JP5403199B2 - Honeycomb type hydrogen production apparatus, fuel cell power generation apparatus using the same, electric vehicle, submarine ship and hydrogen supply system, and reaction tube for hydrogen production cell - Google Patents

Description

  The present invention relates to a hydrogen production apparatus for producing a gas containing hydrogen by decomposing a fuel containing organic matter at a low temperature, a fuel cell power generation apparatus using the hydrogen production apparatus, an electric vehicle, a submarine, and a hydrogen supply system. is there.

As a technique for decomposing a fuel containing organic matter at a low temperature to produce a gas containing hydrogen, a method and an apparatus for generating hydrogen by an electrochemical reaction are known, and hydrogen generated by such an electrochemical method is known. Is known (see Patent Literatures 1 to 4).
Japanese Patent No. 3328993 Japanese Patent No. 3360349 US Pat. No. 6,299,744, US Pat. No. 6,368,492, US Pat. No. 6,432,284, US Pat. No. 6,533,919, US Pat. Publication 2003/0226763 Japanese Patent Laid-Open No. 2001-277779

Patent Document 1 states that “a pair of electrodes is provided on opposite surfaces of a cation exchange membrane, a fuel including at least methanol and water is brought into contact with an electrode including a catalyst provided on one side, and the pair of electrodes is contacted. By applying a voltage to the electrode and taking out electrons from the electrode, a reaction for generating hydrogen ions from the methanol and water is advanced on the electrode, and the generated hydrogen ions are opposed to the cation exchange membrane 1. A hydrogen generation method characterized in that an electrode provided on the other side of the pair is converted into hydrogen molecules by supplying electrons. "(Claim 1) The invention of (Claim 1) is described, and the fuel electrode has a fuel. supplied with methanol and water or water vapor is, through an external circuit, by applying a voltage to draw electrons from the fuel electrode, the fuel _{electrode, CH 3 OH + 2H 2 O} → O ₂ ⁺ 6e - + 6H + reaction allowed to proceed for, thus the hydrogen ions generated in the, passed through a cation exchange membrane, in the opposing electrode side, 6H + ⁺ 6e ^- by → 3H _2, selectively produce hydrogen In addition, Patent Document 2 describes an invention of a fuel cell using hydrogen generated by such a method (paragraph [paragraph [0033] to [0038]). 0052] to [0056]).
According to the inventions described in Patent Documents 1 and 2, hydrogen can be generated at a low temperature (paragraph [0042] of Patent Document 1 and paragraph [0080] of Patent Document 2). In the honeycomb of the present invention, it is necessary to apply a voltage, and hydrogen is generated on the counter electrode side of the fuel electrode (fuel electrode) and does not supply an oxidant to the counter electrode. It is clearly different from type hydrogen production equipment.

  In the invention described in Patent Document 3, as in the inventions described in Patent Documents 1 and 2, protons generated at the anode 112 serving as the fuel electrode permeate the diaphragm 110 and hydrogen is generated at the cathode 114 serving as the counter electrode. The fuel electrode is an anode, the counter electrode is a cathode, a voltage is applied from the DC power source 120, and an organic fuel such as methanol is supplied to the anode (fuel electrode) 112 for electrolysis, Since hydrogen is generated on the counter electrode side of the fuel electrode and does not supply oxidant to the counter electrode, it is clearly different from the honeycomb type hydrogen production apparatus of the present invention.

  Patent Document 4 describes that in a fuel cell system, a hydrogen generating electrode for generating hydrogen is provided (Claim 1). However, “Liquid fuel containing alcohol and water in porous electrode (fuel electrode) 1” is disclosed. If the load is connected between the terminal of the porous electrode 1 and the terminal of the gas diffusion electrode 2, the function of a normal fuel cell Thus, an electrical connection can be established such that a positive potential is applied to the porous electrode 1 via a load from the gas diffusion electrode 2 which is a positive electrode of the MEA 2 having the following: As a result, the alcohol reacts with water to react with carbon dioxide gas and hydrogen. Ions are generated, and the generated hydrogen ions are generated as hydrogen gas in the central gas diffusion electrode 6 via the electrolyte layer 5. In the gas diffusion electrode 6, an electrode reaction occurs at the interface with the other electrolyte layer 7. Happens again with hydrogen ions Thus, it moves through the electrolyte layer 7 and reaches the gas diffusion electrode 2. The gas diffusion electrode 2 reacts with oxygen in the air to produce water "(paragraph [0007]). Then, hydrogen is generated at the hydrogen generating electrode (gas diffusion electrode 6) using the electric energy generated by the fuel cell and supplied to the fuel cell. Hydrogen is generated at the counter electrode of the fuel electrode. It is the same as Patent Documents 1 to 3 in that it is on the side.

