JP2009000659A - Hydrogen permeable membrane module - Google Patents

Abstract

The present invention provides a hydrogen permeable membrane module that does not require a metal support that is essential in the prior art, has a simple structure, and is easy to handle a hydrogen permeable foil membrane that is a hydrogen permeable membrane.
A hydrogen permeable membrane module that does not require a metal support, and is a metal sheet having pores on both sides of a purified hydrogen collecting member in which one or more metal sheets having upper and lower through-holes are laminated. The metal sheets are arranged alternately with metal sheets of different metal materials, and the surfaces of the upper and lower reinforcement members are joined together at the same time. A hydrogen permeable membrane module, comprising a hydrogen permeable membrane bonded to a membrane.
[Selection] Figure 45

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.

  46 to 47 are diagrams disclosed in Japanese Patent Application Laid-Open No. 2001-276558 (referred to as “No. 558” in the present specification). FIG. 46 is an exploded perspective view for explaining the structure of the hydrogen gas separation unit. In FIG. 46, 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.

  47 is a schematic perspective view of a hydrogen gas separator incorporating the unit of FIG. The hydrogen gas separation unit configured as shown in FIG. 46 is fixed to the case 74 by laser welding or the like so that the surface of the metal support plate 73 is inside as shown in FIG. It is said. 75 is a purified hydrogen take-out pipe.

  FIG. 48 is a diagram disclosed in Japanese Patent Laid-Open No. 10-296061 (referred to as “061 publication” in this specification). In FIG. 48, 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 to 0.1 to 20 μm on a base substrate having a surface flatness such as a polyethylene film, and a porous support is formed to 40 to 300 μm thereon. 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 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 (Japanese Patent Application Laid-Open No. 2005-260260). 2007-7565, referred to as “No. 565” 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 JP 2007-7565 A

  The present applicant 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 membrane that is a hydrogen permeable membrane. A membrane module has been filed earlier [Japanese Patent Application No. 2005-371120 (hereinafter referred to as “No. 120 application”)]. When the present inventors examined and pursued the invention according to the 120th application in more detail, it was found that there is room for further improvement, particularly regarding the type of metal sheet material to be laminated.

  That is, the present invention further improves the invention of the 120th application, does not require a metal support that is essential in the prior art, has a simple structure itself, and handles a hydrogen permeable foil film that is a hydrogen permeable film. Another object of the present invention is to provide an easy hydrogen permeable membrane module.

  The present invention (1) is a hydrogen permeable membrane module that does not require a metal support. Then, sequentially, a purified hydrogen collecting member in which one or more metal sheets having no gap, one or more metal sheets having upper and lower through-holes are laminated, and one or more pores are provided. And reinforcing members laminated with metal sheets. At that time, the metal sheets are alternately arranged with metal sheets of dissimilar metal materials, and after they are joined at one time, a hydrogen permeable membrane is formed on the surface of the reinforcing member. It is characterized by joining.

  The present invention (2) is a hydrogen permeable membrane module that does not require a metal support. Then, sequentially, a purified hydrogen collecting member in which one or more metal sheets having no gap, one or more metal sheets having upper and lower through-holes are laminated, and one or more pores are provided. A plurality of reinforcing members laminated with metal sheets are arranged, and in this case, the metal sheets are alternately arranged with metal sheets of dissimilar metal materials, and after they are joined at once, on the surface of the reinforcing member A hydrogen permeable membrane is bonded.

  According to the present invention (3), in the hydrogen permeable membrane module of the above (2), the pores of the plurality of reinforcing members become coarser as they go to the purified hydrogen collecting member (that is, the pores of the pores become larger). Thus, it is a reinforcing member having a gradient in the size of the pores.

  The present invention (4) is a hydrogen permeable membrane module that does not require a metal support. And, on both sides of the purified hydrogen collecting member in which one or more metal sheets having upper and lower through-holes are laminated, a reinforcing member in which one or more metal sheets having pores are laminated, respectively, is disposed. At this time, the metal sheets are characterized in that metal sheets of different metal materials are alternately arranged, and after they are joined at once, a hydrogen permeable membrane is joined to the surfaces of the upper and lower reinforcing members.

  The present invention (5) is a hydrogen permeable membrane module that does not require a metal support. A plurality of reinforcing members in which one or more metal sheets having pores are sequentially laminated on both sides of the purified hydrogen collecting member in which one or more metal sheets having upper and lower through-holes are laminated; In this case, the metal sheets are formed by alternately disposing metal sheets of different metal materials, and bonding them at once, and then bonding hydrogen permeable membranes to the surfaces of the upper and lower reinforcing members. It is characterized by.

  According to the present invention (6), in the hydrogen permeable membrane module of the above (5), 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 (ie, The reinforcing member is characterized in that the pore size is provided with a gradient so that the pore size becomes larger.

  In the hydrogen permeable membrane module according to any one of (1) to (6), the present invention (7) is a metal sheet constituting the purified hydrogen collecting member, and a metal sheet constituting the reinforcing member [the present invention ( 6), the metal sheet constituting the reinforcing member having pores that become coarser toward the purified hydrogen collecting member, which is the central part in the thickness direction, is arranged as a metal sheet and joined at once. It is characterized by.

  In the present inventions (1) to (7), “a purified hydrogen collecting member in which one or more metal sheets having upper and lower through-holes are laminated” means “purified hydrogen comprising a metal sheet having one and the upper and lower through-holes” The meaning includes “collecting member” and “purified hydrogen collecting member in which a plurality of metal sheets having upper and lower through-holes are laminated”. Even in the case of one sheet, the sheet is stacked (stacked) on another adjacent sheet (such as a sheet of another adjacent member). These points are the same for the various reinforcing members.

According to the present invention, the following effects (a) to (g) can be obtained. Among these effects, (a) to (e) and (g) are effects common to the invention of the 120th application, and (f) is an effect unique to the present invention.
(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 and the reinforcing member can be joined at a time, mass production of the hydrogen permeable membrane module can be performed by following the number of purified hydrogen collecting members and reinforcing members on one plane.
(C) Since each metal sheet can be 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 purified hydrogen collecting member side, and the reinforcing members with dense pores in order toward the hydrogen permeable membrane side (reinforcing with the pore size gradually 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.
(F) In the present invention, by alternately laminating dissimilar metal materials, it is possible to relax the bonding conditions as compared to the lamination of the same metal materials, that is, lower the temperature and pressure when joining by diffusion bonding or the like. Thereby, the thermal or mechanical damage of the hydrogen permeable film at the time of bonding can be reduced, and one-step bonding with the hydrogen permeable film can be easily performed.
(G) In the present invention, the degree of freedom of the hydrogen outlet and the extraction shape is high.

  In any one of the hydrogen permeable membrane modules of the present invention (1) to (7), a joined body composed of a purified hydrogen collecting member and a reinforcing member is arranged at a predetermined position defined by each of the present invention and formed by a single joining. To do. 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.

Since the present invention is a further improvement of the invention of the 120th application, the present invention is based on the premise that it takes the same or similar aspects as the invention of the 120th application, and has been improved by the present invention. Embodiments will be added.
From this, the aspect which concerns on this invention is demonstrated below including embodiment common to invention of 120th application.

