JP2009106794A - Hydrogen separation body and hydrogen separation apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen separation body which can prevent a self-supporting type thin hydrogen-permeable membrane from being deformed and damaged and is excellent in hydrogen permeability, and to provide a hydrogen separation apparatus. <P>SOLUTION: The hydrogen separation body is provided with the metallic or alloy-made hydrogen-permeable membranes, and support plates formed of pairs of porous materials supporting the hydrogen-permeable membranes from both sides, the support plate having different mechanical strengths on one side and the other side. The hydrogen separation apparatus is provided with the hydrogen separation body and a pair of metallic casing members sandwiching the hydrogen separation body and forming gas chambers on both sides of the hydrogen separation body, a joint part or a joint member of the hydrogen separation body being jointed to edges of the metallic casing members. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrogen separator and a hydrogen separator provided with a hydrogen permeable membrane used for extracting hydrogen gas from a mixed gas containing hydrogen.

  The hydrogen permeable membrane is used for selectively extracting hydrogen gas from a mixed gas containing hydrogen gas and hydrogen. As the hydrogen permeable membrane, those having the ability to adsorb, dissociate, diffuse, and bond hydrogen are used. As a typical hydrogen permeable membrane, for example, a membrane made of a palladium (Pd) alloy can be cited. Since this palladium (Pd) is a noble metal and is expensive, research on hydrogen permeable membranes such as vanadium (V) and neodymium (Nd) has been actively conducted.

In recent years, fuel cells have been actively developed due to increasing interest in global environmental problems, and a hydrogen permeable membrane is required to selectively obtain hydrogen reformed by a catalyst from liquid fuel. It has become to. In addition to the fuel cell, for example, use of a hydrogen permeable membrane is being studied in order to supply hydrogen to a site that requires hydrogen, such as an internal combustion engine.
For example, considering the mounting of the fuel cell on the vehicle body, the volume (volume) of the entire fuel cell system is preferably as small as possible. In order to reduce the size of the fuel cell system, it is desirable to use liquid fuel rather than hydrogen gas as a fuel source. When liquid fuel is used, hydrogen permeation that can selectively take out reformed hydrogen from the fuel. The function of the membrane is important.

Conventionally, as a hydrogen permeable film, a hydrogen permeable film made of Pd or a Pd alloy is formed on the surface of a porous support by a method such as plating, CVD (gas phase chemical reaction), sputtering, ion plating, or vapor deposition. A film-forming type is known (for example, Patent Document 1).
As the hydrogen permeable membrane is thinner, the hydrogen permeability can be improved. If the film thickness of the hydrogen permeable membrane is thin, the volume (volume) of the hydrogen separator provided with the porous support and the hydrogen permeable membrane can be reduced. For example, it is suitable for use in a fuel cell mounted on a vehicle body. It is.
For example, when the thickness of the hydrogen separation membrane is reduced to 1/10 (1/10), the permeability is increased 10 times, and the volume (volume) of the hydrogen separator is also reduced to 1/10 (1/10). It becomes possible. In this case, the amount of Pd used to form the hydrogen separation membrane is 1 / 100th (1/100), and the amount of Pd used can be reduced, greatly reducing the cost. It becomes possible.
JP 2002-336664 A

  Further, as a hydrogen permeable membrane, a metal or alloy free-standing membrane type hydrogen permeable membrane has been studied. The self-supporting membrane type hydrogen permeable membrane does not need to form a hydrogen permeable membrane on the porous support unlike the above-described film forming type, and thus can be made thinner. On the other hand, since the hydrogen permeable membrane is thinned, sufficient strength cannot be obtained, and a structure for holding the hydrogen permeable membrane is required to supplement the strength.

As a structure for holding such a self-supporting membrane type hydrogen permeable membrane, a structure in which the hydrogen permeable membrane is sandwiched between a pair of metal plates having a large number of through holes has been proposed (Patent Document 2).
In this structure, each through-hole formed in one and the other metal plates is formed so as to communicate with each other through the hydrogen permeable membrane. In addition, the metal plate that supports the hydrogen permeable membrane was set so that the angle with respect to the contact surface with the hydrogen permeable membrane was an obtuse angle at the end of the contact surface that was in contact with the hydrogen permeable membrane other than the through hole. An obtuse angle surface is formed.
JP 2003-165710 A

  However, in such a conventional technique, for example, in the film-forming type hydrogen permeable membrane of Patent Document 1, if the pore size of the porous support for forming the hydrogen permeable film is large, pinholes and the like are formed. There is a problem that it becomes easy. In order to avoid this problem, it is necessary to increase the film thickness or reduce the pore diameter of the porous support, and there is a problem that hydrogen permeability is lowered regardless of which method is employed.

