JP2006015266A - Hydrogen separation membrane structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen separation membrane structure having intensive bonding strength of a metallic substrate with a hydrogen separation membrane, and having high reliability. <P>SOLUTION: This hydrogen separation membrane structure has a lot of through-holes 12a formed on the metallic substrate 12, and the hydrogen separation membrane 13 covering one face of the metallic substrate. Recessed parts 12b are formed on the covered side of the metallic substrate surface with the hydrogen separation membrane, and ceramic particles 14 are filled in the through-holes and recessed parts to form the structure. This structure creates sufficient anchoring effect between the ceramic particles in the metallic substrate and the hydrogen separation membrane to cause little peeling of the hydrogen separation membrane. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an improvement of a hydrogen separation membrane structure.

A hydrogen separation membrane structure as shown in Patent Document 1 is known. In this example, pores are formed by etching on a plate-like metal support such as stainless steel, and an alloy film made of palladium and silver is formed on one surface.
Japanese Patent Laid-Open No. 5-317662

  In the hydrogen separation membrane structure, since the alloy membrane is formed on a smooth metal plane, the bonding force due to the so-called anchor effect does not work between the coating and the support, and the difference in thermal expansion between the alloy membrane and the support metal There is a problem that it is easy to peel off when gas pressure is applied from the metal flat plate side.

  The present invention provides a hydrogen separation membrane structure in which a plurality of through-holes are provided in a metal substrate serving as a support for a hydrogen separation membrane, and one surface of the metal substrate is coated with a hydrogen separation membrane. A recess is formed on the surface of the metal substrate to be coated, and the through hole and the recess are filled with ceramic particles.

  According to the present invention, since the ceramic particles are filled in the through holes and the recesses provided on the metal substrate, a sufficient anchor effect is generated between the ceramic particles and the hydrogen separation membrane, and the hydrogen separation membrane is difficult to peel off. The effect is obtained.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 (FIGS. 1-1 to 1-3) shows a first embodiment of the present invention.

  In the figure, 11 is a hydrogen separation membrane structure, and 12 and 13 are a metal substrate and a hydrogen separation membrane forming the hydrogen separation membrane structure, respectively. The metal substrate 12 is formed in a thin disk shape, and as a material, for example, a stainless alloy material is applied. The hydrogen separation membrane 13 is formed by coating one surface of the metal substrate 12 with an alloy material such as Pd having a hydrogen separation function by plating, vacuum deposition, sputtering, or the like.

  A large number of through holes 12 a are formed in the metal substrate 12 so as to penetrate the front and back surfaces of the substrate, and a large number of recesses 12 b are formed only on the surface that covers the hydrogen separation membrane 13. In this case, the recess 12b is formed in the central portion of the metal substrate 12 and the outer peripheral region. A large number of recesses 12b in the outer peripheral area are annularly arranged at equal intervals so as to surround the through hole 12a. The thicknesses of the metal substrate 12 and the hydrogen separation membrane 13 and the numbers of the through holes 12a and the recesses 12b are different from actual ones for convenience of explanation (the same applies to the following drawings).

  The through holes 12a and the recesses 12b are formed in the metal substrate 12 by a processing method such as etching, drilling, or laser processing. Needless to say, the recess 12b is formed to a required depth so as not to penetrate the metal substrate 12.

  The through holes 12a and the recesses 12b of the metal substrate 12 are filled with ceramic particles 14 and dried and sintered before the hydrogen separation membrane 13 is formed. As a material of the ceramic particles 14, for example, alumina, silica or the like can be applied.

  In the hydrogen separation membrane structure 11, hydrogen gas passes through the porous structure portion formed by the ceramic particles 14 filled in the through holes 12 a of the metal substrate 12 and the hydrogen separation membrane 13. In this embodiment, not only the through-holes 12a on the metal substrate 12 but also the recesses 12b are filled with the ceramic particles 14, and the hydrogen separation membrane 13 is coated thereon. For this reason, the hydrogen separation membrane 13 and the ceramic particles 14 are firmly bonded by the anchor effect, and when the difference in thermal expansion between the metal substrate 12 and the hydrogen separation membrane 13 or the gas pressure acts from the metal substrate 12 side, the hydrogen separation membrane 13 The possibility of peeling from the metal substrate 12 is reduced.