  In any of the hydrogen permeable membrane modules of the present invention (1) to (7), the purified hydrogen collecting member and the reinforcing member are arranged at predetermined positions defined in the present invention and formed by one-time joining. 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.

  And also in any hydrogen permeable membrane module of this invention (1)-(7), a hydrogen permeable membrane is joined to the surface at the side of the reinforcement member with respect to the joined body formed by the said 1 time joining. In the present invention (1) to (2), a hydrogen permeable membrane is bonded to the surface on the reinforcing member side, and in the present invention (3), a hydrogen permeable membrane is bonded to the surface of the reinforcing member on the side of the finest pore, In the present inventions (4) to (5), hydrogen permeable membranes are bonded to the surfaces of the upper and lower reinforcing members, and in the present invention (6), hydrogen permeates to the surfaces of the upper and lower reinforcing members on the fine pore side. Join the membrane. The means for joining the hydrogen permeable membrane to the surfaces of these reinforcing members is not particularly limited, but preferred examples include “diffusion joining”.

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) A multilayer film of Pd alloy film (that is, a multilayer film of Pd alloy film itself),
(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.
A foil film made of these metal materials is produced by various methods such as a rolling method, an ion plating method, and a plating method.

  The aspects of the present invention (1) to (7) will be sequentially described including the production process. Below, the hydrogen permeable membrane module which comprised each member, such as obstruction | occlusion member (the obstruction member has only in the case of this invention (1)-(3)), a refinement | purification hydrogen collection member, a reinforcement member, and a hydrogen permeable membrane, in the rectangular shape. Although described as an example, the shape may be a square shape or any other appropriate shape.

<Aspect of the present invention (1)>
The hydrogen permeable membrane module of the present invention (1) includes, as its material, a metal sheet (a) having one or a plurality of voids, a metal sheet (b) having one or a plurality of voids, 1 A metal sheet (c) having one or more pores and a hydrogen permeable membrane (d) are used. Of these materials, (a) to (c) are sequentially arranged, that is, (b) is arranged on (a), and (c) is arranged on (b) to diffuse at once. After the bonding, it is manufactured by bonding a hydrogen permeable membrane to the surface of (c).

  In the present invention (1), it is important to alternately arrange the metal sheets of different metal materials. The metal sheet is the metal sheet (a), the metal sheet (b), and the metal sheet (c). The metal sheet (a) is one sheet or plural sheets, the metal sheet (b) is one sheet or plural sheets, metal The sheet (c) is one sheet or a plurality of sheets. In the present invention (1), these metal sheets are composed of different metal materials, and the different metal sheets are alternately laminated.

  As an example, when the dissimilar metal sheets are a stainless steel sheet and a nickel sheet (Ni sheet), the metal sheet (a) is one sheet, the metal sheet (b) is three sheets, and the metal sheet (c) is three sheets. Is as follows. Hereinafter, the stainless steel sheet is referred to as “SUS sheet”.

  When the metal sheet (a) is a SUS sheet, the Ni sheet of the metal sheet (b) is brought into contact with the SUS sheet, and the metal sheet (b) is arranged as Ni sheet → SUS sheet → Ni sheet. The SUS sheet of the metal sheet (c) is brought into contact with the Ni sheet of the metal sheet (b), and the SUS sheet → Ni sheet → SUS sheet is arranged in the metal sheet (c).

  When the metal sheet (a) is a Ni sheet, the SUS sheet of the metal sheet (b) abuts on the Ni sheet, and the metal sheet (b) is arranged as SUS sheet → Ni sheet → SUS sheet. . The Ni sheet of the metal sheet (c) abuts on the SUS sheet of the metal sheet (b), and the Ni sheet → SUS sheet → Ni sheet is arranged in the metal sheet (c).

  Then, by the aforementioned joining, a closing member is constituted by the metal sheet (a) having no one or a plurality of voids, and purified hydrogen is collected by the metal sheet (b) having one or a plurality of upper and lower through-holes. A member is comprised and a reinforcement member is comprised by the metal sheet (c) which has the said 1 sheet or several sheets of pore. And a hydrogen permeable membrane module is produced by joining a hydrogen permeable membrane to the surface of a reinforcement member.

Here, since each void in the metal sheet (b) having one or a plurality of upper and lower through-holes collects purified hydrogen in the hydrogen permeable membrane module and circulates it toward the outlet tube, the (b ) Can also be said to be “a metal sheet having one or more 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.

1-7 is a figure explaining the aspect of the hydrogen permeable membrane module of this invention (1). In addition, also about the part which is common in this invention (2)-(7), it has demonstrated suitably in the location of the said <mode of this invention (1)>.
In the following, the case of using a plurality of metal sheets each having a vertically penetrating gap and a metal sheet having pores are exemplified, but one metal sheet having a vertically penetrating gap and a metal having pores. The same applies to the case of using one sheet. In addition, the case where one sheet of metal sheet having upper and lower through-holes and one sheet of metal having pores are used is also described as appropriate.

1 and 2 are diagrams for explaining the manufacturing process.
FIG. 1A 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 (b) is composed of one or more metal sheets having no gaps and a plurality of metal sheets having upper and lower through-holes. At this stage, these metal sheets are simply stacked, that is, stacked. It is 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.

Each metal sheet arrange | positioned like Fig.1 (a)-(b) is diffusion-bonded at once, and a joined body is formed. FIG. 1C shows the joined body formed in this way. Then, as shown in FIG. 2, a hydrogen permeable membrane module is configured by joining a hydrogen permeable membrane to the surface of the reinforcing member 2 in the joined body.
In the stage of FIG. 2 (c), one or a plurality of metal sheets having no voids and a plurality of metal sheets having upper and lower through-holes are joined to form a purified hydrogen collecting member in the hydrogen permeable membrane module. What joined the metal sheet | seat which has a sheet | seat of a fine hole becomes a reinforcement member which has a fine hole in a hydrogen permeable membrane module.

  Hereinafter, each member constituting the hydrogen permeable membrane module, that is, the closing member M, the purified hydrogen collecting member 1, the reinforcing member 2 having pores, and the hydrogen permeable membrane 3 will be sequentially described.

  The constituent material of the closing member M, the purified hydrogen collecting member 1 and the reinforcing member 2 having pores may be any metal that can be bonded to each other. Examples thereof include stainless steel, nickel, nickel-base alloy, copper alloy, iron. Examples thereof include base alloys (such as iron-nickel alloys).

In the present invention, two kinds of metals among these metals are used as sheets, which are alternately laminated. As an example, in the case of a combination of stainless steel and nickel, each of the stainless steel and nickel is used as a sheet, that is, stacked in layers such as an SUS sheet and then an Ni sheet and an Ni sheet and an SUS sheet. .
When the closing member M is a single SUS sheet, the metal sheet of the purified hydrogen collecting member 1 in contact with it is an Ni sheet, and the metal sheet (in the case of three) of the purified hydrogen collecting member 1 is a Ni sheet—SUS sheet— An Ni sheet is used, and the metal sheet of the reinforcing member 2 in contact with the Ni sheet is an SUS sheet.

