JP2005288290A - Hydrogen separation purification apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen separation purification apparatus which is capable of shortening the number of assembling steps, enables the use of a different type material for a hydrogen permeable membrane, and prevents the incorporation of a hydrogen containing gas into a hydrogen-enriched gas. <P>SOLUTION: This hydrogen separation purification apparatus holds the hydrogen permeable membrane 1 and a gasket 2 loaded with compressive load P by a first supporting member 3 and a second supporting member 4. A first gasket 21 is provided with a raw material introduction aperture 21a to introduce the hydrogen containing gas into an opening part 2A and a residual gas flowing out aperture 21b to discharge the residual one of the hydrogen containing gas remaining without permeating the hydrogen permeable membrane among the hydrogen containing gases, and a purified gas flow out aperture 22a to discharge the gas after permeating the hydrogen permeable membrane among the hydrogen containing gases is installed in a second gasket 22 among the gaskets. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrogen separation and purification apparatus for recovering hydrogen from a hydrogen-containing gas through a hydrogen permeable membrane.

  In this type of hydrogen separation and purification device, a pair of porous materials are inserted into the opening in the frame from above and below, and a hydrogen permeable membrane is installed on the upper surface of one porous material and the frame that is flush with the upper surface. In addition, the hydrogen permeable membrane is joined to the frame (for example, resistance welding), and is installed on the lower surface of the other porous material and the frame that is flush with the lower surface, and the hydrogen permeable membrane is used as the frame. A product obtained by laminating a plurality of joined ones via the frame body is known (for example, Patent Document 1).

In the hydrogen separation and purification apparatus configured as described above, by supplying a hydrogen-containing gas between adjacent frames, hydrogen in the gas selectively permeates the hydrogen permeable membrane and then passes through the porous material. As a result, the hydrogen-enriched gas can be recovered through the passage.
Japanese Patent Laid-Open No. 11-300172 (FIG. 6)

  However, in the hydrogen separation and purification apparatus, there is a problem that it takes a lot of man-hours for assembly because it is necessary to join the hydrogen permeable membrane to the frame. In addition, for example, when joining by resistance welding, there is a problem that sufficient joining strength cannot be obtained if the materials of the hydrogen permeable membrane and the frame are different. Furthermore, when the hydrogen permeable membrane and the frame are not sufficiently joined, the hydrogen-containing gas enters from between the hydrogen permeable membrane and the frame, and the hydrogen-rich gas after the hydrogen-containing gas permeates the hydrogen permeable membrane. Since it is mixed in the gas, there is a problem that high purity hydrogen cannot be obtained.

  The present invention has been made in view of the above circumstances, and can be easily assembled with a small number of man-hours, can be made of various materials as a hydrogen permeable membrane, and the hydrogen-containing gas is a hydrogen permeable membrane. It is an object of the present invention to provide a hydrogen separation and purification device that does not mix with the hydrogen-enriched gas after permeation.

In order to solve the above-mentioned problems, a hydrogen separation and purification apparatus according to claim 1 is in close contact with a hydrogen permeable membrane having selective hydrogen permeability and a peripheral portion of a membrane surface of the hydrogen permeable membrane, and is opened inward. The plate-like sealing members having the portions are alternately arranged in layers, and the hydrogen-permeable membrane located at one end in the axial direction, which is the direction in which the layers are arranged, is installed via the sealing members. A plurality of the hydrogen permeable membranes and the seal members with a compressive load; and a second support member installed on the hydrogen permeable membrane located at the other end in the axial direction via the seal member. A hydrogen-containing gas is introduced into the first seal member disposed alternately in the axial direction among the seal members. A source gas introduction hole is provided for In addition, a residual gas outflow hole is provided for flowing out the residual gas that has not passed through the hydrogen permeable membrane among the hydrogen-containing gas introduced by the raw material gas introduction hole. The second seal member other than the first seal member is provided with a purified gas outflow hole through which the gas after passing through the hydrogen permeable membrane out of the hydrogen-containing gas introduced through the source gas introduction hole is provided. It is characterized by being.
The first and second support members and the hydrogen permeable membrane and seal member interposed between them are appropriately arranged so that a uniform compressive load is applied to the entire surfaces in a state where they are arranged in layers in a predetermined order. Are fastened and held using one or a plurality of high-strength bolts or the like arranged in
Therefore, the first and second support members need to be made of a material having at least the same strength, preferably higher strength, even with the same material as compared with the seal member.

  A hydrogen separation and purification apparatus according to a second aspect is the invention according to the first aspect, wherein each of the first seal members is disposed between a pair of adjacent hydrogen permeable membranes.

  According to a third aspect of the present invention, there is provided the hydrogen separation and purification apparatus according to the first or second aspect, wherein the raw material gas is introduced into the first seal member from at least one of the first support member and the second support member. A source gas supply communication hole that communicates with the hole is formed, and a residual gas discharge communication hole that communicates from at least one of the first support member and the second support member to the residual gas outflow hole of the first seal member. A purified gas discharge communication hole formed from at least one of the first support member and the second support member to the purified gas outflow hole of the second seal member is formed.

A hydrogen separation and purification apparatus according to a fourth aspect of the present invention is the invention according to any one of the first to third aspects, wherein at least one of the hydrogen permeable membranes is provided in the opening of the second sealing member among the sealing members. A back-up member having a hole that holds the membrane surface and allows the gas that has permeated through the hydrogen-permeable membrane to flow therethrough is provided.
Usually, there are many cases where the pressure of the hydrogen-containing gas is set higher than that of the hydrogen-enriched gas. In this case, the stress in the direction from the first to the second seal member is applied to the hydrogen permeable membrane surface in contact with the opening of the seal member. Therefore, it is particularly desirable to provide a backup member at the opening of the second seal member.
However, since the pressure of the hydrogen-enriched gas may be higher than the pressure of the hydrogen-containing gas, a backup member is provided at the opening of the first seal member in order to protect the hydrogen-permeable film in this case. You may comprise as follows.

  The hydrogen separation and purification apparatus according to claim 5 is the invention according to any one of claims 1 to 4, wherein the hydrogen permeable membrane is a single membrane made of one of carbon-based material, resin, ceramic, and metal. It is characterized by being formed of a composite film in which two or more kinds are laminated.

