JP2007167797A - Hydrogen permeable membrane module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen permeable membrane module which does not need a metallic support indispensable in the conventional technology, has simple structure, and can easily handle hydrogen permeable foil membrane serving as a hydrogen permeable membrane. <P>SOLUTION: This hydrogen permeable membrane module does not need the metallic support, and is formed by disposing a reinforcing member formed by laminating finely porous metallic sheets, and the hydrogen permeable membrane in this order on both sides of a refined hydrogen collection member formed by laminating a plurality of metallic sheets having vertically penetrated spaces, and by joining them together at once. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hydrogen permeable membrane module, and more specifically, to a hydrogen permeable membrane module that does not require a metal support, which is essential in the prior art.

For example, the reformed gas obtained by the hydrocarbon steam reforming method contains by-products such as CO and CO ₂ and surplus H ₂ O in addition to hydrogen as a main component. 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. Among fuel cells, CO in hydrogen 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 20 μm or less and about 0.5 to 20 μm, a member for supporting the hydrogen permeable membrane is required.

  35 to 36 are diagrams disclosed in Japanese Patent Laid-Open No. 2001-276558 (referred to as “No. 558” in the present specification). FIG. 35 is an exploded perspective view for explaining the structure of the hydrogen gas separation unit. In FIG. 35, reference numeral 71 denotes an extension frame, which is made of a metal such as stainless steel. The extension frame 71 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. 72 is a material having hydrogen gas separation properties such as Pd alloy foil (= hydrogen permeable membrane), 73 is a metal support plate, and b is a pore.

  FIG. 36 is a schematic perspective view of a hydrogen gas separator incorporating the unit of FIG. As shown in FIG. 36, the hydrogen gas separation unit configured as shown in FIG. 35 is fixed to the case 74 by laser welding or the like so that the surface of the metal support plate 73 is on the inside. It is said. 75 is a purified hydrogen take-out pipe.

  FIG. 37 is a diagram disclosed in Japanese Patent Laid-Open No. 10-296061 (referred to as “061 publication” in this specification). In FIG. 37, a reinforcing plate 81 made of a plurality of porous metal plates is placed on a base plate 80 with a ventilation groove, and a hydrogen permeable membrane composite 89 and a frame-like metal plate 82 are placed on the reinforcing plate 81. It is formed by sealing from above the metal plate 82 by welding. In the hydrogen permeable membrane composite 89, a hydrogen permeable membrane such as Pd is formed on an underlying substrate having a surface flatness such as a polyethylene film, and a porous support is formed thereon on a thickness of 40 to 300 µm. After that, the base substrate is incinerated or peeled off.

  As described above, in the publication No. 558, a rolled thin film type hydrogen permeable film 72 is used, and the hydrogen permeable film 72 is fixed to the extension frame 71 and the metal support plate 73 by laser welding or the like. Further, in Japanese Patent No. 061, a hydrogen permeable membrane composite 89 in which a hydrogen permeable membrane such as Pd is arranged on a porous support is used, a reinforcing plate 81 is overlaid on a base plate 80, and a hydrogen permeable membrane is formed thereon. The membrane composite 89 and the frame-shaped metal plate 82 are placed and joined by welding the outer periphery. Japanese Patent Application Laid-Open No. 2005-58939 also describes joining an end portion of a hydrogen permeable membrane to a frame by laser welding when configuring a hydrogen separation module.

  However, since the hydrogen permeable membrane is extremely thin of 20 μm or less, it is difficult to select welding conditions, and only the membrane melts excessively during welding, and the airtightness of the module cannot be ensured in many cases. As a result, the yield rate became considerably low, and the problem was that the module production efficiency was poor.

  The present inventors have previously developed and filed 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. (Application on June 30, 2005: Japanese Patent Application No. 2005-192316, referred to as “Application No. 316” in this specification). According to this hydrogen permeable membrane reinforcing structure, the yield was considerably improved by performing welding after preliminarily joining with another metal frame to ensure airtightness. However, mass production was difficult because the work was performed one by one.

JP 2001-276558 A JP-A-10-296061 JP 2005-58939 A Application for Japanese Patent Application No. 2005-192316

  The present invention does not have the drawbacks described above, does not require a metal support that is essential in the prior art, has a simple structure, and can easily handle a hydrogen permeable foil film that is a hydrogen permeable film. The purpose is to provide modules.

  The present invention (1) is a hydrogen permeable membrane module that does not require a metal support. Then, in sequence, one or more metal sheets having no voids, a purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated, and a reinforcement in which a plurality of metal sheets having pores are laminated The member and the hydrogen permeable membrane are arranged and bonded at a time.

  The present invention (2) is a hydrogen permeable membrane module that does not require a metal support. Then, in sequence, one or more metal sheets having no voids, a purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated, and a reinforcement in which a plurality of metal sheets having pores are laminated A plurality of members and a hydrogen permeable membrane are arranged and bonded at a time.

  According to the present invention (3), in the hydrogen permeable membrane module of the above (2), the plurality of reinforcing members have a gradient in the pore size so that the pores become coarser toward the purified hydrogen collecting member. The reinforcing member is provided.

  The present invention (4) is a hydrogen permeable membrane module that does not require a metal support. Then, on both sides of the purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated, a reinforcing member in which metal sheets having pores are sequentially laminated, and a hydrogen permeable membrane are disposed at a time. It is characterized by being joined.

  The present invention (5) is a hydrogen permeable membrane module that does not require a metal support. And on both sides of the purified hydrogen collecting member laminated with a plurality of metal sheets having upper and lower through gaps, respectively, a plurality of reinforcing members laminated with a plurality of metal sheets having pores, respectively, a hydrogen permeable membrane, It arrange | positions and it joins at once.

  According to the present invention (6), in the hydrogen permeable membrane module according to the above (5), the pores become rougher as the plurality of reinforcing members go to the purified hydrogen collecting member which is the central portion in the thickness direction. The reinforcing member is formed by providing a gradient in the size of the pores.

  In the hydrogen permeable membrane module according to any one of (1) to (6), the present invention (7) includes a plurality of metal sheets constituting the purified hydrogen collecting member and a plurality of sheets constituting the reinforcing member. The metal sheets (in the present invention (6), the metal sheets constituting the reinforcing members having pores that become coarser toward the purified hydrogen collecting member that is the central portion in the thickness direction) are each disposed as they are as the metal sheets. It is characterized by being joined.

According to the present invention, the following effects (a) to (e) can be obtained.
(A) The metal support, which is essential in the prior art, is unnecessary, and the labor for manufacturing it can be saved. Therefore, the cost can be reduced.
In the above-mentioned No. 558, the case 74 corresponds to a metal support, and in the above-mentioned No. 061, the base plate 80 with a ventilation groove corresponds to the metal support. These metal supports need to be prepared separately from other members and joined by laser welding or the like, but in the present invention, those metal supports that are essential in the prior art are unnecessary. Moreover, the above-mentioned problem at the time of welding when using these metal supports can be solved.
(B) Since the purified hydrogen collecting member, the reinforcing member, and the hydrogen permeable membrane can be joined at a time, each material can be modularized in a single process, and several reinforcing members can be provided on one plane. By doing so, mass production of hydrogen permeable membrane modules is possible.
(C) Since each metal sheet is processed by etching, the structure inside the joined body composed of the purified hydrogen collecting member and the reinforcing member can be easily controlled. As a result, cost reduction, weight reduction, and capacity reduction can be expected.
(D) As described later in Japanese Patent Publication No. 985, by laminating thin metal sheets, it is possible to make a fine mesh thick plate that could not be realized with a single thick member. In the present invention, this technique is applied. By doing so, the strength of the reinforcing member can be enhanced and the durability of the hydrogen permeable membrane module can be improved.
(E) A reinforcing member with the coarsest pores is arranged on the side of the purified hydrogen collecting member, and the reinforcing members with fine pores are sequentially dense toward the hydrogen permeable membrane side (reinforcing with the roughness of the pores being successively reduced) The flow resistance of the purified hydrogen flowing from the hydrogen permeable membrane side toward the purified hydrogen collecting member is reduced while maintaining the strength of the hydrogen permeable membrane by arranging the member) and providing a gradient in the pore size. be able to.

