JP2008155118A - Composite membrane for separating hydrogen and module for separating hydrogen using this hydrogen permeable membrane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite membrane for separating hydrogen which can make hydrogen selectively permeate and separate from a mixture gas containing hydrogen, and to provide a module for separating hydrogen using the same. <P>SOLUTION: A flange 5B protruding from an outer edge is formed in such a way that a thin film-like outer edge member 5 using a metal having the affinity for a metal for a hydrogen-permeable membrane 2 is protruded from the outer edge, overlapped and arranged on at least one side of the outer edges of the hydrogen-permeable membrane 2 made of a metal allowing hydrogen selectively permeate from the mixed gas, and that the overlapping parts 5A are connected in a length direction without leakage. Attaching the composite membrane to equipment, members, etc., for example, even in the case of forming the module for separating hydrogen, can substantially performs connection of welding or the like with the above the flange, and reduces the effect by heating of the hydrogen-permeable membrane to suppress the deterioration of the hydrogen permeability. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen separation composite membrane that selectively permeates and separates hydrogen gas in a mixed gas containing hydrogen, and a hydrogen separation module using the same.

  As a next-generation energy source, hydrogen is proposed, for example, by electrolysis of water, or by obtaining hydrogen gas by steam reforming from source gas such as methanol, propane gas, liquefied natural gas, city gas, etc. Has been. In order to use hydrogen gas as a power generation fuel or the like, it is necessary to separate the hydrogen gas from the hydrogen mixed gas with a high purity of 99.99% or more.

  As a method for obtaining hydrogen from the raw material gas as described above, for example, as shown in the case of natural gas in FIG. 9, after desulfurization in a desulfurizer a at 350 ° C., a high temperature of about 800 ° C. is introduced to introduce steam for reforming. Through a reformer b at 400 ° C, a high-temperature CO converter c performed at about 400 ° C, a low-temperature CO converter d at about 250 ° C, and hydrogen at a PSA (hydrogen purifier by catalyst adsorption) e at a temperature of 100 ° C or lower. A hydrogen separation process is used to produce and remove.

  However, in the process using this PSA, the reforming reaction is an equilibrium reaction and is heated at a high temperature of about 800 ° C. The equipment itself is complicated and large, the number of processing steps and the number of equipment are increased, and the equipment cost is high. Maintenance is also difficult. Moreover, the purity of the hydrogen gas obtained is not satisfactory, and improvements are desired in terms of the purification efficiency of hydrogen gas.

In order to improve such a problem, as shown in FIG. 10, in recent years, after reforming the raw material gas with water vapor downstream of the desulfurizer a, a method of obtaining high purity hydrogen gas with the membrane reactor f using a hydrogen separation membrane. Has been tried. Since this system uses a catalyst and is a non-equilibrium reaction, there is an advantage that the reforming temperature can be lowered to about 550 ° C., for example. For example, when natural gas is used as the raw material gas, it is separated and extracted into hydrogen and off-gas (carbon dioxide gas) by the reaction of CH ₄ + 2H ₂ O → 4H ₂ + Co ₂ .

  Accordingly, hydrogen can be purified and separated from the introduced source gas and water vapor in two steps, and the off-gas can be taken out and reused for fuel gas, and its temperature can be utilized. In this process, the membrane reactor f is used in combination and the processing temperature can be processed at a relatively low temperature. Therefore, the process can be greatly reduced in size and simplified as compared with a conventional process apparatus. There is an advantage that it can be used as an on-site device such as a fuel cell, and the use as a high-purity hydrogen generator for fuel cells is also expected.

  The hydrogen separation element used in the membrane rear titer f is a porous hydrogen permeable membrane made of Pd or an alloy thereof known as a metal that selectively permeates hydrogen gas, facing the raw material gas side. It is configured to be supported by a support (porous support), and the hydrogen gas separated by the hydrogen permeable membrane is taken out through the support. Therefore, the support is used as a flow path member for supporting the pressure of the supply gas applied to the hydrogen permeable membrane to prevent deformation of the membrane and for allowing the hydrogen gas after separation to flow down satisfactorily.

  For such a hydrogen separation membrane member, it has been proposed to form a metal thin film that does not form a solid solution with the support on the surface of the porous support, and to provide a thin film of Pd alloy on the film (for example, Patent Document 1). The thin film is formed by a plating method or chemical vapor deposition, and the metal thin film serving as the intermediate layer is used to prevent performance degradation due to diffusion into the hydrogen separation membrane. There has also been proposed a composite in which a sheet-like hydrogen permeable membrane that selectively permeates only hydrogen such as Pd is disposed on a sheet-like substrate having surface flatness (for example, Patent Document 2). This shows that the hydrogen permeable membrane is overlapped with a metal porous plate sandwiched between a base plate having vent holes or grooves for ventilation, and a frame-like metal plate is applied and sealed from above by welding.

  Furthermore, a thin layer containing Pd is superimposed on the surface of a metal porous support that has been perforated by a laser method or etching, so that a thin barrier layer is used for the question of the metal porous support and the thin film containing Pd. There has been proposed a hydrogen gas separation membrane with intervening metal (for example, Patent Document 3). Furthermore, the same document states that the Pd thin film is sandwiched between the porous porous supports, the outer periphery of the end is welded (brazed) to prevent gas leakage, and the shape is flat. In addition, it explains what can be made cylindrical.

Japanese Patent Laid-Open No. 2005-262082 JP-A-10-296061 Japanese Patent No. 2960998

  As described above, all of the inventions of the above patent documents disclose hydrogen separation membrane members that support a hydrogen permeable membrane that selectively permeates hydrogen gas with a porous support. Since the permeable film is formed by a method such as a plating method or a vapor deposition method, there is a problem in terms of uniformity of thin film characteristics and life. That is, the thin film obtained by this method has problems such that the plating thickness changes due to the influence of the surface state of the support, and defects such as pinholes are likely to occur in the plated structure. Furthermore, when using this, there is a concern that metal fatigue fracture may occur due to a shape change such as expansion or contraction of the thin film separation membrane due to a temperature change such as heating for use or a temperature drop due to stopping. Therefore, the generation of cracks due to fatigue and the formation of pinholes due to peeling from the support have become major problems.

  Furthermore, since the separation membrane by this method is in direct or indirect contact with the support or the like, it is difficult to separate and recover only the expensive Pd alloy membrane when it is discarded, for example, Improvements are also desired in terms of resource conservation and the environment.

