JP2005162586A - Apparatus for manufacturing hydrogen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen manufacturing apparatus which has hydrogen manufacturing reaction tubes of a simple structure and which has high durability. <P>SOLUTION: The hydrogen manufacturing apparatus 101 is equipped with a reactor 102, a header part 103 and a heating part 104. The hydrogen manufacturing reaction tube 112 constituting the reactor 102 is equipped with a tube wall 203, a carrier 202 for carrying a steam reforming catalyst, a membrane tube 204 which is a porous tube 205 having a hydrogen separating membrane 206 on the surface, a gaseous raw material supply tube 116, a hydrogen recovering tube 117, and an off gas recovering tube 118. Since the carrier 202 is integrally joined to the tube wall 203 of the hydrogen manufacturing reaction tube 201, the contact of the carrier 202 and the hydrogen separating membrane 206 is completely prevented and the durability of the hydrogen separating membrane 206 is improved. Since the wall surface of the hydrogen manufacturing reaction tube 112 and the carrier 202 are integrally joined, the structure of the hydrogen manufacturing reaction tube can be made simple and the manufacturing is made easy. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a reaction tube for hydrogen production, and more particularly to a reaction tube for hydrogen production using a steam reforming catalyst and a hydrogen separation membrane.

  Hydrogen used for fuel cells is required to have high purity. Therefore, development of a hydrogen production apparatus that can obtain high-purity hydrogen is being promoted.

  One method for realizing a hydrogen production apparatus that obtains high-purity hydrogen is to use a hydrogen production apparatus that includes a steam reforming catalyst and a hydrogen separation membrane. The steam reforming catalyst converts hydrocarbons or oxygen-containing hydrocarbons from which steam has been converted to produce hydrogen. The hydrogen separation membrane separates and removes the generated hydrogen. The hydrogen production apparatus that separates hydrogen using a hydrogen separation membrane can generate high-purity hydrogen.

A hydrogen production apparatus including a steam reforming catalyst and a hydrogen separation membrane can also increase the efficiency of the steam reforming reaction. The steam reforming reaction of hydrocarbon is represented by a reforming reaction of formula (1) and a carbon monoxide shift reaction of formula (2).
C _n H _m + nH ₂ O ← → nCO + (n + m / 2) H ₂ (1)
CO + H ₂ O ← → CO ₂ + H ₂ (2)
When the hydrogen produced by the steam reforming reaction is separated from the reaction site, the reactions of formulas (1) and (2) proceed to the right. Since the hydrogen production apparatus provided with the hydrogen separation membrane can sequentially separate the generated hydrogen, a high conversion rate can be realized at a low reaction temperature.

  It is desirable that the hydrogen production apparatus has a structure that can cope with a change in the flow rate of the raw material gas, that is, a change in the operation load, and can be applied to a steam reforming catalyst that is easily pulverized.

Patent Document 1 discloses such a hydrogen production apparatus. FIG. 7 shows the structure of the hydrogen production apparatus 501 disclosed in Patent Document 1. The known hydrogen production apparatus 501 has an outer cylinder 502 and inner cylinders 503 and 504 sequentially contained inside the outer cylinder, and an upper portion of an annular space 505 formed between the two inner cylinders. Is blocked. The annular space 505 is connected to a source gas supply port 510 for supplying source gas. As the source gas, a hydrocarbon or oxygen-containing hydrocarbon added with water vapor is used. In the annular space 505, a plurality of membrane tubes 506 having hydrogen permeable membranes (not shown) are arranged at regular intervals. The membrane tube 506 is installed so that its upper part becomes a free end. A particulate steam reforming catalyst 507 is filled around the membrane tube 506 in the annular space 505. The membrane tube 506 communicates with each other at the lower end and is connected to the hydrogen outlet 511. A combustion chamber 509 is formed inside the middle cylinder 504. A burner 508 is installed upward in the lower part of the combustion chamber 509.
Japanese Patent No. 3202440

