermediate layer 3, and the hydrogen permeable membrane 4 is used. A Pd—Ag alloy film was used. An alumina layer (thickness: about 0.2 μm) was formed on one side of the stainless steel plate by arc ion plating. It is a two-layer laminate shown in FIG.

  Further, an Ag layer (thickness: about 0.5 μm) was formed on the surface of the diffusion preventing layer 2 by an arc ion plating method. It is a three-layer laminated body shown in FIG.1 (c). After affixing a hydrogen permeable foil film of Pd—Ag alloy to the entire surface of the three-layer laminate formed as described above on the intermediate layer 3 side, the film is pressure-welded by a cold pressure welding method as shown in FIG. A four-layer structure as shown was obtained.

  Masking with a thickness of 8 μm was performed on the peripheral upper surface of the surface of the four-layer structure obtained in this way on the stainless steel plate side, that is, on the portion serving as a frame for supporting the hydrogen permeable membrane 4 as shown in FIG. Masking was performed by applying an aqueous resist by a dip method and then drying. If FIG.1 (f) is shown as a perspective view, it will become like Fig.2 (a).

  Next, etching was performed using a ferric chloride aqueous solution. The etching treatment was performed by etching from the exposed portion of the stainless steel plate not masked to the alumina layer 2, washing with water once to remove the alumina powder, and further etching the Ag layer 3. Thus, an opening laminate having a recess S as shown in FIG. When FIG.1 (g) is shown as a perspective view, it will become like FIG.2 (b). Among the steps of FIGS. 1A to 1G, the steps of (c) to (e) and (g) are shown in FIG. 4B in comparison with FIG.

<Production of test module for hydrogen permeable membrane reinforced structure>
The hydrogen permeable membrane reinforcing structure is usually connected to a hydrocarbon reforming apparatus having a temperature of 500 to 700 ° C., or integrated with a hydrogen production / purification apparatus using hydrocarbon steam reforming like a membrane reactor. Used. Therefore, in this heating test, a comparative hydrogen permeable membrane reinforcing structure and an example hydrogen permeable membrane reinforcing structure prepared as described above were incorporated into a membrane reactor type hydrogen production and purification device, respectively, and a heating test was conducted. did.

  Example A test module incorporating a hydrogen permeable membrane reinforcing structure was produced. FIG. 5 is a diagram for explaining each member including the structure and a manufacturing process thereof. 5B and 5F show two examples of hydrogen permeable membrane reinforcing structures [see FIG. 4B]. 5 (a) and 5 (g), 5 is a punching metal, 6 is a fine hole, 7 is a reinforcing plate having fine holes, and FIG. 5 (d) is a vertically penetrating opening. These are made of the same kind of material as the metallic frame 1. Reference numeral 9 denotes a hydrogen outlet pipe provided in the case 8.

  After arranging and joining the two upper and lower embodiment hydrogen permeable membrane reinforcing structures with the reinforcing plates 7 interposed between the upper and lower sides of the case 8 having the upper and lower through openings, the upper surface of the upper embodiment hydrogen permeable membrane reinforcing structure and The punching metal 5 was arrange | positioned and welded to the lower surface of the lower Example hydrogen permeable membrane reinforcement structure, respectively. FIG. 6A is a perspective view of the test module M1 for the hydrogen permeable membrane reinforcing structure according to the example manufactured in this way.

  Similarly, a test module incorporating a comparative example hydrogen permeable membrane reinforcing structure [see FIG. 4A] was produced. FIG. 6B is a perspective view of the test module M2 of the comparative example hydrogen permeable membrane reinforcing structure manufactured as described above. The comparative example test module M2 includes a diffusion preventing layer 2 and an intermediate layer 3 included in the hydrogen permeable membrane reinforcing structure of the example test module M1, that is, the metal frame 1 and the peripheral surface of the hydrogen permeable membrane 4. The difference is that there is no diffusion prevention layer 2 and intermediate layer 3 between them.

<Heating test>
The example test module M1 and the comparative example test module M2 were each set in a cylindrical steam reformer as shown in FIG. In FIG. 7, 10 is a cylindrical container, 11 is a raw material gas supply pipe, 12 is an off-gas, that is, a hydrogen-separated gas discharge pipe, and 13 is a granular reforming catalyst (Ni-supported alumina catalyst).

