JP2005144363A - Hydrogen separation membrane structure and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that the falling-off, positional shift and volumetric change of particles are caused when the pore parts of a metal base material are filled with particles of ceramics or the like to bake the particles and an expected capacity is not obtained as a hydrogen permeable membrane. <P>SOLUTION: Through-holes 12 filled with ceramics particles 13 are formed to a substrate 11 so that the opening areas thereof become different mutually at both end opening parts and the hydrogen permeable membrane 14 is formed on the surface on the side large in opening area of each of the through-holes. Since the hydrogen permeable membrane is formed on the side large in opening area of each of the through-holes formed to the substrate, the falling-off of the particles can be suppressed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydrogen separation membrane for removing impurities from a hydrogen-containing gas supplied to a fuel cell or the like, and a method for manufacturing the same.

A conventional hydrogen separation membrane as shown in Patent Document 1 is known. The purpose of this is to improve hydrogen permeability and durability, by embedding metal or ceramic particles in a large number of holes provided in a metal base material, and forming a hydrogen permeable membrane containing Pd on its surface. It is formed by a chemical plating method such as tinting.
JP 2002-239352 A

  When particles such as ceramics are filled and fired in the holes of a metal substrate, the particles may fall off or be displaced, or the plating surface roughness may deteriorate due to volume changes. Performance may not be obtained.

The present invention is characterized in that the following hydrogen separation membrane structure is formed. That is, through-holes filled with metal or ceramic particles are formed in the substrate so that the opening areas thereof are different from each other at the opening portions at both ends.
In this substrate, a hydrogen permeable film is formed on the surface on the side where the opening area of the through hole is large.

The present invention also provides a method for producing the hydrogen separation membrane structure comprising the following steps.
A substrate on which the through holes are formed so that the opening areas thereof are different from each other at the opening portions at both ends is coated with a film on the surface of the through hole having the large opening area.
Metal or ceramic particles are filled from an opening having a small opening area of the through hole.
A centrifugal force is applied so that an excitation force and a biasing force in the direction of the film act on the substrate filled with the particles in the through holes.
After the film is peeled off, a baking treatment is performed.
A hydrogen permeable film is formed on the film peeling surface of the substrate.

  In the hydrogen separation membrane structure according to the present invention, since the hydrogen separation membrane is formed on the side of the through-hole formed in the substrate that has a large opening area, it is possible to suppress the dropping of particles.

  According to the method for producing a hydrogen separation membrane structure according to the present invention, the particles filled in the through holes of the substrate are fired after being subjected to vibration and centrifugal force, so that the volume change after sintering can be reduced. .

  FIG. 1 shows a first embodiment of a hydrogen separation membrane structure according to the present invention. In the figure, reference numeral 11 denotes a metal substrate having a large number of through holes 12 penetrating its front and back. In this case, the through hole 12 is formed in a hemispherical shape or a tapered hole shape so that the opening areas of the front surface side and the back surface side of the substrate 11 are different.

  The through holes 12 are filled with ceramic particles 13 and the surface of the substrate having the large opening area of the through holes 12 is covered with a hydrogen permeable membrane 14 having a hydrogen separation function such as Pd. is there. As a material for the particles 13, in addition to ceramics, a metal material such as iron, stainless steel, nickel, or an oxide thereof can be used. As a material of the hydrogen permeable membrane 14 having a hydrogen separation function, there are Nb, V, Ta, Zr, Fe, Ni, Pt, etc. in addition to Pd, and combinations thereof, or further, Ag, Au, Cu, B, Ni, Ru, Ce, Y, etc. may be used in combination. As a method for coating the hydrogen permeable film 14, various film forming methods such as plating, sputtering, vacuum deposition, and the like can be applied regardless of whether they are dry or wet.

  According to this embodiment, since the hydrogen permeable film is formed on the surface of the substrate having the larger opening area, it is possible to prevent the particles from falling off.

  FIG. 2 shows a second embodiment of the hydrogen separation membrane structure according to the present invention. In this configuration, the metal substrate 11 is formed in a cylindrical shape so that the side where the opening area of the through hole 12 is large is the outside. In this case, the hydrogen permeable membrane 14 is formed on the outer surface of the cylindrical substrate 11 in which the opening area of the through hole 12 is large.

  According to this embodiment, since the hydrogen permeable film 14 is formed outside the cylindrical substrate 11, the film 14 itself and the particles 13 are less likely to fall off due to the tension acting on the hydrogen permeable film 14. The holding can be performed more reliably.

  FIG. 3 shows a third embodiment of the hydrogen separation membrane structure according to the present invention. In this case, the through holes 12 of the metal substrate 11 are filled with several kinds of particles 13 having different particle sizes. However, as shown in the figure, the particles 13 are packed in layers so that the average particle diameter becomes larger as the opening area of the through-hole 12 is smaller.

  According to this embodiment, the pressure when hydrogen gas flows through the through-holes 12 by providing particles having a large particle size while ensuring smoothness near the hydrogen permeable membrane 14 with particles having a small particle size. Loss can be reduced.

FIG. 4 shows an embodiment relating to a method for producing the hydrogen separation membrane structure. The figures are numbered (1) to (5) in the order of the manufacturing process described below.
(1) A film 15 is coated on the surface of the through hole 12 on the side where the opening area of the through hole 12 is large, on the substrate 11 in which the opening areas of the through holes 12 are different from each other at the opening portions at both ends.
(2) Slurry ceramic particles 13 are poured into the through holes 12 from the opening side having a small opening area and filled.
(3) The substrate 11 filled with the particles 13 in the through-holes 12 is fixed on a jig 16 formed so as to come into surface contact with the film-coated surface of the substrate, and the surface direction (in the drawing) A vibration force is applied to the particles 13 in the through-holes 12 by vibrating in the horizontal direction. A centrifugal force is applied to the particles 13 in a direction in which an urging force in the direction of the film 15 acts together with or before and after the application of the excitation force. This step is performed, for example, by turning the jig 16 to which the substrate 11 is fixed using a rotating machine.
(4) After drying the slurry in the through-hole 12, the film 15 is peeled off and baked at a high temperature.
(5) Thereafter, a hydrogen permeable film 14 is formed on the film peeling surface of the substrate 11.