  According to a sixth aspect of the present invention, in the hydrogen separation and purification apparatus according to the fifth aspect of the present invention, the metal is mainly composed of palladium, palladium alloy, vanadium, vanadium alloy, niobium, niobium alloy, niobium-titanium-nickel. It is an alloy, an alloy mainly composed of niobium-titanium-cobalt, an amorphous alloy mainly composed of zirconium-nickel, or an amorphous alloy mainly composed of niobium-zirconium-nickel.

  According to a seventh aspect of the present invention, there is provided the hydrogen separation and purification apparatus according to any one of the first to sixth aspects, wherein the seal member is formed of a carbon-based material, a resin, a ceramic, or a metal. .

  According to an eighth aspect of the present invention, in the hydrogen separation and purification apparatus according to the seventh aspect of the present invention, the resin is a polyamide heat-resistant resin.

  According to a ninth aspect of the present invention, in the hydrogen separation and purification apparatus according to the seventh aspect of the present invention, the metal is nickel, nickel alloy, copper, copper alloy, aluminum, aluminum alloy, or stainless steel.

  A hydrogen separation and purification apparatus according to a tenth aspect of the invention is characterized in that, in the invention according to any one of the first to ninth aspects, at least one of the sealing members is constituted by a plurality of members.

  In the first to tenth aspects of the present invention, the first and second support members apply a compressive load to the plurality of hydrogen permeable membranes and the seal member, thereby causing each seal member to undergo elastic deformation or plastic deformation. Thus, the hydrogen permeation membrane is in close contact with the membrane surface and the surface of the first or second support member. For this reason, it is possible to reliably prevent the hydrogen-containing gas supplied from the source gas introduction hole to the inside of the first seal member from leaking between the first seal member and the hydrogen permeable membrane.

  Further, various gases including air can be prevented from entering the inside of the second seal member from between the second seal member and the hydrogen permeable membrane, and the first seal member The gas that has permeated the hydrogen permeable membrane from the inside and has flowed into the inside of the second seal member, that is, the hydrogen-enriched gas, can be reliably prevented from leaking between the second seal member and the hydrogen permeable membrane. Can do.

  Therefore, it is possible to prevent the hydrogen-containing gas or other gas from entering the hydrogen-enriched gas after permeating the hydrogen-permeable membrane, so that high-purity hydrogen can be removed from the purified gas outflow hole of the second seal member. It can be recovered. Moreover, it is possible to reliably prevent the hydrogen-containing gas or the hydrogen-enriched gas from leaking outside.

  Further, since it is not necessary to join the sealing member to the hydrogen permeable membrane or the first and second support members by resistance welding or the like, the sealing member can be easily assembled with less man-hours, and the hydrogen permeable membrane can be assembled to the sealing member, the first and second members. It can be made of various materials (for example, carbon-based material, resin material, ceramic material, metal material, etc.) different from the second support member.

  Further, the seal member is made of a material that can be brought into close contact with the membrane surface of the adjacent hydrogen permeable membrane or the seal surfaces of the first and second support members by the elastic deformation and plastic deformation described above, and the source gas introduction hole and One or a plurality of members having a thickness capable of processing the residual gas outflow hole are laminated. Therefore, since the seal member can be made of a relatively thin material, the dimension in the axial direction, which is the direction in which the seal member and the hydrogen permeable membrane are alternately arranged, can be reduced. That is, a compact and large hydrogen permeation area can be obtained.

  In the invention described in claim 2, since each first sealing member is disposed between a pair of adjacent hydrogen permeable membranes, the hydrogen-containing gas supplied through the source gas introduction hole is always a pair of hydrogen. It will be supplied between the permeable membranes. Therefore, the area through which hydrogen permeates in the hydrogen permeable membrane can be utilized to the maximum extent, so that the recovery efficiency of the hydrogen can be improved.

  In the invention according to claim 3, when the hydrogen-containing gas is supplied to the communication hole for supplying the source gas, the hydrogen-containing gas flows into the first seal member from the source gas introduction hole of each first seal member. Will do. In this case, the residual gas remaining in the first sealing member without passing through the hydrogen permeable membrane is discharged to the outside from the residual gas outflow hole through the residual gas discharge communication hole. Further, the gas that has passed through the hydrogen permeable membrane from each first seal member and has flowed into the second seal member, that is, the hydrogen-enriched gas, is used for exhausting the purified gas from the purified gas outflow hole of the second seal member. It will be discharged through the communication hole. Therefore, high purity hydrogen can be continuously recovered from the purified gas discharge communication hole by simply supplying the hydrogen-containing gas continuously to the raw material gas supply communication hole.

In the invention according to claim 4, while holding one membrane surface of the hydrogen permeable membrane at least in the opening of the second seal member among the first and second seal members sandwiching the hydrogen permeable membrane, Since a backup member having holes that allow the flow of the hydrogen-enriched gas that has permeated through the permeable membrane is provided, a differential pressure is generated between the two, and the hydrogen permeable membrane surface from one of the first seal members side Even if a force acting on is generated, it can be supported by the backup member. Therefore, even when the differential pressure increases, the hydrogen permeable membrane can be prevented from being damaged.
That is, in order to improve the permeation efficiency of hydrogen, it is effective to increase the pressure on the hydrogen-containing gas side and increase the hydrogen partial pressure difference from the hydrogen-enriched gas. It is preferable to provide a backup member on the side of the two sealing member openings.
However, as described above, a backup member may be provided in the opening of the first seal member.

  In the invention of claim 5, the hydrogen permeable membrane is a single membrane made of carbon-based material, a single membrane made of resin, a single membrane made of ceramic, a single membrane made of metal, a composite membrane made of resin and ceramic, By forming a composite film made of metal, a composite film made of ceramic and metal, or a composite film made of resin, ceramic and metal, it is possible to produce a hydrogen-enriched gas in accordance with the required hydrogen purity. For example, when a single membrane made of a resin is used as the hydrogen permeable membrane, it is possible to provide inexpensive hydrogen that is not high in purity, and a single metal membrane or a composite membrane including this metal membrane is used. In some cases, extremely pure and expensive hydrogen can be provided.