  On the other hand, the hydrogen permeable membrane of the self-supporting membrane type of Patent Document 2 has a problem that the thin hydrogen permeable membrane is likely to be deformed and the hydrogen permeable membrane is easily damaged. Since the hydrogen permeable membrane selectively permeates hydrogen by utilizing the pressure difference between the hydrogen partial pressure on the supply side and the hydrogen partial pressure on the extraction side, the hydrogen permeable membrane is easily deformed by this pressure difference. Damage from this deformation is likely to occur. Further, the hydrogen permeable membrane is easily deformed by volume expansion due to occlusion of hydrogen and thermal expansion due to heat, and damage is likely to occur from this deformation. For example, if the hydrogen permeable membrane used in the fuel cell is damaged, platinum (Pt) or the like contained in the electrode is poisoned and the output of the fuel cell is reduced.

  Further, the hydrogen separation device of Patent Document 2 described above forms an obtuse angle surface set so that an angle with respect to the contact surface becomes an obtuse angle at the end of the contact surface of the metal plate holding the hydrogen permeable membrane, We are trying to reduce the stress that the hydrogen permeable membrane receives from the metal plate due to the pressure difference between the supply side and the extraction side. However, depending on the hole diameter of the through hole and the size of the pressure difference, even if the stress applied from the plate is reduced, the deformation of the hydrogen permeable membrane cannot be prevented, and damage to the hydrogen permeable membrane is unavoidable. is there.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to prevent large deformation of a self-supporting membrane type hydrogen permeable membrane and prevent damage. A hydrogen separator excellent in hydrogen permeability and a hydrogen separator using the same and having a simple structure and excellent sealing properties.

  As a result of intensive studies to achieve the above object, the inventors of the present invention supported a metal or alloy hydrogen permeable membrane from both sides with a pair of porous material support plates, and the pair of support plates The inventors have found that the above object can be achieved by making one and the other significantly different, and completed the present invention.

  That is, the hydrogen separator of the present invention comprises a metal or alloy hydrogen permeable membrane and a pair of porous plates that support the hydrogen permeable membrane from both sides. Is different in mechanical strength between one and the other.

  A hydrogen separator according to the present invention includes the hydrogen separator and a pair of metal casing members that form gas chambers on both sides of the hydrogen separator with the hydrogen separator interposed therebetween. Yes, it is formed by joining the joint or member of the hydrogen separator and the edge of the metal housing member.

According to the present invention, the hydrogen permeable membrane made of a metal or an alloy is supported by the support plate made of a pair of porous materials that are significantly different from each other, so that the hydrogen permeable membrane is deformed. Therefore, it is possible to prevent damage caused by large deformation of the hydrogen permeable membrane and to provide a hydrogen separator excellent in hydrogen permeability.
According to the present invention, the hydrogen separator is sandwiched between a pair of metal casing members that form gas chambers on both sides of the hydrogen separator, and the edge of the metal casing member and the hydrogen separator Since the joining part or the joining member formed around the edge of the material is joined, a hydrogen separator having a simple structure and excellent in sealing performance and hydrogen permeability can be provided.

Hereinafter, the hydrogen separator of the present invention will be described in detail.
As described above, the hydrogen separator of the present invention includes a metal or alloy hydrogen permeable membrane and a support plate made of a pair of porous materials that support the hydrogen permeable membrane from both sides, and one of the pair of support plates. And the other have different mechanical strengths.

Examples of the hydrogen permeable membrane include those made of Pd, Pd alloys, V alloys, Nd alloys, and Zr alloys.
Since the hydrogen permeable membrane has a smaller thickness, the hydrogen permeability is improved. Therefore, the thickness is preferably 5 to 10 μm, and more preferably, the membrane is thick enough to prevent large deformation. Use a thickness of 5 μm or less.

As a support plate made of a pair of porous materials that support the hydrogen permeable membrane from both sides, the mechanical strength differs depending on, for example, the material, thickness, porosity, pore diameter, etc. of one and the other. It is preferable that
As described above, by making the mechanical strength of one of the pair of support plates that support the hydrogen permeable membrane from both sides different from the other, deformation of the hydrogen permeable membrane can be prevented.
Next, a mechanism capable of preventing the deformation of the hydrogen permeable membrane by the configuration of the hydrogen separator of the present invention will be described.

FIGS. 1 to 5 show that when the surface on the permeation side of the supply side and the permeation side of the hydrogen permeation membrane is supported by a support plate made of a porous material, the hydrogen permeation membrane is deformed (raised). It is explanatory drawing which shows the state which causes damage to a hydrogen permeable film due to (ii).
1 to 3 are cross-sectional views showing a state in which deformation occurs in the hydrogen permeable membrane supported only on one surface by a support plate, and FIGS. 4 and 5 illustrate the hydrogen permeable membrane in which wrinkles and damage have occurred. It is a photograph (plan view).