  In the present invention (1), a metal sheet having one or a plurality of voids composed of these materials, a metal sheet having one or a plurality of upper and lower through-holes, and one or a plurality of pores are provided. The metal sheets that are held are stacked and diffusion bonded at once.

<Production mode of purified hydrogen collecting member 1>
FIG. 3 is a view for explaining a production mode of the purified hydrogen collecting member 1. As shown in FIG. 3, 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. FIG. 4 is a cross-sectional view of the purified hydrogen collecting member 1 taken along the line AA shown in the lowermost part of FIGS.

  The number of metal sheets having the upper and lower through gaps s is one or more, and the strength and thickness are maintained in the hydrogen permeable membrane module. The thickness of each metal sheet is not particularly limited, but is, for example, about several tens of micrometers to several hundreds of micrometers. 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. Such a thickness can also be achieved with one metal sheet.

  Moreover, although the metal sheet | seat which does not have the space | gap s has shown the example of 1 sheet in FIG. 3, 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 “metal sheet having the gap s”.

<Production aspect of metal sheet having void s>
FIG. 5 is a diagram for explaining a production mode of the “metal sheet having the gap s”. FIG. 5A shows a metal sheet, which is masked except for a portion of the surface that becomes the gap s. FIG. 5B 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. 5C shows this state. Next, by removing the masking, a metal sheet having voids 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. 1B 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. 6 is a diagram for explaining a production mode of the reinforcing member 2 having pores. As shown in FIG. 6, 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, 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. 7 is a diagram for explaining a production mode of a metal sheet having pores. FIG. 7A shows a mask, which has no holes in the peripheral edge portion and has pores inside the peripheral edge portion. This mask is disposed on the surface of the metal sheet shown in FIG. FIG. 7C 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.

  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)>
1 and 2 show the case where there is one reinforcing member having pores as shown in FIG. 1A, 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 above-mentioned <Aspect of the present invention (1)> except that a plurality of reinforcing members having respective 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.

  8-9 is a figure explaining the aspect of the hydrogen permeable membrane module of this invention (3). In contrast to the embodiment shown in FIGS. 1 and 2, a reinforcing member having coarse pores (large pore diameter) is disposed on the purified hydrogen collecting member 10 side as indicated by reference numeral 11 in FIG. 8. Except for using the reinforcing member 11 having coarse pores, the embodiment is the same as the embodiment described in <Aspect of the present invention (1)>.

  That is, in FIG. 8, the purified hydrogen collecting member 10 corresponds to the purified hydrogen collecting member 1 in FIG. 1, and the reinforcing member 12 having pores corresponds to the reinforcing member 2 having pores in FIG. These are arranged together with the reinforcing member 11 having coarse pores as shown in FIGS. 8A to 8C, and diffusion bonded at a time to form a joined body shown in FIG. 8D. Then, as shown in FIG. 9, the hydrogen permeable membrane module is configured by diffusion bonding the hydrogen permeable membrane 13 to the surface of the reinforcing member 12 having pores in the joined body. The hydrogen permeable membrane 13 corresponds to the hydrogen permeable membrane 3 of FIG.

  FIGS. 8 to 9 show a reinforcing member 11 with coarse pores (large pores) and a reinforcing member with dense pores (that is, the pore diameter is smaller than the pore diameter of the reinforcing member 11). 12, the reinforcing member having the coarsest pores is arranged on the purified hydrogen collecting member 10 side, and the pores are sequentially densely reinforced toward the hydrogen permeable membrane side. A member (reinforcing member with the holes sequentially reduced in size) is arranged and configured. In this way, by providing a gradient in the pore size so that the pores become larger 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. 6) and <Manufacturing mode of metal sheet having pores> (FIG. 7). can do. FIG. 10 shows a mode in which the reinforcing member 11 with coarse pores is produced from a plurality of metal sheets having pores with 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 the present invention (1) to (3), a hydrogen lead-out pipe communicating with the gap S of the purified hydrogen collecting member is provided. The hydrogen lead-out pipe is provided at an appropriate location so as to communicate with the gap S of the purified hydrogen collecting member, but is not limited to one, and a plurality of hydrogen outlet pipes may be provided. These points are the same in the hydrogen permeable membrane modules of the present inventions (4) to (6). 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 directly contacting a metal sheet, for example, a stainless steel sheet and a hydrogen permeable membrane, is used 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 “565 publication”). In the invention, this is applied.

  FIGS. 11-12 is a figure explaining the aspect which distribute | arranges any layer of those (A)-(D) between the reinforcement member which has a pore, and a hydrogen permeable film. 11-12, the same code | symbol is used for the member and part which are common in FIGS. 1-2. In FIG. 11, reference numeral 2 'denotes a "metal sheet having pores" in which any one of layers (A) to (D) is arranged on the upper surface leaving a predetermined width from the periphery of the metal sheet.

  The “metal sheet having pores” 2 ′ provided with any one of the layers (A) to (D), together with the closing member M, the purified hydrogen collecting member 1, and the reinforcing member 2 having pores, are shown in FIG. ) To (c), and diffusion-bonded at a time to arrange the closing member M, the purified hydrogen collecting member 1, the reinforcing member 2 having pores, and any one of the layers (A) to (D). The joined body with the “metal sheet having pores” 2 ′ is formed.

  FIG. 11D shows a joined body configured in this manner. 11A to 11C, the respective members are separated from each other for convenience of explanation, but the respective members are overlapped and diffusion-bonded at a time. Then, as shown in FIG. 12, a hydrogen permeable membrane is bonded to the surface of the “metal sheet having pores” 2 ′ in which any one of layers (A) to (D) is arranged in the bonded body. Construct a membrane module. FIG. 12C 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. 13 is a diagram for explaining a mode of forming a diffusion preventing layer on a metal sheet having pores. FIG. 13B shows a metal sheet. The dotted line shown in FIG. 13B is for explanation, and indicates that the inside of the dotted frame is a pore region.

  Mask the metal sheet. As shown in FIG. 13A, the masking can be performed by arranging a mask having no holes in the peripheral portion and having pores in the portion surrounded by the peripheral portion on the metal sheet. That is, the mask of FIG. 13A is arranged on one side of the metal sheet of FIG. FIG. 13C 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. 13 (d) is obtained. The metal sheet having the pores is symmetric with respect to the front and back, and is the same as FIG. 13D when viewed from the back.

  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. At that time, if necessary, masking is performed on a portion of the metal sheet surface excluding a diffusion prevention material construction portion (refer to a predetermined width d in FIG. 15B described later) and the back surface of the metal sheet. Among these, the masking on the back surface of the metal sheet is for preventing the diffusion preventing material from entering the back surface.

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. is a compound comprising, TiN and examples _{thereof, 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 in addition to a single layer, for example, a plurality of Al ₂ O ₃ layers and ZrO ₂ layers may be laminated or mixed to form a diffusion prevention 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 prevention of mutual diffusion between the metal sheet component and the hydrogen permeable membrane component can be achieved. The range is not particularly limited, but is preferably in the range of 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. 13 (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. 11A, 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. 13E 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. 13, the diffusion prevention layer is formed on the metal sheet having pores. However, the metal sheet having the pores provided with the diffusion prevention layer is fitted into a simple frame, and FIG. ). FIG. 14 is a diagram for explaining this aspect. FIG. 14A shows a metal sheet having pores. A diffusion prevention layer is applied to the entire surface of one side of the metal sheet having pores shown in FIG. 14A, as shown in FIG. Then, this metal sheet is fitted into a simple frame as shown in FIG.