  In the invention described in claim 6, as the metal constituting the hydrogen permeable membrane, palladium, palladium alloy, vanadium, vanadium alloy, niobium and niobium alloy, niobium-titanium-nickel alloy, niobium-titanium- By using an alloy containing cobalt as a main component, an amorphous alloy containing zirconium-nickel as a main component, or an amorphous alloy containing niobium-zirconium-nickel as a main component, 100% of the hydrogen-containing gas can be obtained in principle. Hydrogen can be separated and recovered.

  In addition, hydrogen separation in the hydrogen permeable membrane is performed in a high temperature atmosphere of 100 to 600 ° C., but by using the above metal, a hydrogen permeable membrane that can sufficiently withstand these temperature ranges can be configured. it can.

  Furthermore, by using the above metal, the hydrogen permeable membrane can be made very thin, and a hydrogen permeable membrane having high strength that can sufficiently withstand the differential pressure between the membrane surfaces can be obtained. Therefore, it can be configured in a compact manner, and the recovery efficiency of hydrogen can be improved.

  In the seventh aspect of the present invention, the seal member is made of carbon-based material, resin, ceramic or metal, so that the seal member is elastically deformed and / or compressed by compressive load from the first and second support members. It is plastically deformed and is in close contact with the membrane surface of the hydrogen permeable membrane. In particular, when a resin and a metal are used, the sealing member can be brought into close contact with the membrane surface of the hydrogen permeable membrane by sufficiently large elastic deformation and plastic deformation, and airtightness can be improved.

  In the invention described in claim 8, since the polyamide resin having excellent heat resistance is used as the resin constituting the seal member, the seal member is corroded by the corrosive gas contained in the hydrogen-containing gas. And can be used continuously even at an ambient temperature of about 300 ° C.

  In the invention described in claim 9, since nickel, nickel alloy, copper, copper alloy, aluminum, aluminum alloy or stainless steel is used as the metal constituting the sealing member, the corrosive gas contained in the hydrogen-containing gas. Can prevent the seal member from being corroded as much as possible, and can be continuously used even in an atmosphere (for example, 600 ° C.) at the highest temperature when hydrogen is separated.

  In the invention according to claim 10, since at least one seal member is constituted by a plurality of members, for example, the source gas introduction hole and the residual gas outflow hole in the first seal member can be easily formed. This makes it possible to easily form the purified gas outflow hole in the second seal member. That is, for example, the sealing member is configured in three layers with three members, and the shape corresponding to each of these holes is located at a position corresponding to the raw material gas introduction hole, the residual gas outflow hole, and the purified gas outflow hole in the intermediate position member. By forming the notches by means such as punching press processing, it is possible to easily form a seal member having a source gas introduction hole, a residual gas outflow hole, and a purified gas outflow hole.

  As described above, according to the inventions described in claims 1 to 10, the first and second support members apply compressive loads to the plurality of hydrogen permeable membranes and the seal members, so that each seal member Since elastic deformation or plastic deformation occurs and the hydrogen permeable membrane is in close contact with the membrane surface or the surface of the first or second support member, hydrogen-containing gas or other gas passes through the hydrogen permeable membrane. It can be prevented that it is mixed into the subsequent hydrogen-enriched gas. Therefore, high purity hydrogen can be recovered from the purified gas outflow hole of the second seal member. Moreover, it is possible to reliably prevent the hydrogen-containing gas or the hydrogen-enriched gas from leaking outside.

  Further, since it is not necessary to join the sealing member to the hydrogen permeable membrane or the first and second support members by resistance welding or the like, the sealing member can be easily assembled with less man-hours, and the hydrogen permeable membrane can be assembled to the sealing member, the first and second members. The second support member and the like can be made of various materials.

  Further, the seal member is configured to have a thickness capable of being in close contact with the membrane surface of the hydrogen permeable membrane by the elastic deformation or plastic deformation described above, and capable of processing the source gas introduction hole and the residual gas outflow hole. That's fine. Therefore, since the seal member can be made of a very thin member, a compact member having a large hydrogen permeation area can be obtained.

  According to invention of Claim 2, since each 1st sealing member is arrange | positioned between a pair of adjacent hydrogen permeable membranes, a hydrogen containing gas supplied via a raw material gas introduction hole must always be a pair. It will be supplied between the hydrogen permeable membranes. Therefore, the area through which hydrogen permeates in the hydrogen permeable membrane can be utilized to the maximum extent, so that the recovery efficiency of the hydrogen can be improved.

  According to the third aspect of the present invention, high-purity hydrogen can be continuously recovered from the purified gas discharge communication hole only by continuously supplying the hydrogen-containing gas to the raw material gas supply communication hole. .

  According to the invention described in claim 4, while holding one membrane surface of the hydrogen permeable membrane in the opening of the second seal member, it is possible to distribute the hydrogen-enriched gas that has permeated the hydrogen permeable membrane. Since the backup member having the hole to be provided is provided, even when the differential pressure acting on each membrane surface of the hydrogen permeable membrane increases, the hydrogen permeable membrane can be prevented from being damaged. Moreover, by increasing the differential pressure, it is possible to improve the efficiency of hydrogen permeating through the hydrogen permeable membrane, so that the efficiency of hydrogen recovery can be improved.

  According to the invention described in claim 5, the hydrogen permeable membrane is a single membrane made of carbon-based material, a single membrane made of resin, a single membrane made of ceramic, a single membrane made of metal, a composite membrane made of resin and ceramic, a resin By forming a composite film made of metal and metal, a composite film made of ceramic and metal, or a composite film made of resin, ceramic and metal, it is possible to produce a hydrogen-enriched gas in accordance with the required hydrogen purity.

  According to the sixth aspect of the invention, palladium, palladium alloy, vanadium, vanadium alloy, niobium and niobium alloy, niobium-titanium-nickel alloy, niobium-titanium as the metal constituting the hydrogen permeable membrane. -100% from hydrogen-containing gas in principle by using an alloy based on cobalt, an amorphous alloy based on zirconium-nickel or an amorphous alloy based on niobium-zirconium-nickel Of hydrogen can be separated and recovered.