  In addition, the invention of Patent Document 2 discloses a thin film material of the Pd alloy that is formed by cold rolling a material metal to a predetermined thickness, for example, by a plating method or a vapor deposition method. However, the structure is such that a flat base plate, a plurality of reinforcing plates, and the hydrogen permeable membrane are stacked, and further, laser welding or seal welding is performed from above using a frame-shaped metal plate.

  Therefore, in the hydrogen separation module according to this method, the hydrogen separation membrane that is particularly required to have high purity is directly welded to the reinforcing plate and the support that are in contact with the membrane, and the welding direction also has a thickness from the top of the frame-shaped metal plate. It is necessary to heat in a wide range with an excessive current, and the heat-affected zone becomes large. For example, the hydrogen separation membrane forms a heterogeneous alloy phase such as directly melting or diffusing with a support in contact with this. It will be. Therefore, it is difficult to obtain the original hydrogen permeation performance in the heat-affected zone thus changed, resulting in problems such as reducing the effective permeation area and various characteristics such as mechanical characteristics and corrosion resistance. It will cause a decrease in the lifespan associated with use.

  Further, the invention of Patent Document 3 further discloses that the shape of the element is a cylindrical element. However, as in Patent Document 2, the Pd thin film is directly welded to a support or the like. However, there are problems such as a decrease in permeation performance of the hydrogen permeable membrane due to the thermal influence, a decrease in production workability due to structural complexity, and a difficulty in weight reduction. Therefore, even in this patent document, a separation membrane product that is easy to manufacture and has stable hydrogen permeation performance has not been obtained.

  On the other hand, there is a case where such a hydrogen permeable membrane is directly coupled to a mechanical device by a brazing method. However, at this time, it is difficult to solve the problem also by this method, for example, an additive element such as Zn added to the brazing material to increase the solubility affects the Pd alloy and causes a decrease in performance.

  Therefore, the present invention provides a hydrogen separation composite membrane that can solve the above-mentioned problems by attaching an edge member using an affinity metal to the outer edge of a thin hydrogen permeable membrane as an easy-to-attach separation membrane, and An object is to provide a hydrogen separation module using this.

  That is, the invention according to claim 1 is a thin film using a metal having affinity for the metal of the hydrogen permeable film on at least one side of the outer edge of the hydrogen permeable film made of a metal that selectively transmits hydrogen gas from a mixed gas. A sheet-like edge member is left on the hydrogen permeable membrane while leaving a permeation surface, and is overlapped and protrudes from the outer edge, and the overlapping portion is joined without causing leakage, whereby the outer edge is attached to the outer edge of the hydrogen permeable membrane. It is a composite membrane for hydrogen separation characterized in that a flange by protruding the edge member extending outward is integrally provided.

  The invention according to claim 2 is that the edge member has an inner hole having an inner edge inside the outer edge of the hydrogen permeable membrane, and a frame shape in which the outer edge is provided outside the outer edge of the hydrogen permeable membrane. The flange is formed over the entire circumference of the outer edge of the hydrogen permeable membrane by joining the overlapping portion between the edge member and the outer edge of the hydrogen permeable membrane without causing leakage. It is characterized by that.

  According to a third aspect of the present invention, the metal of the hydrogen permeable membrane is made of a Pd—Ag alloy or a Pd—Cu alloy and is in the form of a thin film that is cold-rolled to a thickness of 30 μm or less. In the invention according to claim 5, the edge member is constituted by a metal thin film sheet material containing a congener element having the same generativity as any of the constituent elements of the metal constituting the hydrogen permeable membrane. The invention according to claim 6, wherein the edge member is disposed so as to sandwich one side or both sides of the outer edge portion of the hydrogen permeable membrane and continuously seam welded along the overlapping portion. A composite membrane for hydrogen separation according to any one of claims 1 to 5 and a porous member disposed on at least one side thereof and through which a raw material gas or a hydrogen gas that has permeated the hydrogen permeable membrane can flow. And this porous member Wherein the flange of the hydrogen separation composite membrane has a holding portion for heavy location, and the overlapped portion between the flange and the holding section features a hydrogen separation module formed by heating bonds without causing any leakage.

  In the invention according to claim 7, the composite membrane for hydrogen separation is supported by the porous member on the lower surface side, and a stopper is disposed at least on the upper surface side end of the flange of the composite membrane. The hydrogen separation module is characterized in that an overlapping portion of the brim and the holding portion and the stopper of the support body are coupled by co-welding.

  Further, the invention according to claim 8 is characterized in that the stopper is formed in a ring shape, the porous support body formed in a cylindrical shape, and the ring-shaped stopper member fitted on an end portion of the support body. The invention according to claim 9, wherein at least one pressing surface that presses the flange of the edge member between them is tapered by an angle (θ) along the axial direction thereof, and the invention according to claim 9, The porous support is a cylindrical base that receives the hydrogen permeable membrane and an end fitting that is disposed at the end of the porous support and forms the holding portion. The base and the end fitting are integrated by welding or close fitting. The invention according to claim 10 is characterized in that the porous member has a surface in contact with the hydrogen permeable membrane subjected to a finish treatment by ceramic spraying, and the invention according to claim 11 provides the composite for hydrogen separation. Membrane increases hydrogen gas selective permeation area The folds along the axial direction of the order, respectively, characterized in that formed over the entire surface.

  In the invention according to claim 1, in order to have the above-described configuration, the composite membrane for hydrogen separation is attached to a device or the like, for example, even when a hydrogen separation module is formed, for example, the connection such as welding is substantially performed. Therefore, it is possible to obtain a high-quality and long-life apparatus that can reduce the influence of heating of the hydrogen-permeable membrane itself and suppress the deterioration of the hydrogen-permeation performance.

  In addition, the edge member is a thin-film sheet-like body made of a metal having an affinity for the metal of the hydrogen permeable membrane, and since it is bonded without causing leakage, metallurgically stable and strong bonding is possible. It becomes. Therefore, even when the two metals are bonded by welding or diffusion bonding, the work becomes easy and the heating area can be reduced, so that segregation and generation of impurities can be suppressed systematically, and the same as with a normal thin film material. Pleating can be easily performed.

  Further, in the invention of claim 1, the edge member includes a case where the edge member is provided on at least one side of the outer edge of the hydrogen permeable membrane necessary for attachment, and the reduction of the area of the hydrogen permeable membrane by the edge member is minimized. Therefore, the installation can be performed by effectively utilizing the limited space. In addition, as in the invention according to claim 2, by forming the edge member over the entire circumference of the hydrogen permeable membrane, it is possible to easily attach and also to reinforce the periphery of the hydrogen permeable membrane. In addition, it is easy to handle, store, transport, etc., and enhance versatility.

