JP2007190455A - Hydrogen separation membrane and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To maintain a hydrogen permeation performance of a hydrogen-permeable foil even if it is used for a long period of time and to certainly prevent the hydrogen-permeable foil from being peeling off from a porous reinforcement plate. <P>SOLUTION: A first intermediate layer 12, a barrier layer 13, a second intermediate layer 14 and an adhesion layer 15 are formed between the hydrogen-permeable foil 16 of the hydrogen separation membrane 10 and the porous reinforcement plate 11 in the order from the porous reinforcement plate 11 side. The first and second intermediate layers 12, 14 are constituted by at least one metal selected from the group consisting of metal elements of groups 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and 8 and having a melting point of 600°C or higher. The barrier layer 13 is constituted by a compound of at least one metal element selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y and Hf and at least one non-metal element selected from the group consisting of O, N, B and C. The adhesion layer 15 is constituted by at least one metal comprising Ag, Au, Cu, Pd or Pt. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hydrogen separation membrane suitable for use in a membrane reformer and the like and a method for producing the same.

  The membrane reformer is a hydrogen production apparatus that takes out pure hydrogen by placing a hydrogen separation membrane that selectively transmits only hydrogen in a reaction field of city gas and water vapor. An example of the structure of a conventional hydrogen separation membrane is shown in FIG. The hydrogen permeable foil 56 of the hydrogen separation membrane 50 can improve the hydrogen permeation performance by reducing the foil thickness. However, when the foil is thinned, the foil 56 is easily broken by the differential pressure between the reformed gas on the raw material side and the hydrogen gas on the permeate side. Therefore, the foil 56 is supported by the porous reinforcing plate 51 in order to prevent this breakage.

  If the foil 56 and the reinforcing plate 51 are in direct contact with each other, the element diffuses between the foil 56 and the reinforcing plate 51 during use of the hydrogen separation membrane, and the hydrogen permeability decreases. As a countermeasure, for example, Japanese Patent Laid-Open No. 5-76738 describes that a barrier layer 53 of ceramics or metal oxide is interposed between the foil 56 and the reinforcing plate 51. Japanese Patent Application Laid-Open No. 9-248416 describes that a metal oxide, carbide, boride, or nitride ceramic is used as such a barrier layer 53.

  In such a hydrogen separation membrane 50, the foil 56 expands and contracts greatly due to temperature changes and hydrogen absorption and release due to on / off, while the barrier layer 53 made of ceramics has small expansion and contraction. Therefore, there is a problem that peeling of the foil 56 from the barrier layer 53 occurs due to a difference in expansion coefficient. The foil 56 has a stable structural strength by being supported by the reinforcing plate 51 at a constant interval. However, when the foil 56 is separated from the reinforcing plate 51 by peeling off from the barrier layer 53 in this way, the foil 56 is buckled or wrinkled. There arises a problem that the foil 56 breaks due to the concentration of stress and deformation locally.

Therefore, Japanese Patent Laid-Open No. 2001-286742 discloses a metal made of Ag, Au, Pt, Al, Pd, or Ni between the barrier layer 53 and the foil 56 or between the barrier layer 53 and the reinforcing plate 51. It is described that the bonding strength between them can be improved by forming a layer.
Japanese Patent Laid-Open No. 5-76738 (paragraph 0012, FIG. 11) JP-A-9-248416 (paragraph 0039) JP 2001-286742 A (paragraph 0011)

  However, even if a metal layer made of the metals listed in Japanese Patent Application Laid-Open No. 2001-286742 is simply formed between the barrier layer 53 and the foil 56 or between the barrier layer 53 and the reinforcing plate 51, the bonding strength is surely obtained. However, there is still a problem that peeling of the foil 56 occurs.

  In view of the above problems, the present invention can maintain the hydrogen permeation performance of the hydrogen permeable foil even when used for a long period of time, and reliably prevent the hydrogen permeable foil from peeling from the porous reinforcing plate. An object of the present invention is to provide a hydrogen separation membrane that can be used and a method for manufacturing the same.