  In addition, hydrogen separation in the hydrogen permeable membrane is performed in a high temperature atmosphere of 100 to 600 ° C., but by using the above metal, a hydrogen permeable membrane that can sufficiently withstand these temperature ranges can be configured. it can.

  Furthermore, by using the above metal, the hydrogen permeable membrane can be made very thin, and a hydrogen permeable membrane having high strength that can sufficiently withstand the differential pressure between the membrane surfaces can be obtained. Therefore, it can be configured in a compact manner, and the recovery efficiency of hydrogen can be improved.

  According to the seventh aspect of the present invention, the seal member is made of carbon-based material, resin, ceramic, or metal, so that the seal member is elastically deformed and / or compressed by compressive load from the first and second support members. Alternatively, it is plastically deformed and is in close contact with the membrane surface of the hydrogen permeable membrane. In particular, when a resin and a metal are used, the sealing member can be brought into close contact with the membrane surface of the hydrogen permeable membrane by sufficiently large elastic deformation and plastic deformation, and airtightness can be improved.

  According to the eighth aspect of the present invention, since the polyamide heat-resistant resin having particularly excellent heat resistance is used as the resin constituting the seal member, the seal member is corroded by the corrosive gas contained in the hydrogen-containing gas. And can be used continuously even at an ambient temperature of about 300 ° C.

  According to the invention described in claim 9, since nickel, nickel alloy, copper, copper alloy, aluminum, aluminum alloy or stainless steel is used as the metal constituting the seal member, the corrosiveness contained in the hydrogen-containing gas is used. The seal member can be prevented from being corroded by the gas as much as possible, and can be continuously used even in an atmosphere (for example, 600 ° C.) where the hydrogen is separated at the highest temperature.

  According to the invention described in claim 10, since at least one seal member is constituted by a plurality of members, for example, the source gas introduction hole and the residual gas outflow hole in the first seal member can be easily formed. This makes it possible to easily form the purified gas outflow hole in the second seal member. That is, for example, the seal member is configured in three layers with three members, and a notch having a position and shape corresponding to the raw material gas introduction hole, the residual gas outflow hole, and the purified gas outflow hole is punched in the intermediate position member. By forming by such means, a sealing member having a raw material gas introduction hole, a residual gas outflow hole, and a purified gas outflow hole can be easily formed.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  As shown in FIGS. 1 to 7, the hydrogen separation and purification apparatus shown in this embodiment includes a hydrogen permeable membrane 1 having the ability to selectively permeate hydrogen among hydrogen-containing gases, and a membrane in the hydrogen permeable membrane 1. Plate-shaped gaskets (seal members) 2 that are in close contact with the peripheral edge of the surface 1A and have openings 2A on the inside are alternately arranged in layers, and one end in the axial direction that is the direction in which the layers are arranged A first support member 3 installed on the hydrogen permeable membrane 1 located on the other side through the gasket 2, and a second support member installed on the hydrogen permeable membrane 1 located on the other end in the axial direction through the gasket 2. The support member 4 is configured to hold the plurality of hydrogen permeable membranes 1 and the gaskets 2 in a state where a compression load P is applied.

  As shown in FIGS. 2, 3 and 7, the hydrogen permeable membrane 1 is made of Pd (palladium), Pd alloy, V (vanadium), V alloy, Nb (niobium), Nb alloy, Nb—Ti (titanium) — Depending on the metal such as an alloy containing Ni (nickel) as a main component, an amorphous alloy containing Zr (zirconium) -Ni as a main component, or an amorphous alloy containing Nb-Zr-Ni as a main component, More preferably, it is formed to a thickness of 10 to 50 μm.

Further, in this embodiment, an example in which the hydrogen permeable membrane 1 is formed in a square shape is shown (see FIG. 7), and first corners constituting source gas supply communication holes 5 to be described later are formed at the four corners. A through-hole 1a, a second through-hole 1b that forms a residual gas discharge communication hole 6 that will be described later, and third through-holes 1c and 1c that also form a purified gas discharge communication hole 7 that will also be described later are formed. . The 1st through-hole 1a and the 2nd through-hole 1b are arrange | positioned at each position of the diagonal direction of the hydrogen permeable film 1, and one 3rd through-hole 1c and the other 3rd through-hole 1c are also The hydrogen permeable membrane 1 is disposed at each position in the diagonal direction.
Hydrogen permeable membrane 1, seal member 2, first support member 3, second support member 4, opening 2A, source gas supply communication hole 5, residual gas discharge communication hole 6, and purified gas discharge communication hole 7 Of course, in addition to those shown in the present embodiment, there is no limitation on the shape as long as the function can be satisfied. Further, the number, position, and the like of the raw material gas supply communication holes 5, the residual gas discharge communication holes 6, the purified gas discharge communication holes 7 and the like are not limited to the present embodiment. It can be changed.

  As shown in FIGS. 2, 3, 5, and 6, the gasket 2 is formed in a square shape so that its outer peripheral edge substantially coincides with the outer peripheral edge of the hydrogen permeable membrane 1 and is formed inward. The opening 2A is formed in a square shape coaxial with the outer peripheral edge. In addition, at the four corners of the gasket 2, a first through hole 2a constituting a raw material gas supply communication hole 5 described later, a second through hole 2b constituting a residual gas discharge communication hole 6 described later, Similarly, third through holes 2c and 2c constituting the purified gas discharge communication hole 7 described later are formed. The 1st through-hole 2a and the 2nd through-hole 2b are arrange | positioned at each position of the diagonal direction of the gasket 2, and one 3rd through-hole 2c and the other 3rd through-hole 2c are also gaskets. It arrange | positions at each position of 2 diagonal directions.

  The gasket 2 is formed with an opening 2A, gas through-holes 2a, 2b, 2c, and the like inside by a method such as punching press processing, wire cutting processing, drilling processing, etc., using a predetermined material plate as a starting material. It is manufactured by doing. In the case of a resin material, it can also be manufactured by a method such as injection molding into a mold having a predetermined shape.