As shown in FIG. 1, a hydrogen permeable membrane 1 in which a hydrogen permeable membrane surface of a hydrogen permeable membrane is supported by a support plate 2 has a part of the hydrogen permeable membrane 1 supported by thermal expansion or volume expansion due to hydrogen. 2 is raised (deformed part 1a) so as to protrude to the side without the support plate 2 (supply side) (FIG. 2).
The supply side and the permeate side of the hydrogen permeable membrane 1 generally have a higher pressure on the supply side (the reforming side that reforms the mixed gas of the fuel when used in a fuel cell) than the permeate side. The hydrogen permeable membrane protruding to the supply side is crushed into an acute angle under pressure on the supply side, and a large ridge (deformed portion 1a ′) having a sharp tip is formed (FIGS. 3 and 4).
This large soot (deformed portion 1a ′) is once again shown in FIG. 2 when the pressure difference between the supply side and the permeation side of the hydrogen permeable membrane 1 is alleviated, all the hydrogen is released from the hydrogen permeable membrane, or the temperature is lowered. Through the process, an attempt is made to return to the state of FIG.
Depending on the conditions of use of the hydrogen permeable membrane, the state of FIG. 1, the state of FIG. 2, the state of FIG. 3, the state of FIG. 2 again, and the deformation of the hydrogen permeable membrane are repeated. Cracks occur and the hydrogen permeable membrane is damaged (FIG. 5).

It is considered that the large soot as described above is generated by concentration of the expanded portion of the hydrogen permeable membrane due to the high pressure received from the hydrogen supply side.
On the other hand, the generation of small soot prevents the generation of large soot on the hydrogen permeable membrane. Therefore, if the generation of small soot can be stopped, the hydrogen permeable membrane is unlikely to be damaged.

The hydrogen separator of the present invention is provided with support plates having different mechanical strengths according to the pressure difference on the supply side and the permeation side of the hydrogen permeable membrane having different pressure differences, and the hydrogen permeable membrane is applied by the pair of support plates. Since the stress that creates the soot is distributed on both sides of the hydrogen permeable membrane, it is difficult for large soot to be produced, and even if the hydrogen permeable membrane is deformed, the formation of small soot will stop, so the hydrogen permeable membrane will be damaged. Can be prevented.
Generally, on the supply side and the permeation side of the hydrogen permeable membrane, the pressure on the supply side is higher than that on the permeation side. Therefore, a support plate having a high mechanical strength is provided on the permeation side that receives the pressure on the supply side. It is preferable to provide a support plate having low mechanical strength on the side.

  Thus, the hydrogen separator of the present invention prevents large deformation of the hydrogen permeable membrane and prevents damage to the hydrogen permeable membrane even when a thin hydrogen permeable membrane of a self-supporting membrane type is used. Therefore, the hydrogen separator or the hydrogen separator can be reduced in size (thinned) using a thin self-supporting membrane type hydrogen permeable membrane.

  For example, the mechanical strength can be made different between one and the other by forming each of the pair of support plates with different materials. For example, it is preferable to provide a ceramic support plate on one supply side and a metal support plate on the other transmission side.

  Next, the example (Embodiment 1-14) of embodiment of the hydrogen separator of this invention is described based on drawing. The hydrogen separator of the present invention is not limited to the embodiment shown in FIGS. Members common to the drawings are denoted by the same reference numerals.

(Embodiment 1)
As shown in FIG. 6, the hydrogen separator 10 of Embodiment 1 of the present invention is provided with a thin support plate 2 a on the supply side (reforming side) of the hydrogen permeable membrane 1, and the permeation side of the hydrogen permeable membrane 1. Is provided with a thick support plate 2b. In FIG. 6, reference numeral 20 denotes a joined portion obtained by alloying and joining the support plates 2 a and 2 b.
Thus, the mechanical strength may be varied by changing the thickness of one and the other of the support plates that support the hydrogen permeable membrane from both sides.
In this case, for example, it is preferable to reduce the thickness of the support plate on the supply side of the hydrogen permeable membrane and increase the thickness of the support plate on the permeate side of the hydrogen permeable membrane.

FIG. 7 is a photograph (plan view) showing a state of deformation (flaw) formed in the hydrogen permeation 1 supported by a pair of support plates having different mechanical strengths from both sides.
As shown in FIG. 7, the hydrogen permeable membrane 1 is supported by a pair of support plates having different mechanical strengths from both sides, so that the hydrogen permeable membrane 1 is not greatly deformed (wrinkles) and is small. It is confirmed that the deformation (wrinkles) is stopped and damage is less likely to occur.

  Of the pair of support plates, the thickness of the support plate provided on the hydrogen permeable membrane supply side varies depending on the air permeability of the member, but is preferably about 0.5 mm.

Although not shown, the hydrogen separator 1 is provided with a support plate having a high porosity on the supply side (reforming side) of the hydrogen permeable membrane 1 and a support plate having a low porosity on the permeation side of the hydrogen permeable membrane. May be formed.
In this way, the mechanical strength may be varied by changing the porosity of one and the other of the support plates that support the hydrogen permeable membrane from both sides.

  Of the pair of support plates, the porosity of the support plate provided on the supply side of the hydrogen permeable membrane is set higher than the porosity provided on the permeation side of the hydrogen permeable membrane in order to facilitate the arrival of hydrogen to the hydrogen permeable membrane surface. There is a need to. Each preferable porosity varies depending on the material of the porous body.

