JP4443968B2 - Hydrogen production equipment - Google Patents

Description

  The present invention relates to a hydrogen production apparatus that produces reformed gas by steam reforming of a hydrocarbon-based gas and purifies the produced reformed gas to produce high-purity hydrogen.

In the steam reforming method of hydrocarbon gas, which is one of the industrial production methods of hydrogen, a reformer filled with a reforming catalyst such as a granule is usually used. The reformed gas obtained by the reformer contains by-products such as CO and CO ₂ and surplus H ₂ O in addition to hydrogen, which is the main component. If it is used as it is, battery performance will be hindered. Among the fuel cells, the solid polymer fuel cell (PEFC) has a limit of about 100 ppm (vol ppm, the same applies hereinafter) in the hydrogen gas, and the CO in the hydrogen gas used in the phosphoric acid fuel cell (PAFC) is The upper limit is about 1% (vol%, the same applies hereinafter), and battery performance is significantly deteriorated when these limits are exceeded. For this reason, these by-products must be removed before being introduced into the fuel cell.

  There exists a membrane reactor as an apparatus integrated so that the production | generation of the reformed gas by a reformer and the refinement | purification of the produced | generated reformed gas can be performed by one apparatus. FIG. 1 is a diagram for explaining a configuration example of a membrane reactor. As shown in FIG. 1, it is composed of multiple tubes in which hydrogen separation tubes are arranged in a reaction tube (outer tube). A gap between the outer pipe and the hydrogen separation pipe is filled with a reforming catalyst such as a granule, and a raw material gas, that is, a hydrocarbon-based gas and steam is supplied to reform the hydrocarbon-based gas. The hydrogen separation tube is configured by forming a metal film such as Pd having a hydrogen permeation function on a support such as porous ceramics or porous stainless steel. Thus, the membrane reactor is very useful in principle because the reformed gas can be generated and purified with a single device.

  However, there is a problem that the hydrogen permeable membrane is damaged in the hydrogen separation tube. If the hydrogen permeable membrane breaks, the desired purified hydrogen cannot be obtained, which is fatal as a membrane reactor. Possible causes of the damage include that the hydrogen permeable membrane is damaged by contact with the reforming catalyst, and that (2) hydrogen permeation is inhibited by the support.

  In order to avoid these causes of damage, it is conceivable that the hydrogen permeable membrane and the reforming catalyst are not contacted. For this reason, it is conceivable to arrange a protective tube such as a net outside the hydrogen permeable membrane. However, there arises a problem that the reforming reaction rate is lowered by blowing the raw material gas into the protective tube. Similarly, in order to make the hydrogen permeable membrane and the reforming catalyst non-contact, it has been proposed to support the reforming catalyst on a honeycomb body (Japanese Patent Laid-Open No. 2001-348205). However, in this case, there arises a problem that the reforming reaction rate decreases due to blow-off of the raw material gas in the honeycomb body.

JP 2001-348205 A

  The present inventors have previously developed a hydrogen production apparatus that eliminates the need for a reforming catalyst such as a granular catalyst by using a reforming catalyst / support as a support for the hydrogen permeable membrane (Japanese Patent Application 2002). -313978). The reaction tube used in this hydrogen production apparatus is composed of a cylindrical reforming catalyst / support and a hydrogen permeable membrane disposed on the outer peripheral surface or inner peripheral surface of the reforming catalyst / support. This eliminates the need for a granular reforming catalyst, which was essential in conventional hydrogen production equipment such as membrane reactors, and has various useful effects such as greatly simplified and downsized compared to conventional hydrogen production equipment. can get.

Japanese Patent Application No. 2002-313978

  In the present invention, the porous reforming catalyst / support is configured in a cylindrical shape, and the cylindrical shape for a hydrogen production apparatus is composed of a hydrogen permeable membrane disposed on the outer peripheral surface or the inner peripheral surface of the reforming catalyst / support. It is an object of the present invention to provide a new and useful hydrogen production apparatus based on the use of a reaction tube and further improving and extending the hydrogen production apparatus using the reaction tube.

The present invention uses (1) an outer membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the outer peripheral surface of a porous cylindrical reforming catalyst / support, and a raw material gas is passed through the inside of the reaction tube to make contact. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane while generating reformed gas, comprising the following configurations (a) to (e): I will provide a.
(A) In the casing, a plurality of reaction tubes whose lower ends are closed are arranged at intervals, and a high-purity hydrogen flow path is formed between the reaction tubes in the casing and between adjacent reaction tubes. And
(B) In each reaction tube, a first tube having a smaller diameter, a second tube and a third tube closed at the lower end thereof are arranged at intervals, and the lower end of the third tube is disposed at the lower end. Placing a gap with respect to the lower end closing part of the second tube,
(C) The heating combustion gas is circulated downwardly between the second pipe and the third pipe from the introduction pipe, and then folded at the lower end of the third pipe to move upward in the third pipe. Circulate to the combustion gas exhaust pipe,
(D) The reformed gas is generated by bringing the source gas into contact with the inside of the reaction tube while flowing downwardly from the introduction tube between each reaction tube and the first tube. Producing and purifying high-purity hydrogen by separating and purifying the hydrogen with a hydrogen permeable membrane, and deriving it from a hydrogen outlet pipe provided in the casing,
(E) The remaining raw material gas is folded at the lower end of the first pipe and circulated upward between the first pipe and the second pipe, and then discharged from the off-gas discharge pipe.

The present invention uses (2) an outer membrane cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the outer peripheral surface of a porous cylindrical reforming catalyst / support, and a raw material gas is passed through the inside of the reaction tube to make contact. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane while generating reformed gas, comprising the following configurations (a) to (e): I will provide a.
(A) In the first casing, a plurality of reaction tubes whose lower ends are closed are arranged at intervals, and a gap is formed between the first casing and each reaction tube and between adjacent reaction tubes. A high purity hydrogen flow path,
(B) A small-diameter pipe is arranged at intervals in each reaction pipe, and the reformed gas is brought into contact with the inside of the reaction pipe while the source gas is lowered between the inside of the reaction pipe and the small-diameter pipe. Producing high purity hydrogen by separating and purifying hydrogen in the generated reformed gas with a hydrogen permeable membrane and deriving from a hydrogen outlet pipe provided in the first casing,
(C) raising the remaining raw material gas through the small-diameter pipe and discharging it from the off-gas discharge pipe;
(D) The first casing is disposed in the second casing, and a gap between the lower wall of the second casing and the bottom wall of the first casing is used as a flow path for the combustion gas for heating, and the gap Disposing a combustion gas distribution member on the
(E) The combustion gas for heating is introduced into the lower portion of the second casing through the introduction pipe, and the gap between the second casing and the first casing is raised through the combustion gas distribution member to perform each reaction. As a heating source necessary for the generation of reformed gas in the pipe, and to discharge from the discharge pipe provided in the upper wall of the second casing;

  In the hydrogen production apparatus of the present invention (2), a plurality of first casings configured by arranging the outer membrane cylindrical reaction tubes as described above in the second casing are arranged in parallel at intervals. It is also configured as a hydrogen production apparatus arranged in

The present invention uses (3) an outer membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the outer peripheral surface of a porous cylindrical reforming catalyst / support, and a raw material gas is passed through the inside of the reaction tube to make contact. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane while generating reformed gas, comprising the following configurations (a) to (e): I will provide a.
(A) Arranging a plurality of reaction tubes at intervals in the casing, and disposing a tube having a smaller diameter than the inner diameter in each reaction tube in a state of passing through the reaction tube;
(B) One end of each small-diameter pipe is branched from the upper header connected to the combustion gas introduction pipe for heating, and the other end is connected to the lower header connected to the combustion gas discharge pipe.
(C) The heating combustion gas is passed from one end to the other end of each small-diameter pipe through the introduction pipe and the upper header to heat the reaction pipe, and then discharged from the discharge pipe through the lower header. ,
(D) The reformed gas is generated by bringing the raw material gas into contact with the inside of the reaction tube while descending between each reaction tube and the small-diameter tube through the introduction tube and the upper header. Separating and purifying hydrogen from a hydrogen permeable membrane to produce high-purity hydrogen, which is derived from a hydrogen outlet pipe provided in the casing,
(E) exhausting the remaining raw material gas from between the reaction tube and the small diameter tube through the lower header through the off-gas discharge tube;

The present invention uses (4) an outer membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the outer peripheral surface of a porous cylindrical reforming catalyst / support, and the raw material gas is brought into contact with the inside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane while generating reformed gas, comprising the following configurations (a) to (e): I will provide a.
(A) In the first casing, a plurality of reaction tubes are arranged at intervals, the adjacent reaction tubes are connected in a zigzag manner in the upper and lower directions, and the reaction tube in the forefront is arranged in the flow direction of the source gas. Connecting the source gas introduction pipe to the last reaction pipe and the off-gas discharge pipe;
(B) The first casing is disposed in the second casing, and a space between the lower wall of the second casing and the bottom wall of the first casing is used as a flow path for the combustion gas for heating. Disposing a combustion gas distribution member on the
(C) The combustion gas for heating is introduced into the lower portion of the second casing through the introduction pipe, and the gap between the second casing and the first casing is raised through the combustion gas distribution member to perform each reaction. As a heating source necessary for the generation of reformed gas in the pipe, and to discharge from the discharge pipe provided in the upper wall of the second casing;
(D) The raw material gas is introduced into the foremost reaction tube from the introduction tube, and is passed through the inside of each reaction tube while flowing from the reaction tube connected in a zigzag manner toward the last reaction tube. The reformed gas is generated, and hydrogen is separated and purified from the generated reformed gas by a hydrogen permeable membrane to produce high-purity hydrogen, which is led out from the hydrogen outlet pipe provided in the first casing. ,
(E) exhausting the remaining raw material gas from an off-gas exhaust pipe connected to the last reaction pipe,