In addition, with or without applying a voltage using a reaction apparatus including a diaphragm in which an anode (electrode A) and a cathode (electrode B) are formed via a proton conductive membrane (ion conductor), or Inventions of a method for oxidizing alcohol (methanol) while taking out electric energy (see Patent Documents 5 and 6) are also known, but in each case, a process for oxidizing alcohol using an electrochemical cell (product is: Carbonic acid diester, formalin, methyl formate, dimethoxymethane, etc.) and not a process for generating hydrogen as a reduced product from the viewpoint of alcohol.
JP-A-6-73582 (Claims 1-3, paragraph [0050]) JP-A-6-73583 (Claims 1 and 8, paragraphs [0006] and [0019])

In any of the above techniques, since the diaphragm and the electrode are flat, there is a limit to downsizing the apparatus.
On the other hand, for a liquid fuel direct supply fuel cell (direct methanol fuel cell), the diaphragm (proton conductive solid polymer membrane) has a tubular shape (tube shape), and a fuel electrode and an air electrode are provided on the inner and outer surfaces thereof. Are known (for example, see Patent Documents 7 to 9).
Japanese Patent Publication No. 2001-313046 Japanese Patent Publication No. 2002-222656 Japanese Patent Publication No. 2003-297372

  According to the inventions described in Patent Documents 7 to 9, a direct methanol fuel cell that can be easily miniaturized and can be used as a power source for portable electronic devices can be obtained. It is not suggested to apply to.

Furthermore, for direct methanol fuel cells (DMFC), when open circuit is oxygen-deficient, the battery reaction and the electrolysis reaction coexist in a single cell, and CH ₃ OH + H ₂ O → CO ₂ + 6H ⁺ Non-Patent Documents 1 and 2 show that + 6e ⁻ reaction, 6H ⁺ + 6e ⁻ → 3H ₂ reaction occurs at the fuel electrode, and hydrogen is generated from the fuel electrode side. “Hydrogen generation not only reduces power output in the operating cell, but also consumes fuel continuously in an open circuit, so the DMFC can be either in operation or on standby, It is important to keep supplying oxygen sufficiently and constantly to the cathode. ”Non-Patent Document 2 also stated that“ DMFC with a large MEA area can be used for system shutdown and startup. Neither is intended to produce hydrogen because it concludes that it is necessary to pay attention to the hydrogen accumulation caused by it.
Electrochemical and Solid-State Letters, 8 (1) A52-A54 (2005) Electrochemical and Solid-State Letters, 8 (4) A211-A214 (2005)

In addition, a power generation device (power supply device) incorporating a fuel cell has been proposed. When this fuel cell power generation device is used as a moving power source or an on-site power source, its transportation and installation work is facilitated. A package type fuel cell power generation device is used in which each device constituting the power generation device is integrated and accommodated in a single metal package. For example, in this type of fuel cell power generator, when a hydrocarbon-based fuel such as city gas is used as a raw fuel, a fuel reformer for reforming into a fuel mainly composed of hydrogen is a single package ( Built in the unit case). In addition to this, the package (unit case) is provided in relation to the fuel cell main body, a power conversion device that converts DC power generated in the fuel cell into a power output specification, a control device that performs overall control, and a fuel cell. Auxiliaries such as a pump and a fan are incorporated (for example, see Patent Documents 10 to 14).
JP-A-5-290868 Japanese Patent Laid-Open No. 10-284105 JP 2002-170591 A JP 2003-217635 A JP 2003-297409 A