  In order to achieve the above object, a hydrogen separation membrane according to the present invention is a hydrogen separation membrane comprising a hydrogen permeable foil and a porous reinforcing plate that supports the hydrogen permeable foil, and the hydrogen permeable foil and the porous reinforcing plate. The first intermediate layer, the barrier layer, the second intermediate layer, and the adhesive layer are provided in this order from the porous reinforcing plate side, and the first and second intermediate layers are independent of each other. Selected from the group consisting of 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and Group 8 metal elements of the periodic table and having a melting point of 600 ° C. or higher. And the barrier layer is at least one selected from the group consisting of at least one metal element selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y and Hf and O, N, B and C. A compound with two non-metallic elements Is configured, the adhesive layer is one which is characterized Ag, Au, Cu, that are composed of at least one metal consisting of Pd and Pt.

  As described above, the second intermediate layer made of a predetermined metal having high adhesive strength between both the barrier layer and the adhesive layer is provided on the barrier layer, and the second intermediate layer is provided on the second intermediate layer. By providing an adhesive layer composed of another predetermined metal having high adhesive strength between both the intermediate layer and the hydrogen permeable foil, and providing the hydrogen permeable foil on the adhesive layer, the barrier layer, the second layer The adhesive strength between the interlayers of the intermediate layer, the adhesive layer, and the hydrogen permeable foil is increased, and therefore, the hydrogen permeable foil can be prevented from peeling off from the barrier layer. Moreover, it can prevent that a barrier layer peels from a porous reinforcement board by providing a 1st intermediate | middle layer also between a barrier layer and a porous reinforcement board. Therefore, even if a barrier layer capable of maintaining the hydrogen permeation performance of the hydrogen permeable foil even when used for a long time is provided between the porous reinforcing plate and the hydrogen permeable foil, the hydrogen permeable foil is porous. It is possible to reliably prevent peeling from the reinforcing plate.

  Another aspect of the hydrogen separation membrane according to the present invention is a hydrogen separation membrane comprising a hydrogen permeable foil and a porous reinforcing plate that supports the hydrogen permeable foil, wherein the hydrogen permeable foil is interposed between the hydrogen permeable foil and the porous reinforcing plate. The first intermediate layer, the barrier layer, and the adhesive layer are provided in order from the porous reinforcing plate side, and the surface of the porous reinforcing plate on the side adjacent to the first intermediate layer is Rz0.1. The intermediate layer is selected from the group consisting of 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and Group 8 metal elements of the periodic table And the barrier layer is made of at least one metal element selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y and Hf, and O. Selected from the group consisting of N, B and C Is composed of a compound of at least one non-metallic element, the adhesive layer is one which is characterized Ag, Au, Cu, that are composed of at least one metal consisting of Pd and Pt.

  Thus, since the 1st intermediate | middle layer, the barrier layer, and the contact bonding layer are provided on the surface of the porous reinforcement board which has predetermined | prescribed roughness, both surfaces of these each layer are uneven | corrugated shape. This uneven shape can drastically improve the adhesion between each layer, particularly between the barrier layer and the adhesive layer, and can prevent the hydrogen permeable foil from peeling off from the barrier layer. Therefore, even if a barrier layer capable of maintaining the hydrogen permeation performance of the hydrogen permeable foil even when used for a long time is provided between the porous reinforcing plate and the hydrogen permeable foil, the hydrogen permeable foil is porous. It is possible to reliably prevent peeling from the reinforcing plate.

  The concentration of the nonmetallic element in the compound constituting the barrier layer is determined in the film thickness direction of the barrier layer from the adjacent first intermediate layer to the second intermediate layer or the adhesive layer. It is preferable to change so that it may increase continuously or stepwise and then decrease continuously or stepwise.

  By tilting the composition of the compound and increasing the concentration of the metal element in the vicinity of the surface of the barrier layer, the first intermediate layer adjacent to the barrier layer and the first layer are maintained while maintaining the diffusion preventing function of the barrier layer. Adhesiveness with 2 intermediate | middle layers or an adhesive layer can be improved notably.

  Another aspect of the present invention is a method for producing a hydrogen separation membrane, comprising: a hydrogen permeable foil and a porous reinforcing plate that supports the hydrogen permeable foil; and a surface of the porous reinforcing plate. And 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and at least one metal having a melting point of 600 ° C. or higher in the periodic table. A first intermediate layer comprising: at least one metal element selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y and Hf on the surface of the first intermediate layer; A barrier layer composed of a compound with at least one nonmetallic element selected from the group consisting of O, N, B and C is formed, and Cr, Ni, Al, Ti, Y and rare earth are formed on the surface of the barrier layer Selected from the group consisting of elements A second intermediate layer made of at least one metal is formed, and an adhesive layer made of at least one metal made of Ag, Au, Cu, Pd and Pt is formed on the surface of the second intermediate layer. And forming the hydrogen permeable foil on the surface of the adhesive layer.