  In any one of the hydrogen permeable membrane modules of the present invention (1) to (7), the purified hydrogen collecting member, the reinforcing member, and the hydrogen permeable membrane are arranged at predetermined positions defined in the respective inventions, and are configured by one-time joining. The The bonding means is not particularly limited, but a preferred example is “diffusion bonding”. According to diffusion bonding, these members can be bonded by a single batch heat treatment. In the following description, diffusion bonding is mainly described as an example, but the same applies to cases using other bonding means.

In the present invention, the hydrogen permeable membrane is not particularly limited as long as it is a foil membrane made of a material having a function of selectively permeating hydrogen, and examples thereof include the following (1) to (6).
(1) Pd film,
(2) Pd alloy film,
(3) an alloy film of a Group 5 metal (V, Nb or Ta) and a Group 6 metal (Cr, Mo, W) or other metal,
(4) Pd alloy film multilayer film (that is, Pd alloy film itself multilayer film),
(5) A multilayer film of a Pd film, an alloy film of a Group 5 metal (V, Nb or Ta) and a Group 6 metal (Cr, Mo, W) or other metal,
(6) A multilayer film of a Pd alloy film, an alloy film of a Group 5 metal (V, Nb or Ta), a Group 6 metal (Cr, Mo, W) or other metal.
Among these, (2) Pd alloy film is an alloy film of Pd and other metals, and metals that are alloyed with Pd are Au, Ag, Cu, Pt, Rh, Ru, Ir, Ce, Sm, Tb, Dy, Ho, Er, Yb, Y, Gd are mentioned. Two or more of these metals may be combined and alloyed with Pd.
Foil films made of these metal materials are produced by various methods such as rolling, ion plating, and plating.

  The aspects of the present invention (1) to (7) will be sequentially described including the production process. In the following, a hydrogen permeable membrane module in which each member such as a blocking member, a purified hydrogen collecting member, a reinforcing member, and a hydrogen permeable membrane is formed in a rectangular shape will be described as an example. It can be said that.

<Aspect of the present invention (1)>
In the hydrogen permeable membrane module of the present invention (1), as the material, one or more metal sheets (a) having no voids, a plurality of metal sheets (b) having upper and lower through voids, a plurality of A metal sheet (c) having a single pore and a hydrogen permeable membrane (d) are used. Then, these materials are sequentially arranged, that is, (b) is arranged on (a), (c) is arranged on (b), and (d) is arranged on (c). Thus, a hydrogen permeable membrane module is manufactured by diffusion bonding at a time.

By the joining, a closing member is constituted by the metal sheet (a) having no one or a plurality of voids, and a purified hydrogen collecting member is constituted by the metal sheet (b) having the plurality of upper and lower through-holes, The reinforcing member is constituted by the metal sheet (c) having a plurality of pores.
Here, since each void in the metal sheet (b) having the plurality of upper and lower through-holes is a void that collects purified hydrogen in the hydrogen permeable membrane module and circulates it toward the outlet tube, (b) It can also be said to be a “metal sheet having a plurality of purified hydrogen flow gaps”.
The closing member is located on one opening side of the gap of the purified hydrogen collecting member and serves to close the opening. And a reinforcement member will be located in the other opening side among the space | gap of a refinement | purification hydrogen collection member.

  1-5 is a figure explaining the aspect of the hydrogen permeable membrane module of this invention (1). In addition, also about the part which this invention (1) has in common with this invention (2)-(7), it has demonstrated suitably in the location of the said <mode of this invention (1)>.

FIG. 1 is a diagram for explaining the manufacturing process, and FIG. 1 (c ′) is a cross-sectional view taken along the line AA in FIG. 1 (c). FIG. 1A shows a hydrogen permeable membrane 1.
FIG. 1B is composed of a metal sheet having a plurality of pores. At this stage, the metal sheets are simply stacked, that is, are stacked. And it becomes the reinforcement member 2 by the next diffusion joining.
FIG.1 (c) consists of the metal sheet which does not have a 1 or several sheet | seat space | interval, and the metal sheet which has a plurality of sheet | seats with an up-and-down penetration, and at this stage, those metal sheets were only piled up, that is, laminated. It is just a state. Then, by the next diffusion bonding, the metal sheet having one or a plurality of voids becomes the closing member M, and the metal sheet having the plurality of upper and lower through-holes becomes the purified hydrogen collecting member 1.

  Then, the hydrogen permeable membrane and the metal sheets arranged as shown in FIGS. 1A to 1C are diffusion bonded at a time to constitute a hydrogen permeable membrane module. FIG. 1D shows a hydrogen permeable membrane module configured as described above. In FIGS. 1A to 1C, for the sake of illustration and explanation, the hydrogen permeable membrane and the group of metal sheets to be each member are shown separately, but these materials are overlapped and diffused at once. Join. In addition, the metal sheet of each group was only piled up.

  Hereinafter, each member used in the hydrogen permeable membrane module, that is, the blocking member M, the purified hydrogen collecting member 1, the reinforcing member 2 having pores, and the hydrogen permeable membrane 3 will be described in order.

  The constituent material of the blocking member, the purified hydrogen collecting member, and the reinforcing member having pores may be any metal that can be etched and bonded to each other. Examples include stainless steel, nickel, nickel-base alloy, and copper alloy. And iron-based alloys (such as iron-nickel alloys). Of these, stainless steel is particularly preferable.

  In the present invention (1), one or a plurality of metal sheets made of these materials and having no voids, a plurality of metal sheets having upper and lower through-holes, a metal sheet having a plurality of pores, and hydrogen permeation Diffusion bonding is performed at once by layering the films. As described above, since the closing member, the purified hydrogen collecting member, and the reinforcing member are formed by one diffusion bonding, it is preferable that the metal sheets are made of the same material. Thereby, diffusion bonding can be performed more effectively and cost reduction can be achieved.

<Production mode of purified hydrogen collecting member 1>
FIG. 2 is a view for explaining a production mode of the purified hydrogen collecting member 1. As shown in FIG. 2, a plurality of metal sheets having upper and lower penetrating gaps s are arranged inside, and one or more metal sheets having no gap are arranged at the lowermost part. By superimposing these, the purified hydrogen collecting member 1 and the closing member M are formed. As described above, at this stage, a plurality of metal sheets having upper and lower through-holes s and a metal sheet not having one or more gaps on one side surface are simply overlaid.

  The number of metal sheets having the upper and lower through-holes s is sufficient to maintain strength and thickness in the hydrogen permeable membrane module. For example, the thickness of each metal sheet is about several tens of μm to several hundreds of μm. For this reason, when the thickness is, for example, 100 μm, the purified hydrogen collecting member 1 having the gap S having a thickness of about 2 mm is configured by stacking 20 sheets.

  Moreover, although the metal sheet | seat which does not have the space | gap s has shown the example of 1 sheet in FIG. 2, it is set as the number which can maintain intensity | strength and thickness in a hydrogen permeable membrane module. An example of the thickness of the metal sheet having no gap s is the same as in the case of the above “metal sheet having the upper and lower through gaps s”.

<Production aspect of metal sheet having void s>
FIG. 3 is a view for explaining a production mode of the above-described “metal sheet having upper and lower through-holes s”. FIG. 3A shows a metal sheet, and masking is performed except for a portion of the surface which becomes the gap s. FIG. 3B shows this state. Next, an etching process is performed. By the etching process, portions other than the masking portion are removed, and the gap s is formed. FIG. 3C shows this state. Next, by removing the masking, a metal sheet having a gap s is obtained as shown in FIG.

  Masking can be performed by applying a resist solution such as a PVA-bichromic acid aqueous solution 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 may be any thickness that can be protected during the etching process, and is, for example, about 5 to 10 μm. Then, selective etching, that is, a portion excluding the masking portion is etched.

  For example, a ferric chloride aqueous solution or the like is used as an etchant in the etching process. In this process, etching is selectively performed from the exposed portion of the metal sheet that is not masked, and a gap s is formed as shown in FIG. The laminate having the gap S formed by a plurality of metal sheets having the gap s corresponds to the purified hydrogen collecting member 1 shown in the lower part of FIG. 1 (c) and FIG. Not a metal sheet is placed. The space S of the purified hydrogen collecting member 1 serves as a purified hydrogen collecting unit.

<Preparation mode of reinforcing member 2 having pores>
FIG. 4 is a diagram for explaining a production mode of the reinforcing member 2 having pores. As shown in FIG. 4, a plurality of metal sheets each having a pore are arranged. And the reinforcing member 2 which has a pore is formed by overlapping these. As described above, at this stage, since it is before joining, a plurality of metal sheets having pores are simply stacked.