  A fuel reformer is usually composed of a reformer, a CO converter, and a CO remover. Each of these devices is filled with a predetermined catalyst, and these catalysts all operate at high temperatures. It needs to be heated. For this reason, the reformer is provided with a burner, and at the time of start-up, the raw fuel is burned by this burner, and the temperature of the catalyst in the reformer is raised to about 650 to 700 ° C. As the reformer temperature rises, the temperature of the CO converter and CO remover catalyst also gradually rises. However, the reformed gas at the time of start-up is unstable, so the PG is not immediately supplied to the fuel cell. It is sent to the burner and burned (Patent Document 14, paragraph [0003]).

On the other hand, since the control device is composed of a large number of electronic components, it must be protected from the high heat generated by the fuel reformer. For this reason, a technique for providing a heat insulating partition between the fuel reformer and the controller as in Patent Documents 10 and 12, and a controller that forcibly ventilates the inside of the package with a blower or a ventilation fan as in Patent Documents 10 and 11. A technology for cooling the control device and the like, and a technology for arranging the control device so as not to be affected by the heat of the fuel reformer as in Patent Documents 13 and 14 have been developed.
As described above, when a conventional fuel reformer is used, there is a problem that various measures must be taken in order to prevent the thermal effect.

As a package type fuel cell power generator that does not use a high-temperature fuel reformer, a unit in which a cylinder filled with a hydrogen storage alloy (hydrogen storage cylinder) and a fuel cell are integrated is known (for example, Patent Documents 15 and 16). reference).
JP-A-6-60894 Japanese Patent Laid-Open No. 10-92456

  The fuel cell power generators of Patent Documents 15 and 16 do not require means for preventing thermal effects as in the case of using a conventional fuel reformer, but the hydrogen release process of the hydrogen storage alloy Is an endothermic reaction, the temperature of the hydrogen storage alloy decreases when hydrogen fuel is supplied, and the hydrogen release capacity of the hydrogen storage alloy decreases as the temperature decreases, so that a sufficient hydrogen flow rate is ensured. However, it is necessary to heat the hydrogen storage alloy by guiding the heat generated in the fuel cell main body to the hydrogen storage cylinder. Further, since the cylinder is used, there is a problem that the power generation time is limited.

In addition, regarding an electric vehicle equipped with a fuel cell as a power source for obtaining a driving force, methanol or the like is loaded as a raw fuel, and further, a reforming reaction for reforming the raw fuel to generate a gas containing hydrogen is performed. Those equipped with a reformer are known (see, for example, Patent Documents 17 to 20). Electric vehicles equipped with raw fuel and a reformer in this way, especially when liquid fuel such as methanol is used as raw fuel, are loaded with gaseous fuel over the distance that the electric vehicle can travel with a single refueling. It has the advantage that it becomes longer compared to the case of doing so. Furthermore, raw fuels such as methanol and hydrocarbons have the advantage that they are easier to handle and safer during transportation than hydrogen gas.
JP 2000-149974 A JP 2001-113960 A JP 2001-202980 A JP 2001-298807 A

However, the reformers when methanol, dimethyl ether (DME), ethanol, natural gas, propane, gasoline, etc. are loaded on the electric vehicle as the raw fuel are the methanol reformers with the lowest reforming temperature. Development is the most advanced, and at present, three reforming methods, steam reforming, partial oxidation reforming, and combined reforming using both in combination are employed (see Non-Patent Document 3). Even if the reforming method is adopted, in order to produce a gas containing hydrogen, the reforming must be performed at a high temperature of 200 ° C. or more, the reforming catalyst is poisoned, the reformed gas (hydrogen There are problems such as removal of CO contained in the gas), mixing of nitrogen in the air into the reformed gas in partial oxidation reforming and combined reforming.
"Development and commercialization of polymer electrolyte fuel cells", pages 141 to 166, May 28, 1999, published by Technical Information Association