(Embodiment 2)
FIG. 8 shows Embodiment 2 of the hydrogen separator of the present invention. The hydrogen separator 10 is provided with a support plate 2c having a large hole diameter on the supply side (reformation side) of the hydrogen permeable membrane 1, and the permeation of the hydrogen permeable membrane. A support plate 2d having a small hole diameter is provided on the side.
When the hole diameters of the pair of support plates are different, the mechanical strength can be made different between one and the other.
For example, the average pore diameter A of the support 2c on the supply side and the average pore diameter B of the support 2d on the transmission side are set to A> B, and the average pore diameter A of the support 2c on the supply side is set to the support on the transmission side. The mechanical strength of the permeation-side support 2d may be improved by making it smaller than the average pore diameter B of the body 2d. As described above, when the mechanical strength of the support plate 2d on the permeation side is large, deformation due to expansion of the hydrogen permeable membrane 1 is dispersed without causing deformation due to a large pressure applied from the supply side to the permeation side. It is possible to prevent a large deformation (変 形) from being generated.

  The average pore diameter of the support plate provided on the permeation side of the hydrogen permeable membrane needs to be at least about 0.5 μm. On the other hand, the average pore diameter of the support plate provided on the supply side of the hydrogen permeable membrane needs to be much larger than the average pore size of the support plate provided on the permeation side in order to facilitate the arrival of hydrogen to the surface of the hydrogen permeable membrane. is there. The average pore diameter of the support plate provided on the supply side of the hydrogen permeable membrane needs to be determined in consideration of the air permeability.

(Embodiment 3)
FIG. 9 shows Embodiment 3 of the hydrogen separator of the present invention. The hydrogen separator of the present example includes, as a means for changing the pore diameter between one and the other of the pair of support plates, for example, a metal mesh body is provided as a support plate 2e on the supply side, and a metal porous body is provided on the permeation side. A plate-like body made of a material is provided as the support plate 2f.
When the support plate 2e which is a mesh body is provided on the supply side of the hydrogen permeable membrane 1 (see FIG. 10A), the support plate 2e which is a mesh body is deformed due to the permeation of heat and hydrogen. Although the hydrogen permeable membrane 1 is also deformed, the support plate 2e, which is a network, prevents local large deformation of the hydrogen permeable membrane 1, disperses the deformation of the hydrogen permeable membrane 1, and deforms small at regular intervals. Therefore, damage to the hydrogen permeable membrane 1 can be prevented (see FIG. 10B).
When a metal net is used as the support plate, it is preferable to form an alloying prevention portion to be described later on the surface in contact with the hydrogen permeable membrane.

(Embodiment 4)
11 (a) and 11 (b) show a fourth embodiment of the hydrogen separator of the present invention. In the hydrogen separator 10 of this example, at least one of the pair of support plates 2g and 2h constituting the hydrogen separator 10 has a communication hole 3a that communicates from the opposite surface of the hydrogen permeable membrane 1 to the back surface. I have it. When the support plate 2g has the communication hole 3a, the mechanical strength can be made different between one of the pair of support plates 2g and 2h and the other.
As shown in FIGS. 11A and 11B, the support plate 2g has a communication hole 3a that communicates from the opposing surface to the back surface of the hydrogen permeable membrane 1, so that hydrogen of hydrogen gas reformed on the supply side can be obtained. The supply amount to the permeable membrane 1 can be increased, and a large amount of hydrogen gas can be supplied to the permeable side through the hydrogen permeable membrane 1.

(Embodiment 5)
FIG. 12 shows Embodiment 5 of the hydrogen separator of the present invention. As in this example, the communication hole 3b formed in the support plate 2g of the hydrogen separator is formed between the opposite surface and the back surface of the hydrogen permeable membrane. You may form so that a hole diameter may differ. For example, the hole diameter of the back surface of the support plate (the surface not in contact with the hydrogen permeable membrane, that is, the surface on the supply side) is increased, while the surface of the support plate facing the hydrogen permeable membrane (the surface on the hydrogen permeable membrane side) By forming the pore diameter small, the amount of hydrogen gas reformed on the supply side to the hydrogen permeable membrane can be increased.

(Embodiment 6)
FIG. 13 shows Embodiment 6 of the hydrogen separator of the present invention. As shown in FIG. 13, the hydrogen separator 10 is a selective functional layer having a molecular sieving function that selectively allows hydrogen to permeate through at least one of the pair of support plates 2i, 2j, for example. An example in which 4 is provided is shown. For example, the selective function layer 4 is preferably provided on the surface of the support plate 2 i provided on the supply side of the hydrogen permeable membrane 1 facing the hydrogen permeable membrane 1.
For example, when the hydrogen separator 10 of the present invention is used in a fuel cell, if the gas mixture on the supply side contains carbon monoxide, carbon dioxide, water, methane, etc., hydrogen permeation other than hydrogen is inhibited. When the substances to be passed through the hydrogen permeable membrane, hydrogen permeation is inhibited. For this reason, by providing the support plate 2i with, for example, a selective functional layer 4 having a molecular sieving function that selectively permeates hydrogen, carbon monoxide other than hydrogen contained in the mixed gas on the supply side. Thus, the permeability of the hydrogen permeable membrane can be further improved by preventing carbon dioxide having a permeation blocking performance lower than that of carbon monoxide.