  Further, the gasket 2 has a first gasket (first seal member) 21 and a second gasket (second seal member) 22 that are alternately arranged in the axial direction described above in terms of its function. In this embodiment, the same shape can be used. However, these two types of gaskets may have different shapes due to functional requirements.

  As shown in FIG. 5, the first gasket 21 is provided with a source gas introduction hole 21 a for introducing a hydrogen-containing gas into the inside of the first gasket 21, and this source gas introduction hole A residual gas outflow hole 21b is formed for flowing out the remaining gas that has not passed through the hydrogen permeable membrane 1 out of the hydrogen-containing gas introduced by 21a. The source gas introduction hole 21a communicates with the first through hole 2a and opens on the inner peripheral surface of the corner of the opening 2A near the first through hole 2a. The residual gas outflow hole 21b communicates with the second through-hole 2b and opens on the inner peripheral surface of the corner of the opening 2A in the vicinity of the second through-hole 21b.

  On the other hand, as shown in FIG. 6, the second gasket 22 is formed with a pair of purified gas outflow holes 22a and 22a. Each purified gas outflow hole 22a passes through the hydrogen permeable membrane 1 out of the hydrogen-containing gas introduced into the opening 2A of the first gasket 21 through the source gas introduction hole 21a, and the opening of the second gasket 22. 2A for flowing out gas that has flowed into 2A, that is, hydrogen-enriched gas, and communicates with each of the third through holes 2c, and at the corners of the openings 2A near the third through holes 2c. Open to the inner peripheral surface.

  Further, as shown in FIGS. 2 and 3, the first gasket 21 is always arranged between a pair of adjacent hydrogen permeable membranes 1. In contrast, the second gasket 22 is also disposed between the hydrogen permeable membrane 1 and the first support member 3 and between the hydrogen permeable membrane 1 and the second support member 4. Yes. However, the first gasket 21 may also be provided between the hydrogen permeable membrane 1 and the first support member 3 or between the hydrogen permeable membrane 1 and the second support member 4.

  Each gasket 2 is 0.05 to 5 mm, more preferably 0.08, depending on a metal such as Ni, Ni alloy, Cu (copper), Cu alloy, Al (aluminum), Al alloy or SUS (stainless steel). It is formed to a thickness of ˜3 mm.

  The thickness of the gasket 2 is set to 0.05 mm or more as described above, when the thickness is less than 0.05 mm, when the elastic deformation or plastic deformation is caused by the compression load P described above, the hydrogen permeable membrane 1 and the first support member 3 and the second support member 4 can not take the deformation allowance necessary to keep hermeticity, and the processing of the source gas introduction hole 21a, the residual gas outflow hole 21b or the purified gas outflow hole 22a becomes difficult. In addition, it is difficult to handle because of its small rigidity and easy deformation.

  Further, the thickness of the gasket 2 is set to 5 mm or less as described above, and when the thickness exceeds 5 mm, when the hydrogen permeable membrane 1 is alternately laminated, the axial dimension of the lamination increases, and the volume efficiency is increased. It is because it will fall.

  For this reason, it is more preferable to set the thickness of the gasket 2 to 0.08 to 3 mm for the above-described reasons.

As shown in FIGS. 1 to 2, the first and second support members 3 and 4 are formed in a square shape so that the outer peripheral edge substantially coincides with the outer peripheral edge of the hydrogen permeable membrane 1 or the gasket 2, for example, made of SUS. It is formed of a (metal) plate.
However, the first and second support members 3 and 4 have a compressive load P for maintaining the air-tightness of the hydrogen permeable membrane 1 and the first and second gaskets 21 and 22 arranged in layers between them. These are fastened and held by using one or a plurality of high-strength bolts or the like appropriately arranged so that they are uniformly added.
Accordingly, the first and second support members 3 and 4 are functionally at least equal in strength and preferably higher in strength than the first and second gaskets 21 and 22 in function. Must be used.

The first support member 3 has first through holes 3 a formed at positions corresponding to the first through holes 1 a and 2 a in the hydrogen permeable membrane 1 and the gasket 2.
The second support member 4 has second through holes 4b formed at positions corresponding to the second through holes 1b and 2b in the hydrogen permeable membrane 1 and the gasket 2, and the hydrogen permeable membrane 1 And the 3rd through-hole 4c, 4c is formed in the position corresponding to each 3rd through-hole 1c, 1c, 2c, 2c in the gasket 2, respectively.

  For this reason, the hydrogen gas permeable membrane 1, the gasket 2, and the first through holes 1 a, 2 a, and 3 a of the first support member 3 pass from the first support member 3 to the source gas introduction holes 21 a of the first gaskets 21. The material gas supply communication hole 5 (FIGS. 1, 2, and 4) to be communicated is formed. The hydrogen permeable membrane 1, the gasket 2 and the second through holes 1 b, 2 b and 4 b of the second support member 4 lead from the second support member 4 to the residual gas outflow holes 21 b of the first gasket 21. The remaining gas discharge communication hole 6 (FIGS. 1, 2, and 4) is configured. Further, the hydrogen permeable membrane 1, the gasket 2, and the third through holes 1 c, 2 c, and 4 c of the second support member 4 pass from the second support member 4 to the purified gas outflow holes 22 a of the second gasket 22. The communication hole 7 (FIGS. 1, 3 and 4) through which the purified gas is discharged is configured.

  The first through hole 3 a formed in the first support member 3 may be provided in the second support member 4 or both the first and second support members 3 and 4. The second and third through holes 4b and 4c formed in the second support member 4 may be provided in the first support member 3 or both the first and second support members 3 and 4. .

In addition, as the hydrogen-containing gas described above, for example, a mixed gas obtained by steam reforming a hydrocarbon-based raw material such as methanol, gasoline, LNG, or LPG, or other gas containing hydrogen can be used.
The hydrogen-containing gas is normally supplied from the source gas supply communication hole 5 to the opening 2A of the first gasket 21 through the source gas introduction hole 21a at a pressure of 0.15 to 2.0 MPa. Hydrogen is separated in a position corresponding to the hydrogen permeable membrane 1 while being maintained in a high temperature atmosphere of 100 to 600 ° C.