  The “frame” here is a frame having a shape corresponding to a metal sheet having pores with a diffusion preventing layer, and does not mean a metal frame as in the prior art. In this way, as shown in FIG. 14D, 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. 14 shows the 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 this case, the mere frame is formed by overlapping a plurality of metal sheets having a corresponding shape, and is not a metal frame as in the prior art.

  FIG. 15 is a diagram for explaining the relationship among a metal sheet, a pore region in the metal sheet, a diffusion prevention layer, a metal exposed surface, and the like. FIG. 15A is the same diagram as FIGS. 13E and 14D. FIG.15 (b) expands the right side part of Fig.15 (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. 15B, 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). .

  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.15 (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 preventing layer is formed in FIGS. 11 (a), 11 (d), 12 (b), 13 (e), 14 (d), and 15 (a) to 15 (b). As shown by the hatched lines, the metal sheet is disposed so as to “extend” somewhat from the pore region of the metal sheet and the peripheral edge b of the pore region. 15 (a) to 15 (b), it is a portion indicated by a symbol e, and is a width portion between the peripheral edge b of the pore region and the peripheral edge c of the diffusion preventing layer in the metal sheet.

  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. 16B, a diffusion preventing layer is disposed over the entire pore region. FIG. 16C is an enlarged plan view of the right side portion of FIG. By expanding the pore area of the metal sheet in this way, it is possible to widen the pore area of the metal sheet to the area of the “extrusion” portion. Therefore, the hydrogen permeable membrane module has a hydrogen purification area using a hydrogen permeable membrane on the same scale. Can be spread.

  As described above, in any case, the diffusion prevention layer prevents mutual diffusion of the metal sheet component and the hydrogen permeable membrane component during diffusion bonding and when actually used as a hydrogen permeable membrane module, thereby preventing 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. 17 is a diagram for explaining an aspect in which a first intermediate layer (= reinforcing member side) -a diffusion preventing layer is arranged 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). These metals may be used in the form of a combination of two or more, for example, as an alloy.
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. 18 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. 19 shows a reinforcing member having pores on the hydrogen permeable membrane side, the first intermediate layer (= reinforcing member side) -diffusion prevention layer-second intermediate layer (= hydrogen) on the contact surface with the hydrogen permeable membrane. It is a figure explaining the aspect which arranged the permeable membrane side). Of these, the first intermediate layer is the same as the first intermediate layer (see FIG. 17) in terms of its purpose, constituent material, and its construction method, and the second intermediate layer is both of purpose, constituent material, and its construction method. This is the same as the second intermediate layer (see FIG. 18).

  20 to 21 are the “metal sheet having pores” in which any of layers (A) to (D) is arranged in the embodiment of the hydrogen permeable membrane module of the present invention (3) shown in FIGS. 12 'is arranged. Except that the “metal sheet having pores” 12 ′ is added to the hydrogen permeable membrane side, it is the same as described with reference to FIGS. 20 to 21 show a case where these layers do not have the above-mentioned “protruding” portion, but the same applies to the case where they have the “excessing” portion.

<Aspects Regarding Formation Time of Layers (A) to (D)>
When the layers (A) to (D) are arranged at the joint with the hydrogen permeable membrane, (A) before joining the hydrogen permeable membrane as shown in FIGS. 11 to 12 and FIGS. The layers (A) to (D) may be formed at the stage of forming the joined body, and the layers (A) to (D) are formed after the joined body that does not include the layers (A) to (D) is formed. May be. The same applies to the following aspects. FIG. 22 is a diagram for explaining a mode in which the layers (A) to (D) are formed after the joined body in which the layers (A) to (D) are not arranged is formed.

  Here, the case of (A) the diffusion preventing layer will be described, but the same applies when the layers (B) to (D) are formed. As shown in FIG. 22, the purified hydrogen collecting member 10, the reinforcing member 11 having a coarse pore (large pore) and the reinforcing member 12 having a dense pore (small pore) are arranged. Then, the bonded body shown in FIG. 22 (d) is formed by diffusion bonding at a time. And the diffusion prevention layer is formed in the pore area | region of the reinforcement member 12 which has a pore among the joined bodies. Then, a hydrogen permeable membrane module is configured by diffusion bonding the hydrogen permeable membrane 13 to the surface.

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

As described above, since the reinforcing member and the hydrogen permeable membrane 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 hydrogen permeable membrane module of the present invention (4), one or more metal sheets having pores are laminated on both upper and lower sides of a purified hydrogen collecting member in which one or more metal sheets having upper and lower through-holes are laminated. Reinforcing members are placed and joined together. In addition, as mentioned above, before joining by one time joining, it is in the state which has just piled up those metal sheets, and the same also about the aspect below this point. The hydrogen permeable membrane is joined to the surfaces of both reinforcing members of the joined body.

  23 to 24 are diagrams for explaining the manufacturing process. In FIG. 23, 20 is a purified hydrogen collecting member having upper and lower through-holes S, 21 is a reinforcing member having pores, and 22 is a metal sheet having pores having a diffusion preventing layer. Then, these members are arranged as shown in FIGS. 22A to 22E and diffusion-bonded at a time.

  Thus, a joined body of the purified hydrogen collecting member 20, the reinforcing member 21 having pores, and the metal sheet having pores having a diffusion preventing layer is formed. FIG. 23 (f) shows a joined body configured in this manner. In FIGS. 23A to 23E, for convenience of explanation, the respective members are separated from each other. However, the respective members are overlapped and diffusion-bonded at a time. And as shown in FIG. 24, a hydrogen permeable membrane module is comprised by joining a hydrogen permeable film to the upper and lower surfaces of the metal sheets 22 and 22 having pores on the diffusion preventing layer side.

  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. In such a case, a plurality of sheets (n sheets) of “metal sheets having voids s” are stacked as shown in FIG. In the case of one sheet, the purified hydrogen collecting member 20 having the upper and lower through-holes S is formed by one “metal sheet having a gap” having a predetermined thickness.

  Further, the purified hydrogen collecting member 20 may be formed by using one or a plurality of metal sheets having a plurality of voids s, s, s... As “a metal sheet having a void s”. In the case of a plurality of sheets, as shown in FIG. 26, by collecting a plurality (n sheets) of “metal sheets having a plurality of gaps s”, purified hydrogen collection having a plurality of gaps S, S, S. Member 20 is formed.

  Further, as shown in FIG. 26, the purified hydrogen collecting member 20 has a plurality of (n sheets) of “metal sheets having a plurality of voids s” and has a plurality of voids S, S, S. When forming the hydrogen collecting member 20, a collecting hole for collecting purified hydrogen may be provided. That is, as shown in FIG. 27, by connecting a plurality of voids S, S, S... In advance through the collective holes, connection and communication with the hydrogen lead-out 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)>
In the hydrogen permeable membrane module of the present invention (5), one or more metal sheets each having pores are sequentially formed on both sides of a purified hydrogen collecting member obtained by laminating one or a plurality of metal sheets having upper and lower through-holes. A plurality or a plurality of reinforcing members in which a plurality of sheets are laminated are arranged and joined at a time. The hydrogen permeable membrane is joined to the surfaces of both reinforcing members of the joined body.