  The hydrogen production apparatus 501 generates hydrogen by the following operation. The burner 508 is supplied with air and fuel. The supplied air and fuel are burned by the burner 508, and high-temperature combustion gas is generated. The steam reforming catalyst 507 is heated to the steam reforming reaction temperature of 500 to 600 ° C. by the combustion gas. The raw material gas is introduced into the annular space 505 while the steam reforming catalyst 507 is heated. The introduced source gas is decomposed by the steam reforming catalyst 507, and mainly hydrogen and carbon dioxide are generated. The generated hydrogen is separated by a hydrogen separation membrane, whereby high purity hydrogen is collected inside the membrane tube 506. The collected high-purity hydrogen is recovered from the hydrogen outlet 511.

  The structure of the membrane tube 506 and the burner 508 described above makes it possible to apply a catalyst that can flexibly and stably respond to fluctuations in the operation load and that is easily pulverized to the steam reforming catalyst 507. The membrane tube 506 installed so that the upper part becomes a free end reduces the mutual friction between the steam reforming catalyst 507 and the hydrogen separation membrane caused by thermal expansion. Furthermore, the burner 508 installed upward and downward stabilizes the flame that generates combustion gas. Therefore, the hydrogen production apparatus 501 can flexibly and stably cope with fluctuations in the operation load, and can apply a steam reforming catalyst that is easily pulverized to the steam reforming catalyst 507.

It is also desired that a hydrogen production apparatus be uniformly filled with a steam reforming catalyst and improve the durability of the hydrogen separation membrane. A hydrogen production apparatus that solves the above problems is disclosed in Patent Document 2.
JP 2001-31403 A

  The hydrogen production apparatus disclosed in Patent Document 2 uses a shaped plate catalyst instead of the particulate steam reforming catalyst. The hydrogen production apparatus has an annular space formed between two middle cylinders sequentially contained inside the outer cylinder, similarly to the hydrogen production apparatus of Patent Document 1. A unit including a rectangular parallelepiped membrane tube having a hydrogen permeable membrane and a plate-shaped steam reforming catalyst is accommodated in the annular space. FIG. 8 shows a unit of a membrane tube and a plate-shaped steam reforming catalyst housed in an annular space. The plate-shaped steam reforming catalyst 601 is disposed via a spacer 603 between a plurality of membrane tubes 602 having a hydrogen separation membrane (not shown) on the wall surface. The spacer 603 is fixed to the membrane tube 602 and the plate-shaped steam reforming catalyst 601 by welding. The space inside the middle cylinder is a combustion chamber as in the hydrogen production device disclosed in Patent Document 1. A burner is installed downward in the upper part of the combustion chamber.

  The hydrogen production apparatus disclosed in Patent Document 2 operates in the same manner as the hydrogen production apparatus disclosed in Patent Document 1, although the installation position of the burner is different from the hydrogen production apparatus disclosed in Patent Document 1.

  The structure of the membrane tube 602 and the plate-shaped steam reforming catalyst 601 described above makes it possible to uniformly fill the steam reforming catalyst and extend the life of the hydrogen separation membrane. Since the steam reforming catalyst 601 is formed into a plate shape, the steam reforming catalyst can be uniformly filled around the membrane tube 602. Furthermore, since there is a spacer 603 between the plate-shaped steam reforming catalyst 601 and the hydrogen separation membrane (not shown), an appropriate interval between the steam reforming catalyst and the hydrogen separation membrane is maintained, and the hydrogen separation membrane and Contact with the plate-like steam reforming catalyst can be prevented, and the life of the hydrogen separation membrane can be extended.

  In order to further extend the life of the hydrogen separation membrane, it is important to completely prevent contact between the hydrogen separation membrane and the steam reforming catalyst. In addition, the reaction tube for hydrogen production is desired to have a simple structure and easy production.