  While each of the cylindrical steam reformer set with the example test module M1 and the cylindrical steam reformer set with the comparative example test module M2 was heated to a temperature of 600 ° C. in an electric furnace, A mixed gas of desulfurized city gas 13A and water vapor, S / C ratio = 3.0, reforming pressure: 0.83 MPaG) was supplied, and reforming and purification tests were carried out for 180 hours.

<Observation 1>
Then, after cooling by natural cooling, each of the example test module M1 and the comparative example test module M2 was taken out, pressure was applied to the inside of the module with He gas from the hydrogen lead-out pipe 9, and the leakage situation in water was observed. In the comparative example test module M2, a large amount of gas leaks from the interface between the stainless steel frame plate which is the metal frame 1 of the comparative example hydrogen permeable membrane reinforcing structure and the Pd-Ag alloy film which is the hydrogen permeable foil membrane 5. Observed. On the other hand, no gas leak was observed from the interface between the stainless steel frame plate, which is the metal frame 1 of the example hydrogen permeable membrane reinforcing structure, and the Pd—Ag alloy foil film, which is the hydrogen permeable membrane 5.

<Observation 2>
Next, the example test module M1 and the comparative example test module M2 after the above observation were naturally dried, and each of the example hydrogen permeable membrane reinforcing structure and the comparative hydrogen permeable membrane reinforcing structure was made of a metal frame. The state of the bonding interface between the stainless steel frame plate 1 and the Pd—Ag alloy foil film 5 which is the hydrogen permeable foil film 5 was observed. FIG. 8 is an enlarged view of the SEM photograph of each joint surface. FIG. 8A shows the joint surface of the comparative structure, and FIG. 8B shows the joint surface of the example structure.

  8A, in the comparative hydrogen permeable membrane reinforcing structure, the stainless steel component (Fe) diffuses and diffuses from the stainless steel frame plate side to the Pd—Ag alloy foil membrane. It is observed. On the other hand, as shown in FIG. 8B, in the example hydrogen permeable membrane reinforcing structure, the stainless steel frame plate surface and the Pd—Ag alloy foil membrane surface are clearly separated, and the Pd—Ag alloy membrane No interdiffusion of stainless steel components is observed.

The figure explaining the aspect of this invention The figure explaining the aspect of this invention The figure explaining the other aspect of this invention The figure which shows the preparation process of a comparative example hydrogen permeable membrane reinforcement structure and an Example hydrogen permeable membrane reinforcement structure FIG. 3 is a diagram for explaining each member and its manufacturing process when incorporating the hydrogen permeable membrane reinforcing structure as a test module. The figure which shows the test module M1 incorporating the Example hydrogen permeable membrane reinforcement structure and the test module M2 incorporating the comparative example hydrogen permeable membrane reinforcement structure The figure which set the module M1 for an Example structure test, and the module M2 for a comparative example structure test in the cylindrical steam reformer, respectively <Heating test> The enlarged view of the SEM photograph of each joint surface of the comparative structure and the example structure after the heating test The figure which showed the example of an aspect disclosed in 558 gazette The figure which showed the example of an aspect disclosed in 558 gazette The figure which showed the example of an aspect disclosed in No. 355 gazette

Explanation of symbols

1 Metal plate (metal frame)
DESCRIPTION OF SYMBOLS 2 Intermediate | middle layer 3 Diffusion prevention layer 4 Hydrogen permeable foil film | membrane which is a hydrogen permeable film 5 Punching metal 6 Pore 7 Reinforcing plate having a fine hole 8 Case having upper and lower through openings 9 Hydrogen outlet pipe 10 Cylindrical container 11 Supply of raw material gas Pipe 12 Off-gas lead-out pipe 13 Reforming catalyst 14 Comparative example Penetration diffusion state of stainless steel component observed in structure 21 Metal plate (metal frame)
DESCRIPTION OF SYMBOLS 22 1st intermediate | middle layer 23 Diffusion prevention layer 24 2nd intermediate | middle layer 25 Hydrogen-permeable foil film | membrane S Recessed part of hydrogen-permeable film reinforcement structure 31 Extending frame (frame body)
32 Pd alloy foil and other materials with hydrogen gas separation (hydrogen permeable foil membrane)
33 Metal support plate b Pore 101 Peripheral portion of clad cut plate 102 Central portion of clad cut plate 34 Case 35 Purified hydrogen outlet tube 44 Hydrogen permeation layer 46 Support layer 48 Intermediate layer