  In the hydrogen production apparatus of the present invention (4), a plurality of first casings configured by arranging the outer membrane cylindrical reaction tubes as described above in the second casing are arranged in parallel at intervals. It is also configured as a hydrogen production apparatus arranged in

The present invention uses (5) an outer membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the outer peripheral surface of a porous cylindrical reforming catalyst / support, and the raw material gas is passed through the inside of the reaction tube to make contact. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane while generating reformed gas, comprising the following configurations (a) to (e): I will provide a.
(A) In the first casing, a plurality of reaction tubes are arranged at intervals, and a branch pipe from a lower header connected to a source gas introduction pipe is connected to the lower part of each reaction pipe, Connecting to the branch pipe from the upper header connected to the off-gas exhaust pipe,
(B) The first casing is disposed in the second casing, and the gap between the lower wall in the second casing and the bottom wall of the first casing is used as a flow path for the combustion gas for heating, Disposing a combustion gas distribution member in the gap;
(C) Combustion gas for heating is introduced from the lower portion of the second casing through the introduction pipe, and the gap between the second casing and the first casing is raised through the distribution member of the combustion gas to perform each reaction. As a heating source necessary for the generation of reformed gas in the pipe, and to discharge from the discharge pipe provided in the upper wall of the second casing;
(D) The raw material gas is introduced into each reaction tube from the introduction tube through the header, and is passed through and brought into contact with the inside of each reaction tube to generate reformed gas. Hydrogen is generated from the generated reformed gas through the hydrogen permeable membrane. Producing and purifying high-purity hydrogen by separating and purifying by a hydrogen outlet pipe provided in the first casing,
(E) The remaining raw material gas from each reaction tube is discharged from the off-gas discharge pipe through each branch pipe and the upper header,

  In the hydrogen production apparatus of the present invention (5), a plurality of first casings configured by arranging the outer membrane cylindrical reaction tubes as described above in the second casing are arranged in parallel at intervals. It is also configured as a hydrogen production apparatus arranged in

The present invention uses (6) an inner membrane type cylindrical reaction tube in which a hydrogen permeable membrane is disposed on the inner peripheral surface of a porous cylindrical reforming catalyst / support, and the raw material gas is passed through the outside of the reaction tube for contact. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane while generating reformed gas, and comprising the following configurations (a) to (e) Providing equipment.
(A) Arranging a plurality of reaction tubes whose lower ends are closed in the casing, and sequentially disposing a first tube and a second tube having a small diameter at intervals in each reaction tube,
(B) The first pipe is closed at its lower end, the second pipe is arranged at a lower end with respect to the lower end closed portion of the first pipe, and the heating combustion gas is sent from the introduction pipe to the header. After passing through between the first tube and the second tube through the bottom, it is folded at the lower end of the second tube and then flows upward in the second tube, and the reformed gas in the reaction tube As a heating source necessary for the production of gas, and exhaust from the combustion gas exhaust pipe through the header,
(C) The space between the inner wall of the casing and each reaction tube disposed therein is used as a source gas supply space, a source gas introduction pipe is provided on one side wall of the casing, and the other side wall opposite to the one side wall Providing an off-gas discharge pipe in the
(D) The raw material gas is introduced from the introduction pipe, and is passed through the outside of each reaction pipe to be contacted to produce reformed gas. Hydrogen in the produced reformed gas is separated and purified by a hydrogen permeable membrane and Deriving from the hydrogen outlet tube as pure hydrogen,
(E) exhausting the remaining source gas from the off-gas exhaust pipe;

The present invention uses (7) an inner membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the inner peripheral surface of a porous cylindrical reforming catalyst / support, and the raw material gas is passed through the outside of the reaction tube for contact. A hydrogen production apparatus for producing high-purity hydrogen by purifying with a hydrogen permeable membrane while generating reformed gas, and comprising the following configurations (a) to (f) Providing equipment.
(A) In the first casing, a plurality of reaction tubes whose lower ends are closed are arranged at intervals, and each reaction tube in the casing is connected to a header connected to a hydrogen outlet tube,
(B) The raw material gas introduction pipe faces the bottom wall of the first casing, and the raw material gas distribution member is disposed in the space between the bottom wall and the lower end closed portion of each reaction tube,
(C) The first casing is disposed in the second casing, and the first casing is disposed with a gap between the bottom portion and the lower wall of the second casing, and the gap is used for heating. Arranging a combustion gas distribution member;
(D) The heating combustion gas is introduced from the introduction pipe, distributed and supplied upward from the lower part of the distribution member, and while flowing between the first casing and the second casing upward, Heating the reaction tube in the casing of 1 to give heat necessary for reforming the raw material gas, and then discharging it from the discharge pipe provided in the upper part of the second casing;
(E) The raw material gas is introduced from the introduction pipe, passed through the outside of each reaction pipe to produce reformed gas, and hydrogen in the produced reformed gas is separated and purified by a hydrogen permeable membrane to obtain high purity hydrogen. , Leading out from the hydrogen outlet pipe through the header,
(F) exhausting the remaining raw material gas from an off-gas exhaust pipe provided in the first casing;

  In the hydrogen production apparatus of the present invention (7), a plurality of first casings configured by arranging the intimal cylindrical reaction tubes as described above in the second casing are arranged in parallel at intervals. It is also configured as a hydrogen production apparatus arranged in

The present invention uses (8) an inner membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the inner peripheral surface of a porous cylindrical reforming catalyst / support, and the raw material gas is passed through the outside of the reaction tube for contact. A hydrogen production apparatus for producing high-purity hydrogen by purifying with a hydrogen permeable membrane while generating reformed gas, and comprising the following configurations (a) to (f) Providing equipment.
(A) Arranging a plurality of reaction tubes in the casing, and disposing a tube having a diameter smaller than the inner diameter in each reaction tube in a state of passing through each reaction tube;
(B) One end of each small-diameter pipe is branched from the upper header connected to the combustion gas introduction pipe for heating, and the other end is connected to the lower header connected to the combustion gas discharge pipe.
(C) The heating combustion gas is passed from one end of each small-diameter pipe to the other end through the introduction pipe and the upper header to heat the reaction pipe, and then discharged from the discharge pipe through the lower header. To do,
(D) providing a source gas introduction pipe on one side wall of the casing and providing an off-gas discharge pipe on the other side wall opposite to the one side wall;
(E) The raw material gas is introduced from the introduction pipe, passed through the outside of each reaction pipe to produce reformed gas, and hydrogen in the produced reformed gas is separated and purified by a hydrogen permeable membrane to obtain high purity hydrogen. , Leading from the flow path between the reaction tube and the small diameter tube, through the header and from the hydrogen outlet tube,
(F) exhausting the remaining source gas from the off-gas exhaust pipe;

The present invention uses (9) an inner membrane cylindrical reaction tube in which a hydrogen permeable membrane is disposed on the inner peripheral surface of a porous cylindrical reforming catalyst / support, and the raw material gas is passed through the outside of the reaction tube for contact. A hydrogen production apparatus for producing high-purity hydrogen by purifying with a hydrogen permeable membrane while generating reformed gas, and comprising the following configurations (a) to (f) Providing equipment.
(A) A plurality of reaction tubes are arranged at intervals in the first casing, and a lower portion of each of the reaction tubes is connected by a connecting tube for each pair of reaction tubes. Connecting to the header leading to the hydrogen outlet pipe,
(B) A space is provided between the lower wall of the first casing and the lower end of the connecting pipe, the raw material gas distribution member is disposed in the gap, and the raw material gas introduction pipes are respectively provided on the lower wall and the upper wall of the first casing. (C) The first casing is disposed in the second casing, and the gap between the lower wall in the second casing and the bottom of the first casing is heated by the combustion gas. Disposing a combustion gas distribution member in the gap,
(D) The heating combustion gas is introduced from the introduction pipe, distributed and supplied upward from the lower part of the distribution member, and while flowing between the first casing and the second casing upward, Heating the reaction tube in the casing of 1 to give heat necessary for reforming the raw material gas, and then discharging it from the discharge pipe provided in the upper part of the second casing;
(E) The raw material gas is introduced from the introduction pipe, passed through the outside of each reaction pipe to produce reformed gas, and hydrogen in the produced reformed gas is separated and purified by a hydrogen permeable membrane to obtain high purity hydrogen. , Leading out from the hydrogen outlet pipe through the header,
(F) exhausting the remaining source gas from the off-gas exhaust pipe;

  In the hydrogen production apparatus of the present invention (9), a plurality of first casings configured by arranging the intimal cylindrical reaction tubes as described above in the second casing are arranged in parallel at intervals. It is also configured as a hydrogen production apparatus arranged in

  In the present invention (1) to (5), an outer membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the outer peripheral surface of a porous cylindrical reforming catalyst / support is used, and a raw material gas is placed inside the reaction tube. This is a hydrogen production apparatus that produces high-purity hydrogen by separating and purifying hydrogen from the produced reformed gas through a hydrogen permeable membrane while producing reformed gas through contact. The present inventions (6) to (9) use an inner membrane type cylindrical reaction tube in which a hydrogen permeable membrane is arranged on the inner peripheral surface of a porous cylindrical reforming catalyst / support, and feed the raw material gas into the reaction tube. This is a hydrogen production apparatus for producing high-purity hydrogen by separating and purifying hydrogen from the produced reformed gas through a hydrogen permeable membrane while generating reformed gas through contact with the outside.