On the other hand, an electric vehicle (fuel cell vehicle) equipped with a container storing hydrogen in the form of hydrogen gas or a hydrogen storage alloy has been developed, and a major issue in its spread is the development of a hydrogen supply infrastructure. In other words, there is a problem of how to develop a wide-area hydrogen supply infrastructure for a fuel cell vehicle that freely travels. Therefore, city gas or liquid fuel (desulfurized naphtha, gasoline, kerosene, light oil, methanol, etc.) is steam reformed by a reformer at a hydrogen supply station to produce hydrogen, and this is stored in a hydrogen storage tank. A system for supplying this hydrogen to a hydrogen storage container mounted on a fuel cell vehicle has been most developed because it has the advantage of making the most of existing infrastructure such as city gas piping networks and gas stations (for example, And Patent Documents 21 to 24).
However, the above hydrogen supply system has problems that the reforming apparatus is expensive, the apparatus size is large, or the maintenance and operation of the apparatus is complicated and requires advanced technology.
JP 2002-315111 A JP 2002-337999 A JP 2003-118548 A JP 2004-79262 A

Instead of reforming the fuel containing organic matter as described above, water is electrolyzed to produce hydrogen, which is stored in a hydrogen storage tank, and this hydrogen is stored in a hydrogen storage container mounted on a fuel cell vehicle. A supply system has also been developed (see, for example, Patent Documents 25 and 26).
According to this system, there is a problem that a large amount of electric power is required although it is not necessary to use a high temperature for reforming a fuel containing organic matter.
JP 2002-161998 A JP 2002-36379 A

Further, in a conventional submarine equipped with a fuel cell as a power source for obtaining a driving force, a system for storing the hydrogen gas in high-pressure hydrogen gas and supplying the hydrogen to the fuel cell is generally performed (for example, Patent Documents). 27-29). In this method, the gas container must have a pressure-resistant structure, and the mass of the container increases. However, if the weight of the submersible increases, a buoyant material corresponding to the weight is necessary, and the buoyancy material is inevitably equipped. Therefore, there was a problem that the submarine became larger. In addition, since hydrogen is stored as a high-pressure gas, it is necessary to pay attention to safety, and there is a problem that handling is difficult.
Japanese Patent Laid-Open No. 10-100990 Japanese Patent Laid-Open No. 10-144327 Japanese Patent Laid-Open No. 10-181685

In order to solve the above problems, among hydrogen supply generators such as fuel cells used for power sources of submersibles (including submersibles), hydrogen generation accelerators for metal hydrides (including complex metal hydrides) In the hydrogen generator for generating hydrogen by contacting with a metal hydride or at least one of the hydrogen generation accelerator is in a liquid state, a container in which the liquid state is stored is disposed in the machine, and the water pressure outside the machine is The hydrogen generator for submersibles, characterized in that the pressure is almost equalized to each other "(see Patent Document 30). The metal hydride used in this hydrogen generator is easier to handle than high-pressure hydrogen gas, but has a higher reactivity than a fuel containing an organic substance as a hydrogen raw material. There is a problem that it is necessary to devise measures for preventing contact with water or alcohol, and that it is difficult to control the reaction.
JP 2002-187595 A

It is also known that a reformer that reforms a hydrocarbon fuel to produce hydrogen is installed in a submersible model, and hydrogen produced by the reformer is supplied to a fuel cell (see, for example, Patent Document 31). In this case, there was a problem similar to that of the electric vehicle.
JP-A-8-17456

  The present invention solves the above-described problems, and provides a hydrogen production apparatus that can produce a gas containing hydrogen at a low temperature and that can be downsized, and uses the hydrogen production apparatus. It is an object of the present invention to provide a fuel cell power generator, an electric vehicle, a submarine, a hydrogen supply system, and a reaction tube used for the hydrogen production apparatus.