Claims (9)

  A hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is arranged on one side of a metal frame having an opening penetrating vertically, and a diffusion preventing layer and an intermediate layer are sequentially provided on one side of the metal plate After that, a hydrogen permeable foil reinforced structure is obtained by bonding a hydrogen permeable foil film to the intermediate layer and then selectively etching from the metal plate side to expose the hydrogen permeable foil film.   The hydrogen permeable membrane reinforcing structure according to claim 1, wherein the constituent material of the intermediate layer is Au, Ag, Cu, Al, Ti, Ni, Co, Pt, Pd, Rh, Ru, or two or more of these metals A hydrogen permeable membrane reinforcing structure, characterized by comprising a material comprising:   A hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is arranged on one side of a metal frame having an opening penetrating vertically, and a first intermediate layer and diffusion prevention are sequentially provided on one side of the metal plate. After providing the layer and the second intermediate layer, the hydrogen permeable foil film is bonded to the second intermediate layer, and then the hydrogen permeable foil film is exposed by performing selective etching from the metal plate body side. A hydrogen permeable membrane reinforcing structure.   4. The hydrogen permeable membrane reinforcing structure according to claim 3, wherein the constituent material of the first intermediate layer is made of Au, Ag, Cu, Ni, Co, Pt, Pd, Rh, Ru, or two or more of these metals. The material of the second intermediate layer is Au, Ag, Cu, Al, Ti, Ni, Co, Pt, Pd, Rh, Ru, or a material composed of two or more of these metals. A hydrogen permeable membrane reinforcing structure.   5. The hydrogen permeable membrane reinforcing structure according to claim 1, wherein the constituent material of the metal frame is stainless steel, nickel, a nickel-base alloy, a copper alloy, or an iron-base alloy. A hydrogen permeable membrane reinforcing structure. The hydrogen permeable membrane reinforcing structure according to any one of claims 1 to 5, wherein a constituent material of the diffusion prevention layer is selected from Zr, Mo, Ta, W, Cr, Hf, Nb, and Ru. Melting point metal or TiN, TiC, TiO ₂ , TiB, Si ₃ N ₄ , SiC, SiO ₂ , AlN, Al ₂ O ₃ , MgO, CaO, AlSiO _X , Y ₂ O ₃ , ZrO ₂ , TiAlN, MgO · Al ₂ A hydrogen permeable membrane reinforcing structure, which is a ceramic selected from O ₃ and 2MgO · SiO ₂ .   The hydrogen permeable membrane reinforcing structure according to any one of claims 1 to 6, wherein the hydrogen permeable foil membrane includes (1) a Pd film, (2) a Pd alloy film, (3) a Group 5 metal, and the like. (4) a multilayer film of the Pd alloy film itself, (5) a multilayer film of a Pd film and an alloy film of a Group 5 metal and another metal, or (6) a Pd alloy film A hydrogen permeable membrane reinforcing structure, which is a multilayer film of a group 5 metal and an alloy film of another metal.   A method for producing a hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is disposed on one side of a metal frame having openings extending vertically, wherein a diffusion preventing layer and an intermediate layer are sequentially formed on one side of the metal plate. After forming a layer, a hydrogen permeable foil membrane is bonded to the intermediate layer, and then selectively etched from the metal plate side to expose the hydrogen permeable foil membrane, thereby producing a hydrogen permeable membrane reinforcing structure Method.   A method for producing a hydrogen permeable membrane reinforcing structure in which a hydrogen permeable foil membrane is disposed on one side of a metal frame having an opening penetrating vertically, the first intermediate layer being sequentially formed on one side of the metal plate After the diffusion preventing layer and the second intermediate layer are provided, the hydrogen permeable foil film is joined to the second intermediate layer, and then the hydrogen permeable foil film is exposed by performing selective etching from the metal plate body side. A method for producing a hydrogen permeable membrane reinforcing structure.

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