  According to another aspect of the method for producing a hydrogen separation membrane according to the present invention, in a method for producing a hydrogen separation membrane comprising a hydrogen permeable foil and a porous reinforcing plate that supports the hydrogen permeable foil, the surface of the porous reinforcing plate is After processing to a roughness of Rz 0.1 to 10 μm, on this surface, from 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and Group 8 metal elements of the periodic table Forming a first intermediate layer made of at least one metal having a melting point of 600 ° C. or higher selected from the group consisting of Al, Si, Zr, Ti, Mg on the surface of the first intermediate layer; Forming a barrier layer composed of a compound of at least one metal element selected from the group consisting of Ca, Y and Hf and at least one non-metal element selected from the group consisting of O, N, B and C; On the surface of this barrier layer Ag, Au, Cu, to form an adhesive layer comprised of at least one metal consisting of Pd and Pt, and forming the hydrogen permeable foil on the surface of the adhesive layer.

  The concentration of the nonmetallic element in the compound constituting the barrier layer is determined in the film thickness direction of the barrier layer from the adjacent first intermediate layer to the second intermediate layer or the adhesive layer. It is preferable to adjust the introduction amount of the non-metallic element when forming the barrier layer so that it increases continuously or stepwise and then decreases continuously or stepwise.

  As described above, according to the present invention, the hydrogen permeation performance of the hydrogen permeable foil can be maintained even when used for a long period of time, and the hydrogen permeable foil is reliably prevented from peeling from the porous reinforcing plate. It is possible to provide a hydrogen separation membrane that can be used and a method for manufacturing the same.

  Hereinafter, embodiments of a hydrogen separation membrane and a method for manufacturing the same according to the present invention will be described with reference to the accompanying drawings.

  FIG. 1 is a cross-sectional view schematically showing one embodiment of a hydrogen separation membrane according to the present invention. As shown in FIG. 1, the hydrogen separation membrane 10 includes a porous reinforcing plate 11 provided with a large number of holes 18 penetrating in the thickness direction, and a first provided on the surface of the porous reinforcing plate 5. An intermediate layer 12, a barrier layer 13 provided on the first intermediate layer 12, a second intermediate layer 14 provided on the barrier layer 13, and provided on the second intermediate layer 14 And a hydrogen permeable foil 16 provided on the adhesive layer 15.

  The porous reinforcing plate 11 is preferably made of a material such as Fe alloy such as plain steel or stainless steel, pure Ni, Ni alloy, pure Ti, Ti alloy, or Cr alloy. A particularly preferred material is stainless steel. Further, the shape can be a wave shape, a cylindrical shape, or the like in addition to a planar shape. The multiple holes 18 may be formed by forming a wire mesh or a nonwoven fabric with the above-mentioned material, or the multiple holes 18 may be formed by machining, laser processing, punching, etching, or the like. Note that the number of the porous reinforcing plates 11 may be one, or a plurality of porous reinforcing plates 11 may be joined. The thickness of the porous reinforcing plate 11 is preferably 0.1 to 1 mm.

  The first and second intermediate layers 12 and 14 are each independently composed of a group 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and Group 8 metal elements of the periodic table. And at least one metal having a melting point of 600 ° C. or higher. These metals have adhesive strength due to chemical bonding and diffusion of atoms at the bonding interface with the compound constituting the barrier layer 13 described later, the metal constituting the adhesive layer 15 and the material constituting the porous reinforcing plate 11. It has the feature of becoming higher. Specifically, the material of these intermediate layers 12 and 14 causes metal bonding with the adhesive layer 15 and the porous reinforcing plate 11. Further, it has a solid solubility limit of 0.1 at% or more with respect to O, N, B, and C of the barrier layer 13, and the barrier layer 13 to the intermediate layer 12, at the interface between the intermediate layers 12 and 14 and the barrier layer 13, The movement of O, N, B, and C atoms to 14 occurs, or thermodynamically stable oxides, nitrides, borides, and carbides are formed at the interface between the intermediate layers 12 and 14 and the barrier layer 13. It is.