  The number of metal sheets having pores is set to a number sufficient to maintain strength and thickness in the hydrogen permeable membrane module. For example, since the thickness of each metal sheet is about several tens of μm to several hundreds of μm, when the thickness is, for example, 100 μm, 20 sheets are stacked to have pores of about 2 mm in thickness. The reinforcing member 2 is configured.

<Preparation mode of metal sheet having pores>
FIG. 5 is a diagram for explaining a production mode of a metal sheet having pores. FIG. 5A shows a mask, which has no holes in the peripheral portion and has pores in the interior surrounded by the peripheral portion. This mask is disposed on the surface of the metal sheet shown in FIG. FIG. 5C shows this state. Next, an etching process is performed. By the etching process, portions of the metal sheet corresponding to the pores of the mask are removed by etching, and other portions are not etched.

  Next, by removing the masking, a metal sheet having pores is obtained as shown in FIG. A plurality of laminates of metal sheets having pores correspond to the reinforcing member 2 having pores shown in the lowermost part of FIG. As described above, at this stage, since it is before joining, a plurality of metal sheets having pores are simply stacked.

  Note that a technique for producing a metal thin plate having a plurality of pores by etching means and integrating the plurality of metal thin plates after matching the positions of the holes of the plurality of pores is disclosed in JP 2000-109985A. (Referred to as “985 publication” in this specification). In the present invention, such a technique is applied when producing the metal sheet having the pores and the reinforcing member having the pores.

JP 2000-109985 A

<Aspect of the present invention (2)>
Although FIG. 1 shows a case where there is one reinforcing member having pores as shown in FIG. 1B, two or more reinforcing members having pores may be arranged. The hydrogen permeable membrane module of the present invention (2) corresponds to this case, and is produced in the same manner as in the case of <Aspect of the present invention (1)> except that a plurality of reinforcing members having pores are arranged. can do.

<Aspect of the present invention (3)>
In the hydrogen permeable membrane module of the present invention (3), in the hydrogen permeable membrane module of the present invention (2), the pores of the pores become coarser as the two or more reinforcing members go to the purified hydrogen collecting member. It is a reinforcing member in which a gradient is provided in the size of the pores.

  FIG. 6 is a diagram illustrating an embodiment of the hydrogen permeable membrane module of the present invention (3). In contrast to the embodiment shown in FIG. 1, a reinforcing member having coarse pores is disposed on the purified hydrogen collecting member 10 side as indicated by reference numeral 11 in FIG. At this stage, as in the case where a plurality of metal sheets having pores are stacked, the plurality of metal sheets having coarse pores are simply stacked. In this respect, the bottom part of FIG. The same applies to the state shown in FIG.

  Except for using a reinforcing member having coarse pores, it is the same as the embodiment described in <Aspect of the present invention (1)>. That is, in FIG. 6, the purified hydrogen collecting member 10 corresponds to the purified hydrogen collecting member 1 in FIG. 1, 12 is a reinforcing member having pores, the reinforcing member 2 having pores in FIG. The hydrogen permeable film corresponds to the hydrogen permeable film 3 in FIG.

  FIG. 6 shows two cases of the reinforcing member 11 having coarse pores and the reinforcing member 12 having dense pores (that is, the pore diameter is smaller than the pore diameter of the reinforcing member 11). As shown, a reinforcing member having the coarsest pores is arranged on the side of the purified hydrogen collecting member 10, and thereafter, the reinforcing members having pores that are sequentially dense toward the hydrogen permeable membrane side (that is, pores). The reinforcing member whose roughness is gradually reduced is arranged. In this way, by providing a gradient in the pore size so that the pores become rougher toward the purified hydrogen collection member, the purified hydrogen collection from the hydrogen permeable membrane side while maintaining the strength of the hydrogen permeable membrane. The flow resistance of the purified hydrogen flowing toward the member can be reduced.

  Production of the reinforcing member 11 with coarse pores was carried out in the same manner as described above <Manufacturing mode of reinforcing member 2 having pores> (FIG. 4) and <Manufacturing mode of metal sheet having pores> (FIG. 5). can do. FIG. 7 shows a mode in which the reinforcing member 11 having coarse pores is produced from a plurality of metal sheets having coarse pores. The hydrogen permeable membrane module of the present invention (3) is produced in the same manner as in the above-mentioned <Aspect of the present invention (1)> except that a reinforcing member having a coarse pore is disposed on the purified hydrogen collecting member 10 side. can do.

  In the hydrogen permeable membrane module of <aspect of the present invention (1)> to <aspect of the present invention (3)>, a hydrogen lead-out pipe communicating with the gap S of the purified hydrogen collecting member is provided. The number of hydrogen outlet pipes is not limited to one, and a plurality of hydrogen outlet pipes may be provided. An embodiment in which the hydrogen outlet pipe is provided is as described later.

<Diffusion prevention layer, intermediate layer-diffusion prevention layer, diffusion prevention layer-intermediate layer, or intermediate layer-diffusion prevention layer-intermediate layer between the reinforcing member having pores and the hydrogen permeable membrane>
When a joined body obtained by joining a metal sheet, for example, a stainless steel sheet and a hydrogen permeable membrane in direct contact with each other at a high temperature such as a hydrocarbon steam reforming condition (500 to 700 ° C.), the metal sheet and the hydrogen permeable membrane are used. The components of each other diffused to alter the hydrogen permeable membrane, resulting in a problem that the strength, hermeticity, and hydrogen permeation performance of the membrane are remarkably lowered.

  In the present invention, (A) a diffusion preventing layer and (B) a first intermediate layer at the joint with the hydrogen permeable membrane in the reinforcing member having pores on the hydrogen permeable membrane side (that is, the side in contact with the hydrogen permeable membrane) (= Reinforcement member side) -diffusion prevention layer, (C) diffusion prevention layer-second intermediate layer (= hydrogen permeable membrane side) or (D) first intermediate layer (= reinforcement member side) -diffusion prevention Layer-second intermediate layer (= hydrogen permeable membrane side) is arranged, thereby preventing mutual diffusion of mutual components between the reinforcing member and the hydrogen permeable membrane, preventing alteration of the hydrogen permeable membrane, membrane strength, airtightness And deterioration of hydrogen permeability can be prevented.

  The technique of arranging the layers (A) to (D) at the junction with the hydrogen permeable membrane was previously developed by the present inventors (the above-mentioned “316 application”). In the invention, this is applied.

  FIG. 8 is a diagram illustrating a mode in which any one of the layers (A) to (D) is disposed between the reinforcing member having pores and the hydrogen permeable membrane. In FIG. 8, the same reference numerals are used for members and portions common to FIG. In FIG. 8, reference numeral 2 'denotes a "metal sheet having pores" in which any one of layers (A) to (D) is disposed on the upper surface leaving a predetermined width from the periphery of the metal sheet.

  The “metal sheet having pores” 2 ′ in which any one of layers (A) to (D) is arranged together with the closing member M, the purified hydrogen collecting member 1, the reinforcing member 2 having pores, and the hydrogen permeable membrane 3 8A to 8D are arranged and diffusion bonded at a time to constitute a hydrogen permeable membrane module. FIG. 8E shows a hydrogen permeable membrane module configured as described above.

<Aspect where (A) anti-diffusion layer is disposed on metal sheet or reinforcing member having pores>
FIG. 9 is a diagram for explaining a mode of forming a diffusion preventing layer on a metal sheet having pores. FIG. 9B is a metal sheet, and the dotted line shown in FIG. 9B is for explanation, and indicates that the inside of the dotted line frame is a pore region.

  Mask the metal sheet. As shown in FIG. 9A, the masking can be performed by arranging a mask having no holes in the peripheral portion and having pores in a portion surrounded by the peripheral portion on the metal sheet. That is, the mask of FIG. 9A is arranged on one side of the metal sheet of FIG. FIG. 9C shows the masked state.

  Next, an etching process is performed. By the etching process, portions of the metal sheet corresponding to the pores of the mask are removed by etching, and other portions are not etched. Next, by removing the masking, a metal sheet having pores as shown in FIG. 9 (d) is obtained. The metal sheet having the pores is symmetrical with respect to the front and back, and is the same as FIG.