  In the hydrogen separation and purification apparatus configured as described above, each gasket 2 is formed by applying a compressive load P to the plurality of hydrogen permeable membranes 1 and gaskets 2 by the first and second support members 3 and 4. Elastic deformation or plastic deformation occurs, and the hydrogen permeable membrane 1 is surely in close contact with the membrane surface 1A and the inner surfaces of the first or second support members 3 and 4. For this reason, even when the inside of the opening 2A of the first gasket 21 is pressurized to a pressure of 0.15 to 2.0 MPa, the gasket 2 is sufficiently elastically plastically deformed, so that the hydrogen-containing gas becomes the first gas. Leakage from between the gasket 21 and the hydrogen permeable membrane 1 can be prevented.

  Further, various gases including air can be prevented from entering the opening 2A of the second gasket 22 from between the second gasket 22 and the hydrogen permeable membrane 1, and the first gasket. It is possible to prevent the hydrogen-enriched gas that has permeated the hydrogen permeable membrane 1 from the 21 side and flowed into the second gasket 22 side from leaking between the second gasket 22 and the hydrogen permeable membrane 1.

  Accordingly, it is possible to prevent the hydrogen-containing gas or other gas from being mixed into the hydrogen-enriched gas that has passed through the hydrogen permeable membrane 1, so that high-purity hydrogen can be recovered. Moreover, it is possible to prevent the hydrogen-containing gas or the hydrogen-enriched gas from leaking to the outside.

  Further, since it is not necessary to join the gasket 2 to the hydrogen permeable membrane 1 and the first and second support members 3 and 4 by resistance welding or the like, the gasket 2 can be easily assembled with less man-hours, and the hydrogen permeable membrane 1 can be attached to the gasket. 2 and the first and second support members 3 and 4 can be made of the above-described various metal materials having different materials. Further, the hydrogen permeable membrane 1 can be made of, for example, a carbon-based material, a resin material, a ceramic material, or the like other than metal.

  Furthermore, the gasket 2 has a thickness that allows a deformation allowance that can prevent the above-described gas leakage, and a thickness that can process the source gas introduction hole 21a and the residual gas outflow hole 21b. Since it is good, it can comprise by the very thin thing as mentioned above. Therefore, since the axial dimension can be suppressed, a compact, large hydrogen permeation area and high hydrogen recovery efficiency can be obtained.

  In addition, since each first gasket 21 is necessarily disposed between a pair of adjacent hydrogen permeable membranes 1, a hydrogen-containing gas is necessarily supplied between the pair of hydrogen permeable membranes 1. . Therefore, since the area of the hydrogen permeable membrane 1 can be effectively used to the maximum extent, it is possible to improve the hydrogen recovery efficiency.

  Further, when the hydrogen-containing gas is supplied to the source gas supply communication hole 5, the hydrogen-containing gas flows into the first gasket 21 from the source gas introduction hole 21 a of each first gasket 21, and the hydrogen permeable membrane. The residual gas remaining in the first gasket 21 without passing through 1 is discharged to the outside through the residual gas discharge communication hole 6 from the residual gas outlet hole 21b positioned diagonally to the raw material gas introduction hole 21a. become. Further, the hydrogen-enriched gas that has permeated the hydrogen permeable membrane 1 from each first gasket 21 and flowed into the second gasket 22 is diagonally arranged in which the source gas introduction hole 21a and the residual gas outflow hole 21b are arranged. Are exhausted through the purified gas discharge communication holes 7 from the purified gas outflow holes 22a arranged in the diagonal direction orthogonal to each other. Accordingly, high-purity hydrogen can be continuously recovered from the purified gas discharge communication hole 7 simply by continuously supplying the hydrogen-containing gas to the raw material gas supply communication hole 5. Moreover, the residual gas discharged | emitted from the communicating hole 6 for residual gas discharge | emission can also be used again as hydrogen containing gas as needed.

  Further, by using each of the above-described metals as the hydrogen permeable membrane 1, in principle, 100% hydrogen can be separated and recovered from the hydrogen-containing gas. In this case, since the hydrogen-containing gas is supplied at the pressure of 0.15 to 2.0 MPa described above, and the pressure of the recovered hydrogen-enriched gas is maintained at approximately 0.1 MPa, About 0.05 to 1.9 MPa acts on the film surface 1A as a differential pressure between the two. Here, the hydrogen partial pressure in the hydrogen-containing gas (changes depending on the hydrogen content) is equal to the hydrogen partial pressure in the hydrogen-enriched gas (when the hydrogen-enriched gas is almost 100% hydrogen) ) Is higher, the molecular hydrogen in the hydrogen-containing gas becomes atomic hydrogen from one film surface 1A and enters the lattice formed by the metal atoms of the hydrogen permeable membrane 1, and the hydrogen partial pressure difference By passing through the lattice and becoming molecular hydrogen (gas) again on the other film surface 1A side, only hydrogen gas can be selectively separated and purified.

  Furthermore, hydrogen separation in the hydrogen permeable membrane 1 is performed in a high temperature atmosphere of 100 to 600 ° C., but by selecting a metal hydrogen permeable membrane suitable for the above hydrogen separation conditions, in these temperature ranges. The hydrogen permeable membrane 1 that can withstand sufficiently can be configured.

  In addition, by using the metal as the hydrogen permeable membrane 1, even when the hydrogen permeable membrane 1 is configured to be extremely thin as 5 to 100 μm as described above, it is between the first gasket 21 and the second gasket 22. A hydrogen-permeable membrane 1 having a high strength that can sufficiently withstand a differential pressure (0.05 to 1.9 MPa) can be obtained. Therefore, it can be configured in a compact manner, and the recovery efficiency of hydrogen can be improved. The reason why the thickness of the hydrogen permeable membrane 1 is set to 5 to 100 μm is that if the thickness is less than 5 μm, the hydrogen permeable membrane 1 may be damaged by the above-mentioned differential pressure. This is because the hydrogen separation efficiency decreases. Therefore, for this reason, the thickness of the hydrogen permeable membrane 1 is more preferably set to a thickness of 10 to 50 μm as described above.