  Further, since the metal constituting the intermediate layers 12 and 14 has a melting point of 600 ° C. or higher, the adhesive strength is maintained even when the temperature of the intermediate layers 12 and 14 is as high as 500 to 600 ° C. when the membrane reformer is used. Can be maintained. Particularly preferred metals are Cr, Ni, Al, Ti, Y and rare earth elements, and among these, Ni, Cr and Ti are more preferred. Each of the first and second intermediate layers 12 and 14 may be a single layer or two or more layers made of different metals. The first and second intermediate layers 12 and 14 may be made of an alloy containing two or more kinds of the above metals.

  The first intermediate layer 12 can be formed on the surface of the porous reinforcing plate 11 by vacuum deposition, sputtering, CVD, or the like. Since there are a large number of holes 18 on the surface of the reinforcing plate 11, a large number of holes 18 penetrating in the thickness direction are formed in the first intermediate layer 12 in the same manner as the porous reinforcing plate 11 by the above forming method. be able to. Similarly, the second intermediate layer 14 can be formed on the surface of the barrier layer 13 described later by vacuum deposition, sputtering, CVD, or the like. A number of similar holes 18 can be formed in the second intermediate layer 14. The thickness of each of the first and second intermediate layers 12 and 14 is preferably 0.05 to 2 μm.

The barrier layer 13 includes at least one metal element selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y, and Hf, and at least one non-metal selected from the group consisting of O, N, B, and C. It consists of a compound with a metal element. Examples of such compounds include Al ₂ O ₃ , SiO ₂ , ZrO ₂ , TiO ₂ , MgO, CaO ₂ , Y ₂ O ₃ , TiN, TiC, TiB ₂ , Si ₃ N ₄ , SiC, AlN, AlSiOx, TiAlN, MgO.Al ₂ O ₃ , 2MgO.SiO _{2 and the} like can be mentioned.

These compounds have the ability to prevent the diffusion of elements between the porous reinforcing plate 11 and the hydrogen permeable foil 16. A particularly preferable compound is a compound of a metal element of Si or Al and a non-metal element of N or O, for example, Si ₃ N ₄ or Al ₂ O ₃ . The barrier layer 13 may be a single layer or two or more layers made of different compounds.

  The barrier layer 13 can be formed on the surface of the first intermediate layer 12 by vacuum deposition, sputtering, CVD, or the like. Since there are a large number of holes 18 on the surface of the first intermediate layer 12, a large number of holes 18 penetrating in the thickness direction are formed in the barrier layer 13 in the same manner as the porous reinforcing plate 11 by the above formation method. can do. The thickness of the barrier layer 13 is preferably 0.1 to 30 μm.

  The adhesive layer 15 is made of at least one metal made of Ag, Au, Cu, Pd, and Pt. These metals are characterized by high adhesive strength with the metal constituting the second intermediate layer 14 and high adhesive strength with the hydrogen permeable foil 16. Particularly preferred metals are Ag and Au. The adhesive layer 15 may be a single layer or two or more layers made of different metals. Further, the adhesive layer 15 may be made of an alloy containing two or more of the above metals.

  The adhesive layer 15 can be formed on the surface of the second intermediate layer 14 by vacuum deposition, sputtering, CVD, or the like. Since there are a large number of holes 18 on the surface of the second intermediate layer 14, a large number of holes 18 penetrating in the thickness direction are also formed in the adhesive layer 15 in the same manner as the porous reinforcing plate 11 by the above formation method. can do. The hole 18 communicates from the reinforcing plate 11 to the adhesive layer 15. The thickness of the adhesive layer 15 is preferably 0.05 to 2 μm.