  Then, a diffusion preventing layer is formed. The diffusion preventing layer is formed on one side of a metal sheet having pores. The diffusion preventing layer is formed by applying a material to be the diffusion preventing layer to the pore region (pore region) of the metal sheet. The material for forming the diffusion preventing layer can be applied by dip coating, spraying, printing, arc ion plating, vapor deposition, or the like. Of these, the printing method is particularly useful because the metal sheet is flat.

A refractory metal or ceramic is used as a constituent material of the diffusion preventing layer. 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.

  The diffusion preventing layer may be formed by oxidizing one surface of a metal sheet having pores to form an oxide, and the oxide may be used as the diffusion preventing layer. This oxide formation can be applied in a mode in which only the diffusion preventing layer is disposed on the metal sheet or the reinforcing member, or a mode in which the above-described diffusion preventing layer-second intermediate layer (= hydrogen permeable membrane side) is disposed. In the manufacturing process up to the completion of the hydrogen permeable membrane module, the oxide corresponds to the material that becomes the diffusion preventing layer.

  A hydrogen permeable membrane is disposed on the side of the formed diffusion prevention layer. The thickness of the material to be the diffusion preventing layer can be appropriately selected within the range in which the purpose, that is, the mutual diffusion prevention between the metal sheet component and the hydrogen permeable membrane can be achieved. The range is preferably 0.05 to 1 μm. In addition, since the thickness of the diffusion preventing layer is smaller than the diameter of the pores of the metal sheet, the pores are not clogged with the constituent material of the diffusion preventing layer.

  FIG. 9 (e) shows a state in which the material to be the diffusion preventing layer is formed in this way. The member formed by applying the material to be the diffusion prevention layer corresponds to the “metal sheet having pores” 2 ′ shown in FIG. 8B, and here, (A) “pores having the diffusion prevention layer”. The metal sheet “2 ′” having

  Although the case where the diffusion preventing layer is arranged on the metal sheet having one pore has been described above, the diffusion preventing layer may be arranged on one side of the reinforcing member on which the metal sheet having the pores is stacked. In this case, the diffusion preventing layer as shown in FIG. 9E is arranged on the upper surface of the reinforcing member 2 having the pores shown in FIG. In this respect, the same applies to an aspect in which one or both of the first intermediate layer and the second intermediate layer are arranged in addition to the diffusion preventing layer.

  In the embodiment of FIG. 9, the diffusion prevention layer is formed on the metal sheet having pores. However, the metal sheet having the pores having the diffusion prevention layer is fitted into a simple frame, and FIG. ). FIG. 10 is a diagram for explaining this aspect. FIG. 10A shows a metal sheet having pores. A diffusion preventing layer is applied to the entire surface of one side of the metal sheet having pores shown in FIG. 10A, as shown in FIG. Then, this metal sheet is fitted into a simple frame having an opening corresponding to the outer periphery of the metal sheet as shown in FIG.

  Thus, as shown in FIG. 10D, a configuration similar to that shown in FIG. This formation mode does not require a step such as masking during the formation of the diffusion prevention layer, and also provides merits and effects such as no wraparound of the diffusion prevention material to the back surface of the metal sheet during the formation of the diffusion prevention layer. It is done.

  FIG. 10 shows a case where a metal sheet having one pore is used, but a plurality of metal sheets having pores are stacked (of the plurality of sheets, only the metal sheet on the hydrogen permeable membrane side). And a metal sheet provided with a diffusion preventing layer), and may be fitted to a simple frame in the same manner as described above. In these cases, a simple frame is also formed by overlapping a plurality of metal sheets of corresponding shapes, and is not a metal frame as in the prior art.

  FIG. 11 (a) is the same as FIG. 9 (e) and FIG. 10 (d). FIG.11 (b) expands the right side part of Fig.11 (a), and shows it as a top view. a is the periphery of the metal sheet, b is the periphery of the pore region in the metal sheet, and c is the periphery of the diffusion preventing layer. As shown in FIG. 11B, a predetermined width d is placed between the peripheral edge a of the metal sheet and the peripheral edge c of the diffusion prevention layer. The predetermined width d is the “predetermined width” where “the predetermined width is left from the periphery of the metal sheet”, and the surface of the predetermined width d is a surface where the metal of the metal sheet is exposed (metal exposed surface). Become.

  At the time of bonding, the hydrogen permeable membrane is bonded at the exposed metal surface, and is not bonded at the diffusion preventing layer. In addition, although the dotted line is attached | subjected to the right side in FIG.11 (b), this has shown that the hydrogen permeable film is distribute | arranged to the location of this dotted line roughly. This also applies to the embodiments shown in FIGS.

  In the embodiment described above, the diffusion prevention layer is formed of a metal sheet as shown by hatching in FIGS. 8 (b), 9 (e), 10 (d), and 11 (a) to 11 (b). The pore region is arranged so as to be somewhat “out of” from the peripheral edge b of the pore region. 11 (a) to 11 (b), it is a portion indicated by a symbol e and a width portion between b and c.

  However, since the diffusion preventive layer does not join with the hydrogen permeable membrane, such a “protruding” portion is not essential and may be disposed substantially only in the pore region. As a result, the pore region of the metal sheet can be widened by that amount, that is, only the “excess” portion. This also applies to the case where the layers (B) to (D) are provided. .

  When the “excess” portion is eliminated and the pore region is expanded accordingly, the pore region of the metal sheet can be widened as shown in FIG. Then, as shown in FIG. 12B, a diffusion prevention layer is disposed over the entire pore region. FIG. 12C is an enlarged plan view of the right side portion of FIG. By expanding the pore area of the metal sheet in this way, the pore area of the metal sheet can be expanded to the area of the “extrusion” portion, so that the hydrogen purification area by the hydrogen permeable membrane can be expanded on the same scale as a module. .

  As described above, in any case, the diffusion preventing layer prevents mutual diffusion of the metal sheet component and the hydrogen permeable membrane component, and prevents deterioration of the hydrogen permeable membrane.

<Aspect where (B) first intermediate layer (= reinforcing member side) -diffusion preventing layer is disposed on a metal sheet or reinforcing member having pores>
FIG. 13 is a diagram for explaining a mode in which a first intermediate layer (= reinforcing member side) -a diffusion preventing layer is disposed on the contact surface with the hydrogen permeable membrane for the reinforcing member having pores on the hydrogen permeable membrane side. is there. The first intermediate layer is a layer for increasing the bonding strength between the reinforcing member having pores and the diffusion preventing layer and ensuring adhesion, and is the uppermost thin layer constituting the reinforcing member having pores. It can form by apply | coating to the surface of the metal sheet which has a hole by the plating method, a vapor deposition method, an arc ion plating method, and other appropriate methods.

Au, Ag, Cu, Al, Ti, Ni, Co, Pt, Pd, Rh, Ru, etc. are used as a constituent material of the first intermediate layer (= reinforcing member side). Two or more of these metals may be combined as an alloy, for example.
The thickness of the first intermediate layer can be appropriately selected as long as the object can be achieved. The range is 0.05 to 20 μm, preferably 0.1 to 10 μm. Since the thickness of the “first intermediate layer + diffusion prevention layer” is smaller than the diameter of the pores of the metal sheet, the pores are not clogged.

<Mode in which (C) diffusion preventing layer-second intermediate layer (= hydrogen permeable membrane side) is arranged on a metal sheet or reinforcing member having pores>
FIG. 14 illustrates an aspect in which a diffusion preventing layer-second intermediate layer (= hydrogen permeable membrane side) is arranged on the contact surface with the hydrogen permeable membrane for the reinforcing member having pores arranged on the hydrogen permeable membrane side. It is a figure to do. The second intermediate layer is a layer for increasing the bonding strength between the diffusion preventing layer and the hydrogen permeable membrane and ensuring adhesion. The surface of the diffusion preventing layer is plated, vapor deposited, or arc ionized. It can be carried out by applying a layer by a plating method or other appropriate methods.

As a constituent material of the second intermediate layer (= hydrogen permeable membrane side), Au, Ag, Cu, Ni, Co, Pt, Pd, Rh, Ru, or the like is used. Two or more of these metals may be combined as an alloy, for example.
The thickness of the second intermediate layer can be appropriately selected as long as the purpose can be achieved. The range is 0.05 to 20 μm, preferably 0.05 to 1 μm.