  An object of the present invention is to provide a hydrogen production apparatus having a hydrogen production reaction tube having a simple structure and having high durability.

  A hydrogen production apparatus according to the present invention comprises a carrier for supporting a steam reforming catalyst, a carrier support member for supporting the carrier, a hydrogen production reaction tube containing a hydrogen separation membrane, and a raw material gas in the hydrogen production reaction tube. Supply means for supplying and recovery means for recovering hydrogen from the reaction tube for hydrogen production are provided. The carrier and the carrier support member are integrally joined and are disposed away from the hydrogen separation membrane, preferably a gap between the carrier and the hydrogen separation membrane is 1 mm or less, more preferably Is installed in a state kept at 0.05 mm or less.

  According to the above-described hydrogen production apparatus, the contact between the hydrogen separation membrane and the steam reforming catalyst can be completely eliminated, so that the durability of the hydrogen separation membrane can be improved. Since the steam reforming catalyst is fixed to the support member and is positioned away from the hydrogen separation membrane, thermal expansion causes fluctuations in the position of the hydrogen production reaction tube wall and the hydrogen separation membrane. However, there is no direct contact between the steam reforming catalyst and the hydrogen separation membrane.

  Furthermore, according to the above-described hydrogen production apparatus, the structure of the reaction tube for hydrogen production can be simplified. This is because the carrier carrying the steam reforming catalyst and the carrier supporting member can be assembled and fixed together.

  Furthermore, according to the above-described hydrogen production apparatus, hydrogen can be produced efficiently. By narrowing the gap between the carrier carrying the steam reforming medium and the hydrogen separation membrane, the gas flow rate can be increased, the future diffusion in the direction perpendicular to the gas flow can be improved, and the steam reforming reaction rate can be prevented from decreasing. .

  An inner wall of a reaction tube for hydrogen production may be used as the carrier support member. One method of joining the carrier integrally with the inner wall of the reaction tube for producing hydrogen is to provide the carrier on the inner wall surface. By coating the inner wall of the reaction tube for hydrogen production with a carrier and supporting the steam reforming catalyst thereon, the inner wall and the carrier can be joined together.

  In the hydrogen production reaction tube, the inner wall of the hydrogen production reaction tube supports the carrier carrying the steam reforming catalyst, and the membrane tube having a hydrogen separation membrane on the surface is provided in the hydrogen production reaction tube. It can be manufactured by a step of installing it opposite to the hydrogen separation membrane.

  The carrier can be supported on the inner wall of the reaction tube for hydrogen production by the step of providing the carrier on the inner wall and the step of supporting the steam reforming catalyst on the carrier. In addition to the method described above, the wall surface and the water vapor can also be obtained by forming the support into a predetermined shape and supporting the steam reforming catalyst on the support and fixing the support to the inner wall of the hydrogen production reaction tube. The reforming catalyst can be joined together.

  When the carrier support member is an inner wall of a hydrogen production reaction tube, the hydrogen production reaction tube has an outer wall facing the inner wall, and the outer wall is contacted with a heating fluid generated by a heating means. Good. The heating fluid is, for example, a high-temperature combustion gas obtained by burning hydrocarbons or oxygen-containing hydrocarbons.

  According to the above-described hydrogen production reaction tube, the steam reforming catalyst can be directly heated through the wall of the hydrogen production reaction tube. Heat necessary for the steam reforming reaction is efficiently supplied.

  A metal plate having a through hole may be used as the carrier support member. The metal plate is covered with a carrier, and the carrier carries a steam reforming catalyst. In this way, the carrier and the carrier support member can be joined together. The metal plate integrated with the carrier is attached to the hydrogen separation membrane via a spacer, and is placed at a position facing the hydrogen separation membrane. Preferably, the gap between the support and the hydrogen separation membrane is 1 mm or less, more preferably 0.05 mm or less.