The hydrogen permeable foil 16 has a property of allowing only hydrogen to selectively permeate from a mixed gas containing hydrogen (for example, a reformed gas containing CH ₄ , H ₂ O, H ₂ , CO _2, etc.). It is. The hydrogen permeable foil 16 is preferably composed of a group 5 element (V, Nb, Ta) or an alloy thereof in addition to Pd or a Pd alloy. As the Pd alloy, an alloy composed of Pd and Ag, and an alloy composed of one or more metals selected from the group consisting of Y and rare earth elements and Pd are preferable. Particularly preferred Pd alloys are Pd—Ag alloys and Pd—rare earth element alloys. Alloys of Group 5 elements include alloys of two or more Group 5 elements, Group 5 elements and alloys of Group 8-11 elements such as Ni, Co, Pd, Cu, etc. Group 5 elements and Ti, Mo, Ag, Au A single layer or a stack of Cu alloys is preferable. The thickness of the hydrogen permeable foil 16 is preferably 0.5 to 20 μm. The hydrogen permeable foil 16 can be fixed on the surface of the adhesive layer 15 by superimposing on the surface of the adhesive layer 15 and performing diffusion bonding or brazing.

  According to such a configuration, the first and second intermediate layers 12 and 14 made of a predetermined metal are provided between the porous reinforcing plate 11 and the barrier layer 13 and between the barrier layer 13 and the adhesive layer. Are provided, and an adhesive layer 15 made of a predetermined metal is provided between the second intermediate layer 14 and the hydrogen permeable foil 16, so that the porous reinforcing plate 11, the first Adjacent layers of the intermediate layer 12, the barrier layer 13, the second intermediate layer 14, the adhesive layer 15, and the hydrogen permeable foil 16 are securely bonded. Therefore, even if the barrier layer 13 made of a predetermined compound having an excellent barrier property with respect to element diffusion is provided between the porous reinforcing plate 11 and the hydrogen permeable foil 16, the hydrogen permeable foil 16 Peeling from the porous reinforcing plate 11 can be reliably prevented.

(Other embodiments)
FIG. 2 is a cross-sectional view schematically showing another embodiment of the hydrogen separation membrane according to the present invention. In addition, the same code | symbol is attached | subjected about the structure similar to FIG. As shown in FIG. 2, in this embodiment, unlike FIG. 1, the second intermediate layer 14 is not provided between the barrier layer 13 and the adhesive layer 15. Instead, the porous reinforcing plate 11 is processed so that the surface on the side where the first intermediate layer 12 is adjacent has a roughness of Rz 0.1 to 10 μm. Such surface treatment can be performed by, for example, mechanical polishing or chemical polishing. A more preferable roughness range is Rz 0.5 to 5 μm. The surface roughness can be measured by using a stylus type surface roughness measuring machine according to JIS B 651, and Rz can be calculated according to JIS B 601.

  Since the surface of the porous reinforcing plate 11 has the above-mentioned roughness, both surfaces of the first intermediate layer 12, the barrier layer 13, and the adhesive layer 15 formed thereon are uneven. . Due to this uneven shape, the layer is deformed during bonding and fills the unevenness, whereby an anchor effect is generated and the adhesion between each layer, particularly between the barrier layer 13 and the adhesive layer 15 is dramatically improved. Therefore, even if the second intermediate layer 14 is not provided as shown in FIG. 1, it is possible to reliably prevent the hydrogen permeable foil 17 from peeling from the barrier layer 13. In addition, you may provide the 2nd intermediate | middle layer 14 like FIG.

  3 and 4 are graphs showing changes in the composition of the compounds constituting the barrier layer in the film thickness direction of the barrier layer. The composition of the compound constituting the barrier layer may be constant in the film thickness direction, but is preferably changed as shown in FIGS.

As shown in FIG. 3, the composition of the compound constituting the barrier layer 13 is such that the atomic percent of aluminum (Al) and oxygen (O) is about 40% and about 60% in the central portion 13a of the barrier layer. This shows that alumina (Al ₂ O ₃ ) is formed. On the other hand, the surface portion 13b of the barrier layer, in 13c, toward the surface from the center, O concentration is decreasing continuously, that is, from the Al concentration is increasing continuously, from Al ₂ O ₃ Also has an aluminum-rich composition.

  As described above, in the surface portions 13b and 13c of the barrier layer, the concentration of the Al element in the alumina is high, so that the element diffusion prevention function is lowered, but the adjacent intermediate layer and adhesive layer are made of metal. For this reason, the number of metal-metal bonds that have better adhesion than the alumina-metal bond increases, and thus the adhesion with the adjacent layers can be improved. Further, since alumina is formed in the central portion 13a of the barrier layer, an excellent diffusion preventing function is exhibited. Therefore, the barrier layer 13 as a whole can retain the diffusion preventing function.