<Mode in which (D) first intermediate layer (= reinforcing member side) -diffusion prevention layer-second intermediate layer (= hydrogen permeable membrane side) is arranged on a metal sheet or reinforcing member having pores>
FIG. 15 shows a reinforcing member having pores on the hydrogen permeable membrane side, the first intermediate layer (intermediate layer between the reinforcing member and the diffusion preventing layer) -diffusion preventing layer-second layer on the contact surface with the hydrogen permeable membrane. It is a figure explaining the aspect which has arrange | positioned the intermediate | middle layer (intermediate layer between a diffusion prevention layer and a hydrogen permeable film). Of these, the first intermediate layer is the same as the first intermediate layer (see FIG. 13) in terms of the purpose, constituent material, and its construction method, and the second intermediate layer is both objective, constituent material, and construction method. This is the same as the second intermediate layer (see FIG. 14).

  FIG. 16 corresponds to the “metal sheet having pores” 2 ′ in which any one of layers (A) to (D) is arranged in the embodiment of the hydrogen permeable membrane module of the present invention (3) shown in FIG. 12 'is arranged. FIG. 16 shows a case where the above-described “excess” portion is included in these layers, but the same applies to the case where the “excess” portion is not included.

<< Aspects of the present invention (4) to (6) >>
The hydrogen permeable membrane module of the present invention (4) to (6) is a reinforcing member in which a metal sheet having pores is laminated on both sides of a purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated, or A reinforcing member with a gradient in the pore size and a hydrogen permeable membrane are arranged so that the pores become coarser toward the purified hydrogen collecting member, which is the central part in the thickness direction, or a plurality of reinforcing members It is configured to be joined at a time.

As described above, since the hydrogen permeable membrane and the reinforcing member are arranged on both sides of the purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated, the present inventions (4) to (6) are compact. Moreover, a high-performance hydrogen permeable membrane module can be obtained.
In addition, in the following, (A) Although it demonstrates using drawing which arranged the metal sheet which has the pore which distribute | arranged the diffusion prevention layer, the pore which distribute | arranged the layer in any one of (B)-(D) The same applies to the case where the metal sheet is provided or the case where the layers (A) to (D) are not provided.

<Aspect of the present invention (4)>
In the present invention (4), a reinforcing member in which metal sheets having pores are sequentially laminated and a hydrogen permeable membrane are arranged on both sides of a purified hydrogen collecting member in which metal sheets having a plurality of upper and lower through-holes are laminated. It is characterized by being joined at once by joining. In addition, as mentioned above, before joining by one joining, it is in the state of having only piled up those metal sheets, and the same is true for the aspects below this point.

  FIG. 17 is a diagram illustrating an embodiment of the hydrogen permeable membrane module of the present invention (4). As shown in FIG. 17, a plurality of metal sheets having pores are sequentially provided on the upper and lower sides of the purified hydrogen collecting member having the upper and lower through-holes S in which a plurality of metal sheets having upper and lower through-holes s are laminated as shown in FIG. The laminated reinforcing members 21 and 22 and the hydrogen permeable membrane 23 are arranged and diffusion-bonded at a time. In addition, 22 is a metal sheet having pores provided with a diffusion prevention layer (A), which is a metal sheet having pores, and becomes a reinforcing member by one diffusion bonding.

  The purified hydrogen collecting member 20 having the upper and lower through-holes S is formed by laminating a plurality of “metal sheets having gaps s” produced as shown in FIG. That is, as shown in FIG. 18, a plurality (n sheets) of “metal sheets having gaps s” are stacked.

  Further, the purified hydrogen collecting member 20 may be formed using a metal sheet having a plurality of voids s, s, s... As a “metal sheet having voids s”. As shown in FIG. 19, a plurality of (n sheets) of “metal sheets having a plurality of voids s” are stacked to form a purified hydrogen collecting member 20 having a plurality of voids S, S, S. Is done.

  Further, the purified hydrogen collecting member 20 is formed by laminating a plurality (n sheets) of “metal sheets having a plurality of voids s” as shown in FIG. When forming the purified hydrogen collecting member 20 having the structure, a collecting hole for collecting purified hydrogen may be provided as shown in FIG. By connecting a plurality of voids S, S, S... In advance through the collecting holes, the connection with the hydrogen outlet pipe can be performed more easily. The purified hydrogen separated by the hydrogen permeable membrane and flowing through the voids S, S, S... Is taken out from the hydrogen outlet pipe through the collecting holes.

<Aspect of the present invention (5)>
The present invention (5) includes a plurality of reinforcing members each having a metal sheet having pores sequentially laminated on both sides of a purified hydrogen collecting member having a plurality of metal sheets having upper and lower through-holes, and a hydrogen permeable membrane. It arrange | positions and it joins at once, It is characterized by the above-mentioned.

  In FIG. 17, as indicated by reference numerals 21 and 21, one reinforcing member having a pore on one side of the purified hydrogen collecting member 20 and two on both sides of the purified hydrogen collecting member 20 are shown. Two or more reinforcing members having pores on one side and four or more reinforcing members on both sides may be arranged. The present invention (5) corresponds to this case, and the reinforcing member having each pore and other members can be produced in the same manner as in the case of <Aspect of the present invention (4)>.

<Aspect of the present invention (6)>
According to the present invention (6), in the present invention (5), the size of the pores is such that the pores become coarser as the plurality of reinforcing members go to the purified hydrogen collecting member which is the central portion in the thickness direction. Is equivalent to a gradient.

  FIG. 21 is a diagram for explaining an aspect of the present invention (6). As shown in FIG. 21, the reinforcing member 31 having a plurality of metal sheets each having a coarse pore is sequentially laminated on both sides of a purified hydrogen collecting member 30 having a plurality of metal sheets laminated having upper and lower through-holes S. Then, the reinforcing members 32 and 33 having fine pores (that is, the pores are smaller than the pores of the reinforcing member 31) and the hydrogen permeable membrane 34 are disposed and diffusion-bonded at a time. Note that 33 is a metal sheet having pores provided with a diffusion prevention layer (A), and is a metal sheet having pores, and becomes a reinforcing member by one diffusion bonding.

  FIG. 21 shows a case where there are two reinforcing members 31 having a coarse pore and a dense reinforcing member 32, 33 having a fine pore. The purified hydrogen collecting member is the central portion in the thickness direction. The reinforcing member with the coarsest pores is arranged on the side of 30, and thereafter, the reinforcing members with the pores successively dense toward the hydrogen permeable membrane side (reinforcing members with the pore roughness being successively reduced) ) Is configured. Thus, by providing a gradient in the pore size, the flow resistance of the purified hydrogen flowing from the hydrogen permeable membrane side toward the purified hydrogen collecting member can be reduced while maintaining the strength of the hydrogen permeable membrane. .

  FIG. 22A shows a hydrogen permeable membrane module configured as shown in FIG. The scale of the hydrogen permeable membrane module of the present invention can be set as appropriate. For example, the scale can be 30 cm long, 3 cm wide, and 1 cm thick. In FIG. 21, “× 10” indicates an example of the number of metal sheets constituting each member.

<Mode for integrally joining the metal sheet of the purified hydrogen collecting member and the reinforcing member together with the hydrogen permeable membrane with the metal sheet as it is>
In the hydrogen permeable membrane module of the present invention, (1) the metal sheet constituting the purified hydrogen collecting member and the metal sheet constituting the reinforcing member may be stacked as they are and joined together including the hydrogen permeable membrane. (2) As will be described later, a purified hydrogen collecting member in which each metal sheet is stacked (becomes a purified hydrogen collecting member by one diffusion bonding), and a reinforcing member in which each metal sheet is stacked (integrated diffusion bonding) (Which will be a reinforcing member) may be individually formed and then diffusion bonded together including the hydrogen permeable membrane. In the case of (1), for example, a sheet positioning die, that is, a metal sheet including a hydrogen permeable film is laminated in a mold, heated and pressed, and bonded together by diffusion bonding. A hydrogen permeable membrane module.

<Arrangement of hydrogen outlet pipe to hydrogen permeable membrane module>
In the hydrogen permeable membrane module configured as described above, a hydrogen lead-out tube for taking out purified hydrogen is arranged. Hereinafter, the arrangement | positioning aspect is demonstrated sequentially.

<Mode in which a hydrogen lead-out portion T is provided for the purified hydrogen collecting member>
A purified hydrogen outlet is provided for the purified hydrogen collecting member. That is, in the hydrogen permeable membrane module of the aspect described above, a purified hydrogen lead-out portion connected to the gap S of the purified hydrogen collecting member is separately provided. When the hydrogen permeable membrane module manufactured in the embodiment of FIG. 21 is taken as an example, it is configured so as not to have a hydrogen lead-out portion as shown in FIG.