  Furthermore, the invention according to claim 6 uses the hydrogen separation member according to claims 1 to 5, and the hydrogen separation composite membrane is heat-bonded to the porous support using the flange of the edge member. Moreover, the heating reduces the thermal influence on the hydrogen permeable membrane and stabilizes the performance. Further, as in the invention according to claim 7, by using a stopper, the collar can be easily hermetically fixed, and the stopper serves as a protective means when the hydrogen separation module is handled.

  Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. 1A is a plan view illustrating a composite membrane 1 for hydrogen separation according to the present invention, FIG. 1B is an end view thereof, and FIG. 1C is an exploded view thereof. The hydrogen separation composite membrane 1 can be used alone, or used to form the hydrogen separation module 3 illustrated in FIGS. 6 and 7, for example. In this embodiment, as shown in FIGS. 1B and 1C, the hydrogen separation composite membrane 1 includes, for example, a rectangular thin film sheet-like hydrogen permeable membrane 2 and at least one side of the outer edge of the hydrogen permeable membrane 2, In this embodiment, there are two hollow edge members 5 and 5 which are arranged over the entire outer edge and are integrally coupled.

  The hydrogen permeable membrane 2 is a metal film that selectively transmits hydrogen gas, and the principle of selectively transmitting only hydrogen is, for example, “functional material” (2003 No. 4, P76 to 87). ) Etc., for example, in the case of a Pd alloy, when hydrogen molecules in the source gas come into contact with the Pd film, at that moment, they dissociate into hydrogen atoms and ionize, and pass through the Pd film as protons. It is explained that when it reaches, it becomes a hydrogen molecule by combining with electrons.

  In order to improve such characteristics as hydrogen permeation performance, durability, or workability, for example, in addition to Pd metal, for example, 10 mass% or more (preferably 20% to 50%) of Cu, Ag, or Au is used. There are Pd alloys such as Pd—Ag alloy and Pd—Cu alloy containing any one or more of them. Furthermore, V and V—Ni based metals can be alloyed and amorphous can be used. Further, for other purposes, a trace amount of a third element can be added in combination. As the third element in this case, for example, one or more selected from group VIII elements such as Pt, Rh, Ru, In, Fe, Ni and Co, and group VIa elements such as Mo, the amount of which is Preferably it is 5 mass% or less. The Pd—Ag alloy containing 20 to 45% by mass of Ag improves the hydrogen permeation performance, and the Pd—Cu alloy containing 35 to 45% by mass of Cu has durability along with the hydrogen permeation performance. Can be increased. In order to obtain desirable “hydrogen permeation performance”, the type, amount, and composition of the metal composition are adjusted in advance, and a film-like body having a thickness of about 30 μm or less, which is difficult to maintain the film shape by itself, is used. Here, “hydrogen permeation performance” refers to the property of selecting and permeating only hydrogen gas. For example, it is confirmed by measuring the hydrogen purity of the permeated gas with a mass flow meter. The purity of the hydrogen gas according to the present invention is usually desirably 99.99% or more.

  The hydrogen permeation performance capable of permeating hydrogen is related to the film thickness, and the permeation time can be shortened by making it as thin as possible, and a thickness of 30 μm or less is usually used. That is, when the thickness exceeds 30 μm, it takes a long time for hydrogen protons to pass through the membrane, and the hydrogen permeation efficiency decreases. Further, the amount of expensive Pd alloy used can be reduced by thinning the film. On the other hand, thin film materials with excessively thin thickness are difficult to handle, easily damaged, and susceptible to microscopic segregation and internal defects such as pinholes, affecting separation accuracy and life. Therefore, the thickness is usually set to 2 μm or more. More preferably, the thickness is about 5 to 25 μm.

  Since the Pd alloy is relatively rich in workability, for example, a rolled film formed into a thin film by rolling is used. For example, a cold working performed in a normal room temperature environment or a warm working performed in a state preliminarily heated to a predetermined temperature can be employed as the rolling process, but the cold working is usually performed. By such rolling, internal defects can be greatly reduced or refined, and the toughness is improved, so that the service life can be extended and the present invention can be applied to various forms. In addition, metal dissolution does not generate segregation, non-metallic inclusions, various compounds, and other inevitable impurities, and high purity dissolution methods such as vacuum melting using a cold crucible, double melt method, etc. Adopted.

  FIG. 2 shows a rolling process of the Pd—Ag alloy (the main composition is Pd: 77%, Ag: 23%) as an example for confirming the quality of the rolled film (perform this test to observe the structure). Is a micrograph of the microstructure of a hydrogen-permeable membrane that has been subjected to heat treatment repeatedly and cold-worked to a thickness of 20 μm and further heat-treated at 800 ° C., magnified 1000 times. The roll-formed film is structurally stable and free of pinholes, improves mechanical properties such as elasticity and toughness, and has good hydrogen permeation performance.

  As described above, the hydrogen permeable membrane 2 has, for example, a rectangular shape. Therefore, the hydrogen separation composite membrane 1 is also formed in a rectangular shape in this example.

  The edge member 5 is arranged over at least one side s of the outer edge of the hydrogen permeable membrane 2, in this embodiment, all the outer edges 2 a to 2 d, that is, the entire periphery. Therefore, as shown in FIG. 1B, the edge member 5 is provided with an inner hole 6 along the outer edges 2a to 2d of the hydrogen permeable membrane 2 and smaller than the entire peripheral shape of the outer edges 2a to 2d. Reference numeral 5 denotes a thin sheet body that is hollowed out in a frame shape having inwardly facing inner edges 5a to 5d. The edge member 5 has a width w5B extending from the outer edges 5e to 5h to a position where the outer edges 5e to 5h protrude beyond the outer edges 2a to 2d.