  In FIG. 3, the composition of alumina is changed over the entire surface portions 13b and 13c of the barrier layer. However, as shown in FIG. The composition may be maintained. 3 and 4, the Al concentration on the surface of the barrier layer 13 is about 70%. However, the Al concentration on the surface of the barrier layer 13 is not limited to this, and the range is 50 to 80%. Can do. The film thickness of the central portion 13a of the barrier layer can be 40 to 90% of the film thickness of the entire barrier layer 13.

  As a method for forming a barrier layer in which the composition of the compound is tilted in this way, for example, when vacuum deposition of a compound constituting the barrier layer such as alumina is performed without supplying a nonmetallic element such as oxygen, When non-metallic elements such as aluminum are deficient and a compound with high metal element concentration such as aluminum-rich alumina is deposited, the supply amount of non-metal such as oxygen is continuously or stepwise when vacuum-depositing the barrier layer. By increasing or decreasing the concentration, a compound in which the concentration of the nonmetallic element is increased or decreased continuously or stepwise in the thickness direction of the barrier layer can be deposited.

  The hydrogen separation membrane 10 can be made into a hydrogen separation membrane module by bonding to a base member (not shown). For a planar hydrogen separation membrane module, for example, a hydrogen separation membrane is placed on a planar base member having a ventilation groove or hole, and the outer periphery is joined by brazing, diffusion bonding, seal welding, or the like. Can be produced. The cylindrical hydrogen separation membrane module can be manufactured, for example, by winding the hydrogen separation membrane 10 around the outer periphery of a tubular base pipe having a vent hole and performing seal welding on the outer periphery.

Example 1
A hydrogen separation membrane was produced by the following procedure. First, a porous reinforcing plate of SUS430 was set in a holder in a vacuum deposition apparatus, and the degree of vacuum in the apparatus was evacuated to 8 × 10 ⁻³ Pa or less. Then, after heating to 200 ° C., Ni was used as a raw material, and Ni having a thickness of 0.1 μm was vapor-deposited on the reinforcing plate at an EB voltage of 10 kV and an EB current of 0.2 A. Next, the EB voltage was set to 10 kV, the EB current was set to 0.3 A, Al ₂ O ₃ was used as a raw material, and vapor deposition was performed for 100 min while supplying an oxygen supply amount from an external cylinder at 50 sccm. As a result, alumina having a thickness of 2 μm was deposited on the Ni layer. The composition of the alumina layer was such that the atomic percent of Al and O was about 40% and about 60%. Further, there was no change in composition in the film thickness direction.

Then, the EB voltage was returned to 10 kV and the EB current was 0.2 A, and Ni having a thickness of 0.1 μm was deposited on the alumina layer using Ni as a raw material. Finally, an EB voltage of 10 kV and an EB current of 0.5 A were used, and Ag having a thickness of 0.2 μm was deposited on the Ni layer using Ag as a raw material. After completion of deposition, onto were deposited in the reinforcing plate faces, sets the hydrogen-permeable foil Pd alloy thick 20 [mu] m, pressing pressure 0.5 kg / mm ^2, joining time temperature 500 ° C., bonding time 60min, Diffusion bonding was performed at a degree of vacuum of 1 × 10 ⁻⁴ torr or less. Thereby, a hydrogen separation membrane was obtained.

(Example 2)
When performing vapor deposition of alumina, the oxygen supply rate at the start of vapor deposition is set to 0 sccm, and simultaneously with the start of vapor deposition, the oxygen supply rate is increased by 2.5 sccm / min. Then, the vapor deposition was performed for 60 minutes with the supply amount kept at 50 sccm, and then the oxygen supply amount was decreased at 2.5 sccm / min, the oxygen supply amount was set to 0 sccm at 20 minutes, and the vapor deposition of alumina was finished. A hydrogen separation membrane was produced by the same procedure as described above. The change in the composition of the alumina layer of this hydrogen separation membrane is shown in the graph of FIG.