  In FIGS. 23 to 24, as shown by reference numerals 21 and 21, one reinforcing member having pores 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 thereof 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.

  FIGS. 28-29 is a figure explaining the aspect of the hydrogen permeable membrane module of this invention (6). As shown in FIG. 28, a reinforcing member 31 in which a plurality of metal sheets each having a coarse pore (= large pore) are sequentially laminated on both sides of the purified hydrogen collecting member 30 having the upper and lower through-holes S; The reinforcing member 32 having a dense pore (that is, the pore having a pore smaller than the pore of the reinforcing member 31) and the metal sheet 33 having the diffusion preventing layer are disposed at a time. Join.

  FIG. 28 (h) shows a joined body configured as described above. And as shown in FIG. 29, a hydrogen permeable membrane module is comprised by joining a hydrogen permeable film to the surface of the metal sheets 33 and 33 which have a pore which has a diffusion prevention layer of the upper and lower sides among the joined bodies. FIG. 29D shows a hydrogen permeable membrane module configured as described above. FIG. 30 (a) shows it in an enlarged manner.

  28 to 29 show two cases of the reinforcing member 31 having a coarse pore and the reinforcing member 32 having a dense pore, the purified hydrogen collecting member which is the central portion in the thickness direction. The reinforcing member with the coarsest pores is arranged on the 30th side, and the reinforcing members with the dense pores (reinforcing members with progressively smaller pore roughness) are arranged sequentially toward the hydrogen permeable membrane side. And configure. 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. .

  Although the scale of the hydrogen permeable membrane module of the present invention, that is, the scale can be set as appropriate, for example, the scale can be 30 cm in length, 3 cm in width, and 1 cm in thickness. In FIG. 28, “× 10” is an example of the number of metal sheets constituting each member.

<Embodiment of integrally joining each metal sheet of the purified hydrogen collecting member and each metal sheet of the reinforcing member including the hydrogen permeable membrane while maintaining the metal sheet>
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 at one time. As in the case of fixing or pinning, a purified hydrogen collecting member in which each metal sheet (when there are a plurality of metal sheets having voids) is overlapped (becomes a purified hydrogen collecting member by one joining), and each metal sheet is You may join at once, after forming the overlapping reinforcement member (it becomes a reinforcement member by joining once) individually. In the case of (1), for example, each metal sheet is laminated in a sheet positioning die, that is, a mold, heated and pressurized, and bonded together by diffusion bonding. And a hydrogen permeable membrane is joined to the surface of the metal sheet which has the upper and lower pores among the joined bodies, and it is set as 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. Taking the hydrogen permeable membrane module manufactured in the mode of FIGS. 28 to 29 as an example, the hydrogen permeable membrane module is configured to have no hydrogen deriving portion as shown in FIG.

  A portion of the purified hydrogen collecting member 30 (of course, including the upper and lower reinforcing member portions may be perforated) is used as a purified hydrogen lead-out portion. A hole indicated as “T” in FIG. 30B, and this hole T communicates with the gap S shown in FIG. The drilling can be easily performed by machining with a cutting tool or the like, for example. Then, as shown in FIG. 30C, the hydrogen lead-out pipe 35 is connected to the purified hydrogen lead-out part T.

  In FIGS. 30B to 30C, the hydrogen lead-out pipe is provided on the right side, but the hydrogen lead-out pipe can be provided at an appropriate location so as to communicate with the gap S of the purified hydrogen collecting member. Taking FIG. 30A as an example, the left side, the near side, or the other side may be used, and the number is not limited to one, and a plurality may be provided. This also applies to the case where the shape of each member such as the purified hydrogen collecting member, the reinforcing member, and the hydrogen permeable membrane is a square shape or other shapes.

  The shape of the perforations may be any of circular cross-section, square cross-section, cross-section rectangle, and others, but in particular, when the cross-section is circular as shown by T in FIG. And it can be done easily. In addition, it is advantageous in that, for example, a union joint can be used for joining a pipe to a round pipe for extracting purified hydrogen fitted into a hole having a circular cross section.

  This hole T communicates with the space S of the purified hydrogen collecting member in the embodiment shown in FIGS. 1-2, 8-9, 11-11, 20-22, 22-24. Also in these embodiments, the hydrogen outlet pipe 35 is connected to the hole, that is, the purified hydrogen outlet portion T in the same manner as described above. In addition, as shown in FIG. 27, when the collecting holes for collecting purified hydrogen are provided, a plurality of voids S, S, S... A hydrogen lead-out pipe 35 can be connected to the hole, that is, the purified hydrogen lead-out part T, and communicated.

  FIG. 31 is a view 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. 31 (a) is the same as FIG. 30 (c). FIG. 31B is an enlarged view of the cross section taken along the line AA in FIG. 31A, and FIG. 31C is an enlarged view of the cross section taken along the line BB in FIG. is there. As shown in FIG. 31 (b), the hydrogen lead-out pipe 35 is fitted into the purified hydrogen lead-out portion T, and is sealed and fixed in a gastight manner. The sealing and fixing are performed by welding, brazing or other appropriate methods.

  In the case of a purified hydrogen collecting member provided with a plurality of voids S as shown in FIG. 26, the purified hydrogen lead-out portion T is perforated so as to communicate with any of the voids S. FIG. 32 is a diagram for explaining this aspect. As shown in FIG. 32 (a), the appearance of the purified hydrogen collecting member 30 before it is perforated is the same as that shown in FIG. 30 (a), but the purified hydrogen collecting member shown as reference numeral 30 in FIG. As shown in FIG. 26, the purified hydrogen collecting member is provided with a plurality of voids S. Since the purified hydrogen lead-out portion T needs to communicate with any of the plurality of voids S, the purified hydrogen lead-out portion T is formed by perforating in a rectangular shape as shown in FIG. Then, as shown in FIG. 32 (c), the hydrogen lead-out pipe 36 corresponding to the shape is connected to the purified hydrogen lead-out part T.

<Deformation aspect 1 which concerns on refinement | purification hydrogen derivation | leading-out 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 recess S or the gap S of the purified hydrogen collecting member is provided. On the other hand, with respect to the purified hydrogen collecting member, the portion of the recess S or the gap S is previously set wider than the pore region of the reinforcing member (that is, the portion where the purified hydrogen outlet portion T is drilled). By making the width small), the length for drilling as the purified hydrogen lead-out portion can be shortened.

  FIG. 33 is a diagram for explaining this aspect. In FIG. 33, the end of the pore region of the reinforcing member is indicated by a dotted line. As shown in FIG. 33 (d), in the purified hydrogen collecting member 30, the portion of 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. 33, each member is arrange | positioned and laminated | stacked on a surface parallel, and it joins at once.