  Here, hydrogen is obtained by reforming the hydrocarbon-based gas with water vapor, and city gas, natural gas, petroleum gas, or the like is used as the hydrocarbon-based gas. The reforming catalyst / support is poisoned by a sulfur compound and deteriorates its performance. Therefore, when the hydrocarbon gas contains a sulfur compound, it is desulfurized and used. In the present invention, a mixed gas of hydrocarbon-based gas and water vapor is supplied to the inside of the outer membrane type cylindrical reaction tube or the outside of the inner membrane type cylindrical reaction tube. In the present specification and claims, the mixed gas is referred to as a raw material gas.

The steam reforming reaction when the hydrocarbon gas is, for example, methane gas is represented by CH ₄ + H ₂ O → CO + 3H ₂ . Since this steam reforming reaction is an endothermic reaction, it is necessary to heat to a high temperature of about 500 to 700 ° C. In the present invention, a combustion gas obtained by burning a fuel such as city gas, natural gas, or petroleum gas is used as the heating heat source. Further, since the off-gas discharged from the hydrogen production apparatus contains CO generated as a by-product during the reforming reaction, unused hydrogen, etc., the off-gas combustion gas may be used as a heat source for heating. it can. In the present specification and claims, those combustion gases as the heating heat source are referred to as heating combustion gases, but are also simply referred to as combustion gases.

  The reforming catalyst and support in the outer membrane type cylindrical reaction tube and the inner membrane type cylindrical reaction tube are porous, and simultaneously serve as a reforming catalyst and a hydrogen permeable membrane. This is an important configuration. The reforming catalyst / support supports steam reforming of the hydrocarbon gas to generate a reformed gas. In the present specification and claims, the porous cylindrical reforming catalyst / support is porous and cylindrical, maintains its own structure, and functions as a reforming catalyst and a hydrogen permeable membrane. It means the structure that plays the supporting role at the same time. The outer membrane type cylindrical reaction tube is configured by placing and supporting a hydrogen permeable membrane outside the porous cylindrical reforming catalyst / support, and the inner membrane type cylindrical reaction tube is modified with a porous cylindrical shape. The hydrogen permeable membrane is disposed and supported inside the porous catalyst / support. The reformed gas produced by the porous cylindrical reforming catalyst / support is purified by a hydrogen permeable membrane to produce high purity hydrogen.

  FIG. 2 is a view showing an example of an outer membrane type cylindrical reaction tube used in the present invention (1) to (5). As shown in FIG. 2, a hydrogen-permeable membrane is arranged outside the cylindrical and porous reforming catalyst / support, that is, on the outer peripheral surface. FIG. 3 is a view showing an example of an embodiment of the inner membrane type cylindrical reaction tube used in the present inventions (6) to (9). As shown in FIG. 3, a hydrogen permeable membrane is arranged on the inner side of the porous cylindrical reforming catalyst / support, that is, the inner peripheral surface. As a constituent material of members other than the outer membrane type cylindrical reaction tube and the inner membrane type cylindrical reaction tube, a heat resistant material such as a heat resistant alloy is used. As an example, an inexpensive material such as stainless steel (for example, SUS304 steel) can be used, which is advantageous in this respect.

  As a constituent material of the reforming catalyst / support, a porous material having a function as a reforming catalyst and a function of supporting the hydrogen permeable membrane is used. Examples thereof include a sintered body (Ni-YSZ cermet or the like) of a mixture of nickel and yttria stabilized zirconia, and other porous ceramics and porous cermets having these functions.

  In the case of Ni-YSZ cermet, for example, Ni particles, NiO particles and YSZ (= yttria-stabilized zirconia) particles are mixed, the mixture is formed by extrusion molding, pressure molding or the like and sintered. As an example, when the reforming temperature = 600 ° C. and the S / C ratio = 3.0, this sintered body shows a methane conversion rate of about 39% as a single catalyst and is almost the same as a conventional granular reforming catalyst. Has reforming performance. The content of the Ni component in the sintered body can be selected in the range of 10 to 98 wt%, but the content of the Ni component is further supported in consideration of the performance as a reforming catalyst and the coefficient of thermal expansion. It can be appropriately set within the above range in consideration of the type of constituent material of the permeable membrane.

  The hydrogen permeable membrane, that is, a membrane that selectively permeates hydrogen is not particularly limited as long as it is a membrane that can selectively permeate hydrogen. For example, a metal film such as a Pd film or a Pd alloy film is used. It is done. In the Pd alloy, the metal alloyed with Pd includes Ag, Pt, Rh, Ru, Ir, Ce, Y, or Gd. The metal film is supported on the reforming catalyst / support by a plating method, a vapor deposition method, or other appropriate methods. Here, the pore diameter of the porous ceramic is not particularly limited, but the pore diameter is preferably 10 μm or less in relation to the thickness of the metal film. For example, when the thickness of the metal film is 20 μm, the pore diameter of the porous ceramic is preferably about 10 μm. When the thickness of the metal film is 20 μm or less, the pore diameter of the porous ceramic is 10 μm correspondingly. It is preferable to make it about or less.

  The reforming catalyst / support simultaneously plays a role as a reforming catalyst and a role of supporting the hydrogen permeable membrane, so that a reforming catalyst layer that is essential in the conventional membrane reactor is not required. For this reason, the hydrogen production apparatus of the present invention using the reforming catalyst / support can be remarkably reduced in size as compared with the conventional hydrogen production apparatus. In particular, this reforming catalyst and support itself plays a role as a reforming catalyst and does not require a separate reforming catalyst layer. Therefore, hydrogen permeation due to contact with the reforming catalyst, which occurs in a conventional hydrogen production apparatus, is generated. Does not cause membrane damage problems. The hydrogen production apparatus of the present invention is much simpler and smaller than conventional hydrogen production apparatuses, and can produce a large amount of hydrogen in a compact manner. Therefore, the fuel for hydrogen supply stations for fuel cell vehicles and the fuel for stationary fuel cells It is useful as a processing apparatus, an industrial on-site hydrogen production apparatus, and the like.

  Hereinafter, aspects of the present inventions (1) to (9) will be sequentially described including examples. In each embodiment, the mixed gas of city gas, natural gas, methane, other hydrocarbon gas and water vapor is used as the raw material gas. Further, as the combustion gas for heating, a combustion gas obtained by burning off-gas discharged from a fuel such as city gas, natural gas, or petroleum gas or a hydrogen production apparatus of each aspect with a combustion device is used. As the combustion equipment, a burner or other appropriate combustion equipment can be used. In addition, when assembling the hydrogen production equipment, it is necessary to join and seal the reaction tubes, pipes, closing members, headers, conduits, casings, and other components that make up the hydrogen production equipment. It is appropriately selected by using metal brazing material or glass bonding material.

<Aspect of the present invention (1): outer membrane type cylindrical reaction tube>
In the present invention (1), an outer membrane type cylindrical reaction tube as shown in FIG. 2 is used, and a raw material gas is passed through the inside of the reaction tube to be brought into contact therewith to produce a reformed gas and purified by a hydrogen permeable membrane. This is a hydrogen production device that produces high-purity hydrogen. 4-5 is a figure which shows the aspect of this invention (1). 4B is a longitudinal sectional view, and FIG. 4A is a sectional view taken along line AA in FIG. 4B. 5A is a left side view of FIG. 4B, FIG. 5B is a right side view of FIG. 4B, and FIG. 5C is a plurality of reaction tubes in FIG. 4B. It is the figure which took out one of these and expanded and showed it.

  Strictly speaking, FIG. 4A is a cross-sectional view of a hydrogen production apparatus having the configuration of FIG. 4B and FIGS. 5A to 5B, and FIG. 5A is FIG. 4A. FIG. 5B is a diagram of the hydrogen production apparatus having the configuration of (b) viewed from the left side, and FIG. 5B is a diagram of the hydrogen production apparatus having the configuration of FIGS. For convenience, it is described as above. The same applies to the corresponding drawings for explaining the aspects of the present inventions (2) to (9). Moreover, among FIGS. 4-5, the flow direction of each gas, such as source gas and combustion gas, is shown by the arrow in FIG.4 (b) and FIG.5 (c). The same applies to the corresponding drawings for explaining the aspects of the present inventions (2) to (9).