  Therefore, the inner edges 5a to 5d of the edge member 5 are parallel to the outer edges 2a to 2d of the hydrogen permeable membrane 2, and the edge member 5 is overlapped with the hydrogen permeable membrane 2 and joined together. In this embodiment, the edge members 5 are arranged on both the upper and lower surfaces of the hydrogen permeable membrane 2. As a result, an overlapping portion 5A is formed over the entire circumference between the inner edges 5a to 5d of the edge member 5 and the outer edges 2a to 2d of the hydrogen permeable membrane 2. Further, by this superposition, a flange 5B consisting of a protruding portion is formed on the outer periphery of the outer edges 2a to 2d between the outer edges 2a to 2d of the hydrogen permeable membrane 2 and the outer edges 5e to 5h of the edge member 5. Has been. Note that the width w5A of the overlapping portion 5A and the width w5B of the flange 5B can be the same or different over the entire circumference. The width w5A of the overlapping portion 5A is usually 2 to 50 mm, preferably 3 to 15 mm, and the width w5B of the flange 5B is usually 3 to 50 m, preferably 3 to 15 mm. The width w5A of the overlapping portion 5A and the width of the flange 5B The strip width w5 of the frame, which is the total width of w5B, is about 4 to 100 mm, preferably about 5 to 40 mm. Also, as in the present embodiment, the thickness is 0.5 to 20 μm, preferably 1 to 15 μm when the film is attached to both surfaces of the hydrogen permeable membrane 2, and 1 to 100 μm when disposed only on one side, Preferably, it is about 2 to 60 μm, and the thickness (total thickness when there are a plurality of sheets) is about 1.1 to 2.2 times the thickness of the hydrogen permeable membrane 2 to enhance the reinforcing effect. By such setting, a substantial decrease in the effective permeation area of the hydrogen permeable membrane 2 can be suppressed, and a flange 5B for isolating the hydrogen permeable membrane 2 is formed on the outside thereof. The flange 5B of the edge member 5 is used as a protective means for protecting the hydrogen permeable membrane 2 in strength when the hydrogen permeable membrane 2 is attached to a member such as an apparatus such as a hydrogen separator, and is welded or brazed. As a thermal protection means for preventing the heating from directly affecting the hydrogen permeable membrane 2 during heating by, for example, the hydrogen permeable membrane 2 is protected and reinforced to enhance the handling of the hydrogen permeable membrane 2.

The overlapping portion 5A is coupled without causing a leak. Here, “without leaking” refers to forming a continuous coupling portion 7 that is continuously and reliably coupled without hydrogen leakage at each side s to which the edge member 5 of the hydrogen permeable membrane 2 is attached, and When there is a connecting portion 7 that intersects the adjacent side s, it means that there is no leak continuously over the adjacent sides s. It should be noted that the presence or absence of leakage at the joint or the like is determined by whether more permeable He is used and the level is 1 × 10 ⁻¹⁰ P am ³ / sec or less.

  As this bonding method, for example, a heat bonding method such as diffusion bonding, pressure welding, or welding can be used. In particular, in seam welding, the width of the joint portion 7 can be reduced to narrow the heat affected zone, and a strong, uniform and stable joint state can be continuously obtained with high productivity. Further, according to this method, for example, the hydrogen permeable membrane 2 and the edge member 5 in the vicinity of the heating portion are perforated, and damage such as penetration and reduction can be reduced.

  Here, the edge member 5 is formed using a metal that is compatible with the hydrogen permeable membrane 2 in order to stably bond with the hydrogen permeable membrane 2 without leaks. Here, the “affinity metal” refers to a metal that is dissimilar to other metals, but is stable in metallurgy, and can be strongly heat-bonded without creating a different phase such as a carbide or an intermetallic compound. As an example, one of the constituent elements constituting the hydrogen permeable membrane 2, or a metal or alloy containing the same group element having the same group relationship with the element, or a metal having both the same crystal structure Material can be selected. In the former case, in the case of a metal or an alloy containing any one of the constituent elements, or a congener element that has the same genera as a related element, the amount of the element is, for example, 5% by mass or more.

  As the edge member 5, when the metal of the hydrogen permeable membrane 2 is a Pd alloy, the edge member 5 is made of any metal element such as Pd, Ag, or Cu constituting the metal (alloy), or these metal elements and metallurgy For example, a congener element such as Cu, Ni, or Ag that can be bonded with a stable and strong affinity is selected. These metals have a face-centered cubic structure similar to the constituent elements of the hydrogen permeable membrane 2, and the interatomic bonding state approximates, and the occurrence of heterogeneous defects as described above due to heat bonding does not occur, preventing performance and quality deterioration. In addition, it is possible to obtain a reliable coupling state. Furthermore, since the target gas is hydrogen, it is also preferable to use an oxygen-free copper material having oxygen of 0.001% or less as shown in, for example, JISH2123, which does not cause hydrogen embrittlement. Ag is excellent in spreadability and is preferable when the crease is drawn. As for the edge member 5, it is preferable that the thermal expansion coefficient between the hydrogen permeable membrane and the hydrogen permeable membrane be selected so that thermal distortion does not occur between the two metals. Alloy materials obtained by adding other elements to Cu, Ni, and Ag can also be used.

  Further, the edge member 5 is provided over the entire outer edges 2a to 2d so as to surround the entire side s of the hydrogen permeable membrane 2, as shown in FIG. 1, for example, as shown in FIG. For example, two sides s of the two outer edges 2a and 2b of the hydrogen permeable membrane 2 facing each other may be formed on three sides s depending on the attachment state. As shown in FIG. 4B, when the straight belt-like edge member 5 is connected to another adjacent side s, the edge member 5 can be cut into the shape in advance. In addition, also when using the linear strip | belt-shaped edge member 5, the connection part 7 is made to continue in each corner part.

  Further, the edge member 5 may be bent as shown in FIG. 3A and disposed on both sides of the outer edge portion of the hydrogen permeable membrane 2 as shown in FIG. 3B. It can also be arranged only on one side of the permeable membrane 2. In the sandwiched structure in FIG. 3A (sandwich structure), the degree of bending in bending can be reduced, and the occurrence of delamination, cracks, and the like is suppressed. In these cases, one surface of the hydrogen permeable membrane 2 and one surface of the edge member 5 are aligned to form a flat surface, which facilitates attachment to a member having a flat surface.

  FIG. 6A shows one form of the hydrogen separation module 3 using the above-described composite membrane 1 for hydrogen separation. In this embodiment, the hydrogen separation module 3 is formed as a cylindrical product having a circular cross section and extending in the axial direction. ing. The upper half is shown in cross section. The hydrogen separation module 3 includes a porous support 11 that supports the hydrogen separation composite membrane 1 on the downstream side in which hydrogen gas passes from the outside to the inside in this example, and the porous support 11 includes Has a holding portion 15 that fixes at least the flange 5B of the edge member 5 of the composite membrane 1 for hydrogen separation without causing leakage.