  In the hydrogen production reaction tube described above, the carrier is integrally joined to the metal plate by the step of coating the surface of the metal plate having through holes with the carrier and the step of supporting the steam reforming catalyst on the carrier. The The metal plate is fixed to a membrane tube having a hydrogen separation membrane on the surface by a step of fixing the metal plate so as to face and separate from the hydrogen separation membrane. It may be fixed via a spacer between the metal plate and the hydrogen separation membrane. The metal plate and the membrane tube are fixed integrally and installed in a reaction tube for hydrogen production. As described above, the hydrogen production reaction tube includes a step of bonding the metal plate and the hydrogen separation membrane through the spacer, and a step of inserting the integrated metal plate and the hydrogen separation membrane into the hydrogen production reaction tube. Can only be manufactured.

  According to the above-described hydrogen production apparatus, in addition to the effects produced by the hydrogen production apparatus using the wall surface of the hydrogen production reaction tube as a carrier support member, there is provided a hydrogen production reaction pipe having a simple structure with fewer production steps. There is an effect that can be.

  According to the present invention, the hydrogen separation membrane is installed at a position facing the steam reforming catalyst, and the steam reforming catalyst and the hydrogen separation membrane do not contact each other. Is not damaged, and the durability of the hydrogen separation membrane is improved.

  Further, according to the present invention, the wall surface of the reaction tube and the steam reforming catalyst are integrally joined, and the structure of the reaction tube can be simplified. Further, since the gap between the reaction tube wall and the hydrogen separation membrane can be reduced, the reaction tube can be made compact.

  In addition, according to the present invention, since the path of the raw material gas is a space formed between the steam reforming catalyst and the hydrogen separation membrane, the gas flow rate is increased by narrowing the gap, and the gas flow is perpendicular to the gas flow. Gas mixture diffusion can be promoted, gas is likely to diffuse near the hydrogen separation membrane where the hydrogen concentration is low and near the steam reforming catalyst where the hydrogen concentration is high, and the uneven hydrogen concentration distribution is eliminated. Increases the efficiency of the reaction.

  Since the steam reforming catalyst is directly heated by the high-temperature combustion gas through the reaction tube wall, the heat necessary for the steam reforming reaction is efficiently supplied.

(Embodiment 1)
FIG. 1 is a schematic diagram of a hydrogen production apparatus 101 according to Embodiment 1 of the present invention. The hydrogen production apparatus 101 includes a reactor 102, a header unit 103, and a heating unit 104. The reactor 102 includes reaction tube units 105 (9 rows horizontally in FIG. 1) arranged vertically and horizontally. The header portion 103 includes supply pipes 106 and 107 which are supply means for supplying the raw material gas to the reaction tube unit 105, hydrogen recovery pipes 108 and 109 which are recovery means for recovering the produced hydrogen from the reaction tube unit, and unreacted. The raw material gas and carbon dioxide (off gas) are recovered from an off gas recovery pipe (not shown) for recovering from the reaction tube unit 105. In the present embodiment, the header portion 103 is installed on the upper side of the reactor 102. The heating unit 104 includes a combustion burner 110 and a combustion chamber 119 which are heating means. In the present embodiment, the heating unit 104 is installed below the reactor 102.

  FIG. 2 is a view of one reaction tube unit 105 as viewed from above. In FIG. 2, the header portion 103 is removed. The reaction tube unit 105 includes a plurality of hydrogen production reaction tubes 112 (six in FIG. 2), a unit frame 113, and a reinforcing member 115. The hydrogen production reaction tube 112 and the reinforcing member 115 are fixed to the unit frames 113a and 113b. Reinforcing members 115 are arranged between the hydrogen production reaction tubes 112 and between the hydrogen production reaction tube 112 at the end and the unit frame 113a. The reinforcing member 115 has a combustion gas passage 114, and the combustion gas passage 114 extends along the hydrogen production reaction tube 112. Each hydrogen production reaction tube 112 is provided with a source gas supply tube 116, a hydrogen recovery tube 117, and an off-gas recovery tube 118.