  FIG. 2 (FIGS. 2-1 to 2-2) shows a second embodiment of the present invention. In this embodiment, an annular groove 12 c is formed as a recess along the outer periphery of the metal substrate 12, and a circular recess region 15 is formed concentrically with the annular groove 12 c or the metal substrate 12 in the inner area. Is formed. A large number of through holes 12 a for gas permeation are formed in the recessed area 15. In this case, the ceramic particles 14 are filled in the annular groove 12c and the recessed region 15 and then sintered. Although formation of the hydrogen separation membrane is omitted in the drawing, it is the same as in FIG. 1 in that the surface on the side where the annular groove 12c and the recessed region 15 are formed is covered.

  In this embodiment, when the metal substrate surface on the side where the hydrogen separation membrane is formed is polished smoothly, the metal portion of the metal substrate 12 is not interposed in the layer of the ceramic particles 14 in the region where the recessed region 15 is formed. There is an advantage that a smooth surface with higher accuracy can be obtained.

  FIG. 3 (FIGS. 3-1 to 3-2) shows a third embodiment of the present invention. The shape of the metal substrate 12 is the same as in FIG. However, the difference is that the particle size of the ceramic particles 14 filled in the through holes 12a is smaller than that of the ceramic particles 14 filled in the recesses 12b. The hydrogen separation membrane is not shown.

  If there is a pinhole in the film portion on the through-hole 12a, there arises a problem that gas other than hydrogen leaks. However, by reducing the particle size of the ceramic particles 14 filled in the through-hole 12a as in this embodiment. A hydrogen separation membrane that is uniform and hardly generates pinholes can be formed. On the other hand, since hydrogen does not permeate into the recess 12b, pinholes do not become a problem. Rather, a strong anchor effect is generated by increasing the particle size of the ceramic particles 14. Thereby, it is possible to obtain a strong adhesion between the ceramic particles and the hydrogen separation membrane.

  FIG. 4 (FIGS. 4-1 to 4-3) shows a fourth embodiment of the present invention. This embodiment is different from that shown in FIG. 1 in that an annular groove 12c is formed in an annular shape along the outer diameter of the substrate in the outer peripheral region of the metal substrate 12. The through holes 12a and the annular grooves 12c of the metal substrate 12 are filled with ceramic particles 14, dried and sintered, and then the hydrogen separation membrane 13 is coated on the substrate surface on the side where the annular grooves 12c are formed.

  According to this embodiment, the outer peripheral portion of the hydrogen separation membrane 13 is held by the anchor effect of the ceramic particles 14 filled in the annular groove 12c, so that even if the edge A of the hydrogen separation membrane 13 is peeled off, the inner side of the annular groove 12c. It becomes difficult to peel to the region, and the required hydrogen separation function can be maintained.

  In addition, since the through hole 12a is provided in the inner region of the annular groove 12c, the hydrogen separation membrane facing the through hole 12a is hardly peeled off, and the risk of impurity gases other than hydrogen leaking can be more reliably prevented.

  FIG. 5 shows a fifth embodiment of the present invention. In this embodiment, the metal substrate 12 is formed in a cylindrical shape, annular grooves 12c are formed in the vicinity of both ends of the cylindrical substrate 12 along the outer periphery of the cylinder, and a through hole 12a is formed inside thereof. The annular groove 12c and the through hole 12a are filled with ceramic particles 14, dried and sintered, and then coated with a hydrogen separation membrane (not shown) on the outer peripheral surface of the substrate so as to cover the annular groove 12c and the through hole 12a. To do.

  Also in this embodiment, since the annular groove 12c is formed at both ends of the cylindrical metal substrate 12, a highly reliable hydrogen separation membrane structure that is unlikely to cause the separation of the hydrogen separation membrane is obtained as in FIG. It is done.

  FIG. 6 shows a sixth embodiment of the present invention. In this embodiment, in the same manner as shown in FIG. 4, in the metal substrate 12 in which the annular groove 12c is formed in the outer peripheral region, the hydrogen separation membrane 13 is formed so that its contour is within the groove width of the annular groove 12c. It is.

  According to this embodiment, since the edge A of the hydrogen separation membrane 13 is firmly adhered by the ceramic particles 14 filled in the annular groove 12c, the separation from the edge is eliminated, and the hydrogen separation membrane structure is reliable. The sex can be increased.

  FIG. 7 shows a seventh embodiment of the present invention. In this embodiment, as shown in the drawing, the cross-sectional shape of the recess 12b formed in the central portion and the annular groove 12c formed in the outer peripheral region is formed so that the width on the bottom side is larger than the width on the opening end side. It is characterized by that.