  According to the method for manufacturing the hydrogen separation membrane structure, since the particles 13 filled in the through holes 12 of the substrate 11 are fired after being subjected to vibration and centrifugal force, the volume change after sintering can be suppressed. it can. By using the jig 16 at the time of the processing, it is possible to ensure the holding strength of the film 15 when the exciting force and the centrifugal force are applied to the substrate 11.

  When a centrifugal force is applied to the substrate 11, when the substrate 11 is formed in a cylindrical shape as shown in FIG. 2, the through-hole 12 is filled by rotating the cylindrical substrate 11 around its center line. Centrifugal force can be easily and effectively applied to the particles.

FIG. 5 shows a second embodiment relating to a method for manufacturing a hydrogen separation membrane structure. This is an embodiment relating to a process for producing a hydrogen permeable membrane structure having a structure in which particles 13 having different particle sizes shown in FIG. 3 are packed in layers, and the process corresponds to (2) in FIG. The numbers (2-1) to (2-4) are given in the order of the steps.
(2-1) A substrate 11 coated with the same film 15 as in FIG. 4 is fixed on a jig 16, and a slurry of ceramic particles 13 a having the smallest particle size is poured into the through hole 12 to the middle of the through hole 12. The first particle layer 13A is formed by applying an excitation force and a centrifugal force and then drying.
(2-2) Next, a slurry of ceramic particles 13b having the second smallest particle diameter is poured halfway from above the first particle layer 13A, and after applying an excitation force and a centrifugal force, the slurry is dried to be second. The particle layer 13B is formed.
(2-3) Next, a slurry of ceramic particles 13c having the largest particle size is poured from above the second particle layer 13B until the through hole 12 is filled, and after applying an excitation force and a centrifugal force, drying is performed. Thus, the third particle layer 13C is formed.
(2-4) The film 15 is peeled off and fired at a high temperature. Thereafter, as in (5) of FIG. 4, a hydrogen permeable membrane is coated and completed. The film 15 may be peeled off at any time after the step (2-1) is completed.

  According to this method for producing a hydrogen separation membrane structure, when particles having a plurality of different particle sizes shown in FIG. 3 are formed into a laminated structure, the particles are surely layered so that different types of particles do not mix with each other. Can do.

The principal part longitudinal cross-sectional view of 1st Embodiment of the hydrogen separation membrane structure by this invention. The principal part longitudinal cross-sectional view of 2nd Embodiment of the hydrogen separation membrane structure by this invention. The principal part longitudinal cross-sectional view of 3rd Embodiment of the hydrogen separation membrane structure by this invention. Process explanatory drawing of the 1st Example regarding the manufacturing method of the hydrogen separation membrane structure by this invention. Process explanatory drawing of the 2nd Example regarding the manufacturing method of the hydrogen separation membrane structure by this invention.

Explanation of symbols

11 Substrate 12 Through-hole 13 Particle 14 Hydrogen-permeable membrane 15 Film 16 Jig

Claims (9)

A hydrogen separation membrane comprising a substrate having a large number of through holes, metal or ceramic particles filled in the through holes, and a hydrogen permeable membrane coated on the substrate in the state where the particles are filled in the through holes In the structure,
While forming the through-holes so that their opening areas are different from each other at the openings at both ends,
The hydrogen separation membrane structure, wherein the hydrogen permeable membrane is formed on the surface of the substrate on the side where the opening area of the through hole is large.   2. The hydrogen separation membrane structure according to claim 1, wherein the particles are filled with particles having different particle sizes such that the smaller the opening area of the through-hole, the larger the average particle size.   2. The hydrogen permeable membrane structure according to claim 1, wherein the substrate is formed in a cylindrical shape so that a side where the opening area of the through hole is large is an outside.   The hydrogen permeable membrane structure according to claim 1, wherein the through hole is formed in a tapered hole shape.   The hydrogen permeable membrane structure according to claim 1, wherein the through hole is formed in a hemispherical shape. After the substrate is formed so that the opening area of the through hole is different from each other at the opening at both ends, a film is coated on the surface on the side where the opening area of the through hole is large,
Filling metal or ceramic particles from an opening having a small opening area of the through-hole,
A centrifugal force is applied to the substrate filled with the particles in the through-holes in a direction in which an excitation force and a biasing force in the film direction act on the particles,
After peeling off the film, it is fired.
Thereafter, a hydrogen permeable membrane is formed on the film peeling surface of the substrate, and a method for producing a hydrogen separation membrane structure.   7. When filling the through holes with particles, ceramic particles having different particle diameters, which are slurried, are stacked in the through holes by repeatedly filling and drying for each particle diameter. Method for producing a hydrogen separation membrane structure.   The substrate is formed in a cylindrical shape so that the side with the large opening area of the through-hole is on the outside, and the cylindrical substrate is rotated around its center line, whereby the particles filled in the through-hole are centrifuged. The method for producing a hydrogen separation membrane structure according to claim 6, wherein force is applied.   The hydrogen separation membrane structure according to claim 6, wherein when applying the excitation force or centrifugal force, the substrate is supported on a jig formed so as to be in surface contact with the film coating surface. Manufacturing method.

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