  FIG. 3 is a cross-sectional view of the reaction tube 112 for hydrogen production shown in FIG. The hydrogen production reaction tube 112 includes a tube wall 203, a carrier 202 carrying a steam reforming catalyst, a membrane tube 204, a source gas supply tube 116, a hydrogen recovery tube 117, and an off-gas recovery tube 118. Yes. As the support 202, a ceramic substrate such as alumina can be used. The support 202 is joined to the tube wall 203 of the hydrogen production reaction tube 112 so as not to be separated. The carrier 202 is placed facing the hydrogen separation membrane 206 and separated. The membrane tube 204 is installed in the reaction tube 112 for hydrogen production. The membrane tube 204 has a hydrogen separation membrane 206 supported on the surface of a porous tube 205. The hydrogen production reaction pipe 112 is further branched from a source gas supply pipe 116 branched from the supply pipe 107 of the header portion 103, a hydrogen recovery pipe 117 branched from the hydrogen recovery pipe 109, and an off-gas recovery pipe. An off-gas recovery pipe 118 is installed.

  The hydrogen production reaction tube 112 is produced by the following production method. First, the support 202 is formed on the inner wall of the hydrogen production reaction tube 112 by PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition). Next, the support 202 is loaded with a steam reforming catalyst selected from a Ni-based steam reforming catalyst and a Ru-based steam reforming catalyst. For example, when Ni is supported, it is fired after being immersed in a partially nickel nitrate aqueous solution on which the carrier 202 is formed.

  After firing, the membrane tube 204 is inserted into the reaction tube 112 for hydrogen production. The membrane tube 204 has a hydrogen separation membrane 206 on the outer surface of a porous tube 205. The membrane tube 204 is installed such that the distance between the hydrogen separation membrane 206 and the carrier 202 is 0.05 mm to 1 mm.

  The hydrogen production apparatus 101 of FIG. 1 incorporating the hydrogen production reaction tube 112 of FIG. 3 produces hydrogen by the following operation. As shown in FIG. 1, the burner 110 burns hydrocarbons or oxygen-containing hydrocarbons and generates a high-temperature combustion gas 111. With reference to FIG. 2, the combustion gas 111 passes between the reaction tube units 105 and through the combustion gas flow path 114 provided in the reinforcing member 115 of the reaction tube unit 105. The combustion gas 111 contacts the outer wall of the hydrogen production reaction tube 112 when passing through the combustion gas flow path 114, and heats the hydrogen production reaction tube 112 to a steam reforming reaction temperature of 500 to 600 ° C.

  Referring to FIG. 3, the hydrocarbon or oxygen-containing hydrocarbon is mixed with water vapor to become raw material gas 120. The source gas 120 is preheated and introduced from the source gas supply pipe 116 to the hydrogen production reaction pipe 112 via the supply pipes 106 and 107. The source gas 120 introduced from the source gas supply pipe 116 is introduced into a space formed between the carrier 202 and the hydrogen separation membrane 206. A steam reforming reaction occurs in this space, and hydrogen and carbon dioxide are generated. Of these, only hydrogen passes through the hydrogen separation membrane 206 and is separated into the membrane tube 204. The separated hydrogen 121 is sent to the hydrogen recovery pipes 108 and 109 by the hydrogen recovery pipe 117 and recovered. Examples of the recovery method include discharge with an inert gas and recovery-side pressure reduction with a vacuum pump. Off-gas 122 consisting of unreacted raw material gas or carbon dioxide is recovered from the off-gas recovery pipe 118 and used as fuel for generating combustion gas by the burner 110.

  According to the hydrogen production apparatus of the present embodiment, since the contact between the carrier 202 and the hydrogen separation membrane 206 can be completely prevented, the hydrogen separation membrane 206 is not damaged due to the strong contact between the carrier 202 and the hydrogen separation. The durability of the film 206 is improved.