  In FIG. 6A, the porous support 11 has a base 14 that is porous and receives the hydrogen permeable membrane 2, and a through hole 18 that is disposed at one end on the hydrogen gas extraction side. One end fitting 16A to be formed and an end cap-like end fitting 16B which closes the other end of the base portion 14 in this embodiment, which are fitted with a spigot and integrated by fixing means such as welding as appropriate. Yes. In this embodiment, the outer peripheral surfaces of the end fittings 16A and 16B constitute the holding portion 15 to which the hydrogen separation composite membrane 2 is attached.

  The end fitting 16A is provided with a threaded portion 16Ac on a short cylindrical portion 16Aa having an outer peripheral surface having the same diameter as the base portion 14 via a hexagonal latching portion 16Ab, and the through hole 18 is opened. . Further, the end fitting 16B closes the inside of the short cylinder portion 16Ba having the outer peripheral surface having the same diameter as the base portion 14 by a cover portion 16Bb.

  In the present embodiment, the base portion 14 is a porous cylindrical body in which a large number of openings 14a are provided over the entire surface, for example, a perforated porous plate formed into a cylindrical shape, for example, a porous plate having a thickness of about 0.1 to 2 mm. In addition to the above, various porous materials such as a wire mesh, an expansion mesh, a powder sintered body, and the like can be used.

It is also preferable to form a barrier layer at least in the contact area with the hydrogen permeable film 2 in order to prevent atomic diffusion at the contact interface with the hydrogen permeable film 2 disposed on the surface. For this barrier layer, for example, TiN, ceramic, or metal oxide is adopted. In particular, in the case where a ceramic made of magnesia stabilized zirconia (also referred to as OZM, for example, ZrO ₂ -MgO (24%)) is coated, Since the coefficient of thermal expansion is close to that of the base metal such as the perforated plate (for example, stainless steel), the difference in the degree of thermal change due to heating and cooling during the use process is small, and the barrier layer itself is cracked or peeled off. Can solve such problems. In addition, as thickness of this barrier layer shape | molded, it shall be about 0.5-100 micrometers, for example. The purpose cannot be achieved with a thin film having a thickness of less than 0.5 μm. On the other hand, a thin film with a thickness exceeding 100 μm increases the processing cost of the film or increases the risk of delamination. Preferably it is 5-50 micrometers, More preferably, it is 15-45 micrometers.

  Moreover, as a method of forming this barrier layer, for example, a method in which the ceramic particles (for example, a particle diameter of 0.01 to 20 μm) are suspended on the base of the porous body and a gelled suspension is applied and fired, Alternatively, a method of spraying the ceramic particles can be employed relatively easily. For example, as an example of the latter thermal spraying method, in addition to a method of pre-cleaning the porous metal body of the base, followed by powder spraying by heating at a high temperature with a low pressure plasma spraying apparatus, the coating film is a TiN coating film, for example, A CVD method can be employed. Selection of the type of the technology and the processing conditions can be arbitrarily set in consideration of the material, shape, dimensions, formed film thickness, and the like of the support itself to be coated.

  When such fine particles are formed by thermal spraying, the outer surface can be microscopically formed with fine irregularities such as fine particles deposited, and contact with the hydrogen permeable film placed on the surface is not possible. Since this is a local point contact, a micro flow channel through which permeated hydrogen gas flows can be formed at the contact interface between the two. Therefore, when using an uncoated support as in the prior art, for example, in a smooth portion other than the opening of the support, it is in close contact with the permeable membrane, resulting in a substantially dead space and an effective transmission area. The problem that was reduced can be solved. Therefore, the hydrogen gas transmission efficiency can be greatly increased. Further, as shown in FIG. 6A, when the porous support member 5 is assembled by close fitting of the base portion 14 and the end fitting 16, the base portion 14 may be made of a non-metallic material such as ceramic other than metal. it can.

  Such a hydrogen separation module 3 includes the base 14 of the porous support 11, the hydrogen separation composite membrane 1, preferably the hydrogen permeable membrane 2, and the edge member 5 ( The collar 5B alone may be positioned) and wound, and the mating portions are welded into a cylindrical shape. Further, a wide ring-shaped stopper 21 is externally fitted to the holding portion 15 via the edge member 5, and the stopper 21 is attached together with the flange 5 </ b> B and the end fitting 16 of the edge member 5. Can be joined without causing leakage by welding. In some cases, the stopper 21 can be omitted. Prior to the co-welding, the gap Y due to the thickness change between the hydrogen permeable membrane 2 and the edge member 15, which tends to occur between the inner surface of the stopper 21 and the holding portion 15, is appropriately combined with the co-welding W. It can embed by sealing means S, such as. Further, the outer diameters of the stopper 21 and the holding portion 15 may be formed with steps or the like according to the thickness variation.

  The hydrogen separating member 1 is connected in the length direction by, for example, a coupling portion 26 that couples flanges 5B and 5B that extend in the length direction and face each other along the welding line X as shown by a one-dot chain line shown in FIG. Combine. In this case, the hydrogen permeable membranes 2 may be directly overlapped and bonded. The hydrogen separation module 3 is shown as a cylindrical product having an outer diameter of 10 to 200 mm and a length of about 50 to 1000 mm, for example.

  Thus, in the hydrogen separation module 3, the hydrogen separation composite membrane 1 is indirectly attached to the porous support 11 by the flange 5B of the edge member 5 that is separated outward from the hydrogen permeable membrane 2, and Since the welding heat at the time of attachment is isolated by the edge member 5, it is possible to reduce degradation of the performance of the hydrogen permeable membrane 2. As shown by the arrow direction in FIG. 6A, the raw material gas supplied by such a configuration flows from the outside to the hydrogen permeable membrane 3 to be separated into hydrogen, and the hydrogen gas is supplied to the end of the porous support 11. Although it is taken out from the through hole 18 of the metal fitting 16A and carried out to the next process, when the supply pressure is large, it is pressed by the support 14 and may be deformed along the opening 14a to cause damage. The gas supply direction can also be reversed.

  In the present embodiment, the other end fitting 16B is exemplified by the end cap that seals one end. However, as shown in FIG. 7, the other end fitting 16B is connected to a screw port of another hydrogen separation module 3. An end fitting 16B1 provided with a screw hole can also be used, and a large-capacity hydrogen separation membrane reformer in which a suitable number of pieces are connected can also be configured.