(Example 3)
When performing vapor deposition of alumina, the oxygen supply amount at the start of vapor deposition is set to 0 sccm, the oxygen supply amount is increased at 2.5 sccm / min 5 minutes after the start of vapor deposition, the oxygen supply amount is increased to 50 sccm at 20 minutes, and the oxygen supply amount is increased to 50 sccm. After that, vapor deposition is performed for 50 minutes with the supply amount kept at 50 sccm, and then the oxygen supply amount is decreased at 2.5 sccm / min, the oxygen supply amount is set to 0 sccm at 20 minutes, and the oxygen supply amount is 0 sccm for 5 minutes. A hydrogen separation membrane was produced in the same procedure as in Example 1 except that the vapor deposition was finished. The change in the composition of the alumina layer of this hydrogen separation membrane is shown in the graph of FIG.

Example 4
Hydrogen was prepared in the same procedure as in Example 1 except that the surface of the porous reinforcing plate was polished to a roughness of Rz 0.5 μm and the Ni layer was not deposited between the alumina layer and the Ag layer. A separation membrane was produced.

(Examples 5 to 11)
The same procedure as in Example 1 except that instead of the Ni layer, a Cr, Al, Ti, Y, Ce, La layer or a Ni + Cr layer (Ni: 70%, Cr: 30%) was deposited. A hydrogen separation membrane was produced.

(Examples 12 to 15)
A hydrogen separation membrane was produced in the same procedure as in Example 1, except that each layer of Au, Cu, Pt, and Pd was deposited instead of the Ag layer.

(Examples 16 and 17)
A hydrogen separation membrane was produced in the same procedure as in Example 1 except that a Si ₃ N ₄ layer and a ZrO ₂ layer were deposited instead of the alumina layer.

(Comparative Examples 1-3)
A hydrogen separation membrane was produced in the same procedure as in Example 1 except that the Ag layer was not deposited. Moreover, the hydrogen separation membrane was manufactured in the procedure similar to Example 1 except the point which did not perform Ni layer vapor deposition between an alumina layer and an Ag layer. Furthermore, a hydrogen separation membrane was produced in the same procedure as in Example 1 except that no alumina layer was deposited and only one Ni layer was provided.

(Performance confirmation test)
Next, the hydrogen separation membranes of Examples 1 to 17 and Comparative Examples 1 to 3 were tested to evaluate the change in hydrogen permeation performance and the bonding strength of the hydrogen permeable foil. The results are shown in Table 1. The hydrogen permeation performance was measured under the conditions of an operating temperature of 550 ° C., a differential pressure of 0.2 MPa, a total operating time of 3000 h, and a start / stop frequency of 20 times.

※ 無：水素透過能力の減少が１０％未満。有：水素透過能力の減少が１０％未満。

* None: Reduction in hydrogen permeation capacity is less than 10%. Existence: Reduction in hydrogen permeation capacity is less than 10%.

  As shown in Table 1, in Comparative Example 1 without an Ag layer and Comparative Example 2 without an Ni layer between an alumina layer and an Ag layer, the hydrogen permeation performance was not deteriorated, but the bonding strength was weak. Peeling of the hydrogen permeable foil occurred. In Comparative Example 3 without the alumina layer, the hydrogen permeable foil was not peeled off, but the hydrogen permeation ability was deteriorated by 10% or more. On the other hand, any of the hydrogen separation membranes of Examples 1 to 17 had neither peeling of the hydrogen permeable foil nor deterioration of the hydrogen permeability.

It is sectional drawing which shows typically one Embodiment of the hydrogen separation membrane which concerns on this invention. It is sectional drawing which shows typically another embodiment of the hydrogen separation membrane which concerns on this invention. It is a graph which shows an example of the change of the composition of the alumina which comprises a barrier layer in the film thickness direction of a barrier layer. It is a graph which shows another example of the change of the composition of the alumina which comprises a barrier layer in the film thickness direction of a barrier layer. It is a schematic diagram which shows an example of the conventional hydrogen separation membrane, Comprising: It is a cross-sectional perspective view which cut | disconnected each layer of the film | membrane in steps.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Hydrogen separation membrane 11 Porous reinforcement board 12 1st intermediate | middle layer 13 Barrier layer 14 2nd intermediate | middle layer 15 Adhesion layer 16 Hydrogen permeable foil 18 Hole

Claims (6)