<Deformation aspect 2 which concerns on refinement | purification hydrogen derivation | leading-out part T>
34 to 35 are diagrams for explaining other aspects. As shown in FIG. 34, the purified hydrogen collecting member 30 having the void S in FIG. 28 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 same as that described above except that the purified hydrogen deriving portion T is provided. (See FIG. 3). However, in this embodiment, there is no “metal sheet M having no gap s” at the bottom of FIG.

  As shown in FIG. 36, a plurality of “metal sheets having a gap s and an opening t continuous with the gap s” are arranged inside. 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. 37 is a diagram for explaining a production mode of the “metal sheet having the gap s and the opening t continuous with the gap s”. FIG. 37 (a) shows a metal sheet, and masking is performed except for a portion to be a gap s and a portion to be an opening t that follows the portion of the surface of the metal sheet. FIG. 37 (b) 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. 37 (c) shows this state. Next, by removing the masking, as shown in FIG. 37 (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. 34, on the upper and lower sides of the purified hydrogen collecting member 40, a reinforcing member 41 in which a plurality of metal sheets each having a coarse pore (increase in size) are sequentially laminated and the pores in the pores are densely arranged. The reinforcing member 42 (that is, the pores of the pores are smaller than the pores of the reinforcing member 41) and the metal sheet 43 having the pores having the diffusion preventing layer are arranged and joined at once by diffusion joining. FIG. 34 (h) shows a joined body configured in this manner. Then, as shown in FIG. 35, a hydrogen permeable membrane module is formed by joining a hydrogen permeable membrane to the surface of the metal sheet 43 having pores having upper and lower diffusion prevention layers in the joined body.

<Connection of hydrogen outlet pipe 45 to purified hydrogen outlet section T>
FIG. 38 is a diagram for explaining the structure of the hydrogen permeable membrane module configured as shown in FIGS. FIG. 38A 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.38 (b) is the figure which connected the hydrogen derivation | leading-out pipe | tube 45 to the refinement | purification hydrogen derivation | leading-out part T shown in Fig.38 (a). FIG.38 (c) is the figure which expanded and showed the AA line cross section in Fig.38 (a).

<Deformation mode 1 when producing hydrogen permeable membrane module>
The hydrogen permeable membrane module of the present invention has a pore size so that the pores become coarser as it goes to “a reinforcing member having pores + a purified hydrogen collecting member” or “a plurality of purified hydrogen collecting members”. It is manufactured by laminating a reinforcing member '+ purified hydrogen collecting member' having a gradient and joining by diffusion bonding to form a joined body, and joining a hydrogen permeable membrane thereto.

In producing them, the members can be easily attached by attaching “joins” to each other and leaving the frame. FIG. 39 is a diagram for explaining this aspect.
FIG. 39A 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. 39 (b) shows a reinforcing member with fine pores (small pores). As shown by a one-dot chain line, a predetermined width is placed from the outer peripheral edge of the reinforcing member, and this width portion is referred to as “joining”. To do. 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. 39 (c) shows a reinforcing member having pores coarser than those shown in FIG. 39 (b). 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. 39D 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. 39 (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.

  Then, the reinforcing member having the fine pores configured as described above, the reinforcing member having a coarser pore than the fine pores, and the purified hydrogen collecting member are laminated and diffusion-bonded at a time. Next, a hydrogen permeable membrane is diffusion bonded to the bonded body. Then, the hydrogen permeable membrane module is formed by cutting at a “connecting” portion at a time. In this case, in FIG. 39 (a) to (d), by removing the linear portion that becomes the connecting frame shown by the one-dot chain line by etching at a predetermined interval in advance (the hydrogen permeable membrane or the like). 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 is, for example, “reinforcing member having a gradient in pore size and purified hydrogen collecting member so that the pores become coarser toward a plurality of“ purified hydrogen collecting members ”. In such a manner, a joined body of each member is formed by diffusion bonding at a time, and then a hydrogen permeable film is diffusion bonded to the joined body. When forming the joined body, it is preferable to temporarily fix the respective members in advance. Temporary fixing may be performed for each member.

  FIG. 40 is a diagram for explaining the mode. As shown in FIG. 40, the reinforcing member (b) having pores, the reinforcing member (c) having pores coarser than (b), the purified hydrogen collecting member (d), and the purified hydrogen collecting member (not shown). A reinforcing member (c) having pores coarser than (b) and a reinforcing member (b) having pores are sequentially arranged and laminated also below the member (d).

  Then, the laminated body is temporarily fixed by spot welding as shown as p, p, p... In FIG. In FIG. 40, each member (b) to (d) is shown as a plan view. However, the members are arranged in parallel to each other, stacked, temporarily fixed by spot welding, and the temporarily fixed stacked body is formed at a time. Diffusion bonding is performed. Next, the hydrogen permeable membrane of FIG. 40A is diffusion bonded to the joined body. Then, a hydrogen permeable membrane module is formed by cutting at a “connecting” portion at a time.

  Here, the reinforcing member (b) having pores is composed of a plurality of “metal sheets having pores” as shown in FIG. The reinforcing member (c) having coarser pores than the reinforcing member (b) having fine pores is composed of a plurality of “metal sheets having coarse pores” as shown in FIG. The purified hydrogen collecting member (d) is composed of a plurality of “metal sheets having voids s + s ′” corresponding to the purified hydrogen collecting member having voids 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 is, for example, a “reinforcing member having a gradient in pore size so that the pores become coarser toward the plurality of“ purified hydrogen collecting members ”+ the purified hydrogen collecting member Are formed by stacking and diffusion bonding at a time, and bonding a hydrogen permeable film to the bonded body. 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. 41 is a diagram for explaining the mode. As shown in FIG. 41 (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 is formed by the purified hydrogen lead-out portion T, the hydrogen lead-out 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. 41 (b) and 41 (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 laminated, 41 (b) and 41 (c), the laminated body is temporarily fixed by spot welding, and the temporarily bonded laminated body is diffusion bonded at one time. The hydrogen permeable membrane shown in Fig. 41 (a) is diffusion bonded to the joined body, and cut at once at the "joint" portion indicated by the one-dot chain line to form a hydrogen permeable membrane module.

  FIG. 42 is a view for explaining the hydrogen permeable membrane module with a hydrogen outlet tube formed in this way. 42 (a) is a plan view, FIG. 42 (b) is a perspective view, and FIG. 42 (c) is an enlarged cross-sectional view taken along line AA in FIG. 42 (a). As shown in FIG. 42 (c), as S, (T), S ″, a void portion, a fractionated hydrogen deriving portion, and a hydrogen deriving tube are formed at once. 52 is a hydrogen deriving tube having a void S ″. Part.

  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. 42D is a cross-sectional view when the reinforcing member 51 having a coarser pore is also provided.

<Deformation mode 4 when producing hydrogen permeable membrane module>
"Metal sheet having pores" as shown in Fig. 7 (d), "Metal sheet having coarse pores" as shown in Fig. 10, "Diffusion prevention layer" as shown in Figs. It has “pores” in which “first intermediate layer + diffusion prevention layer”, “diffusion prevention layer + second intermediate layer” or “first intermediate layer + diffusion prevention layer + second intermediate layer” is formed. A plurality of “metal sheets” can be produced simultaneously.