  On the other hand, the stopper 21 strengthens the bond of the hydrogen separation composite membrane 1 and is used for temporary fixing or surface protection. For example, when the hydrogen separation module 1 is the cylindrical body, it is formed in a wide ring shape having a diameter that can be fitted to the cylindrical body. In addition, since the stopper 21 becomes a dead space in the case of hydrogen permeation as shown in FIG. 6A, it is preferably set to be equal to or less than the width w5 of the edge member 5. Thereby, it can suppress that the effective permeable area of hydrogen permeable membrane 2 itself is reduced. From such a surface, for example, a stainless steel ring having a width of about 1 to 10 mm and a thickness of about 0.5 to 2 mm and having heat resistance and corrosion resistance is used as the stopper 21.

  Further, as shown in FIG. 6 (B), the porous support 11 is connected to the edge member 5 (the flange 5B or the hydrogen permeable membrane 2) by pushing the separation module 1 inward in the axial direction. In order to press firmly on the outer peripheral surface of the porous support 11 (including the end fitting 16) and fix it firmly and airtightly, the taper is pressed so as to increase in diameter toward the inner side in the axial direction. The surface can be formed on at least one of the outer peripheral surface of the porous support 11 and the inner peripheral surface of the stopper 21, preferably both. The taper angle θ is preferably about 10 to 40 °.

  Further, the stopper 21 can be omitted when the bonding strength between the hydrogen separation composite membrane 1 and the porous support 11 is high, and when the hydrogen separation module 1 is formed in a flat plate shape, for example, It can also be made into the frame shape shape | molded in frame shape according to the shape.

  Further, as the hydrogen separation module 3, for example, as shown in FIG. 8, an annularly formed hydrogen separation composite membrane 1 shown in FIG. 5A and 5B illustrate a case where the hydrogen separation composite membrane 1 is formed in a pleated shape. The hydrogen permeable membrane 2 is creased at a predetermined angular pitch (α), and a mesh 9 is overlapped along the inner surface of the hydrogen permeable membrane 2. Thereby, the fold shape of the thin hydrogen permeable membrane 2 can be maintained. And since both are not couple | bonded, the shape change which expand | swells or shrinks | contracts accompanying the heating and cooling operation at the time of use can be followed, and problems, such as a crack by heat fatigue and pinhole generation | occurrence | production, can be improved. In addition, the total area of the hydrogen permeable membrane 2 is increased and the effective hydrogen permeable area is increased. The edge member 5 is disposed at the end of the fold-like hydrogen permeable membrane 2. In this embodiment, the edge member 5 is curved in contact with the outer peripheral surface of the hydrogen permeable membrane 2 and joined without leakage, and the protruding portion from one side s of the hydrogen permeable membrane 1 forms the flange 5B. It can be used for corner welding by beam to member C.

  The mesh 9 is made by weaving a wire W using a refractory metal having a melting point higher than that of the hydrogen permeable membrane 2, for example, 1800 ° C. or more, preferably 2000 ° C. or more. A net material obtained by plain weaving or twill weaving of fine wires of about 30 to 100 # is used. In addition, for example, knitted knitted fabrics and expanded meshes can be used.

As the refractory metal, for example, molybdenum, vanadium, niobium, tantalum and the like, and those having the above-described melting point obtained by adding other third elements to these are suitable. These metals prevent diffusion even when in contact with the hydrogen permeable membrane 2, and provide the pressure resistance and shape maintenance. In particular, the molded mesh made of the molybdenum wire has a very high melting point of about 2600 ° C., and the difference between the melting points is 1000 ° C. or more, thereby preventing mutual diffusion of the two, and its mechanical properties are, for example, 250 even in the soft state. , a high modulus of elasticity of about 000~350,000N / mm ^2, has a 400~600N / mm ² approximately yield strength, another advantage of the spring-back can be reduced easily shaping when shaping the creasing is there. Therefore, it is preferable that a thinner wire can be used.

  In addition, in the form of FIG. 8, the meshes 9 and 9 are arranged on the outer surface as well as the inner surface. The porous support 11 is disposed on the radially inner side of the mesh-protecting pleated hydrogen separating member 1, and the hydrogen separating member 1 is separated from the outer end of the hydrogen separating member 1 on the radially outer side. A porous outer cylinder 27 surrounding the member 1 is arranged.

In addition, a catalyst powder G that enhances hydrogen separation performance is filled in a gap S1 between the hydrogen separation member 1 and the porous outer cylinder 27. The catalyst G is arbitrarily selected depending on the type of raw material gas used, processing conditions, and the like. For example, since the raw material gas reacts with CH ₄ + 2H ₂ O → 4H ₂ + CO ₂ in the case of hydrocarbons and CH ₃ OH + H ₂ O → 4H ₂ + CO ₂ with methanol, for example, Fe, Co, Ni, Ru, Rh, Those containing a first group metal such as Pt, Nio, etc. are selected, and usually have a particle size of, for example, about several hundred μm to several mm.

  Further, in the gap S2 formed between the inside of the hydrogen separation composite membrane 1 and the porous support 11, the hydrogen permeable membrane 2 of the hydrogen separation composite membrane 1 is formed in order to keep the gap S2. It is also possible to load a particulate filler using a material that does not impair the function. FIG. 7 is a partial cross-sectional view of the module 3 using the separation composite membrane 1 creased in this way.

  In addition to the cylindrical shape, for example, the hydrogen separation module 3 includes, for example, two hydrogen separation composite membranes 1 and 1 with a gap therebetween, and the raw material gas is placed in the gap around the periphery. It is also possible to form a flat hollow module for taking out purified hydrogen gas to the outside by disposing a frame body provided with through holes for injection or hydrogen gas extraction, and tightly closing and integrally bonding. Also in this case, since the flange of the edge member around the hydrogen separation member 1 is attached to the inner and outer surfaces of the frame body by welding or the like, the direct thermal influence on the hydrogen permeable membrane 2 can be reduced. High quality and long life products are possible. Accordingly, the present invention can be variously used as a small and simple high-purity hydrogen generator, for example, in a wide range of fields such as the fuel cell, semiconductor industry, and optical fiber manufacturing.

(Example 1)
<< Hydrogen permeable membrane >>: An ingot obtained by vacuum melting a Pd-23 mass% Ag alloy was used as a raw material, and this was thinned into a sheet having a thickness of 15 μm while being repeatedly rolled and heat-treated. The final rolling process was performed with a rolling mill at a reduction rate of 15% to obtain a hydrogen permeable membrane. The hydrogen permeable membrane used here has a size of width 100 mm × length 200 mm. This Pd—Ag metal had a purity of 99.99% by vacuum melting.
<< Edge member >>: A Cu sheet material having a thickness of 30 μm and a width of 15 mm, and having a purity of 99.8%. The Cu is in the same genera as the constituent element Ag of the permeable membrane.