In order to solve the above problems, the following means are adopted in the present invention.
(1) In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, it has a cylindrical diaphragm and has a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and on the other side. A hydrogen production cell in which a large number of reaction tubes provided with oxidation electrodes are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidant to the oxidation electrode, hydrogen from the fuel electrode side Provided with a means for generating and taking out a gas that is contained, and providing a region where the supply of the oxidizing agent is insufficient on the oxidation electrode side by masking only a part of the gas diffusion layer of the oxidation electrode A honeycomb type hydrogen production apparatus.
(2) In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, it has a cylindrical diaphragm and has a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and on the other side. A hydrogen production cell in which a large number of reaction tubes provided with oxidation electrodes are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidant to the oxidation electrode, hydrogen from the fuel electrode side Provided with a means for generating and taking out the contained gas, and providing the region where the supply of the oxidant is insufficient on the oxidation electrode side by masking only a part of the gas diffusion layer of the fuel electrode. A honeycomb type hydrogen production apparatus.
(3) In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, the fuel cell has a cylindrical diaphragm and is disposed on one side of the inner and outer surfaces of the cylindrical diaphragm on the fuel electrode and the other side. A hydrogen production cell in which a large number of reaction tubes provided with oxidation electrodes are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidant to the oxidation electrode, hydrogen from the fuel electrode side Masking a portion of the gas diffusion layer on both sides of the oxidation electrode and the fuel electrode in a region where the supply of the oxidant is insufficient on the oxidation electrode side. In addition, a honeycomb type hydrogen production apparatus provided by shifting at least a part of the masking on both opposing sides.
(4) The honeycomb type hydrogen production apparatus according to any one of (1) to (3), wherein the masking is performed in a band shape.
(5) The honeycomb type hydrogen production apparatus according to any one of (1) to (3), wherein the masking is performed in a spot shape.
(6) The honeycomb type hydrogen according to any one of (1) to (5), wherein the masking is performed by impregnating the gas diffusion layer with a resin or applying a resin to a surface of the gas diffusion layer. manufacturing device.
(7) The honeycomb type hydrogen production apparatus according to any one of (1) to (6), wherein the masking is performed by screen printing.
(8) In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, it has a cylindrical diaphragm and has a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and on the other side. A hydrogen production cell in which a large number of reaction tubes provided with oxidation electrodes are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidant to the oxidation electrode, hydrogen from the fuel electrode side A honeycomb comprising a means for generating and taking out a gas containing the gas, and a region where the supply of the oxidant is insufficient is provided on the oxidation electrode side with a non-uniform gas diffusion layer of the oxidation electrode. Type hydrogen production equipment.
(9) The honeycomb type hydrogen production apparatus according to (8), wherein the gas diffusion layer of the oxidation electrode is made non-uniform by forming it densely or by combining different materials.
(10) The honeycomb type hydrogen production apparatus according to (8) or (9), wherein the gas diffusion layer of the oxidation electrode is made uneven by forming irregularities on the surface.
(11) The open circuit having no means for taking out electric energy from the hydrogen production cell constituting the hydrogen production apparatus and means for applying electric energy from the outside to the hydrogen production cell. The honeycomb type hydrogen production apparatus according to any one of to (10).
(12) The honeycomb type hydrogen production apparatus according to any one of (1) to (10), characterized in that the fuel electrode is used as a negative electrode and the oxidation electrode is used as a positive electrode.
(13) The honeycomb type hydrogen production apparatus according to any one of (1) to (10), further comprising means for applying electric energy from the outside using the fuel electrode as a cathode and the oxidation electrode as an anode.
(14) The honeycomb type hydrogen production apparatus according to any one of (1) to (13), wherein a voltage between the fuel electrode and the oxidation electrode is 400 to 600 mV.
(15) The amount of generation of the gas containing hydrogen is adjusted by adjusting a voltage between the fuel electrode and the oxidation electrode, wherein any one of (1) to (14) is characterized. Honeycomb type hydrogen production equipment.
(16) The voltage between the fuel electrode and the oxidation electrode and / or the generation amount of the gas containing hydrogen is adjusted by adjusting the supply amount of the oxidant (1). A honeycomb type hydrogen production apparatus according to any one of to (15).
(17) The honeycomb type hydrogen production apparatus according to any one of (1) to (16), wherein the operating temperature is 100 ° C. or lower.
(18) The organic substances supplied to the fuel electrode are one or two or more organic substances selected from the group consisting of alcohols, aldehydes, carboxylic acids, and ethers (1) to (17) Any one of the honeycomb type hydrogen production apparatuses.
(19) The honeycomb type hydrogen production apparatus according to (18), wherein the alcohol is methanol.
(20) The honeycomb type hydrogen production apparatus according to any one of (1) to (19), wherein the oxidizing agent supplied to the oxidation electrode is a gas containing oxygen or oxygen.
(21) The honeycomb type hydrogen production apparatus according to any one of (1) to (20), wherein the diaphragm is a proton conductive solid electrolyte membrane.
(22) The honeycomb type hydrogen production apparatus according to (21), wherein the proton conductive solid electrolyte membrane is a perfluorocarbon sulfonic acid based solid electrolyte membrane.
(23) The honeycomb type hydrogen production apparatus according to any one of (1) to (22), wherein the catalyst of the fuel electrode is a platinum-ruthenium alloy supported on carbon powder.
(24) The honeycomb-type hydrogen production apparatus according to any one of (1) to (23), wherein the catalyst of the oxidation electrode is obtained by supporting platinum on carbon powder.