  A portion of the purified hydrogen collecting member 30 is perforated to serve as a purified hydrogen lead-out portion. 22 (b) is a hole indicated as “T”, and this hole T communicates with the gap S (see FIGS. 1, 6, 8, 16, 17, 17, etc.) of the purified hydrogen collecting member. Yes. The drilling can be easily performed with a cutting tool, for example. Then, as shown in FIG. 22C, the hydrogen outlet pipe 35 is connected to the purified hydrogen outlet section T.

  Further, as shown in FIG. 20, when the collecting holes for collecting purified hydrogen are provided, a plurality of voids S, S, S... Are connected in advance by the collecting holes. A hydrogen outlet pipe 35 can be connected to the purified hydrogen outlet section T.

  FIG. 23 is a diagram for explaining the inside of the hydrogen permeable membrane module with the hydrogen outlet pipe 35 thus formed and the connecting portion of the hydrogen outlet pipe 35. FIG. 23 (a) is the same as FIG. 22 (c). FIG. 23B is an enlarged view of the cross section taken along the line AA in FIG. 23A, and FIG. 23C is an enlarged view of the cross section taken along the line BB in FIG. is there. As shown in FIG. 23B, the hydrogen lead-out pipe 35 is fitted into the purified hydrogen lead-out portion T, and is sealed and fixed in a gas-tight manner. The sealing and fixing are performed by welding or brazing.

  In the case of a purified hydrogen collecting member provided with a plurality of voids S as shown in FIG. 19, the purified hydrogen lead-out portion T is perforated so as to communicate with any of the voids S. FIG. 24 is a diagram for explaining this aspect. As shown in FIG. 24 (a), the appearance of the purified hydrogen collecting member 30 before it is perforated is the same as that shown in FIG. 22 (a), but the purified hydrogen collecting member shown as reference numeral 30 in FIG. FIG. 19 shows a purified hydrogen collecting member provided with a plurality of voids S. Since the purified hydrogen lead-out part T needs to communicate with any of the plurality of voids S, the purified hydrogen lead-out part T is formed by drilling in a rectangular shape as shown in FIG. Then, as shown in FIG. 24C, the hydrogen lead-out pipe 36 corresponding to the shape is connected to the purified hydrogen lead-out part T.

<Deformation aspect 1 concerning purified hydrogen deriving part T>
Various aspects are possible for the purified hydrogen outlet T in the purified hydrogen collecting member. In the hydrogen permeable membrane module described above, the purified hydrogen lead-out portion T connected to the gap S of the purified hydrogen collecting member is provided. On the other hand, with respect to the purified hydrogen collecting member, the space S is previously made wider than the pore region of the reinforcing member (that is, the width of the portion where the purified hydrogen lead-out portion T is drilled is reduced). In this case, the length of the purified hydrogen lead-out portion can be shortened.

  FIG. 25 is a diagram for explaining the mode. In FIG. 25, the end of the pore region of the reinforcing member is indicated by a dotted line. As shown in FIG. 25 (e), in the purified hydrogen collecting member 30, the void S is taken wider than the pore region of the reinforcing member as indicated by S '. As a result, the gap length becomes “S + S ′”, which is longer than the end of the pore region of the reinforcing member, and accordingly, the perforated portion for providing the purified hydrogen lead-out portion T can be shortened. In addition, although each member is shown as a top view in FIG. 25, each member is arrange | positioned in plane parallel, and it overlaps (stacks | stacks) and it joins at once.

<Deformation aspect 2 concerning purified hydrogen deriving part T>
FIGS. 26-29 is a figure explaining another aspect. As shown in FIG. 26, the purified hydrogen collecting member 30 having the void S in FIG. 21 corresponds to the purified hydrogen collecting member 40 having the void S and the purified hydrogen lead-out portion T connected to the void S.

  Here, the purified hydrogen collecting member 40 having the void S and the purified hydrogen deriving portion T connected to the void S is the above-described <Preparation mode of the purified hydrogen collecting member 1> except that the purified hydrogen deriving portion T is provided (FIG. 2). However, in this embodiment, there is no “metal sheet M having no gap s” at the bottom of FIG.

  As shown in FIG. 27, a plurality of “metal sheets each having an air gap s and an opening t connected to the air gap s” are arranged therein. And the refinement | purification hydrogen collection member 40 which has the space | gap S and the refinement | purification hydrogen derivation | leading-out part T continuing to this space | gap S is formed by overlapping these.

  FIG. 28 is a diagram for explaining a production mode of the “metal sheet having the gap s and the opening t connected to the gap s”. FIG. 28A shows a metal sheet, and masking is performed except for a portion that becomes a gap s and a portion that becomes an opening t following the surface of the metal sheet. FIG. 28B shows this state. Next, an etching process is performed. By the etching process, the portion other than the masking portion is removed, and the gap s and the opening t following this are formed. FIG. 28 (c) shows this state. Next, by removing the masking, as shown in FIG. 28 (d), a metal sheet having a gap s and an opening t subsequent thereto is obtained. The other points are the same as those described above <Preparation mode of metal sheet having void s>.

  A hydrogen permeable membrane module is configured using the purified hydrogen collecting member 40 thus configured. As shown in FIG. 26, the reinforcing member 41 in which a plurality of metal sheets having coarse pores are sequentially laminated on the upper and lower sides of the purified hydrogen collecting member 40 and the pores of the pores are dense (that is, the pores are dense). The hydrogen permeable membrane module is formed by diffusing and bonding at once the reinforcing member 42, the metal sheet 43 having the pores having the diffusion preventing layer, and the hydrogen permeable membrane 44. Constitute.

<Connection mode of hydrogen outlet pipe to purified hydrogen outlet section T>
FIG. 29 is a diagram illustrating the structure of the hydrogen permeable membrane module configured as shown in FIG. FIG. 29A is a perspective view of the hydrogen permeable membrane module. The hydrogen lead-out pipe 45 is fitted into the purified hydrogen lead-out part T, and is sealed and fixed in a gas tight manner. The sealing and fixing are performed by welding or brazing. FIG. 29B is a diagram in which a hydrogen lead-out pipe 45 is connected to the purified hydrogen lead-out part T shown in FIG. FIG. 29C is a cross-sectional view taken along line AA in FIG.

<Deformation mode 1 when producing hydrogen permeable membrane module>
The hydrogen permeable membrane module of the present invention includes “hydrogen permeable membrane + reinforcing member having pores + purified hydrogen collecting member”, “hydrogen permeable membrane + a plurality of 'reinforcing members having pores' + purified hydrogen collecting member” Or “hydrogen permeable membrane + reinforcing member with a gradient in pore size so that the pores become coarser as they go to a plurality of“ purified hydrogen collecting members ”+ purified hydrogen collecting member” It is manufactured by stacking and bonding.

In producing them, the members can be easily attached by attaching “joins” to each other and leaving the frame. FIG. 30 is a diagram for explaining this aspect.
FIG. 30A shows a hydrogen permeable membrane. As shown by a one-dot chain line, a predetermined width is set from the outer peripheral edge of the hydrogen permeable membrane, and this width portion is referred to as “joining”. The membrane within the frame indicated by the one-dot chain line is incorporated into the product hydrogen permeable membrane module.

FIG. 30B shows a reinforcing member having pores. As shown by a one-dot chain line, a predetermined width is set from the outer peripheral edge of the reinforcing member, and this width portion is referred to as “joining”. The size of the connecting frame is the same as that of the hydrogen permeable membrane. A reinforcing member in a frame indicated by a one-dot chain line is incorporated into the product hydrogen permeable membrane module.
FIG. 30C shows a reinforcing member having pores coarser than those shown in FIG. 30B. As shown by a one-dot chain line, a predetermined width is set from the outer peripheral edge of the reinforcing member, and the width portions are connected to each other. ". The size of the connecting frame is the same as that of the hydrogen permeable membrane. A reinforcing member in a frame indicated by a one-dot chain line is incorporated into the product hydrogen permeable membrane module.

  FIG. 30D shows a purified hydrogen collecting member. As shown by a one-dot chain line, a predetermined width is set from the outer peripheral edge of the purified hydrogen collecting member, and this width portion is defined as “joining”. The size of the connecting frame is the same as that of the hydrogen permeable membrane. The purified hydrogen collecting member within the frame indicated by the one-dot chain line is incorporated into the product hydrogen permeable membrane module. FIG. 30 (d) shows the purified hydrogen collecting member having the above-mentioned gap length “S + S ′”, but the same applies to the purified hydrogen collecting member of other embodiments.