  And the said edge member was overlap | superposed on the one surface side of the both ends along the length direction of the said hydrogen permeable film, respectively, and the overlap part was seam-welded and the composite film was formed. The seam welding was performed under the conditions of a welding width of 2 mm, a welding current of 40 A, and a welding speed of 0.6 m / min, and the edge member was such that only a part of the end of the hydrogen permeable membrane overlapped. Aligned. As a result, a flange having a width of about 10 mm where the hydrogen permeable membrane does not exist is formed outside the edge member. In addition, although the peeling test was done in order to see the joint strength of this weld part, both metals were firmly joined and peeling etc. did not arise. Moreover, the welding state was uniform as a whole and no leaks were observed.

  Next, in order to make this composite membrane into a cylindrical shape, the short sides are simultaneously overlapped so as to have a diameter of 32 mm, and the overlapped portion is seam-welded in the same manner as described above to form a cylindrical composite for hydrogen separation. A membrane was obtained. In this configuration, the edge member is disposed at the circumferential length at both ends.

  On the other hand, a stainless steel punching plate having a thickness of 100 mm and an opening having a diameter of 1 mm over the entire surface provided at intervals of about 1.5 mm as a porous support is formed into a cylindrical body having an outer diameter of 32 mm. The OZM layer having a thickness of 25 μm was formed as a barrier layer on the surface thereof by using a plasma spraying apparatus, and a firm ceramic layer was formed almost uniformly.

  As shown in FIG. 6 (A), the end cap prepared in advance as shown in FIG. 6 (A) is fitted to both ends of the cylindrical body so as to form a porous support body, and the composite membrane cylinder body is inserted on the support body. At the same time, a module in which both end portions were respectively squeezed but a separate ring-shaped end fitting was fitted and the end surfaces thereof were co-welded to obtain an integrated module. Although this welding was performed through the flange of the edge member, this flange was substantially the same as the height of the end fitting, and the transmission area was hardly reduced.

Example 2
The same hydrogen permeation membrane as obtained in Example 1 (width 100 mm × length 200 mm, thickness 20 μm) is hollowed out in a frame shape so that the overall width is 20 mm and the flange width is 10 mm. Sandwiched between two edge members made of an oxygen-free copper (O: 0.0005% or less) sheet material having a thickness of 30 μm, and the overlapped portion is seam welded in the same manner as in Example 1 to form a composite film. Produced.
FIGS. 11 (A) and 11 (B) show the cross-sectional photograph (100 times) in the thickness direction of the joint and the results of line analysis (based on X-ray fluorescence analysis) measured corresponding to the thickness direction. Show. As can be seen from this result, the diffusion width at the boundary between the two metals was limited to a very narrow region, and a good bonding state was obtained.

  The composite membrane thus produced was wound on the surface of the porous support with a barrier layer produced in the same manner as in Example 1, and the butt portion was welded. Further, ring-shaped holding metal fittings were provided at both ends thereof. Then, the support, the flange of the composite membrane, and the holding metal fitting were integrally attached and joined together by TIG welding to obtain a hydrogen separation module without leakage. The effect of heat on the hydrogen permeable membrane due to this integral bonding can be suppressed by the collar, and wrinkles and deformation such as thermal strain can be prevented.

Example 3
In order to see the bonding performance with other permeable membrane alloys, Pd-35% Cu alloy and V-Ni alloy are used as the hydrogen permeable membrane, while the edge member is made of the same oxygen-free copper sheet material as described above. Using line analysis to see the bonding state and the diffusion state when seam welding was used, it was confirmed that both were well bonded without leakage.

Example 4
The outer periphery of a hydrogen permeable membrane having a width of 100 mm and a length of 500 mm made of a Pd-23 mass% Ag alloy having a thickness of 20 μm similar to that used in Example 1 overlaps the entire periphery of the outer edge. The two edge members made of the same oxygen-free copper as used in Example 2 having a thickness of 20 μm, which are hollowed out in a frame shape as described above, are stacked in a sandwich shape, and the overlapping portion is seamed in the same manner as described above. The composite film was formed by welding. In addition, the used edge member was a frame-shaped thing dimensioned so that the width | variety might be set to 15 mm in width 15mm, and the joint state was favorable.

  And on both sides of this composite film, two shape-keeping meshes (# 100) made of molybdenum metal thin wires with a wire diameter of 0.2 mm and having the same size are arranged and sandwiched. While the laminated product was supplied to a crease-folding machine, a molded laminated film corrugated at a peak height of 20 mm and a pitch of 6.5 mm was obtained.

  In this state, the hydrogen permeable membrane and the shape retaining mesh were in close contact with each other, but were in close contact with each other, and there was little return of spring back and the like, and a pleated shape could be easily imparted. Further, in this state, the membrane material has elasticity as a whole, and it becomes possible to impart a pleat shape that cannot be obtained only by the hydrogen permeable membrane, and the mesh texture of the mesh is transferred to the surface of the hydrogen permeable membrane, There were no problems such as cracks in the seam weld.

  Therefore, the tip flanges of the folded composite film are butted and welded to form a bellows-like cylindrical body, and this is a perforated perforated plate (punching) having an outer diameter of 32 mm, a length of 100 mm, and a thickness of 0.9 mm. Plate: made of SUS316 stainless steel) is fitted into an interior cylindrical support body, and a similar exterior cylindrical porous body is concentrically arranged on the outside, and combined with end fittings 16 disposed at both ends thereof. 7 and 8 were produced. In this embodiment, the gaps S1, S2 between the inner and outer porous bodies 11, 27 and the shape retaining mesh 9 are filled with catalyst powder for promoting reforming, The connection between the end fitting 16 and the permeable membrane is performed by welding through the flange 5B of the edge member 5 so as not to leak from the outside.

<< Test 1 >> Hydrogen Permeation / Thermal Cycle Test Therefore, in order to evaluate the performance of the hydrogen permeation module obtained in Example 2, each was mounted in a predetermined housing container and heated to a temperature of 600 ° C. The hydrogen gas permeation performance and temperature are repeated 100 times in total after the hydrogen mixed raw material gas is supplied under the condition of a differential pressure of 0.1 MPa and hydrogen permeation is performed for 1 Hr, and then replaced with N 2 gas and cooled. The presence or absence of cracks associated with the raising and lowering of the steel was investigated. In this test, the permeated hydrogen gas had a purity of 99.99% or more, and the barrier layer applied to the surface of the support had fine irregularities formed on the surface, and was in contact with the hydrogen permeable membrane. However, it is possible to form a complicated fine channel at the interface, and it is possible to discharge the hydrogen gas effectively using the entire surface of the permeable membrane. Further, neither cracks in the permeable membrane nor leakage of N2 gas was observed.