  In addition, the wall surface of the hydrogen production reaction tube 112 and the carrier 202 are integrally joined, eliminating the need for a separate filling step with the steam reforming catalyst, the structure of the hydrogen production reaction tube 112 can be simplified, and the production is easy. become. Since the gap between the tube wall 203 of the hydrogen production reaction tube 112 and the hydrogen separation membrane 206 can be reduced, the hydrogen production reaction tube 112 can be made compact, and the hydrogen production apparatus 101 can be miniaturized.

  Since the source gas passage is a space formed between the carrier 202 and the hydrogen separation membrane 206, by narrowing the gap, the gas flow velocity is increased, and the gas mixture diffusion in the direction perpendicular to the gas flow is promoted. The gas easily diffuses in the vicinity of the hydrogen separation membrane 206 having a low hydrogen concentration and in the vicinity of the support 202 having a high hydrogen concentration, thereby eliminating the uneven hydrogen concentration distribution and increasing the efficiency of the steam reforming reaction.

  Since the steam reforming catalyst is directly heated by the high temperature combustion gas through the tube wall 203 of the reaction tube 112 for hydrogen production, heat necessary for the steam reforming reaction is efficiently supplied.

  In addition to the above-described method, the carrier 202 and the tube wall 203 are joined together by adhering a plate-shaped carrier carrying a steam reforming catalyst to the wall surface of the hydrogen production reaction tube. There is also a method.

(Embodiment 2)
The hydrogen production apparatus of Embodiment 2 uses a metal plate having a through-hole instead of the inner wall of a hydrogen production reaction tube as a carrier support member.

  FIG. 4 is a cross-sectional view of the hydrogen production reaction tube 112 used in the hydrogen production apparatus 101 according to the second embodiment of the present invention. The reaction tube 112 for hydrogen production forms the reaction tube unit 105 shown in FIG. 2, and is used by being incorporated in the hydrogen production apparatus 101 shown in FIG.

  4 is a porous tube 306 having a tube wall 303, a metal plate 304, a carrier 302 carrying a steam reforming catalyst, a spacer 308, and a hydrogen separation membrane 307 on the surface. A membrane tube 305, a source gas supply tube 116, a hydrogen recovery tube 117, and an off-gas recovery tube 118. The metal plate 304 has a through hole 312 as shown in FIG. As shown in FIG. 4, as in the first embodiment, a membrane tube 305 is inserted into the hydrogen production reaction tube 112. As the carrier 302, a ceramic substrate such as alumina can be used. By covering the surface of the metal plate 304 with the carrier 302, the carrier 302 and the metal plate 304 are joined together inseparably. The metal plate 304 is fixed to the membrane tube 305 via the spacer 308. As described above, the carrier 302 and the hydrogen separation membrane 307 are placed facing each other. The source gas supply pipe 116, the hydrogen recovery pipe 117, and the off-gas recovery pipe 118 are arranged so as to be connected to the header section 103 of the hydrogen production apparatus 101 as in the first embodiment.

  The hydrogen production reaction tube 112 of the present embodiment is produced by the following production method. First, the surface of the metal plate 304 having the through holes 312 is covered with the carrier 302. Next, a steam reforming catalyst is supported on the carrier 302. For example, when alumina is used as the carrier 302 and Ni catalyst is used as the steam reforming catalyst, the metal plate 304 is immersed in an alumina solution and fired to coat the surface with alumina, and the metal plate is immersed in an aqueous nickel nitrate solution. Bake.

  After the carrier 302 and the metal plate 304 are joined so as not to be separated by the above method, the carrier 302 and the metal plate 304 are fixed to the membrane tube 305 via the spacer 308. The hydrogen production reaction tube 112 is produced by inserting a membrane tube in which a metal plate 304 is fixed via a spacer 308 into the hydrogen production reaction tube 112.