  And each member comprised as mentioned above is laminated | stacked, and it joins at once by diffusion bonding. In addition, in FIG. 30, although each member (a)-(d) is shown as a top view, each member is arrange | positioned in parallel and is piled up (stacked), and is joined at once. Then, the hydrogen permeable membrane module is formed by cutting at a “connecting” portion at a time. In this case, in FIG. 30 (a) to (d), by removing the linear portion that becomes the connecting frame indicated by the one-dot chain line by etching at a predetermined interval in advance (the hydrogen permeable membrane etc. Among these members, the outer peripheral edge and the connecting frame are connected only at a connecting portion that is not etched away), and can be easily cut.

<Deformation mode 2 when producing hydrogen permeable membrane module>
The hydrogen permeable membrane module of the present invention includes, for example, “a hydrogen permeable membrane + a reinforcing member having a gradient in pore size so that the pores become coarser toward a plurality of“ purified hydrogen collecting members ”+ It is formed by one-time diffusion bonding such as “purified hydrogen collecting member”. It is preferable to temporarily fix the laminated body in advance for the joining. Temporary fixing may be performed for each member.

  FIG. 31 is a diagram for explaining the mode. As shown in FIG. 31, the hydrogen permeable membrane (a), the reinforcing member (b) having pores, the reinforcing member (c) having coarser pores than (b), the purified hydrogen collecting member (d), and the illustration are omitted. However, a reinforcing member (c) having pores coarser than (b), a reinforcing member (b) having pores, and a hydrogen permeable membrane (a) are also sequentially provided at the lower portion of the purified hydrogen collecting member (d). Arranged and stacked.

  Then, the laminated body, that is, the stacked one is temporarily fixed by spot welding as indicated by p, p, p... In FIG. In FIG. 31, the members (a) to (d) are shown as plan views, but the members are arranged in parallel to each other, stacked (stacked), and temporarily fixed by spot welding. Then, the laminated body temporarily fixed is bonded at once by diffusion bonding, and cut at a “joining” portion at a time to form a hydrogen permeable membrane module.

  Here, the reinforcing member (b) having pores is composed of a plurality of “metal sheets having pores” as shown in FIG. (B) The reinforcing member (c) having coarser pores is composed of a plurality of “metal sheets having coarse pores” as shown in FIG. Further, the purified hydrogen collecting member (d) is composed of a plurality of “metal sheets having gaps s + s ′” corresponding to the purified hydrogen collecting member having gaps S + S ′ shown as reference numeral 30 in FIG.

<Deformation mode 3 when producing hydrogen permeable membrane module>
The hydrogen permeable membrane module of the present invention includes, for example, “a hydrogen permeable membrane + a reinforcing member having a gradient in pore size so that the pores become coarser toward a plurality of“ purified hydrogen collecting members ”+ It is formed by laminating like “purified hydrogen collecting member” and diffusion bonding at once. In this modified embodiment 3, the purified hydrogen collecting member is further extended from the gap length “S + S ′” in <Modified embodiment 1 relating to purified hydrogen deriving portion T>, thereby providing the purified hydrogen deriving portion T. Therefore, it is a structure that eliminates the need for a cutting process, that is, drilling, and eliminates the joining of the hydrogen lead-out pipe.

  FIG. 32 is a diagram for explaining the mode. As shown in FIG. 32 (c), with respect to the purified hydrogen collecting member, the void portion is further extended from the void S portion as indicated by S ″, and the void S ″ portion includes the purified hydrogen outlet portion T, the hydrogen outlet pipe, and the like. To be. The reinforcing member having pores also has a shape corresponding to the space S ″ as shown in FIG.

  Here, as shown in FIGS. 32 (b) and 32 (c), a plurality of metal sheets serving as reinforcing members and a plurality of metal sheets (having gaps s + s ″) serving as purified hydrogen collecting members are respectively laminated. 32 (b) and 32 (c), p, p, p... Are temporarily fixed by spot welding, and the laminate is shown in FIG. A hydrogen permeable membrane module is formed by performing diffusion bonding together with the hydrogen permeable membrane shown in FIG.

  FIG. 33 is a view for explaining the hydrogen permeable membrane module with a hydrogen outlet tube formed in this way. 33 (a) is a plan view, FIG. 33 (b) is a perspective view, and FIG. 33 (c) is an enlarged view of a section taken along line AA in FIG. 33 (a). In FIG. 33 (c), as indicated by S, (T), S ″, a void portion, a fractionated hydrogen deriving section, and a hydrogen deriving tube are formed at once. 52 is a hydrogen deriving tube having a void S ″. It is.

  The hydrogen permeable membrane module using a plurality of 'reinforcing members having a gradient in pore size so that the pores become coarser as they go to the purified hydrogen collecting member' is configured in the same manner as described above. Is done. FIG. 33 (d) is a cross-sectional view when the reinforcing member 51 having a coarse pore is also provided.

<Deformation mode 4 when producing hydrogen permeable membrane module>
"Metal sheet having pores" as shown in FIG. 5 (d), "Diffusion prevention layer", "First intermediate layer + diffusion prevention layer", "Diffusion prevention" as shown in FIGS. A plurality of “metal sheet having pores” in which “layer + second intermediate layer” or “first intermediate layer + diffusion prevention layer + second intermediate layer” is formed can be produced simultaneously.

  FIG. 34 is a diagram for explaining this aspect. In FIG. 34A, reference numeral 61 denotes a metal sheet having pores in two regions, and each region is shown in a frame indicated by a one-dot chain line. In this way, a metal sheet having many pores in one plane can be modeled. A diffusion preventing layer is formed in each pore region. The formation process of the diffusion preventing layer on the portion excluding the exposed metal surface is the same as that described with reference to FIGS.

  Similarly, the “metal sheet having voids” that forms the purified hydrogen collecting member is also formed as a “metal sheet having coarse pores” that forms a reinforcing member having coarse pores by forming several sheets in one plane. As for, follow a number of reinforcing members on a single plane. FIG. 34B shows the hydrogen permeable membrane 62 corresponding to them.

  Then, a plurality of “metal sheets having coarse pores” forming a reinforcing member having coarse pores in the upper and lower sides of the plurality of “metal sheets having voids s” forming the purified hydrogen collecting member in the center. Sheets, multiple sheets of “metal sheet with coarse pores” that form reinforcing members with pores, “metal sheet with pores with diffusion prevention layer”, and hydrogen permeable membrane 62 are laminated to diffuse at once Join. Although FIG. 34 is shown as a plan view, the members are arranged in parallel to each other, stacked, and joined at once.

  And it cut | disconnects into a hydrogen permeable membrane module unit, and comprises a hydrogen permeable membrane module. In this case, in FIG. 34 (a), the linear portion indicated by the alternate long and short dash line is removed by etching at a predetermined interval in advance (by this, the outer peripheral edge of each member such as the hydrogen permeable membrane). And the connecting frame are connected only at a connecting portion that is not removed by etching), and can be easily cut.

  FIG. 34 shows a case where two hydrogen permeable membrane modules are manufactured at a time. Similarly, three or more hydrogen permeable membrane modules can be manufactured at a time. Thus, mass production of the hydrogen permeable membrane module becomes possible.

  The hydrogen permeable membrane module of the present invention is used to separate and purify hydrogen from various hydrogen-containing gases such as hydrocarbon reformed gas, and the reformed gas is produced and purified by the hydrogen permeable membrane. It is also used as a hydrogen permeable membrane module for a so-called membrane reactor integrated as in an apparatus.