  As shown in FIGS. 4 to 5, a plurality of reaction tubes 2 whose lower ends are closed are placed in the casing 1 having a rectangular cross section at intervals. Reference numeral 3 denotes a closing portion at the lower end of the reaction tube 2, and the closing member is a disk corresponding to the outer diameter of the reaction tube 2. In each reaction tube 2, a first tube 4, a second tube 5, and a third tube 6 having small diameters are sequentially arranged at intervals in the radial direction. Among these, the 2nd pipe | tube 5 obstruct | occludes the lower end. Reference numeral 7 denotes a closed portion, which is a disk corresponding to the outer diameter of the second tube 5. Moreover, the 1st pipe | tube 4 is arrange | positioned so that a space | interval (space | gap) may be maintained between the lower end and the lower end obstruction | occlusion part 3 of the reaction tube 2, and the space | gap turns into a return part of source gas. Further, the third pipe 6 is disposed so as to maintain a space (gap) between the lower end thereof and the lower end closing part 7 of the second pipe 5, and the gap serves as a fuel gas turning part.

  8 is a combustion gas introduction pipe for heating, 9 is a combustion gas supply header (heading) connected to this, and a combustion gas is provided between the header 9 and the second pipe 5 and the third pipe 6 in each reaction pipe 2. Is supplied. The combustion gas flows downward between the second pipe 5 and the third pipe 6, then turns back at the lower end of the third pipe 6, and flows upward in the third pipe 6. Reference numeral 10 denotes a header facing the opening of each third pipe 6, and the combustion gas is discharged from the combustion gas discharge pipe 11 through the header 10.

  On the other hand, the raw material gas is introduced from the raw material gas introduction pipe 12 provided on the side wall of the casing 1 and is passed through the inside of the reaction tube while being circulated downward between the reaction tube 2 and the first tube 4. Then, reformed gas is generated, and hydrogen is separated and purified from the generated reformed gas by a hydrogen permeable membrane to produce high purity hydrogen. High-purity hydrogen is led out from a hydrogen lead-out pipe 13 provided on the side wall of the casing 1 on the side facing the source gas introduction pipe 12. The remaining source gas is folded back at the lower end of the first pipe 4 and flows upward between the first pipe 4 and the second pipe 5, and is discharged from the discharge pipe 15 as an off-gas through the header 14. The

  As described above, the present hydrogen production apparatus does not require a separate reforming catalyst layer and uses an outer membrane cylindrical reaction tube that does not cause a problem of damage to the hydrogen permeable membrane. Since it is arranged in a compact manner in the casing, hydrogen can be produced in a small size and with high efficiency. These effects are the same also about the aspect of this invention (2)-(5) described below.

<Aspect of the present invention (2): outer membrane cylindrical reaction tube>
In the present invention (2), an outer membrane type cylindrical reaction tube is used, and the generated reformed gas is purified by the hydrogen permeable membrane while the reformed gas is generated by bringing the raw material gas into contact with the inside of the reaction tube. This is a hydrogen production device that produces high-purity hydrogen. 6-8 is a figure which shows the aspect of this invention (2). 6B is a longitudinal sectional view, and FIG. 6A is a longitudinal sectional view taken along line AA in FIG. 6B. 7A is a left side view of FIG. 6B, FIG. 7B is a right side view of FIG. 6B, and FIG. 7C is a plurality of reaction tubes in FIG. 6B. It is the figure which took out one of these and expanded and showed it.

  As shown in FIGS. 6 to 7, a plurality of outer membrane cylindrical reaction tubes 23 whose lower ends are closed are arranged in the first casing 21 having a rectangular cross section at intervals. Reference numeral 24 denotes a lower end closing portion of each reaction tube 23, which is a disk corresponding to the outer diameter of the reaction tube 23. And in each reaction tube 23, the pipe | tube 25 smaller in diameter than the internal diameter of a reaction tube is arrange | positioned. The small-diameter tube 25 is arranged with its lower end spaced from the lower end closing portion 24 of the reaction tube. In this way, the first casing 21 configured by juxtaposing a plurality of reaction tubes 23 is arranged in the second casing 22 with an interval. In the drawing, 26 is a bottom wall of the first casing 21, 27 is an upper wall of the first casing 21, 28 is a lower wall of the second casing 22, and 29 is an upper wall of the second casing 22.

  At this time, the first casing 21 is disposed with a space between the bottom wall 26 and the lower wall 28 of the second casing 22, and a combustion gas distribution member 31, such as a perforated plate, is disposed in the gap. And distribute the combustion gas upward from its lower part. The combustion gas is introduced from the introduction pipe 30, passes through the distribution member 31, and flows upward through the gap between the first casing 21 and the second casing 22. After the pipe 23 is heated to give heat necessary for reforming the raw material gas, the pipe 23 is discharged from a discharge pipe 32 provided on the upper wall 29 of the second casing 22.

  The raw material gas is circulated downwardly between the reaction tube 23 and the small diameter tube 25 from the introduction tube 33 and is brought into contact with the inside of the reaction tube 23 to generate a reformed gas. Hydrogen is separated and purified by a hydrogen permeable membrane to produce high purity hydrogen. High-purity hydrogen is led out from a hydrogen lead-out pipe 34 provided on the upper wall 27 of the first casing 21 through a gap between the first casing 21 and each reaction pipe 23. The remaining source gas is folded at the lower end of the small-diameter pipe 25 and flows upward in the small-diameter pipe 25, and is discharged from the off-gas discharge pipe 36 through the header 35.

  In the aspect of the present invention (2), a plurality of the first casings 21 configured as described above may be located in the second casing 22. FIG. 8 is a diagram showing a configuration example in this case, and shows a case where three of the first casings 21 are positioned as a cross-sectional view. As shown in FIG. 8, a plurality of first casings 21 are arranged in the second casing 22 at intervals. In this case, the source gas is introduced from each introduction pipe 33 provided in each first casing 21, and the high purity hydrogen obtained in each reaction pipe is a hydrogen lead-out pipe provided in each first casing 21. The remaining raw material gas is discharged from an off-gas discharge pipe 35 provided in each first casing 21. The source gas may be branched from one conduit and introduced into each introduction pipe 33. High-purity hydrogen is led out from the hydrogen lead-out pipe 34, but the hydrogen lead-out pipes 34 may be combined into one by a header or the like. In this case, high-purity hydrogen is led out from the single hydrogen lead-out pipe. The Further, the off-gas discharge pipes 36 may be combined into one by a header or the like. In this case, the off-gas is discharged from the single discharge pipe. Other points are the same as in the case where one first casing 21 is arranged in the second casing 22.

<Aspect of the present invention (3): Outer membrane type cylindrical reaction tube>
In the present invention (3), an outer membrane type cylindrical reaction tube is used, a reformed gas is produced by passing a raw material gas through the inside of the reaction tube, and hydrogen is generated from the produced reformed gas through a hydrogen permeable membrane. This is a hydrogen production device that produces high purity hydrogen by separation and purification. 9-10 is a figure which shows the aspect of this invention (3). 9B is a longitudinal sectional view, and FIG. 9A is a longitudinal sectional view taken along line AA in FIG. 9B. 10A is a left side view of FIG. 9B, FIG. 10B is a right side view of FIG. 9B, and FIG. 10C is a plurality of reaction tubes in FIG. 9B. It is the figure which took out one of these and expanded and showed it.

  As shown in FIG. 9, a plurality of outer membrane cylindrical reaction tubes 42 are juxtaposed in a casing 41 having a rectangular cross section, and each reaction tube 42 is provided with a tube 43 having a diameter smaller than the inner diameter of each reaction tube 42. Place in a penetrating state. The space between the inner wall of the casing 41 and each reaction tube 42 and between each reaction tube 42 serves as a flow path for the purified hydrogen obtained in each reaction tube 42. In FIG. 9, 44 is a lower wall of the casing 41, and 45 is an upper wall of the casing 41.

  The small-diameter pipe 43 is for heating the reaction tube 42 through the combustion gas from one end to the other end. One end of the small-diameter pipe 43 is branched from an upper header 47 connected to the combustion gas introduction pipe 46, and the other end is a combustion gas discharge pipe 49. It is connected to the lower header 48 connected to the. The raw material gas introduction pipe 50 is connected to an upper header 51 for branching the raw material gas into each reaction tube 42, and communicates between each reaction tube 42 and the small diameter tube 43 via the header 51. As shown in FIG. 9B, each small-diameter pipe 43 branched from the upper header 47 connected to the combustion gas introduction pipe 46 passes through the inside of each reaction pipe 42 from the back of the header 51 for branching the source gas to each reaction pipe 42. It penetrates and is connected to a lower header 48 that continues to the combustion gas discharge pipe 49.

  After the combustion gas is introduced from the introduction pipe 46 and passes through the upper header 47 and flows through each small diameter pipe 43 downward, the reaction pipe 42 is heated to give heat necessary for reforming the raw material gas. The gas is discharged from the discharge pipe 49 through the lower header 48. The raw material gas is circulated downwardly between the reaction tube 42 and the small-diameter tube 43 from the introduction tube 50 through the header 51 and is brought into contact with the inside of the reaction tube 42 to generate a reformed gas. High purity hydrogen is produced by separating and purifying hydrogen from a gas through a hydrogen permeable membrane. The obtained high-purity hydrogen is led out from the hydrogen lead-out pipe 53 provided in the casing 41, and the remaining raw material gas is discharged from the discharge pipe 54 as off-gas through the lower header 52.