  In the hydrogen production reaction tube 112 shown in FIG. 4, the source gas 120 is introduced from the source gas supply tube 116 into the space between the reaction tube wall 303 and the metal plate 304, and further passes through the through hole 312 of the metal plate 304. Then, it is also introduced into the space between the metal plate 304 and the hydrogen separation membrane 307. A steam reforming reaction occurs in these spaces, and mainly hydrogen and carbon dioxide are generated. Of these, only hydrogen passes through the hydrogen separation membrane 307 and is separated into the membrane tube 305. The separated hydrogen 121 and off gas 122 are recovered in the header section 103 by the hydrogen recovery pipe 117 and the off gas recovery pipe 118, respectively, as in the first embodiment.

  According to the hydrogen production apparatus of this embodiment, the contact between the carrier 302 and the hydrogen separation membrane 307 can be completely prevented, so that the durability of the hydrogen separation membrane 307 is improved. In addition, since the carrier 302 and the membrane tube 305 are fixed together and installed in the hydrogen production reaction tube 112, the production of the hydrogen production reaction tube 112 can be facilitated.

(Embodiment 3)
In the third embodiment, both the wall of a reaction tube for hydrogen production and a metal plate having a through hole are used as a carrier support member.

  FIG. 6 is a cross-sectional view of a hydrogen production reaction tube 112 used in a hydrogen production apparatus according to Embodiment 3 of the present invention. The reaction tube 112 for hydrogen production forms the reaction tube unit 105 shown in FIG. 2, and is used by being incorporated in the hydrogen production apparatus 101 shown in FIG.

  A reaction tube 112 for hydrogen production shown in FIG. 6 includes a tube wall 402, carriers 403 and 404 supporting a steam reforming catalyst, a metal plate 405 having a through hole 410, a spacer 406, and a hydrogen separation membrane 409 on the surface. A membrane tube 407 made of a porous tube 408 having a gas source, a raw material gas supply tube 116, a hydrogen recovery tube 117, and an off-gas recovery tube 118 are provided.

  The inside of the hydrogen production reaction tube 112 has the following structure. The carrier 403 and the tube wall 402 are joined together by the method described in the first embodiment. The carrier 404 and the metal plate 405 are integrally joined by the method described in the second embodiment, and are fixed to the membrane tube 407 via the spacer 406. The membrane tube 407 is installed in the hydrogen production reaction tube as in the other embodiments.

  The hydrogen production reaction tube 112 of the present embodiment includes a step of integrally joining the steam reforming catalyst 403 to the tube wall 402 described in the first embodiment, and a metal having a through hole described in the second embodiment. The steam reforming catalyst 404 is integrally joined to the plate 405 and fixed to the membrane tube 407, and the membrane tube 407 is inserted into the hydrogen production reaction tube 112.

  In the hydrogen production reaction tube 112 shown in FIG. 6, the source gas 120 is introduced from the source gas supply tube 116 into the space between the reaction tube wall 402 and the metal plate 405, and further passes through the through hole 410 of the metal plate 405. Then, it is also introduced into the space between the metal plate 405 and the hydrogen separation membrane 409. A steam reforming reaction occurs in these spaces, and mainly hydrogen and carbon dioxide are generated. Of these, only hydrogen passes through the hydrogen separation membrane 409 and is separated into the membrane tube 407. The separated hydrogen 121 and off gas 122 are recovered in the header section 103 by the hydrogen recovery pipe 117 and the off gas recovery pipe 118, respectively, as in the first and second embodiments.

    According to the hydrogen production apparatus of the present embodiment, the contact between the carriers 403 and 404 and the hydrogen separation membrane can be completely prevented, so that the durability of the hydrogen separation membrane is improved. While the simple structure is easy to manufacture, the contact area between the raw material gas and the steam reforming catalyst can be increased.