Examples of the selective function layer include a silica layer having a molecular sieving function formed on one surface of a support plate made of a porous material by a CVD method or a sol-gel method, Al ₂ O ₃ formed by a CVD method, or the like. And a ceramic layer having a molecular sieving function.

(Embodiment 7)
FIG. 14 shows Embodiment 7 of the hydrogen separator of the present invention. As shown in FIG. 14, the hydrogen separator 10 includes a catalyst layer 5 for reforming fuel, for example, on at least one of the pair of support plates 2c and 2d. Also good. The catalyst layer 5 is preferably provided, for example, on the outer side (the side opposite to the side in contact with the hydrogen permeable membrane 1) that is easily in contact with the mixed gas of the support plate 2c on the supply side of the hydrogen permeable membrane 1.
As the catalyst layer 5, for example, the same catalyst as that for reforming the fuel to generate hydrogen can be used. When the catalyst layer 5 is provided on the support plate 2c, it is preferable because the reforming efficiency can be improved by increasing the number of catalyst layers for reforming the fuel before permeating the hydrogen permeable membrane 1.

  When a hydrogen permeable membrane made of a metal or an alloy and a pair of support plates made of a metal or an alloy are used as the hydrogen separator of the present invention, the hydrogen permeable membrane and the support plate are alloyed to form an integral body. (See FIGS. 6, 8, 10, 11, and 14).

(Embodiment 8)
As described above, when the metal or alloy hydrogen permeable membrane and the pair of metal or alloy support plates are alloyed and joined, the support plates 2k and 2l are formed as in the eighth embodiment shown in FIG. An alloying blocking portion 6 for blocking alloying is formed on at least a part of the surface facing the hydrogen permeable membrane 1, preferably all of the support plates 2k and 2l except for the entire circumference of the edge of the facing surface. It is preferable to provide (in the figure, the arrow indicates the joining direction of the support plates 2k and 2l). The entire circumference of the edge where the alloying prevention portion is not provided functions as an alloying promotion portion 20 ′, and this alloying promotion portion joins to become the joint portion 20. In addition, although illustration was abbreviate | omitted, also in another example, when using a metal or alloy support plate as a support plate, the support plate which provided the alloying prevention part in the surface facing a hydrogen permeable film is used. It is preferable.
By providing this alloying prevention part 6, when the whole peripheries of the support plates 2k and 2l and the hydrogen permeable film are alloyed and integrated, hydrogen permeation of the hydrogen permeable film 1 is blocked by alloying. The hydrogen permeable membrane 1 and the support plates 2k and 2l can be integrated without any problems.

The alloying blocking unit, _SiO 2, _Al 2 _{O 3} and heat-resistant inorganic oxide film made of a ZrO ₂ or the like formed on the surface of the support plate and the like. This film can be formed by a CVD method such as plating, a PVD method such as vacuum deposition or sputtering, or coating.

(Embodiment 9)
FIG. 16 shows Embodiment 9 of the hydrogen separator 10 of the present invention. As shown in FIG. 16, for example, when the ceramic support plates 2m and 2n of the hydrogen separator 10 are used, the support plates 2m and 2n are less rigid than the metal support plates. Further, support members 7a and 7b may be provided as second support plates having a porous material or a plurality of through-holes on the back side of the surfaces of the support plates 2m and 2n facing the hydrogen permeable membrane 1. .
As shown in FIG. 16, when the support members 7a and 7b as the second support plate are made of a metal porous material, the support member 7a provided on the supply side and the support member 7a provided on the transmission side are provided. The support member 7b may have a different average hole diameter or the like formed in each of the support members 7a and 7b.

The support member 7 may be provided to support only one support plate of the hydrogen permeable membrane, or may be provided to support both support plates as shown in FIG.
When a ceramic support plate is provided as a pair of support plates, and a pair of metal plate-shaped support members are further provided on the back surface of the pair of support plates facing the hydrogen permeable membrane, The entire periphery of the edge of the metal support member may be alloyed and joined, and integrated to form a hydrogen separator.

(Embodiment 10)
FIG. 17 shows Embodiment 10 of the hydrogen separator 10 of the present invention. As shown in FIG. 17, as the hydrogen separator 10, for example, the thickness of one support plate 2p of the pair of supports 2o and 2p is shown. Even when the hydrogen permeable membrane 1 cannot be prevented from being deformed even if the thickness is increased, a support member 7c may be further provided as a second support plate on the back surface of the support plate 2p facing the hydrogen permeable membrane 1. Good. In addition, in FIG. 17, the example using the support plate 2o which has the selection function layer 4 is shown.
For example, when the pressure on the supply side of the hydrogen permeable membrane 1 is as high as several hundred kPa, the deformation of the hydrogen permeable membrane 1 and the support plate 2p can be achieved only by increasing the thickness of the support plate 2p on the permeate side of the hydrogen permeable membrane 1. May not be prevented. In this case, by providing a support member 7c that is a second support plate that further supports the support plate 2p on the permeation side of the hydrogen permeable membrane 1, and increasing the rigidity of the member on the permeate side, the hydrogen permeable membrane 1 Can be prevented from being greatly deformed.
In this case, it is preferable that a large number of through holes 8 are formed in the support member 7c so that the hydrogen gas that has permeated from the permeation side support plate 2p can easily escape to the permeation side.