<< Test 2 >> Confirmation Test for Diffusion Occurrence Further, in order to see the presence or absence of diffusion in the thermal cycle test, Auger analysis of each metal element in the thickness direction by disassembling the module and cutting out the composite film including the hydrogen permeable film Was done. As a result, the permeable membrane could be effectively isolated by the barrier layer applied to the downstream support, and there were no systematic defects associated with intrusion of other metal elements, joints with edge members, and hydrogen embrittlement. In addition, as shown in the cross-sectional photograph of FIG. 11A, no significant systematic abnormality was observed at the joint between the edge member and the hydrogen permeable membrane, and the two horizontal lines in FIG. The line analysis results obtained by qualitative analysis are shown in FIG. 5B. The peaks of Pd and Cu are clear and the boundary width is very narrow and good.

<< Test 3 >>
Next, the module of Example 4 was also subjected to a hydrogen permeation / thermal cycle test and a confirmation test for systematic defects such as diffusion, similar to the above tests.
In this test, the module used was made bellows to increase the permeation area, so that the hydrogen permeation amount was 11 L / min. Since molybdenum metal having a high melting point of about 2600 ° C. is used as a shape-retaining mesh arranged on both sides of the permeable membrane, the above-mentioned porous for internal / exterior contact with this is used. Despite being made of stainless steel, diffusion with the hydrogen permeable membrane and the edge member could be prevented.

(A) is a top view which shows one form of the composite membrane for hydrogen separation, (B) is the 1-1 sectional view, (C) is an exploded perspective view. It is the structure | tissue photograph which expanded the metal structure of the hydrogen permeable film 1000 times. (A) is sectional drawing which illustrates the case where an edge member is attached to both surfaces of a hydrogen permeable membrane, (B) is sectional drawing which illustrates the case where an edge member is attached to one side. (A) is a top view which illustrates the other form of the member for hydrogen separation, (B) is a top view of the edge member used for (A). (A) is a cross-sectional view illustrating the case where the hydrogen separation member is pleated, and (B) is a front view in which a part of the 2-2 cross section of FIG. It is. (A) is a partial cross-sectional view showing an example of a module for hydrogen separation, and (B) is an end view illustrating a case where a porous support and a stopper are tapered. It is the partially broken front view which illustrates the module for hydrogen separation of another form. FIG. 8 is a cross-sectional view taken along line 3-3 in FIG. 7. It is a block diagram which illustrates a conventional hydrogen production process. It is a block diagram which illustrates the hydrogen assault process by a membrane reactor. It is the graph (B) which shows the cross-sectional photograph (A) of the coupling | bond part based on an Example, and the result of the line analysis.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrogen separation composite membrane 2 Hydrogen permeable membrane 2a-2d Outer edge 3 Hydrogen separation module 5 Edge member 5A Overlapping part 5B Overhead 5a-5d Inner edge 5e-5h Outer edge 7 Joint part 9 Mesh 11 Porous support body 14 Base 16, 16A, 16B End fitting 21 Stopper 18 Through hole W Joint

Claims (11)

  A thin film sheet-like edge member using a metal having an affinity for the metal of the hydrogen permeable film is provided on at least one side of the outer edge of the hydrogen permeable film made of a metal that selectively transmits hydrogen gas from the mixed gas. The edge member of the edge member that extends outwardly beyond the outer edge of the hydrogen permeable membrane by leaving the permeation surface on the membrane and overlapping the outer edge of the membrane and joining the overlapping portions without causing leakage. A composite membrane for hydrogen separation, characterized in that a flange by protrusion is provided integrally.   The edge member is formed by hollowing out an inner hole having an inner edge inside the outer edge of the hydrogen permeable membrane, and a frame shape in which the outer edge is provided outside the outer edge of the hydrogen permeable membrane, and The flange is formed over the entire periphery of the outer edge of the hydrogen permeable membrane by joining the overlapping portion between the edge member and the outer edge of the hydrogen permeable membrane without causing leakage. 2. A composite membrane for hydrogen separation according to 1.   3. The hydrogen according to claim 1, wherein the metal of the hydrogen permeable membrane is made of a Pd—Ag alloy or a Pd—Cu alloy and has a thin film shape that is cold-rolled to a thickness of 30 μm or less. Composite membrane for separation.   The said edge member was comprised with the thin film sheet material of the metal containing the same genus element of the same genus relation with either of the structural elements of the metal which comprises the said hydrogen permeable film. Composite membrane for hydrogen separation.   The said edge member is arrange | positioned on both sides of the one side or both surfaces of the said outer edge part of the said hydrogen permeable film, and is continuously seam-welded along the overlap part. The composite membrane for hydrogen separation in any one of -4.   A composite membrane for hydrogen separation according to any one of claims 1 to 5, comprising a porous member that is arranged on at least one side thereof and through which hydrogen gas that has permeated the raw material gas or the hydrogen permeable membrane can flow. The porous member has a holding portion for placing the flange of the composite membrane for hydrogen separation, and the overlapping portion of the flange and the holding portion is heat-bonded without causing leakage. Hydrogen separation module.   The composite membrane for hydrogen separation is supported by the porous member on the lower surface side, and a stopper is disposed at least on the upper surface side end of the flange of the composite membrane to hold the flange and the support. The hydrogen separation module according to claim 6, wherein the overlapping portion between the portion and the stopper is joined by co-attach welding.   The stopper has a ring shape, and the flange of the edge member is pressed between the porous support body formed in a cylindrical shape and the ring-shaped stopper that is fitted around the end of the support body. 8. The hydrogen separation module according to claim 7, wherein at least one of the pressing surfaces is tapered at an angle (θ) along an axial direction thereof to press the flange.   The porous support is a cylindrical base that receives the hydrogen permeable membrane and an end fitting that is disposed at the end of the porous support and forms the holding portion. The base and the end fitting are integrated by welding or close fitting. The hydrogen separation module according to claim 7 or 8, wherein the module is a hydrogen separation module.   The hydrogen separation module according to any one of claims 6 to 9, wherein the porous member has a surface in contact with the hydrogen permeable membrane that has been subjected to a finish treatment by ceramic spraying.   11. The hydrogen separation composite membrane according to claim 6, wherein folds along the axial direction for increasing the selective permeation area of hydrogen gas are formed over the entire surface. 11. The module for hydrogen separation as described.