<Aspect of the present invention (4): outer membrane cylindrical reaction tube>
The present invention (4) uses an outer membrane type cylindrical reaction tube to produce a high-purity hydrogen by purifying it with a hydrogen permeable membrane while generating a reformed gas by contacting the raw material gas through the inside of the reaction tube. This is a hydrogen production device. 11-13 is a figure which shows the aspect of this invention (4). FIG. 11B is a longitudinal sectional view, and FIG. 11A is a longitudinal sectional view taken along line AA in FIG. 11B. 12 (a) is a left side view of FIG. 11 (b), FIG. 12 (b) is a right side view of FIG. 11 (b), and FIG. 12 (c) is a plurality of reaction tubes in FIG. 11 (b). It is the figure which took out one of these and expanded and showed it.

  As shown in FIG. 11, a plurality of outer membrane type cylindrical reaction tubes 63 are juxtaposed at intervals in a first casing 61 having a rectangular cross section. Then, in the flow direction of the source gas, the source gas introduction pipe 64 is connected to the foremost reaction tube, the off-gas discharge pipe 67 is connected to the rearmost reaction tube, and the adjacent reaction tubes are connected in a zigzag manner. That is, the lower part of the foremost reaction tube and the lower part of the second reaction tube are connected by a connecting tube (U-shaped tube or the like) 65, and the upper part of the second reaction tube and the upper part of the third reaction tube are connected. The connection pipe 66 is connected, the lower part of the third reaction tube and the lower part of the fourth reaction tube are connected by the connection pipe 65, and the adjacent reaction tubes are sequentially connected in the same manner. In the example of FIG. 11, six reaction tubes are arranged, but they are similarly connected by connecting tubes corresponding to the number of reaction tubes.

  In this way, the first casing 61 configured by arranging a plurality of reaction tubes 63 is disposed in the second casing 62 at intervals. At that time, the first casing 61 is arranged such that its bottom 69 is spaced from the lower wall 70 of the second casing 62, and a combustion gas distribution member 73 such as a perforated plate is arranged in the gap. Then, the combustion gas is distributed upward from its lower part. Combustion gas is introduced from the introduction pipe 72 and distributed by the distribution member 73. The distributed combustion gas flows upward between the first casing 61 and the second casing 62 and heats the reaction tube 63 in the first casing to generate heat necessary for reforming the raw material gas. Is then discharged from a discharge pipe 74 provided on the upper wall 71 of the second casing 62.

  On the other hand, the raw material gas is introduced into the foremost reaction tube 63 from the introduction tube 64, flows downward through the reaction tube 63, and is brought into contact with the inside of the reaction tube to generate a reformed gas. Hydrogen from the reformed gas is separated and purified by a hydrogen permeable membrane to produce high purity hydrogen. The raw material gas that has passed through the foremost reaction tube 63 flows through the second reaction tube 63 upward through the lower connecting tube 65 and is brought into contact with the inside of the reaction tube 63 to generate a reformed gas. Then, high purity hydrogen is produced by separating and purifying hydrogen from the generated reformed gas through a hydrogen permeable membrane. Thereafter, the raw material is circulated in the third reaction tube 63, the fourth reaction tube 63, and so on to produce high-purity hydrogen in the same manner as described above, and the raw material that has passed through the last reaction tube 63. The gas is discharged from the discharge pipe 67 as off-gas. The high-purity hydrogen obtained in each reaction tube 63 is provided in the first casing 61 through a gap between the first casing 61 and each reaction tube 63 and between each cylindrical reaction tube 63. It is discharged from the hydrogen outlet pipe 68.

  In the present invention (4), a plurality of first casings 61 configured as described above may be located in the second casing 62. FIG. 13 is a diagram showing a configuration example in this case, and shows a case where three of the first casings 61 are positioned as a cross-sectional view. As shown in FIG. 13, a plurality of first casings 61 are arranged in the second casing 62 at intervals. In this case, the hydrogen lead-out pipes 68 for the respective first casings 61 may be combined into one by a header or the like. In this case, high-purity hydrogen is led out from the single hydrogen lead-out pipe. Further, the off-gas discharge pipes 67 for the respective first casings 61 may be combined into one by a header or the like. In this case, the off-gas is discharged from the single discharge pipe. The other points are the same as the case where one first casing 61 is arranged in the second casing 62.

<Aspect of the present invention (5): outer membrane cylindrical reaction tube>
In the present invention (5), an outer membrane type cylindrical reaction tube is used, a reformed gas is generated by contacting a raw material gas through the inside of the reaction tube, and hydrogen is generated from the generated reformed gas through a hydrogen permeable membrane. This is a hydrogen production device that produces high purity hydrogen by separation and purification. 14-16 is a figure which shows the aspect of this invention (5). 14B is a longitudinal sectional view, and FIG. 14A is a longitudinal sectional view taken along line AA in FIG. 14B. 15 (a) is a left side view of FIG. 14 (b), FIG. 15 (b) is a right side view of FIG. 14 (b), and FIG. 15 (c) is a plurality of reaction tubes in FIG. 14 (b). It is the figure which took out one of the left ends of them, and expanded and showed.

  As shown in FIGS. 14 to 15, a plurality of reaction tubes 83 are juxtaposed at intervals in a first casing 81 having a rectangular cross section. Then, a branch pipe 86 from the lower header 85 is connected to the lower end of each reaction pipe 83. The lower header 85 continues to the source gas introduction pipe 84. Further, the upper part of each reaction tube 83 is connected to a branch pipe 87 from the upper header 88. The upper header 88 continues to the off-gas exhaust pipe 89. Reference numeral 91 denotes a hydrogen outlet pipe provided on the upper wall 90 of the first casing 81.

  Thus, the first casing 81 constituted by arranging a plurality of reaction tubes 83 in the second casing 82 is arranged in the second casing 82 with a space from the inner wall (the inner wall of the second casing 82). To do. Further, a space is disposed between the bottom 92 of the first casing 81 and the lower wall 94 of the second casing 82, and a combustion gas distribution member 95 such as a perforated plate is disposed in the gap. Combustion gas is introduced from a combustion gas introduction pipe 93 provided at the lower part of the second casing 82, distributed by a gas distribution member 95, passes through the lower part of the first casing 81, and the first casing 81 and the first casing 81. The upper wall of the second casing 82 is heated after the reaction tube 83 in the first casing 81 is heated to provide heat necessary for reforming the raw material gas while flowing upwardly between the two casings 82. The gas is discharged from a discharge pipe 97 provided in 96.

  The raw material gas is sequentially reformed from the introduction pipe 84 through the lower header 85 and the branch pipe 86 connected to the feed pipe 83 in the respective reaction tubes 83, that is, through the inside of the reaction tube 83 to be reformed. Gas is produced, and hydrogen is separated and purified from the produced reformed gas through a hydrogen permeable membrane to produce high purity hydrogen. The high-purity hydrogen obtained in each reaction tube 83 is led out from the hydrogen lead-out tube 91 through a gap between the first casing 81 and each reaction tube 83. The remaining source gas that has passed through each reaction tube 83 is discharged from an off-gas discharge tube 89 through an upper header 88.

  In the present invention (5), a plurality of the first casings 81 configured as described above may be disposed in the second casing 82. FIG. 16 is a diagram showing a configuration example in this case, and shows a case where three of the first casings 81 are arranged in the second casing 82 as a cross-sectional view. As shown in FIG. 16, a plurality of first casings 81 are arranged in the second casing 82 at intervals. The hydrogen lead-out pipes 91 for each first casing 81 may be combined into one by a header or the like. In this case, high-purity hydrogen is led out from the single hydrogen lead-out pipe. Further, the off-gas discharge pipes 89 for the respective first casings 81 may be combined into one by a header or the like. In this case, the off-gas is discharged from the single discharge pipe. The other points are the same as the case where one first casing 81 is arranged in the second casing 82.

<Aspect of the present invention (6): Inner membrane type cylindrical reaction tube>
In the present invention (6), an inner membrane type cylindrical reaction tube as shown in FIG. 3 is used, and a raw material gas is passed through the outside of the reaction tube to be brought into contact therewith to produce a reformed gas and purified by a hydrogen permeable membrane. This is a hydrogen production device that produces high-purity hydrogen. 17-18 is a figure which shows the aspect of this invention (6). FIG. 17B is a longitudinal sectional view, and FIG. 17A is a longitudinal sectional view taken along line AA in FIG. 18 (a) is a left side view of FIG. 17 (b), FIG. 18 (b) is a right side view of FIG. 17 (b), and FIG. 18 (c) is a plurality of reaction tubes in FIG. 17 (b). It is the figure which took out one of these and expanded and showed it.

  As shown in FIGS. 17 to 18, a plurality of reaction tubes 102 whose lower ends are closed are placed in the casing 101 having a rectangular cross section at intervals. Reference numeral 103 denotes a closed portion, which is a disk corresponding to the outer diameter of the reaction tube 102. Then, in each reaction tube 102, a first tube 104 and a second tube 106 having a small diameter are sequentially arranged at intervals. Among these, the 1st pipe | tube 104 obstruct | occludes the lower end. Reference numeral 105 denotes a closed portion, which is a disk corresponding to the outer diameter of the first tube 104. Moreover, the 2nd pipe | tube 106 is arrange | positioned so that a space | interval (space | gap) may be maintained between the lower end and the lower end obstruction | occlusion part 105 of the 1st pipe | tube 104, The space | gap may become a return part of combustion gas.