  According to this embodiment, the ceramic particles 14 filled in the recesses 12b or the annular grooves 12c are difficult to drop off, and the holding strength for the hydrogen separation membrane (not shown) coated on the surface can be further increased.

FIG. 8 shows an example of a method for producing the hydrogen separation membrane structure 11 according to the present invention. This is an example of a manufacturing process for the hydrogen separation membrane structure described as the third embodiment, that is, the ceramic particle 14 having a structure in which a small diameter is filled in the through hole 12a and a large diameter is filled in the recess 12b. It is. Hereinafter, a manufacturing method is demonstrated according to a process.
Process 1
Through holes 12a, recesses 12b, and annular grooves 12c are formed in the metal substrate 12 by etching or the like.
Process 2
After masking 16 is performed on the upper surface of the metal substrate 12 so as to cover only the through holes 12a, the concave portions 12b and the annular grooves 12c are filled with a ceramic slurry 14 'having a large particle size and dried.
Process 3
The masking 16 of the through-hole 12a is removed, and the masking 17 is applied so as to cover the recess 12b and the annular groove 12c, and then the through-hole 12a is filled with a ceramic slurry 14 'having a small particle diameter and dried.
Process 4
The masking 17 is removed, and the ceramic slurry 14 'is fired and solidified.
Process 5
The hydrogen separation membrane 13 is covered over substantially the entire surface of the metal substrate 12 on the side where the concave portion 12b is formed by vacuum deposition or the like. Thereby, the hydrogen separation membrane structure 11 according to the present invention is obtained.

The top view of the metal substrate of the hydrogen separation membrane structure which concerns on the 1st Embodiment of this invention. The longitudinal cross-sectional view of FIGS. The longitudinal cross-sectional view which shows the state in which the hydrogen separation membrane was formed in 1st Embodiment. The top view of the metal substrate of the hydrogen separation membrane structure which concerns on the 2nd Embodiment of this invention. The longitudinal cross-sectional view of FIGS. The top view of the metal substrate of the hydrogen separation membrane structure which concerns on the 3rd Embodiment of this invention. The longitudinal cross-sectional view of FIGS. The top view of the metal substrate of the hydrogen separation membrane structure which concerns on the 4th Embodiment of this invention. FIG. 4 is a longitudinal sectional view of FIG. The longitudinal cross-sectional view which shows the state in which the hydrogen separation membrane was formed in 4th Embodiment. The external appearance perspective view of the metal substrate of the hydrogen separation membrane structure which concerns on the 5th Embodiment of this invention. The longitudinal cross-sectional view of the hydrogen separation membrane structure which concerns on the 6th Embodiment of this invention. The longitudinal cross-sectional view of the metal substrate of the hydrogen separation membrane structure which concerns on the 7th Embodiment of this invention. Explanatory drawing which shows the example of a manufacturing process of the hydrogen separation membrane structure which concerns on this invention.

Explanation of symbols

11 Hydrogen separation membrane structure 12 Metal substrate 12a Through hole 12b Recess 12c Recess (annular groove)
13 Hydrogen separation membrane 14 Ceramic particles 15 Recessed area

Claims (7)

In the hydrogen separation membrane structure in which a large number of through holes are provided in a metal substrate that is a support for the hydrogen separation membrane, and one surface of the metal substrate is coated with a hydrogen separation membrane.
Forming a recess in the metal substrate surface on the side covering the hydrogen separation membrane,
A hydrogen separation membrane structure having a structure in which the through holes and the recesses are filled with ceramic particles.   2. The hydrogen separation membrane structure according to claim 1, wherein the ceramic particles filled in the through holes have a smaller particle diameter than the ceramic particles filled in the recesses.   The hydrogen separation membrane structure according to claim 1, wherein an annular groove is formed as the recess along the outer shape of the metal substrate.   The hydrogen separation membrane structure according to claim 3, wherein the through hole is formed in a region inside the annular groove of the metal plate.   The hydrogen separation membrane structure according to claim 3, wherein the hydrogen separation membrane is formed so that a contour thereof falls within a groove width of the annular groove.   4. The hydrogen separation membrane structure according to claim 3, wherein the metal substrate includes a recessed region in which a large number of through holes are formed in an inner region of the annular groove, and the recessed region is filled with ceramic particles.   2. The hydrogen separation membrane structure according to claim 1, wherein the recess has a cross-sectional shape formed so that a width on a bottom side is larger than a width on an opening end side.

Images