(25) The honeycomb type hydrogen production apparatus according to any one of (1) to (24), wherein a circulation means for fuel containing the organic matter is provided.
(26) The honeycomb type hydrogen production apparatus according to any one of (1) to (25), wherein a carbon dioxide absorbing section that absorbs carbon dioxide contained in the gas containing hydrogen is provided.
(27) A fuel cell is connected to the honeycomb type hydrogen production apparatus according to any one of (1) to (26), and electric energy supplied to an auxiliary machine for operating the honeycomb type hydrogen production apparatus is supplied to the fuel. A honeycomb type hydrogen production apparatus obtained from a battery.
(28) The honeycomb type hydrogen production apparatus according to any one of (1) to (27) is connected to a fuel cell, and a gas containing hydrogen produced by the honeycomb type hydrogen production apparatus is supplied to the fuel cell. A fuel cell power generator.
(29) The honeycomb type hydrogen production apparatus according to any one of (14) to (27), and means for taking out electric energy from the hydrogen production cell to the outside, and electric energy from the outside to the hydrogen production cell A honeycomb-type hydrogen production apparatus that is an open circuit that does not have means for applying, a honeycomb-type hydrogen production apparatus that has means for taking out electric energy from the fuel electrode as a negative electrode and the oxidation electrode as a positive electrode, and the fuel electrode as a cathode A honeycomb type hydrogen production apparatus using a combination of two or more honeycomb type hydrogen production apparatuses selected from the group of honeycomb type hydrogen production apparatuses having means for applying electric energy from the outside with an oxidation electrode as an anode is connected to a fuel cell. and characterized by supplying a gas containing hydrogen produced in the honeycomb hydrogen generating device to the fuel cell That fuel cell power plant.
(30) The fuel cell power generation device produces a fuel cell, the honeycomb type hydrogen production device for producing a gas containing hydrogen to be supplied to the fuel cell, and the electric power for converting the DC power generated by the fuel cell into predetermined power The fuel cell power generator according to (28) or (29) , wherein the converter and the control device for controlling the entire power generator are built in at least the package.
(31) The fuel cell power generator according to any one of (28) to (30), wherein the hydrogen-containing gas produced by the honeycomb-type hydrogen production apparatus is supplied to the fuel cell without being cooled. .
(32) The oxidant supplied to the oxidation electrode of the hydrogen production apparatus is exhaust gas discharged from the fuel cell or other honeycomb type hydrogen production apparatus or a gas containing unreacted oxygen (oxygen off-gas). The fuel cell power generator according to any one of the above (28) to (31).
(33) The fuel cell power generator according to any one of (28) to (32), wherein a heat insulating material for shutting off heat generated by the honeycomb-type hydrogen production apparatus is not provided.
(34) An electric vehicle comprising the fuel cell power generator according to any one of (28) to (33).
(35) A submarine ship equipped with the fuel cell power generator according to any one of (28) to (33).
(36) The honeycomb type hydrogen production apparatus according to any one of (1) to (27) is connected to a hydrogen storage means, and a gas containing hydrogen produced by the honeycomb type hydrogen production apparatus is supplied to the hydrogen storage means. A hydrogen supply system characterized by:
(37) The hydrogen supply system according to (36), wherein the hydrogen storage means is a hydrogen storage container mounted on an electric vehicle (fuel cell vehicle).
(38) In a reaction tube for a hydrogen production cell having a cylindrical diaphragm and having a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and an oxidation electrode on the other side, gas diffusion of the oxidation electrode A reaction tube for a hydrogen production cell, wherein a region where the supply of oxidant is insufficient is provided in a layer by masking only a part of the gas diffusion layer of the oxidation electrode.
(39) In a reaction tube for a hydrogen production cell having a tubular diaphragm and having a fuel electrode on one side of the inner and outer faces of the tubular diaphragm and an oxidation electrode on the other side, gas diffusion of the oxidation electrode A reaction tube for a hydrogen production cell, wherein a region where the supply of oxidant is insufficient is provided in a layer by masking only a part of the gas diffusion layer of the fuel electrode.
(40) In a reaction tube for a hydrogen production cell having a tubular diaphragm and having a fuel electrode on one side of the inner and outer surfaces of the tubular diaphragm and an oxidation electrode on the other side, gas diffusion of the oxidation electrode By masking a region where the oxidant is insufficiently supplied to a layer to a part of the gas diffusion layer on both sides of the oxidation electrode and the fuel electrode, and by shifting at least a part of the masking on both sides facing each other A reaction tube for a hydrogen production cell, which is provided.
(41) The reaction tube for a hydrogen production cell according to any one of (38) to (40), wherein the masking is performed in a band shape.
(42) The reaction tube for a hydrogen production cell according to any one of (38) to (40), wherein the masking is performed in a spot shape.
(43) The hydrogen production cell according to any one of (38) to (42), wherein the masking is performed by impregnating the gas diffusion layer with a resin or applying a resin to a surface of the gas diffusion layer. Reaction tube.
(44) The reaction tube for a hydrogen production cell according to any one of (38) to (43), wherein the masking is performed by screen printing.
(45) In a reaction tube for a hydrogen production cell having a tubular diaphragm and having a fuel electrode on one side of the inner and outer surfaces of the tubular diaphragm and an oxidation electrode on the other side, gas diffusion of the oxidation electrode A reaction tube for a hydrogen production cell, characterized in that a region where the supply of oxidant is insufficient is provided in the layer with the gas diffusion layer of the oxidation electrode being non-uniform.
(46) The reaction tube for a hydrogen production cell according to (45), wherein the gas diffusion layer of the oxidation electrode is made non-uniform by forming it densely or by combining different materials.
(47) The reaction tube for a hydrogen production cell according to (45) or (46), wherein the gas diffusion layer of the oxidation electrode is made uneven by forming irregularities on the surface.