  Reference numeral 107 denotes a combustion gas introduction pipe, and 108 denotes a header (heading) connected to the combustion gas introduction pipe 107. The combustion gas is introduced from the introduction pipe 107 and heats necessary for reforming the raw material gas by heating the reaction pipe 102 while flowing downwardly between the first pipe 104 and the second pipe 106. Then, it is folded at the lower end of the second pipe 106 and flows upward in the second pipe 106, and is discharged from the combustion gas discharge pipe 109 through the header 108.

  A space between the inner wall of the casing 101 and each of the reaction tubes 102 disposed therein becomes a source gas supply space. A raw material gas introduction pipe 110 is provided on one side wall of the casing 101, and an off-gas discharge pipe 111 is provided on the other side wall opposite thereto. The raw material gas is introduced from the introduction pipe 110 and is made to contact with the outside of each reaction pipe 102 to be refined by a hydrogen permeable membrane while producing reformed gas to produce high purity hydrogen. High-purity hydrogen passes between the inner wall (hydrogen permeable membrane side) of each reaction tube 102 and the outer wall of the first tube 104 and is led out from the hydrogen outlet tube 113 through the header 112. The remaining source gas is discharged from the offgas discharge pipe 111.

  As described above, the present hydrogen production apparatus does not require a separate reforming catalyst layer and uses an inner membrane cylindrical reaction tube that does not cause a problem of damage to the hydrogen permeable membrane. Since it is arranged in a compact manner in the casing, hydrogen can be produced in a small size and with high efficiency. These effects are the same for the embodiments of the present invention (7) to (9) described below.

<Aspect of the present invention (7): Inner membrane cylindrical reaction tube>
The present invention (7) uses an inner membrane type cylindrical reaction tube to produce high-purity hydrogen by refining with a hydrogen permeable membrane while producing a reformed gas by contacting the raw material gas through the outside of the reaction tube. This is a hydrogen production device. 19-21 is a figure which shows the aspect of this invention (7). FIG. 19B is a longitudinal sectional view, and FIG. 19A is a longitudinal sectional view taken along line AA in FIG. 19B. 20 (a) is a left side view of FIG. 19 (b), FIG. 20 (b) is a right side view of FIG. 19 (b), and FIG. 20 (c) is a plurality of reaction tubes in FIG. 19 (b). It is the figure which took out one of these and expanded and showed it.

  As shown in FIGS. 19 to 20, a plurality of reaction tubes 123 whose lower ends are closed are arranged in the first casing 121 having a rectangular cross section at intervals. The closed portion 124 is a disk corresponding to the outer diameter of the reaction tube 123. Each reaction tube 123 in the first casing 121 is connected to a header 125, and the header 125 is connected to a hydrogen outlet tube 126. Reference numeral 127 denotes a bottom wall of the first casing 121, and 128 denotes an upper wall of the first casing 121. The source gas introduction pipe 129 faces the bottom wall 127 of the first casing 121, and the off-gas discharge pipe 130 faces the upper wall 128 of the first casing 121. A source gas distribution member 131, for example, a perforated plate, is disposed in a space between the bottom wall 127 and the lower end closing portion 124 of each reaction tube.

  In this way, the first casing 121 configured by arranging a plurality of reaction tubes is disposed in the second casing 122 at intervals. Reference numeral 132 denotes a bottom wall of the second casing 122, and 133 denotes an upper wall of the second casing 122. The first casing 121 is disposed with a gap between its bottom wall 127 and the lower wall 132 of the second casing 122, and a combustion gas distribution member 134, for example, a perforated plate is disposed in the gap. Distribute the combustion gas upward from the bottom. The combustion gas introduced from the combustion gas introduction pipe 135 is distributed by the distribution member 134, and flows upward between the first casing 121 and the second casing 122, while in the first casing 121. Each reaction tube 123 is heated to give heat necessary for reforming the raw material gas, and then discharged from a discharge tube 136 provided on the upper wall 133 of the second casing.

  The raw material gas is introduced from the introduction pipe 129, distributed by the distribution member 131, and flows through the outer side of each reaction pipe 123 while contacting the outer side to generate the reformed gas, while passing the produced reformed gas through hydrogen. Purify by membrane to produce high purity hydrogen. High purity hydrogen is led out from the hydrogen lead-out pipe 126 through the header 125, and the remaining raw material gas is discharged from the off-gas discharge pipe 130.

  In the present invention (7), a plurality of the first casings 121 configured as described above may be disposed in the second casing 122. FIG. 21 is a diagram showing a configuration example in this case, and shows a case where three of the first casings 121 are arranged in the second casing 122 as a cross-sectional view. The hydrogen lead-out pipes 126 for the respective first casings 121 may be combined into one by a header or the like. In this case, high-purity hydrogen is led out from the single hydrogen lead-out pipe. Further, the off-gas discharge pipes 130 for the respective first casings 121 may be combined into one by a header or the like, and in this case, the off-gas is discharged from the single discharge pipe. Other points are the same as in the case where one first casing 121 is arranged in the second casing 122.

<Aspect of the present invention (8): Inner membrane type cylindrical reaction tube>
The present invention (8) uses an inner membrane cylindrical reaction tube to produce high-purity hydrogen by purifying it with a hydrogen permeable membrane while generating a reformed gas by contacting the raw material gas through the outside of the reaction tube. This is a hydrogen production device. 22-23 is a figure which shows the aspect of this invention (8). 22B is a longitudinal sectional view, and FIG. 22A is a longitudinal sectional view taken along line AA in FIG. 22B. 23 (a) is a left side view of FIG. 22 (b), FIG. 23 (b) is a right side view of FIG. 22 (b), and FIG. 23 (c) is a plurality of reaction tubes in FIG. 22 (b). It is the figure which took out one of these and expanded and showed it.

  As shown in FIGS. 22 to 23, a plurality of inner-film cylindrical reaction tubes 142 are arranged in parallel at intervals in a casing 141 having a rectangular cross section, and a tube 143 having a smaller diameter than the inner diameter is placed in each reaction tube. It arranges in the state which penetrated. The small-diameter pipe 143 is for heating the reaction tube through the combustion gas from one end to the other end in the pipe. One end of the small-diameter pipe 143 is branched from the upper header 145 connected to the combustion gas introduction pipe 144 and the other end is the combustion gas discharge pipe. The lower header 146 is connected to the lower header 146. After the combustion gas is introduced from the introduction pipe 144 and flows through the small diameter pipes 143 through the upper header 145 in the downward direction, the reaction pipe 142 is heated to give heat necessary for reforming the raw material gas. Then, it is discharged from the combustion gas discharge pipe 147 through the lower header 146.

  The space between the inner wall surface of the casing 141 and each of the reaction tubes 142 disposed therein becomes a source gas supply space from the source gas introduction tube 148. The source gas introduction pipe 148 is provided on one side wall of the casing 141, and an off-gas discharge pipe 149 is provided on the other side wall opposite to the one side wall. Source gas is supplied from the introduction pipe 148. Then, the raw material gas is brought into contact with the outside of each reaction tube 142 to generate a reformed gas, and the generated reformed gas is purified by a hydrogen permeable membrane to become high purity hydrogen. High-purity hydrogen joins the header 150 from the gap between the reaction tube 142 and the small-diameter tube 143 and is led out from the hydrogen lead-out tube 151. The remaining source gas is discharged from the off-gas discharge pipe 149.

<Aspect of the present invention (9): Inner membrane type cylindrical reaction tube>
The present invention (9) uses an inner membrane type cylindrical reaction tube to produce high-purity hydrogen by purifying it with a hydrogen permeable membrane while generating a reformed gas by contacting the raw material gas through the outside of the reaction tube. This is a hydrogen production device. 24-26 is a figure which shows the aspect of this invention (9). 24B is a longitudinal sectional view, and FIG. 24A is a longitudinal sectional view taken along line AA in FIG. 24B. 25 (a) is a left side view of FIG. 24 (b), FIG. 25 (b) is a right side view of FIG. 24 (b), and FIG. 25 (c) is a plurality of reaction tubes in FIG. 24 (b). It is the figure which took out one of these and expanded and showed it.

  As shown in FIGS. 24 to 25, a plurality of reaction tubes 163 are arranged in a first casing 161 having a rectangular cross section at intervals, and a lower portion of each of the reaction tubes is connected to a connecting tube (such as a U-shaped tube). Connect at 164. The upper part of each reaction tube 163 is connected to a header 165 connected to the hydrogen outlet tube 166. A space is provided between the lower wall 168 of the first casing 161 and the lower end of the connecting pipe 164, and a raw material gas distribution member 171 such as a perforated plate is disposed in the gap. A source gas introduction pipe 167 is provided on the lower wall 168 of the first casing 161, and an off-gas discharge pipe 170 is provided on the upper wall 169.