The figure explaining the aspect of the hydrogen permeable membrane module of this invention (1) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (1) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (1) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (1) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (1) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (3) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (3) The figure explaining the aspect which distribute | arranges a diffusion prevention layer etc. between the reinforcement member which has a pore, and a hydrogen permeable film The figure explaining the formation aspect of the diffusion prevention layer to the metal sheet which has a pore The figure explaining the aspect which inserts the metal sheet which has the pore which gave the diffusion prevention layer to the simple frame A diagram explaining the “extrusion” part of the diffusion prevention layer The figure explaining the aspect which expands the pore region by eliminating the "protruding" part of the diffusion prevention layer The figure explaining the aspect which has arrange | positioned the 1st intermediate | middle layer-diffusion prevention layer on the contact surface with a hydrogen permeable membrane about the reinforcement member which has the pore distribute | arranged to the hydrogen permeable membrane side The figure explaining the aspect which distribute | arranged the diffusion prevention layer-second intermediate | middle layer to the contact surface with a hydrogen permeable film about the reinforcement member which has the pore distribute | arranged to the hydrogen permeable film side The figure explaining the aspect which arranged the 1st intermediate | middle layer-diffusion prevention layer-2nd intermediate | middle layer in the contact surface with a hydrogen permeable membrane about the reinforcement member which has the pore distribute | arranged to the hydrogen permeable membrane side The figure which shows the aspect which has arrange | positioned the diffusion prevention layer etc. in the aspect of the hydrogen permeable membrane module shown in FIG. The figure explaining the aspect of the hydrogen permeable membrane module of this invention (4) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (4) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (4) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (4) The figure explaining the aspect of this invention (6) The figure explaining the aspect of this invention (6) The figure explaining the aspect of this invention (6) The figure explaining the aspect which concerns on the refinement | purification hydrogen derivation | leading-out part T The figure explaining the deformation | transformation aspect 1 which concerns on the refinement | purification hydrogen derivation | leading-out part T The figure explaining the deformation | transformation aspect 2 which concerns on the refinement | purification hydrogen derivation | leading-out part T The figure explaining the deformation | transformation aspect 2 which concerns on the refinement | purification hydrogen derivation | leading-out part T The figure explaining the deformation | transformation aspect 2 which concerns on the refinement | purification hydrogen derivation | leading-out part T The figure explaining the connection aspect of the hydrogen lead-out pipe to the purified hydrogen lead-out part T The figure explaining the deformation | transformation aspect 1 at the time of hydrogen permeable membrane module preparation The figure explaining the deformation | transformation aspect 2 at the time of hydrogen permeable membrane module preparation The figure explaining the deformation | transformation aspect 3 at the time of hydrogen permeable membrane module preparation The figure explaining the deformation | transformation aspect 3 at the time of hydrogen permeable membrane module preparation The figure explaining the deformation | transformation aspect 4 at the time of hydrogen permeable membrane module preparation Exploded perspective view for explaining the structure of the hydrogen gas separation unit (No. 558) Schematic perspective view of a hydrogen gas separator incorporating the unit of FIG. 35 (No. 558) Figure disclosed in Japanese Patent No. 061

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Purified hydrogen collecting member 2 Reinforcing member having pores 3 Hydrogen permeable membrane s Void inside metal sheet S Void M Blocking member 10 Purified hydrogen collecting member 11 Reinforcing member having pores (rough pores) 12 Reinforcing having pores Member 13 Hydrogen permeable membrane 2 'Metal sheet or reinforcing member having pores provided with a diffusion prevention layer or the like a Periphery of metal sheet b Perimeter of diffusion prevention layer c Perimeter of pore region of metal sheet 12' Diffusion prevention layer or the like Metal sheet or reinforcing member having fine pores arranged 20 Purified hydrogen collecting member 21 Reinforcing member having fine pores 22 Metal sheet or reinforcing member having fine pores arranged with a diffusion preventing layer 23 Hydrogen permeable membrane 30 Purified hydrogen collecting member 31 Reinforcing member having pores (rough pores) 32 Reinforcing member having pores 33 Metal sheet or reinforcing member having pores provided with a diffusion prevention layer or the like 34 Hydrogen Overmembrane 35, 36 Hydrogen outlet tube S 'Extension part of gap S 40 Purified hydrogen collecting member 41 Reinforcing member having pores (rough pores) 42 Reinforcing member having pores 43 Metal sheet or reinforcing member having 44 Hydrogen permeable membrane T Opening, hydrogen lead-out part of purified hydrogen collecting member t Opening continuing to part to become gap s 45 Hydrogen lead-out pipe p Spot welded part S ″ gap 52 52 hydrogen lead-out pipe having gap S ″ 61 Metal sheet 62 Hydrogen permeable membrane 71 Expanding frame 72 Pd alloy foil and other materials having hydrogen gas separation properties (hydrogen permeable foil membrane)
73 metal support plate 101 peripheral portion of clad cut plate 102 central portion of clad cut plate b pore 80 base plate with ventilation groove 81 reinforcing plate made of a plurality of porous metal plates 82 columnar metal plate 89 hydrogen permeable membrane composite body

Claims (15)

  A hydrogen permeable membrane module that does not require a metal support, and sequentially includes one or more metal sheets having no voids, a plurality of purified hydrogen collecting members in which metal sheets having upper and lower through holes are laminated, and a plurality of sheets A hydrogen permeable membrane module comprising: a reinforcing member formed by laminating a metal sheet having a plurality of pores; and a hydrogen permeable membrane, which are joined at a time.   A hydrogen permeable membrane module that does not require a metal support, and sequentially includes one or more metal sheets having no voids, a plurality of purified hydrogen collecting members in which metal sheets having upper and lower through holes are laminated, and a plurality of sheets A hydrogen permeable membrane module comprising: a plurality of reinforcing members in which metal sheets having a plurality of pores are laminated, and a hydrogen permeable membrane, which are joined at a time.   3. The hydrogen permeable membrane module according to claim 2, wherein the plurality of reinforcing members are reinforcing members having a gradient in pore size such that the pores become coarser toward the purified hydrogen collecting member. A hydrogen permeable membrane module.   A hydrogen permeable membrane module that does not require a metal support, and is reinforced by sequentially laminating a plurality of metal sheets having pores on both sides of a purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated. A hydrogen permeable membrane module comprising a member and a hydrogen permeable membrane arranged and bonded together.   A hydrogen permeable membrane module that does not require a metal support, and is reinforced by sequentially laminating a plurality of metal sheets having pores on both sides of a purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated. A hydrogen permeable membrane module comprising a plurality of members and a hydrogen permeable membrane arranged and bonded together.   6. The hydrogen permeable membrane module according to claim 5, wherein the plurality of reinforcing members have a gradient in pore size such that the pores become coarser toward the purified hydrogen collecting member that is the central portion in the thickness direction. A hydrogen permeable membrane module, which is a reinforcing member provided.   The hydrogen permeable membrane module of any one of Claims 1-6 WHEREIN: The several metal sheet which comprises the said refinement | purification hydrogen collection member, and the several metal sheet which comprises the said reinforcement member, respectively, A hydrogen permeable membrane module characterized by being arranged as it is and bonded at once.   The hydrogen permeable membrane module according to any one of claims 1 to 6, wherein the constituent material of the metal sheet is stainless steel, nickel, a nickel-base alloy, a copper alloy, or an iron-base alloy. module.   The hydrogen permeable membrane module according to claim 1, wherein the bonding is a diffusion bonding.   7. The hydrogen permeable membrane module according to claim 1, wherein a diffusion preventing layer is disposed between the reinforcing member having pores and the hydrogen permeable membrane.   The hydrogen permeable membrane module according to any one of claims 1 to 6, wherein a first intermediate layer and a diffusion layer are sequentially formed between the reinforcing member having pores and the hydrogen permeable membrane as viewed from the reinforcing member having pores. A hydrogen permeable membrane module comprising a prevention layer.   The hydrogen permeable membrane module according to any one of claims 1 to 6, wherein a diffusion preventing layer and a second layer are sequentially formed between the reinforcing member having pores and the hydrogen permeable membrane as viewed from the reinforcing member side having pores. A hydrogen permeable membrane module comprising an intermediate layer.   The hydrogen permeable membrane module according to any one of claims 1 to 6, wherein a first intermediate layer and a diffusion layer are sequentially formed between the reinforcing member having pores and the hydrogen permeable membrane as viewed from the reinforcing member having pores. A hydrogen permeable membrane module comprising a prevention layer and a second intermediate layer.   The hydrogen permeable membrane module according to any one of claims 10 to 13, wherein the diffusion preventing layer, the first intermediate layer-the diffusion preventing layer, and the diffusion preventing layer are substantially only in the pore region of the reinforcing member having pores. A hydrogen permeable membrane module comprising a layer-second intermediate layer or a first intermediate layer-diffusion prevention layer-second intermediate layer. The hydrogen permeable membrane module according to any one of claims 1 to 14, wherein the hydrogen permeable membrane module is a hydrogen permeable membrane module for a membrane reactor.

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