  FIG. 43 is a diagram for explaining the mode. Here, the case where “a metal sheet having pores in which a diffusion prevention layer is formed” among the above layers is used will be described as an example. A plurality of hydrogen permeable membrane modules are manufactured simultaneously by forming a plurality of “metal sheets having pores with a diffusion preventing layer” on one metal sheet. FIG. 43 shows two examples. In FIG. 43A, reference numeral 61 denotes a metal sheet having pores in two regions, and a frame indicated by a one-dot chain line is each region. Thus, a number of reinforcing members can be modeled on a single metal sheet. 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 s” that forms the purified hydrogen collecting member is formed in a single metal sheet for several sheets, and has “rough pores” that form reinforcing members having coarse pores. The “metal sheet” and the “metal sheet having fine pores” that form the reinforcing member having fine pores are also traced to one metal sheet. FIG. 43B shows the hydrogen permeable membrane 62 corresponding to them.

  Then, a plurality of “metal sheets having voids s” forming a purified hydrogen collecting member are arranged in the center, and a plurality of metal sheets in the form of a plurality of “metal sheets having coarse pores” are sequentially arranged above and below them. A plurality of metal sheets in the form of a plurality of “metal sheets having fine pores” and a “metal sheet having pores in which a diffusion preventing layer is formed” are laminated and bonded at once by diffusion bonding. The hydrogen permeable film 62 of FIG. 43B is diffusion bonded to the bonded body.

  And it cut | disconnects into a hydrogen permeable membrane module unit, and comprises a hydrogen permeable membrane module. In this case, in FIG. 43 (a), the linear frame portion indicated by the alternate long and short dash line is removed by etching at a predetermined interval in advance. The peripheral edge and the connecting frame are connected only at a connecting portion that is not removed by etching), and can be easily cut.

  FIG. 43 shows a case where two joined bodies are produced at a time and two hydrogen permeable membrane modules are produced by diffusion joining a hydrogen permeable membrane thereto. A joined body can be produced at a time, and a hydrogen permeable membrane can be diffusion-bonded thereto to produce a plurality of three or more hydrogen permeable membrane modules. Thus, mass production of the hydrogen permeable membrane module becomes possible.

<Deformation mode 5 when producing hydrogen permeable membrane module>
As described above in <Modification Mode 2 when Fabricating Hydrogen Permeable Membrane Module>, instead of temporarily fixing the stacked metal sheets by spot welding, pinning may be performed. According to the pinning method, the positioning of the metal sheets constituting each member is easy, and the handling thereof is easy, for example, the labor of spot welding can be saved. FIG. 44 is a diagram for explaining the mode.

  As shown in FIG. 41 (c), with respect to the purified hydrogen collecting member, the void portion is further extended from the void S portion as shown by S ″, and the void S ″ portion is the purified hydrogen lead-out portion T and the hydrogen lead-out pipe. 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. 44 (a) and 44 (b), pin holes (pins) are formed at a plurality of positions on the outer peripheral edge of each metal sheet (having gaps s + s ″) each serving as a reinforcing member and each purified hydrogen collecting member. A pin-fixing member having a hole for insertion is provided, the metal sheets are stacked, and a pin is inserted and positioned in each pin hole, and the laminated body is diffusion-bonded at a time. A hydrogen permeable membrane as shown in FIG. 43 (a) is diffusion bonded to the surface of the metal sheet having holes.

  Next, as shown by the one-dot chain line in FIGS. 44A and 44B, the hydrogen permeable membrane module is formed by cutting at once. FIG. 44 (c) is a perspective view of the hydrogen permeable membrane module. The square pipe as shown in FIG. 44 (c) can be machined such as polishing and cutting, and FIG. 44 (d) is a perspective view of an embodiment in which such a square pipe is processed into a cylinder (round pipe). .

<Examples of Embodiments of Inventions (4) to (6)>
As described above in <Aspect of the present invention (1)>, in the present inventions (1) to (6), it is important to alternately dispose metal sheets of different metal materials. Here, the aspect example in invention of this invention (4)-(6) is demonstrated among this invention (1)-(6). FIG. 45 is a diagram for explaining an example of the mode.

  In FIG. 45, 90 is a purified hydrogen collecting member obtained by laminating a plurality of metal sheets having upper and lower through-holes, 91 is a reinforcing member obtained by laminating a plurality of metal sheets having rough pores arranged on both sides thereof, 92 is a reinforcing member which is sequentially arranged on both sides thereof, and the pores of the pores are dense (that is, the pores of the pores are smaller than the pores of the reinforcing member 91), and 93 is a reinforcing member having the pores provided with a diffusion preventing layer. It is.

  When the purified hydrogen collecting member 90 is formed of a plurality of metal sheets, the SUS sheet and the Ni sheet are alternately stacked. In this embodiment, the Ni sheet is placed at the center of the stack, and the SUS is sequentially placed above and below the Ni sheet. Both sheets are alternately arranged as a sheet, Ni sheet, SUS sheet, etc., and a total of n SUS sheets and 11 Ni sheets (for example, 11 sheets) are stacked. Similarly, the reinforcing member 91 is formed by alternately stacking SUS sheets and Ni sheets. However, when n = 11 sheets, the surface side of the purified hydrogen collecting member 90 (the back side is the same) is the SUS sheet, so the purified hydrogen collection is performed. The side in contact with the member 90 is an Ni sheet, and m sheets (for example, 5 sheets) are stacked such as Ni sheet / SUS sheet / Ni sheet / SUS sheet / Ni sheet.

  The reinforcing member 92 is, for example, one SUS sheet and one Ni sheet, and the reinforcing member 93 is one SUS sheet provided with a diffusion prevention layer. The metal sheets of the purified hydrogen collecting member 90 and the reinforcing members 91 to 93 are all arranged with different metal sheets alternately.

  Since each SUS sheet and each Ni sheet are provided with pinning members having pin insertion holes at a plurality of locations on the outer peripheral edge, as shown by a one-dot chain line in FIG. Each member is constituted by inserting a pin, ... SUS sheet / Ni sheet / SUS sheet ... are aligned, positioned, overlapped, heated and pressed, and bonded at once by diffusion bonding. Next, a hydrogen permeable film, for example, a Pd film, is placed on the uppermost and lowermost surfaces of the joined body, heated and pressurized, and joined by diffusion bonding to form a hydrogen permeable membrane module.

  In the present invention, the thickness of each metal sheet may be the same thickness or an appropriate thickness. In the case of an appropriate thickness, if the SUS sheet is a sheet that plays a main role as a structural material, the Ni sheet serves as an auxiliary sheet for bonding between the SUS sheets on both sides thereof, that is, an insertion material. In this case, the thickness of the Ni sheet that is the insertion material may be smaller than the SUS sheet that is the structural material and may be a constant thickness, and the thickness of the SUS sheet that is the structural material may be arbitrarily set. Can be selected.