  Next, examples (embodiments 11 to 14) of an embodiment of a hydrogen separator in which a hydrogen permeable membrane and a pair of support plates are integrated, and a manufacturing method thereof will be described with reference to the drawings. 18-21 is explanatory drawing which shows the example of the manufacturing method of a hydrogen separator.

  As the hydrogen separator 10 of the present invention, when a hydrogen permeable membrane 1 made of metal or alloy and a support plate made of metal or alloy (for example, support plates 2a and 2b) are used, the hydrogen permeable membrane and a pair of support plates Are joined together by alloying them, and the alloyed parts are joined together as joints 20 to produce a hydrogen separator (FIGS. 6, 8, 10, and 11). And FIG. 14 etc.).

(Embodiment 11)
FIG. 18 shows Embodiment 11 of the hydrogen separator of the present invention. As shown in FIG. 18, as the hydrogen separator 10, the hydrogen permeable membrane 1 and the support plates 2 a and 2 b that support the hydrogen permeable membrane 1 from both sides are provided on the outer edges of the hydrogen permeable membrane 1 and the support plates 2 a and 2 b. A joining member 21 composed of a frame-like body surrounding the entire outer edge portion is provided, and a part or all of the end edge portions of the pair of support plates 2a and 2b are welded and integrated to the joining member 21 to form the hydrogen separator 10. May be manufactured. In FIG. 18, 2a ′ and 2b ′ indicate welded portions, and 6 indicates an alloying prevention portion.
For example, when the support plates 2a and 2b are made of stainless steel, if the stainless steel member is used as the joining member 21, the support plates 2a and 2b can be easily welded to the joining member 21 and the assembly workability is improved. Can be made.

Embodiment 12
FIG. 19 shows Embodiment 12 of the hydrogen separator of the present invention. As shown in FIG. 19, as the hydrogen separator 10, a part of the outer edge part or the entire outer edge part is formed on the outer edge part of the hydrogen permeable membrane 1 and the support plates 2 a and 2 b that support the hydrogen permeable film from both sides. For example, a joining member 22 may be provided that crimps and fixes the hydrogen permeable membrane 1 and the pair of support plates 2a and 2b in the stacking direction at a temperature of 600 ° C. or lower. Using this bonding member 22, the hydrogen permeable membrane 1 and the pair of support plates 2 a and 2 b are pressed in the stacking direction and airtightly integrated to manufacture the hydrogen separator 10. In FIG. 19, the arrow indicates the direction in which the joining member 22 is caulked, and 6 indicates the alloying prevention portion.
When the hydrogen permeable membrane and the pair of support plates are caulked and fixed in the laminating direction using the joining member, the hydrogen permeable membrane or the support plate is caused by a local temperature rise as in the case of fixing by welding. Has the advantage that no distortion occurs after assembly.

(Embodiment 13)
FIG. 20 shows a thirteenth embodiment of the hydrogen separator of the present invention. As shown in FIG. 20, the hydrogen separator 10 may compress the joint 20 or the part of the joining member of the support plates 2a and 2b from the outer side. By compressing the joint portion 20 or the joint member portion from the outer side, the gap between the support plates 2a and 2b and / or the support member can be crushed to increase the density, and the hydrogen separator is assembled to the apparatus. Furthermore, gas leakage from the supply side to the permeation side can be prevented.
In addition, the arrow in FIG. 20 has shown the direction which compresses the junction part 20 or the part of a joining member of support plate 2a, 2b.
When compressing the joined portion or joining member of the hydrogen separator, the joining portion or joining member is formed thick in advance, and after compression processing, the compressed portion and the uncompressed portion have the same thickness. By doing so, the assembly of the hydrogen separator into the apparatus can be facilitated.

(Embodiment 14)
FIG. 21 shows Embodiment 14 of the hydrogen separator of the present invention. As shown in FIG. 21, the hydrogen separator 10 of this example uses ceramics as the support plates 2m and 2n of the hydrogen permeable membrane 1, and the second separator 10 further supports the ceramic support plates 2m and 2n. A pair of metal support members 7a and 7b are used as the support plates.
As shown in FIG. 21, the hydrogen separator 10 includes a hydrogen permeable membrane 1, support plates 2 m and 2 n, on a part or all of the edges of the metal support members 7 a and 7 b that are the second support plates. A joining member 22 made of a porous body for caulking and fixing the support members 7a and 7b as the second support plate in the stacking direction is provided, and a holding frame made of a metal porous body is further provided on the outer periphery of the joining member 22 23 is provided, and the joining member 22 and the holding frame 23 are welded to form a strong structure.

  In the hydrogen separator 10 shown in FIG. 21, the outer edge of the hydrogen permeable membrane 1 protrudes from the support plates 2 m and 2 n and the support members 7 a and 7 b so that the protruding hydrogen permeable membrane 1 is in contact with the inner surface of the bonding member 22. It is preferable to bend (folded part 1b) and assemble. The hydrogen separator 10 is arranged so that the side where the hydrogen permeable membrane 1 is bent (folded portion 1b) is the supply side, so that components other than hydrogen reformed on the supply side (reformed side) can be contained. This has the advantage of not leaking to the transmission side.