  A hydrogen separation membrane comprising a hydrogen permeable foil and a porous reinforcing plate that supports the hydrogen permeable foil, wherein a first intermediate layer, a barrier layer, a second layer are provided between the hydrogen permeable foil and the porous reinforcing plate. The intermediate layer and the adhesive layer are provided in order from the porous reinforcing plate side, and the first and second intermediate layers are independently of each other 1B, 2A, 2B, 3A, 3B, 4A of the periodic table. 4B, 5A, 6A, 7A and a group consisting of at least one metal selected from the group consisting of metal elements of Group 8 and having a melting point of 600 ° C. or higher, and the barrier layer is made of Al, Si, Zr, Ti, The adhesive layer is composed of a compound of at least one metal element selected from the group consisting of Mg, Ca, Y and Hf and at least one non-metal element selected from the group consisting of O, N, B and C. , Au, Cu, Pd and P At least one of the hydrogen separation membrane and a metal consisting of.   A hydrogen separation membrane comprising a hydrogen permeable foil and a porous reinforcing plate supporting the same, wherein a first intermediate layer, a barrier layer, and an adhesive layer are interposed between the hydrogen permeable foil and the porous reinforcing plate. Are provided in order from the porous reinforcing plate side, and the surface of the porous reinforcing plate on the side adjacent to the first intermediate layer has a roughness of Rz 0.1 to 10 μm, The first intermediate layer is selected from the group consisting of 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and Group 8 metal elements of the periodic table and has a melting point of 600 ° C. or higher. A group consisting of at least one metal, and wherein the barrier layer is made of at least one metal element selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y and Hf, and O, N, B and C Compound with at least one non-metallic element selected from It consists, the adhesive layer is Ag, Au, Cu, hydrogen separation membranes are composed of at least one metal consisting of Pd and Pt.   The concentration of the nonmetallic element in the compound constituting the barrier layer is continuous in the film thickness direction of the barrier layer from the adjacent first intermediate layer to the second intermediate layer or the adhesive layer. The hydrogen separation membrane according to claim 1 or 2, wherein the hydrogen separation membrane is changed so as to decrease continuously or stepwise after increasing stepwise.   A method for producing a hydrogen separation membrane comprising a hydrogen permeable foil and a porous reinforcing plate supporting the hydrogen permeable foil, wherein 1B, 2A, 2B, 3A, 3B, 4A of the periodic table are formed on the surface of the porous reinforcing plate. Forming a first intermediate layer made of at least one metal selected from the group consisting of Group 4B, 5A, 6A, 7A and Group 8 metal elements and having a melting point of 600 ° C. or higher. On the surface of the intermediate layer, at least one metal element selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y and Hf and at least one non-selection selected from the group consisting of O, N, B and C A barrier layer composed of a compound with a metal element is formed, and the metals of Groups 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A, and 8 of the periodic table are formed on the surface of the barrier layer. 60 selected from the group consisting of elements A second intermediate layer composed of at least one metal having a melting point of not lower than ° C. is formed, and the surface of the second intermediate layer is composed of at least one metal composed of Ag, Au, Cu, Pd and Pt. A method for producing a hydrogen separation membrane, wherein an adhesive layer is formed and the hydrogen permeable foil is formed on a surface of the adhesive layer.   A method for producing a hydrogen separation membrane comprising a hydrogen permeable foil and a porous reinforcing plate supporting the hydrogen permeable foil, after the surface of the porous reinforcing plate is treated to have a roughness of Rz 0.1 to 10 μm, On this surface, at least selected from the group consisting of 1B, 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A and Group 8 metal elements of the periodic table and having a melting point of 600 ° C. or higher A first intermediate layer composed of one metal is formed, and at least one selected from the group consisting of Al, Si, Zr, Ti, Mg, Ca, Y, and Hf is formed on the surface of the first intermediate layer. A barrier layer composed of a compound of a metal element and at least one non-metallic element selected from the group consisting of O, N, B and C is formed, and Ag, Au, Cu, Pd and the like are formed on the surface of the barrier layer. At least consisting of Pt One of the adhesive layer is formed made of a metal, a manufacturing method of the hydrogen separation membrane to form the hydrogen-permeable foil on the surface of the adhesive layer.   The concentration of the nonmetallic element in the compound constituting the barrier layer is continuous in the film thickness direction of the barrier layer from the adjacent first intermediate layer to the second intermediate layer or the adhesive layer. The production of the hydrogen separation membrane according to claim 4 or 5, wherein the amount of the nonmetallic element introduced is adjusted when forming the barrier layer so as to decrease continuously or stepwise after increasing stepwise. Method.

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