  A first casing 161 configured by arranging a plurality of reaction tubes 163 in this manner is arranged in the second casing 162. At that time, the first casing 161 is arranged with a space between the bottom wall 168 and the lower wall 173 of the second casing, and a combustion gas distribution member 174 such as a perforated plate is arranged in the gap. Then, the combustion gas is distributed upward from its lower part. Combustion gas introduced from the combustion gas introduction pipe 172 and distributed by the distribution member 174 flows through the gap between the first casing 161 and the second casing 162 upward, and each of the combustion gases in the first casing 161 is distributed. After the reaction tube 163 is heated to give heat necessary for reforming the raw material gas, the reaction tube 163 is discharged from a discharge tube 176 provided on the upper wall 175 of the second casing 162.

  The raw material gas is introduced from the introduction pipe 167 and distributed by the distribution member 171, passes through the outside of each reaction pipe 163, is contacted to generate a reformed gas, and the generated reformed gas is purified by the hydrogen permeable membrane. It becomes high purity hydrogen and is led out from the hydrogen lead-out pipe 166 through the header 165. The remaining raw material gas is discharged from the off-gas discharge pipe 170.

  In the present invention (9), a plurality of the first casings 161 configured as described above may be arranged in the second casing 162. FIG. 26 is a diagram showing a configuration example in this case, and shows a case where three of the first casings 161 are arranged in the second casing 162 as a cross-sectional view. The hydrogen lead-out pipes 166 for each first casing 161 may be bundled together by a header or the like. In this case, high-purity hydrogen is led out from the single hydrogen lead-out pipe. Further, the off-gas discharge pipes 170 for the respective first casings 161 may be collected together by a header or the like, and in this case, the off-gas is discharged from the single discharge pipe. Other points are the same as in the case where one first casing 161 is arranged in the second casing 162.

The figure explaining the example of composition of the conventional membrane reactor The figure which shows the aspect of the outer membrane type | mold cylindrical reaction tube used with the hydrogen production apparatus of this invention The figure which shows the aspect of the inner membrane type | mold cylindrical reaction tube used with the hydrogen production apparatus of this invention The figure which shows the aspect of this invention (1) The figure which shows the aspect of this invention (1) The figure which shows the aspect of this invention (2) The figure which shows the aspect of this invention (2) The figure which shows the aspect of this invention (2) The figure which shows the aspect of this invention (3) The figure which shows the aspect of this invention (3) The figure which shows the aspect of this invention (4) The figure which shows the aspect of this invention (4) The figure which shows the aspect of this invention (4) The figure which shows the aspect of this invention (5) The figure which shows the aspect of this invention (5) The figure which shows the aspect of this invention (5) The figure which shows the aspect of this invention (6) The figure which shows the aspect of this invention (6) The figure which shows the aspect of this invention (7) The figure which shows the aspect of this invention (7) The figure which shows the aspect of this invention (7) The figure which shows the aspect of this invention (8) The figure which shows the aspect of this invention (8) The figure which shows the aspect of this invention (9) The figure which shows the aspect of this invention (9) The figure which shows the aspect of this invention (9)

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,41 Casing 2,23,42,63,83 Outer-membrane-type cylindrical reaction tube 3 Blocking part of the lower end of the reaction tube 3 1st tube 5 2nd tube 6 3rd tube 7 2nd tube 5 8 Combustion gas introduction pipe 9 Combustion gas supply header (pipe header)
DESCRIPTION OF SYMBOLS 10 Header which opening of each 3rd pipe | tube 6 11 Combustion gas discharge pipe 12 Raw material gas introduction pipe 13 Hydrogen outlet pipe 14 Header 15 Off-gas discharge pipe 21, 61, 81 1st casing 22, 62, 82 2nd casing 101, 141 Casing 102, 123, 142, 163 Inner membrane cylindrical reaction tube 103 Lower end closed portion of reaction tube 102 104 First tube 105 Lower end closed portion of first tube 104 106 Second tube 107 Combustion gas introduction Tube 108, 112 Header (heading)
109 Combustion gas discharge pipe 110 Raw material gas introduction pipe 111 Off gas discharge pipe 113 Hydrogen outlet pipe 121, 161 First casing 122, 162 Second casing

Claims (17)