  Next, a hydrogen separator using the hydrogen separator of the present invention and a manufacturing method thereof will be described with reference to the drawings. FIG. 22 is an exploded perspective view for explaining an example (embodiment 15) of an embodiment of a hydrogen separator using the hydrogen separator of the present invention, and FIG. 23 is a hydrogen separation using the hydrogen separator of the present invention. It is sectional drawing explaining the other example (Embodiment 16) of embodiment of an apparatus. The hydrogen separator according to the present invention is not limited to the embodiment shown in FIGS.

(Embodiment 15)
As shown in FIG. 22, the hydrogen separator 100 includes a hydrogen separator 10 having a hydrogen permeable membrane 1 and a pair of support plates 2a and 2b, and a hydrogen separator 10 with the hydrogen separator 10 interposed therebetween. 10 are provided with a pair of metal casing members 30 and 30 that form gas chambers on both sides, and a joining portion or a joining member (not shown) of the hydrogen separator 10 and a pair of metal casing members 30 and 30. And are joined. The junction between the hydrogen separator 10 or the junction member and the housing members 30 and 30 may be alloyed or welded. In addition, in FIG. 22, 6 shows an alloying prevention part.
The hydrogen separation apparatus 100 has good airtightness by joining the joint or joining member of the hydrogen separator 10 and the frame edge of the pair of housing members 30 and 30 by alloying or welding. Have

  Further, as shown in FIG. 22, the hydrogen separation apparatus 100 forms a stepped portion 31 corresponding to the thickness of the hydrogen separator 10 inside the frame portion of one housing member 30, and hydrogen separation is performed on the stepped portion 31. After the body 10 is fitted and the hydrogen separator 10 is welded to the inside of the frame portion of the housing member 30, the other housing member 30 may be alloyed or welded to the one housing member 30. Good.

(Embodiment 16)
Further, as shown in FIG. 23, the hydrogen separation device 100 may be provided with catalyst members 40, 40 between the hydrogen separator 10 and the pair of housing members 30, 30.
The hydrogen separation apparatus 100 shown in FIG. 23 has two hydrogen separators 10 and 10 and a modified gas reforming gas mixture on one side and the other side with the two hydrogen separators 10 and 10 interposed therebetween. And a pair of reforming catalyst members 40 and 40 each including a quality catalyst heating unit 41 and a reforming catalyst unit 42, and further including a pair of casing members 30 and 30 sandwiching the reforming catalyst members 40 and 40. Yes.
In this example, in the hydrogen separator 100, the joining member 22 of the hydrogen separator 10 and the fixing portions 43, 43 located around the entire periphery of the edge of the reforming catalyst members 40, 40 are joined by alloying or welding, The fixed portions 43, 43 of the reforming catalyst members 40, 40 and the entire periphery of the edge portions of the housing members 30, 30 are joined by alloying or welding.

As described above, the hydrogen separator and the hydrogen separator according to the above embodiments belonging to the scope of the present invention can prevent the hydrogen permeable membrane from being greatly deformed and prevent the hydrogen permeable membrane from being damaged. A type of hydrogen permeable membrane can be used, and the size can be reduced (thinned). Therefore, the hydrogen separator and the hydrogen separator of these embodiments can be suitably used for a fuel cell or an internal combustion engine.
In addition, since the hydrogen separator and the hydrogen separator of the above embodiment can be reduced in size (thinned), the amount of heat required at startup can be reduced, and for example, the efficiency of the fuel cell system can be increased. .