  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 (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 which shows the aspect which produces the reinforcement member 11 with a coarse pore from the several sheets of the metal sheet which has a pore with a coarse pore. 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 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 The figure explaining the relationship between the metal sheet, the pore area in the metal sheet, the diffusion prevention layer, the exposed metal surface, etc. The figure explaining the aspect which eliminated the "protrusion" part of the diffusion prevention layer The figure explaining the aspect which has arrange | positioned the 1st intermediate | middle layer (= reinforcement member side) -diffusion prevention layer on the contact surface with a hydrogen permeable membrane about the reinforcing member which has the pore by the side of a hydrogen permeable membrane. The figure explaining the aspect which distribute | arranged the diffusion prevention layer-second intermediate | middle layer (= hydrogen permeable membrane side) to 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 has arrange | positioned the 1st intermediate | middle layer-diffusion prevention layer-2nd intermediate | middle layer in the contact surface with a hydrogen permeable film about the reinforcement member which has the pore by the side of a hydrogen permeable film. The figure explaining the aspect which has arrange | positioned the diffusion prevention layer etc. in the aspect of the hydrogen permeable membrane module shown to FIGS. The figure explaining the aspect which has arrange | positioned the diffusion prevention layer etc. in the aspect of the hydrogen permeable membrane module shown to FIGS. The figure explaining the aspect which forms the layer of (A)-(D), after forming the conjugate | zygote which does not distribute the layer of (A)-(D). The figure explaining the preparation process of the hydrogen permeable membrane module of this invention (4) The figure explaining the preparation process of the hydrogen permeable membrane module of this invention (4) The figure explaining the aspect of the refinement | purification hydrogen collection member 20 which has the upper and lower through-holes S The figure explaining the aspect of the refinement | purification hydrogen collection member 20 which has the upper and lower through-holes S The figure explaining the aspect of the refinement | purification hydrogen collection member 20 which has the upper and lower through-holes S The figure explaining the aspect of the hydrogen permeable membrane module of this invention (6) The figure explaining the aspect of the hydrogen permeable membrane module of this invention (6) The figure explaining the aspect which provides the hydrogen derivation | leading-out part T with respect to a refinement | purification hydrogen collection member The figure explaining the connection part of the inside of the hydrogen permeable membrane module with the hydrogen outlet pipe 35 formed like FIG. 29, and the hydrogen outlet pipe 35 The figure explaining the aspect which forms the refinement | purification hydrogen derivation | leading-out part T with respect to the refinement | purification hydrogen collection member which provided the several space | gap S as shown in FIG. 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 deformation | transformation aspect 2 which concerns on the refinement | purification hydrogen derivation | leading-out part T The figure explaining the structure of the hydrogen permeable membrane module comprised as FIG. 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 The figure explaining the deformation | transformation aspect 5 at the time of hydrogen permeable membrane module preparation The figure explaining the example of an aspect of invention of this invention (4)-(6) 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

1, 10, 20, 30, 40 Purified hydrogen collecting member 2, 12, 21, 32, 42 Reinforcing member having pores 3, 13, 23, 34, 44, 62 Hydrogen permeable membrane s Void in metal sheet S Void M Closing member 11 Reinforcing member having pores (rough pores) 2 'Metal sheet or reinforcing member having pores provided with a diffusion preventing layer or the like a Periphery of metal sheet b Perimeter of diffusion preventing layer c Pore of metal sheet 12 'Metal sheet or reinforcing member having pores with a diffusion preventing layer or the like 22 Metal sheet or reinforcing member having pores with a diffusion preventing layer or the like 31 Reinforcing member having pores (rough pores) 33 Metal sheet or reinforcing member having pores provided with a diffusion preventing layer or the like 35, 36, 45 Hydrogen outlet tube S ′ Extension portion of gap S S ″ Void serving as a purified hydrogen outlet portion extending from the portion of gap S 4 Reinforcing member having pores (rough pores) 43 Metal sheet or reinforcing member having pores with a diffusion prevention layer or the like T opening, hydrogen outlet part of purified hydrogen collecting member t opening following the part to be the gap s p spot Welding portion 51 Reinforcing member with rough pores 52 Hydrogen outlet tube portion having void S ″ 61 Metal sheet having pores in two regions 71 Expanding frame 72 Material having hydrogen gas separation property such as Pd alloy foil (hydrogen permeation) Foil film)
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 90 Purified hydrogen collecting member 91, 92, 93 Reinforcing member

Claims (17)

  A hydrogen permeable membrane module that does not require a metal support, and a purified hydrogen collecting member in which one or more metal sheets having no voids and one or more metal sheets having upper and lower through-holes are sequentially laminated The reinforcing member is formed by laminating one or more metal sheets having pores. At this time, the metal sheets are alternately arranged with metal sheets of different metal materials, and they are joined at a time. After that, a hydrogen permeable membrane module is formed by bonding a hydrogen permeable membrane to the surface of the reinforcing member.   A hydrogen permeable membrane module that does not require a metal support, and a purified hydrogen collecting member in which one or more metal sheets having no voids and one or more metal sheets having upper and lower through-holes are sequentially laminated A plurality of reinforcing members formed by laminating one or a plurality of metal sheets having pores, wherein the metal sheets are alternately arranged with metal sheets of dissimilar metal materials, and they are once A hydrogen permeable membrane module comprising a hydrogen permeable membrane joined to the surface of the reinforcing member after being joined to the surface.   3. The hydrogen permeable membrane module according to claim 2, wherein the one or more reinforcing members are provided with a gradient in pore size such that the pores become coarser toward the purified hydrogen collecting member. A hydrogen permeable membrane module, characterized in that   A hydrogen permeable membrane module that does not require a metal support, and one or more metal sheets having pores on both sides of a purified hydrogen collecting member in which one or more metal sheets having upper and lower through-holes are laminated. In this case, the metal sheets are alternately arranged with metal sheets of different metal materials, and after they are joined at once, the hydrogen permeable membranes are formed on the surfaces of the upper and lower reinforcement members. A hydrogen permeable membrane module characterized by being joined.   A hydrogen permeable membrane module that does not require a metal support, and one or more metal sheets each having a pore on each side of a purified hydrogen collecting member in which one or more metal sheets having upper and lower through-holes are laminated, or A plurality of reinforcing members in which a plurality of sheets are laminated are arranged. In this case, the metal sheets are alternately arranged with metal sheets of different metal materials, and after they are joined at once, the upper and lower reinforcing members are arranged. A hydrogen permeable membrane module comprising a hydrogen permeable membrane bonded to a surface.   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 metal sheet which comprises the said refinement | purification hydrogen collection member, and the metal sheet which comprises the said reinforcement member are each arrange | positioned with a metal sheet, and once A hydrogen permeable membrane module, characterized by being bonded to.   The hydrogen permeable membrane module according to any one of claims 1 to 6, wherein one or more metal sheets constituting the purified hydrogen collecting member and one or more metal sheets constituting the reinforcing member. The hydrogen permeable membrane module is characterized in that each of the metal sheets is arranged as a metal sheet by pinning and bonded together.   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 any one of claims 1 to 6, wherein the junction to be joined at one time is a diffusion junction.   6. The hydrogen permeable membrane module according to claim 1, wherein the hydrogen permeable membrane is bonded to the surface of the reinforcing member by 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.   16. The hydrogen permeable membrane module according to any one of claims 12 to 15, wherein a diffusion preventing layer, a first intermediate layer-diffusion preventing layer, and a diffusion preventing layer are formed 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 claim 1, wherein the hydrogen permeable membrane module is a hydrogen permeable membrane module for a membrane reactor.

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