  In addition, for the gasket 2, by selecting a metal material suitable for each hydrogen separation condition, it is possible to prevent the gasket 2 from being corroded by the corrosive gas contained in the hydrogen-containing gas as much as possible. It can be used continuously in an atmosphere (for example, 600 ° C.) at the highest temperature when separating hydrogen.

  In the above embodiment, the hydrogen permeable membrane 1 is composed of the above-described metal single membrane. However, the hydrogen permeable membrane 1 may be a single membrane made of a carbon-based material or a single membrane made of a resin. A single film made of ceramic, a composite film made of resin and ceramic, a composite film made of resin and each of the above metals, a composite film made of ceramic and each of the above metals, or a composite film of resin, ceramic and each of the above metals may be used. Thus, by selecting the material constituting the hydrogen permeable membrane 1, it becomes possible to produce a hydrogen-enriched gas that conforms to the required purity of hydrogen. For example, when the hydrogen permeable membrane 1 is constituted by a single membrane of resin, it is possible to provide inexpensive hydrogen that is not high in purity, but also a single membrane of each metal or a composite membrane including this metal membrane. In the case where the hydrogen permeable membrane 1 is configured, hydrogen with extremely high purity and high price can be provided.

  The gasket 2 may be made of a carbon-based material, resin, ceramic, or the like. For example, when using a resin, it is preferable to use a polyamide-based heat-resistant resin. When the gasket 2 is made of a polyamide-based heat-resistant resin, the gasket 2 can be prevented from being corroded by the corrosive gas contained in the hydrogen-containing gas, and continuously at an ambient temperature of about 300 ° C. Can be used for Moreover, since a large elastic-plastic deformation occurs due to the compressive load P, it is possible to reliably prevent the hydrogen-containing gas from leaking between the hydrogen permeable membrane 1 and the gasket 2 even when a high-pressure hydrogen-containing gas is supplied. Can do.

  Further, the hydrogen permeable membrane 1, the gasket 2, the first support member 3 and the second support member 4 are shown in the form of a square, but these are rectangular, other polygonal, circular, elliptical. You may comprise in other shapes, such as a shape.

  On the other hand, in the above-described embodiment, the second gasket 22 having the square opening 2A on the inside is shown, but the opening 2A of the second gasket 22 has the hydrogen permeable membrane 1 in the opening 2A. You may comprise so that the backup member which has the hole which enables the distribution | circulation of the hydrogen rich gas which permeate | transmitted the said hydrogen permeable film 1 while holding one membrane surface 1A may be provided. The backup member in this case is, for example, a porous material having a plurality of holes communicating with the purified gas outflow hole 22a, a member having a meandering slit communicating with the purified gas outflow hole 22a, or a punching metal member having a plurality of holes Or the like.

FIG. 8 shows a first other example in which a backup member having a slit 22b meandering in the opening 2A of the second gasket 22 is integrally formed. That is, on the square plate constituting the second gasket 22, the slit 22 b is formed to meander a plurality of times in the portion corresponding to the opening 2 A described above, and each end of the meandering slit 22 b is purified. It is configured by communicating with the gas outflow hole 22a.
The first gasket 21 may also be configured in the same manner as in the first other example of the second gasket 22. However, in this case, each end of the slit 22b is communicated with the source gas introduction hole 21a and the residual gas outflow hole 21b.

FIG. 9 shows a second other example in which a punching metal member (backup member) having a plurality of holes is integrally formed in the opening 2 </ b> A of the second gasket 22. That is, a flat plate 22c integrated with the second gasket 22 is formed on the side corresponding to the one membrane surface 1A of the hydrogen permeable membrane 1 at a portion corresponding to the opening 2A, and the hydrogen permeable membrane on the flat plate 22c is formed. A recess 22d having the same size as that of the opening 2A is formed on the opposite side to 1. The flat plate portion 22c is formed with a plurality of holes 22e through which the hydrogen-enriched gas that has passed through the hydrogen permeable membrane 1 can pass, and a purified gas outflow hole 22a is opened on the inner peripheral surface of the corner of the recess 22d. doing. The second gasket 22 configured in this way is used in a state where the surfaces on the concave portion 22d side are overlapped.
The first gasket 21 may also be configured similarly to the second other example of the second gasket 22.

  When the second gasket 22 having the respective backup members as described above is used, it acts on each membrane surface 1A of the hydrogen permeable membrane 1 by the pressure of the hydrogen-containing gas supplied into the first gasket 21. Even when the differential pressure increases, the hydrogen permeable membrane 1 can be supported by the backup member. Therefore, since the differential pressure can be increased, the efficiency of hydrogen permeating the hydrogen permeable membrane 1 can be improved, and the hydrogen recovery efficiency can be improved.

  Further, when each of the backup members as described above is provided in the first gasket 21, the hydrogen permeable membrane 1 can be protected even when a back flow of gas occurs due to a high back pressure or the like. it can.

  The first gasket 21 and the second gasket 22 may be constituted by a plurality of members (three in the example shown here) as shown in FIGS.

  That is, as shown in FIG. 10, the first gasket 21 is configured in three layers by an upper surface member 211, an intermediate surface member 212, and a lower surface member 213 formed in a square plate shape. That is, FIG. 10 shows a third other example of the first gasket 21. Each member 211, 212, 213 is formed with the above-described opening 2A, first through hole 2a, second through hole 2b, and third through hole 2c. In addition, the intermediate surface member 212 has notches 21A and 21B having the same shape in plan view as the holes 21a and 21b at positions corresponding to the raw material gas introduction holes 21a and the residual gas outflow holes 21b. .

Therefore, by laminating the upper surface member 211, the intermediate surface member 212, and the lower surface member 213, the first gasket 21 having the source gas introduction hole 21a, the residual gas outflow hole 21b, and the like can be configured.
In this case, the notches 21A and 21B corresponding to the source gas introduction hole 21a and the residual gas outflow hole 21b are punched, wire cut, drilled, etc., like the opening 2A and the through holes 2a, 2b, and 2c. By this method, the intermediate surface member 212 can be easily formed. Therefore, the thin first gasket 21 having the source gas introduction hole 21a and the residual gas outflow hole 21b can be easily manufactured.