It is sectional drawing explaining the state before a deformation | transformation (a wrinkle) arises in a hydrogen permeable film, when the surface of a permeable side is supported by the support plate among the supply side and the permeable side of a hydrogen permeable film. FIG. 2 is a cross-sectional view for explaining a state in which deformation (wrinkles) has occurred in the hydrogen permeable membrane shown in FIG. 1. FIG. 3 is a cross-sectional view illustrating a state in which further deformation has occurred in the hydrogen permeable membrane in which the deformation (皺) illustrated in FIG. 2 has occurred. It is a photograph (plan view) illustrating a hydrogen permeable membrane in which a large deformation (wax) has occurred. It is a photograph (plan view) illustrating a hydrogen permeable membrane that has been damaged due to a large deformation (flaw). It is sectional drawing explaining the example of embodiment of the hydrogen separator of this invention. It is the photograph (plan view) which shows the state of the deformation | transformation (soot) formed in hydrogen permeation | transmission by the hydrogen separator of this invention. It is sectional drawing explaining the example of embodiment of the hydrogen separator of this invention. It is a disassembled perspective view explaining the example of embodiment of the hydrogen separator of this invention. FIG. 10 is a cross-sectional view illustrating a state before (a) and after (b) the formation of wrinkles on the hydrogen permeable membrane of the hydrogen separator illustrated in FIG. 9. (A) is sectional drawing which shows the example of embodiment of the hydrogen separator of this invention, (b) is an expanded sectional view which shows a part of support body of a hydrogen separator. It is an expanded sectional view which shows the example of embodiment of the hydrogen separator of this invention, and shows a part of support body which comprises a hydrogen separator. It is sectional drawing explaining the example of embodiment of the hydrogen separator of this invention. It is sectional drawing explaining the example of embodiment of the hydrogen separator of this invention. It is an exploded sectional view explaining an example of an embodiment of a hydrogen separator of the present invention. It is sectional drawing explaining the example of embodiment of the hydrogen separator of this invention. It is sectional drawing explaining the example of embodiment of the hydrogen separator of this invention. It is a partial cross section figure explaining the example of the manufacturing method of the hydrogen separator of this invention. It is a partial cross section figure explaining the example of the manufacturing method of the hydrogen separator of this invention. It is a partial cross section figure explaining the example of the manufacturing method of the hydrogen separator of this invention. It is a partial cross section figure explaining the example of the manufacturing method of the hydrogen separator of this invention. It is a disassembled perspective view which shows the example of embodiment of the hydrogen separator of this invention. It is sectional drawing which shows the example of embodiment of the hydrogen separator of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydrogen permeation membrane 1a Deformation part 1a '皺 1b Bending part 2a-2p Support body 3a, 3b Communication hole 4 Selection function layer 5 Catalyst layer 6 Alloying prevention part 7a-7c Support member 8 Through hole 10 Hydrogen separator 20 Joining Part 20 'alloying promotion part 21, 22 joining member 23 holding frame 30 housing member 31 step part 40 catalyst member 41 reforming catalyst heating part 42 reforming catalyst layer 43 fixing part 100 hydrogen separator

Claims (18)

  A metal or alloy hydrogen permeable membrane and a support plate made of a pair of porous materials for supporting the hydrogen permeable membrane from both sides, wherein one of the pair of support plates and the other have different mechanical strengths. Hydrogen separator.   The hydrogen separator according to claim 1, wherein a material is different between one of the pair of support plates and the other.   The hydrogen separator according to claim 1 or 2, wherein the thickness of one of the pair of support plates is different from that of the other.   The hydrogen separator according to any one of claims 1 to 3, wherein a porosity is different between one and the other of the pair of support plates.   The hydrogen separator according to any one of claims 1 to 4, wherein a hole diameter is different between one of the pair of support plates and the other.   The hydrogen separator according to any one of claims 1 to 5, wherein at least one of the pair of support plates has a communication hole that communicates from a surface facing the hydrogen permeable membrane to a back surface.   The hydrogen separator according to claim 6, wherein the communication hole has a hole diameter different between a surface of the support plate facing the hydrogen permeable membrane and a back surface thereof.   The hydrogen separator according to any one of claims 1 to 7, wherein a catalyst layer for reforming a mixed gas containing hydrogen is provided on at least one of the support plates.   The hydrogen separator according to any one of claims 1 to 8, wherein a selective functional layer that selectively permeates hydrogen is provided on at least one of the support plates.   The hydrogen according to any one of claims 1 to 9, wherein at least one of the pair of support plates is made of metal, and the support plate and the hydrogen permeable membrane are alloyed and joined. Separation body.   11. The hydrogen separator according to claim 10, wherein an alloying prevention portion for preventing alloying with the hydrogen permeable membrane is provided on at least a part of a surface of the support plate facing the hydrogen permeable membrane. .   12. The hydrogen according to claim 10, wherein an alloying promoting portion that promotes alloying with the hydrogen permeable membrane is provided on at least a part of a surface of the support plate facing the hydrogen permeable membrane. Separation body.   The support member which is a 2nd support plate which supports at least one of said pair of support plates from the back surface of the opposing surface with the said hydrogen-permeable film was provided. The hydrogen separator according to item.   The pair of support plates is made of metal, and has a joint portion formed by alloying and joining the pair of support plates and the entire periphery of the edge of the hydrogen permeable membrane. The hydrogen separator according to one item.   14. A bonding member that presses the hydrogen permeable membrane and the support plate in the laminating direction and fixes them by caulking is provided on the entire periphery of the edge of the hydrogen permeable membrane and the support plate. A hydrogen separator according to one of the sections.   14. A metal joining member that welds and joins the hydrogen permeable membrane and the metal support plate to the entire periphery of the edge of the hydrogen permeable membrane and the support plate. Or a hydrogen separator according to any one of the paragraphs.   A hydrogen separator according to any one of claims 1 to 16, and a pair of metal casing members that form gas chambers on both sides of the hydrogen separator with the hydrogen separator interposed therebetween. A hydrogen separation apparatus comprising: a joining portion or a joining member of the hydrogen separator; and an edge portion of the housing member.   Provided between the hydrogen separator and the housing member is a catalyst member for reforming a mixed gas containing hydrogen, and a catalyst member provided with a fixed portion on the entire periphery of the edge, and the joint of the hydrogen separator Alternatively, the hydrogen separation apparatus according to claim 17, wherein the joining member and the fixing portion of the catalyst member, and the edge portion of the casing member and the fixing portion of the catalyst member are joined.

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