FIG. 1 is a schematic view of a hydrogen production apparatus according to an embodiment of the present invention. FIG. 2 is a top view of the reaction tube unit according to the embodiment of the present invention. FIG. 3 is a cross-sectional view of a reaction tube for hydrogen production according to Embodiment 1 of the present invention. FIG. 4 is a cross-sectional view of a reaction tube for hydrogen production according to Embodiment 2 of the present invention. FIG. 5 is a front view of a metal plate that is a part of a reaction tube for hydrogen production according to Embodiment 2 of the present invention. FIG. 6 is a cross-sectional view of a reaction tube for hydrogen production according to Embodiment 3 of the present invention. FIG. 7 is a schematic view of a conventional hydrogen production apparatus. FIG. 8 is a schematic view of a unit of a membrane tube and a plate-shaped steam reforming catalyst used in a conventional hydrogen production apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Hydrogen production apparatus 102 Reactor 103 Header part 104 Heating part 105 Reaction pipe unit 112 Hydrogen production reaction pipe 116 Raw material gas supply pipe 117 Hydrogen recovery pipe 118 Off gas recovery pipe 120 Raw material gas 121 Hydrogen 122 Off gas 202, 302, 403, 404 Carrier 203, 303, 402 Tube wall 204, 309, 407 Membrane tube 206, 307, 409 Hydrogen separation membrane 304, 405 Metal plate 308, 406 Spacer

Claims (11)

A hydrogen carrying reaction tube containing a carrier carrying a steam reforming catalyst, a carrier supporting member for supporting the carrier, and a hydrogen separation membrane;
Supply means for supplying a source gas to the hydrogen production reaction tube;
Recovery means for recovering hydrogen from the hydrogen production reaction tube,
The hydrogen production apparatus, wherein the carrier and the carrier support member are integrally joined and are disposed away from the hydrogen separation membrane. The carrier support member is an inner wall of the hydrogen production reaction tube;
The hydrogen production apparatus according to claim 1, wherein the carrier is integrally joined to the inner wall. A heating means for heating the hydrogen production reaction tube;
The hydrogen production apparatus according to claim 1, wherein the heating fluid generated by the heating means is brought into contact with an outer wall of the hydrogen production reaction tube. The carrier support member is a metal plate having a through hole;
The hydrogen production apparatus according to any one of claims 1 to 3, wherein a surface of the metal plate is covered with the carrier. The hydrogen production apparatus according to claim 4, wherein the metal plate is fixed to the hydrogen separation membrane via a spacer. The hydrogen production apparatus according to any one of claims 1 to 5, wherein the carrier and the preceding hydrogen separation membrane are installed with an interval of 1 mm or less. Supporting a carrier carrying a steam reforming catalyst on the inner wall of a reaction tube for hydrogen production;
A method for producing a reaction tube for hydrogen production, comprising: a step of installing a membrane tube having a hydrogen separation membrane on a surface thereof in the reaction tube for hydrogen production so as to face and separate from the hydrogen separation membrane. The step of supporting the carrier comprises
Providing a support on the inner wall of a reaction tube for hydrogen production;
The method for producing a reaction tube for hydrogen production according to claim 7, further comprising a step of supporting a steam reforming catalyst on the carrier. The method for producing a reaction tube for hydrogen production according to claim 8, wherein the step of providing a carrier on the inner wall of the reaction tube for hydrogen production is a step of providing the carrier on the inner wall by CVD or PVD. The step of supporting the carrier comprises
Forming the carrier into a predetermined shape;
Supporting a steam reforming catalyst on the carrier;
The method for producing a reaction tube for hydrogen production according to claim 7, further comprising a step of fixing the carrier to the inner wall of the reaction tube for hydrogen production. Coating the surface of the metal plate having a through hole with a carrier;
Supporting a steam reforming catalyst on the carrier;
Fixing the metal plate and a membrane tube having a hydrogen separation membrane on the surface so that the steam reforming catalyst is separated from the hydrogen separation membrane;
A method for producing a reaction tube for hydrogen production, comprising the step of installing the membrane tube in a reaction tube for hydrogen production.

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