  On the other hand, as shown in FIG. 11, the second gasket 22 is configured in three layers by an upper surface member 221, an intermediate surface member 222, and a lower surface member 223 formed in a square plate shape. That is, FIG. 11 shows a third other example of the second gasket 22. Each member 221, 222, 223 is formed with the above-described opening 2A, first through hole 2a, second through hole 2b, and third through hole 2c. Further, the intermediate surface member 222 has notches 22A and 22A having the same shape in plan view as the holes 22a and 22a at positions corresponding to the purified gas outflow holes 22a and 22a.

  Therefore, the first gasket 21 having the purified gas outflow holes 22a, 22a and the like can be configured by laminating the upper surface member 221, the intermediate surface member 222, and the lower surface member 223. Therefore, for the same reason as the three-layered first gasket 21 described above, the thin second gasket 22 having the purified gas outflow holes 22a and 22a can be easily manufactured.

  Moreover, you may combine the 2nd other example which has the backup member mentioned above, and the 3rd other example with respect to the 2nd other example of the 1st gasket 21 and the 1st gasket 21. FIG.

It is a top view of the hydrogen separation refinement | purification apparatus shown as one embodiment of this invention. It is a figure which shows the same hydrogen separation refinement | purification apparatus, Comprising: It is sectional drawing which follows AC (centroid) -B of FIG. It is a figure which shows the same hydrogen separation refinement | purification apparatus, Comprising: It is sectional drawing in alignment with ACD of FIG. It is a bottom view of the same hydrogen separation purification apparatus. It is a front view which shows the 1st gasket in the same hydrogen separation refinement | purification apparatus. It is a front view which shows the 2nd gasket in the same hydrogen separation refinement | purification apparatus. It is a front view which shows the hydrogen permeable membrane in the hydrogen separation refinement | purification apparatus. It is a front view which shows the 1st other example of the 2nd gasket in the hydrogen separation refinement | purification apparatus. It is a front view which shows the 2nd other example of the 2nd gasket in the same hydrogen separation refinement | purification apparatus. It is a figure which shows the 3rd other example of the 1st gasket in the hydrogen separation refinement | purification apparatus, Comprising: (a) is a disassembled perspective view, (b) is sectional drawing which follows the BB line in (a). . It is a figure which shows the 3rd other example of the 2nd gasket in the same hydrogen separation refinement | purification apparatus, Comprising: (a) is a disassembled perspective view, (b) is sectional drawing which follows the BB line in (a). .

Explanation of symbols

1 Hydrogen permeable membrane 1A Membrane surface 2 Gasket (seal member)
2A Opening 3 First support member 4 Second support member 5 Material gas supply communication hole 6 Residual gas discharge communication hole 7 Purified gas discharge communication hole 21 First gasket (first seal member)
21a Raw material gas introduction hole 21b Residual gas outflow hole 22 Second gasket (second seal member)
22a Purified gas outflow hole 22e Hole P Compressive load

Claims (10)

A hydrogen permeable membrane having selective hydrogen permeability and a plate-like sealing member having an opening inward in close contact with the peripheral portion of the membrane surface of the hydrogen permeable membrane are alternately arranged in layers. A first support member installed via the seal member on the hydrogen permeable membrane located at one end in the axial direction, which is the direction in which the gas is disposed, and the hydrogen permeation located at the other end in the axial direction With the second support member installed on the membrane via the seal member, the plurality of hydrogen permeable membranes and the seal member are held in a state where a compression load is applied,
Of the sealing members, the first sealing members arranged every other in the axial direction are provided with source gas introduction holes for introducing the hydrogen-containing gas into the inside of the first sealing member. In addition, a residual gas outflow hole is provided for flowing out the residual gas remaining without passing through the hydrogen permeable membrane among the hydrogen-containing gas introduced by the raw material gas introduction hole.
The second sealing member other than the first sealing member among the sealing members is purified to flow out the gas after passing through the hydrogen permeable membrane among the hydrogen-containing gas introduced by the source gas introduction hole. A hydrogen separation and purification apparatus, wherein a gas outflow hole is provided.   2. The hydrogen separation and purification apparatus according to claim 1, wherein each of the first seal members is disposed between a pair of adjacent hydrogen permeable membranes. A source gas supply communication hole communicating from at least one of the first support member and the second support member to the source gas introduction hole of the first seal member is formed,
A residual gas discharge communication hole communicating from at least one of the first support member and the second support member to the residual gas outflow hole of the first seal member is formed;
The purified gas discharge communication hole is formed from at least one of the first support member and the second support member to the purified gas outflow hole of the second seal member. 2. The hydrogen separation and purification apparatus according to 2.   At least the second sealing member of the sealing member has a back-up having a hole that holds one membrane surface of the hydrogen permeable membrane and allows the gas that has permeated the hydrogen permeable membrane to flow therethrough. The hydrogen separation and purification apparatus according to any one of claims 1 to 3, wherein a member is provided.   The hydrogen permeable membrane is formed of a single membrane made of one of a carbon-based material, a resin, a ceramic, and a metal, or a composite membrane in which two or more are laminated. The hydrogen separation and purification apparatus according to claim 1.   The metal is palladium, palladium alloy, vanadium, vanadium alloy, niobium, niobium alloy, an alloy mainly composed of niobium-titanium-nickel, an alloy mainly composed of niobium-titanium-cobalt, and mainly composed of zirconium-nickel. The hydrogen separation and purification apparatus according to claim 5, wherein the hydrogen separation and purification apparatus is an amorphous alloy or an amorphous alloy mainly composed of niobium-zirconium-nickel.   The hydrogen separation and purification apparatus according to claim 1, wherein the seal member is formed of a carbon-based material, a resin, a ceramic, or a metal.   The hydrogen separation and purification apparatus according to claim 7, wherein the resin is a polyamide-based heat-resistant resin.   The hydrogen separation and purification apparatus according to claim 7, wherein the metal is nickel, nickel alloy, copper, copper alloy, aluminum, aluminum alloy, or stainless steel.   The hydrogen separation and purification apparatus according to claim 1, wherein at least one of the sealing members is constituted by a plurality of members.

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