Using an outer membrane cylindrical reaction tube with a hydrogen permeable membrane disposed on the outer peripheral surface of a porous cylindrical reforming catalyst / support, a reformed gas is generated by contacting the raw material gas through the inside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by purification using a hydrogen permeable membrane, comprising the following configurations (a) to (e).
(A) In the casing, a plurality of reaction tubes whose lower ends are closed are arranged at intervals, and a high-purity hydrogen flow path is formed between the reaction tube and the adjacent reaction tubes in the casing. And
(B) In each reaction tube, a first tube having a smaller diameter, a second tube and a third tube closed at the lower end thereof are arranged at intervals, and the lower end of the third tube is disposed at the lower end. Placing a gap with respect to the lower end closing part of the second tube,
(C) The heating combustion gas is circulated downwardly between the second pipe and the third pipe from the introduction pipe, and then folded at the lower end of the third pipe to move upward in the third pipe. Circulate to the combustion gas exhaust pipe,
(D) The reformed gas is generated by bringing the source gas into contact with the inside of the reaction tube while flowing downwardly from the introduction tube between each reaction tube and the first tube. Producing and purifying high-purity hydrogen by separating and purifying the hydrogen with a hydrogen permeable membrane, and deriving it from a hydrogen outlet pipe provided in the casing,
(E) The remaining raw material gas is folded at the lower end of the first pipe and circulated upward between the first pipe and the second pipe, and then discharged from the off-gas discharge pipe. Using an outer membrane cylindrical reaction tube with a hydrogen permeable membrane disposed on the outer peripheral surface of a porous cylindrical reforming catalyst / support, a reformed gas is generated by contacting the raw material gas through the inside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by purification using a hydrogen permeable membrane, comprising the following configurations (a) to (e).
(A) In the first casing, a plurality of reaction tubes whose lower ends are closed are arranged at intervals, and a gap is formed between the first casing and each reaction tube and between adjacent reaction tubes. A high purity hydrogen flow path,
(B) A small-diameter pipe is arranged at intervals in each reaction pipe, and the reformed gas is brought into contact with the inside of the reaction pipe while the source gas is lowered between the inside of the reaction pipe and the small-diameter pipe. Producing high purity hydrogen by separating and purifying hydrogen in the generated reformed gas with a hydrogen permeable membrane and deriving from a hydrogen outlet pipe provided in the first casing,
(C) raising the remaining raw material gas through the small-diameter pipe and discharging it from the off-gas discharge pipe;
(D) The first casing is disposed in the second casing, and the gap between the lower wall of the second casing and the bottom wall of the first casing is used as a flow path for the combustion gas for heating, and the gap Disposing a combustion gas distribution member on the
(E) The combustion gas for heating is introduced into the lower portion of the second casing through the introduction pipe, and the gap between the second casing and the first casing is raised through the combustion gas distribution member to perform each reaction. As a heating source necessary for the generation of reformed gas in the pipe, and to discharge from the discharge pipe provided in the upper wall of the second casing;   The hydrogen production apparatus according to claim 2, wherein a plurality of the first casings are arranged in parallel at intervals in a second casing. Using an outer membrane cylindrical reaction tube with a hydrogen permeable membrane disposed on the outer peripheral surface of a porous cylindrical reforming catalyst / support, a reformed gas is generated by contacting the raw material gas through the inside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by purification using a hydrogen permeable membrane, comprising the following configurations (a) to (e).
(A) Arranging a plurality of reaction tubes at intervals in the casing, and disposing a tube having a smaller diameter than the inner diameter in each reaction tube in a state of passing through the reaction tube;
(B) One end of each small-diameter pipe is branched from the upper header connected to the combustion gas introduction pipe for heating, and the other end is connected to the lower header connected to the combustion gas discharge pipe.
(C) The heating combustion gas is passed from one end to the other end of each small-diameter pipe through the introduction pipe and the upper header to heat the reaction pipe, and then discharged from the discharge pipe through the lower header. ,
(D) The reformed gas is generated by bringing the raw material gas into contact with the inside of the reaction tube while descending between each reaction tube and the small-diameter tube through the introduction tube and the upper header. Separating and purifying hydrogen from a hydrogen permeable membrane to produce high-purity hydrogen, which is derived from a hydrogen outlet pipe provided in the casing,
(E) exhausting the remaining raw material gas from between the reaction tube and the small diameter tube through the lower header through the off-gas discharge tube; Using an outer membrane cylindrical reaction tube with a hydrogen permeable membrane disposed on the outer peripheral surface of a porous cylindrical reforming catalyst / support, a reformed gas is generated by contacting the raw material gas through the inside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by purification using a hydrogen permeable membrane, comprising the following configurations (a) to (e).
(A) In the first casing, a plurality of reaction tubes are arranged at intervals, the adjacent reaction tubes are connected in a zigzag manner in the upper and lower directions, and the reaction tube in the forefront is arranged in the flow direction of the source gas. Connecting the source gas introduction pipe to the last reaction pipe and the off-gas discharge pipe;
(B) The first casing is disposed in the second casing, and a gap between the lower wall of the second casing and the bottom wall of the first casing is used as a flow path for the combustion gas for heating. Disposing a combustion gas distribution member on the
(C) The combustion gas for heating is introduced into the lower portion of the second casing through the introduction pipe, and the gap between the second casing and the first casing is raised through the combustion gas distribution member to perform each reaction. As a heating source necessary for the generation of reformed gas in the pipe, and to discharge from the discharge pipe provided in the upper wall of the second casing;
(D) The raw material gas is introduced into the foremost reaction tube from the introduction tube, and is passed through the inside of each reaction tube while flowing from the reaction tube connected in a zigzag manner toward the last reaction tube. The reformed gas is generated, and hydrogen is separated and purified from the generated reformed gas by a hydrogen permeable membrane to produce high-purity hydrogen, which is led out from the hydrogen outlet pipe provided in the first casing. ,
(E) exhausting the remaining raw material gas from an off-gas exhaust pipe connected to the last reaction pipe,   6. The hydrogen production apparatus according to claim 5, wherein a plurality of the first casings are arranged in parallel at intervals in the second casing. Using an outer membrane cylindrical reaction tube with a hydrogen permeable membrane disposed on the outer peripheral surface of a porous cylindrical reforming catalyst / support, a reformed gas is generated by contacting the raw material gas through the inside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by purification using a hydrogen permeable membrane, comprising the following configurations (a) to (e).
(A) In the first casing, a plurality of reaction tubes are arranged at intervals, and a branch pipe from a lower header connected to a source gas introduction pipe is connected to the lower part of each reaction pipe, Connecting to the branch pipe from the upper header connected to the off-gas exhaust pipe,
(B) The first casing is disposed in the second casing, and the gap between the lower wall in the second casing and the bottom wall of the first casing is used as a flow path for the combustion gas for heating, Disposing a combustion gas distribution member in the gap;
(C) Combustion gas for heating is introduced from the lower portion of the second casing through the introduction pipe, and the gap between the second casing and the first casing is raised through the distribution member of the combustion gas to perform each reaction. As a heating source necessary for the generation of reformed gas in the pipe, and to discharge from the discharge pipe provided in the upper wall of the second casing;
(D) The raw material gas is introduced into each reaction tube from the introduction tube through the header, and is passed through and brought into contact with the inside of each reaction tube to generate reformed gas. Hydrogen is generated from the generated reformed gas through the hydrogen permeable membrane. Producing and purifying high-purity hydrogen by separating and purifying by a hydrogen outlet pipe provided in the first casing,
(E) The remaining raw material gas from each reaction tube is discharged from the off-gas discharge pipe through each branch pipe and the upper header,   8. The hydrogen production apparatus according to claim 7, wherein a plurality of the first casings are arranged in parallel at intervals in the second casing. Using an inner membrane type cylindrical reaction tube with a hydrogen permeable membrane on the inner peripheral surface of a porous cylindrical reforming catalyst and support, the reformed gas is generated by contacting the raw material gas through the outside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane while having the following configurations (a) to (e).
(A) Arranging a plurality of reaction tubes whose lower ends are closed in the casing, and sequentially disposing a first tube and a second tube having a small diameter at intervals in each reaction tube,
(B) The first pipe is closed at its lower end, the second pipe is arranged at a lower end with respect to the lower end closed portion of the first pipe, and the heating combustion gas is sent from the introduction pipe to the header. After passing through between the first tube and the second tube through the bottom, it is folded at the lower end of the second tube and then flows upward in the second tube, and the reformed gas in the reaction tube As a heating source necessary for the production of gas, and exhaust from the combustion gas exhaust pipe through the header,
(C) The space between the inner wall of the casing and each reaction tube disposed therein is used as a source gas supply space, a source gas introduction pipe is provided on one side wall of the casing, and the other side wall opposite to the one side wall Providing an off-gas discharge pipe in the
(D) The raw material gas is introduced from the introduction tube, and is passed through the outside of each reaction tube to be contacted to generate reformed gas. The hydrogen in the generated reformed gas is separated and purified by the hydrogen permeable membrane, Deriving from the hydrogen outlet tube as pure hydrogen,
(E) exhausting the remaining source gas from the off-gas exhaust pipe; Using an inner membrane type cylindrical reaction tube with a hydrogen permeable membrane on the inner peripheral surface of a porous cylindrical reforming catalyst and support, the reformed gas is generated by contacting the raw material gas through the outside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane, comprising the following configurations (a) to (f).
(A) In the first casing, a plurality of reaction tubes whose lower ends are closed are arranged at intervals, and each reaction tube in the casing is connected to a header connected to a hydrogen outlet tube,
(B) The raw material gas introduction pipe faces the bottom wall of the first casing, and the raw material gas distribution member is disposed in the space between the bottom wall and the lower end closed portion of each reaction tube,
(C) The first casing is disposed in the second casing, and the first casing is disposed with a gap between the bottom portion and the lower wall of the second casing, and the gap is used for heating. Arranging a combustion gas distribution member;
(D) The heating combustion gas is introduced from the introduction pipe, distributed and supplied upward from the lower part of the distribution member, and while flowing between the first casing and the second casing upward, Heating the reaction tube in the casing of 1 to give heat necessary for reforming the raw material gas, and then discharging it from the discharge pipe provided in the upper part of the second casing;
(E) The raw material gas is introduced from the introduction pipe, passed through the outside of each reaction pipe to produce reformed gas, and hydrogen in the produced reformed gas is separated and purified by a hydrogen permeable membrane to obtain high purity hydrogen. , Leading out from the hydrogen outlet pipe through the header,
(F) exhausting the remaining raw material gas from an off-gas exhaust pipe provided in the first casing;   The hydrogen production apparatus according to claim 10, wherein a plurality of the first casings are arranged in parallel at intervals in a second casing. Using an inner membrane type cylindrical reaction tube with a hydrogen permeable membrane on the inner peripheral surface of a porous cylindrical reforming catalyst and support, the reformed gas is generated by contacting the raw material gas through the outside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane, comprising the following configurations (a) to (f).
(A) Arranging a plurality of reaction tubes in the casing, and disposing a tube having a diameter smaller than the inner diameter in each reaction tube in a state of passing through each reaction tube;
(B) One end of each small-diameter pipe is branched from the upper header connected to the combustion gas introduction pipe for heating, and the other end is connected to the lower header connected to the combustion gas discharge pipe.
(C) The heating combustion gas is passed from one end of each small-diameter pipe to the other end through the introduction pipe and the upper header to heat the reaction pipe, and then discharged from the discharge pipe through the lower header. To do,
(D) providing a source gas introduction pipe on one side wall of the casing and providing an off-gas discharge pipe on the other side wall opposite to the one side wall;
(E) The raw material gas is introduced from the introduction pipe, passed through the outside of each reaction pipe to produce reformed gas, and hydrogen in the produced reformed gas is separated and purified by a hydrogen permeable membrane to obtain high purity hydrogen. , Leading from the flow path between the reaction tube and the small diameter tube, through the header and from the hydrogen outlet tube,
(F) exhausting the remaining source gas from the off-gas exhaust pipe; Using an inner membrane type cylindrical reaction tube with a hydrogen permeable membrane on the inner peripheral surface of a porous cylindrical reforming catalyst and support, the reformed gas is generated by contacting the raw material gas through the outside of the reaction tube. A hydrogen production apparatus for producing high-purity hydrogen by refining with a hydrogen permeable membrane, comprising the following configurations (a) to (f).
(A) A plurality of reaction tubes are arranged at intervals in the first casing, and a lower portion of each of the reaction tubes is connected by a connecting tube for each pair of reaction tubes. Connecting to the header leading to the hydrogen outlet pipe,
(B) A space is provided between the lower wall of the first casing and the lower end of the connecting pipe, the raw material gas distribution member is disposed in the gap, and the raw material gas introduction pipes are respectively provided on the lower wall and the upper wall of the first casing. (C) The first casing is disposed in the second casing, and the space between the lower wall in the second casing and the bottom of the first casing is heated with combustion gas. Disposing a combustion gas distribution member in the gap,
(D) The heating combustion gas is introduced from the introduction pipe, distributed and supplied upward from the lower part of the distribution member, and while flowing between the first casing and the second casing upward, Heating the reaction tube in the casing of 1 to give heat necessary for reforming the raw material gas, and then discharging it from the discharge pipe provided in the upper part of the second casing;
(E) The raw material gas is introduced from the introduction pipe, passed through the outside of each reaction pipe to produce reformed gas, and hydrogen in the produced reformed gas is separated and purified by a hydrogen permeable membrane to obtain high purity hydrogen. , Leading out from the hydrogen outlet pipe through the header,
(F) exhausting the remaining source gas from the off-gas exhaust pipe;   The hydrogen production apparatus according to claim 13, wherein a plurality of the first casings are arranged in parallel at intervals in a second casing.   The hydrogen production apparatus according to any one of claims 1 to 14, wherein the porous cylindrical reforming catalyst / support is made of a sintered body of a mixture of nickel and yttria-stabilized zirconia. Hydrogen production equipment.   The hydrogen production apparatus according to claim 1, wherein the hydrogen permeable film is a Pd film or a Pd alloy film. 15. The hydrogen production apparatus according to claim 1, wherein the combustion gas for heating is a fuel gas such as a city gas or an off-gas combustion gas from the off-gas discharge pipe. apparatus.

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