Here, (1) to (3), (8), (38) to (40), and (45) “providing a region where the supply of the oxidant is insufficient on the oxidation electrode side” On the pole side, it means that a region where supply of oxidant is insufficient is provided so that the discharge reaction is suppressed and a hydrogen generation reaction occurs, and the above (1) , (3) , (38) and (40) As described above, masking is performed on a part of the gas diffusion layer of the oxidation electrode, or the gas diffusion layer of the oxidation electrode is formed densely as described in (8) to (10) and (45) to (47). combine different in material, by heterogeneous with means such as forming irregularities, it encompasses a case provided directly an area of insufficient supply of the oxidant gas diffusion layer of the oxidizing electrode not limited thereto, the (2) and one only gas diffusion layer of the fuel electrode as shown in (39) Encompasses a means, such as to perform masking, even if provided with a region where the lack of supply of the oxidizing agent to the oxidizing electrode side indirectly.
As the shape of the masking, a band shape or a spot shape can be adopted as in the above (4) , (5) , (41) and (42) , and as the masking material, the above (6) and (43) As the masking means, impregnation, coating, and screen printing can be employed as in the above (6) , (7) , (43) and (44) , The shape, material, and means of masking are not limited to these, and any shape, material, and means may be included as long as they can form a “region where the supply of the oxidizing agent is insufficient on the oxidation electrode side”. Oh Ru.

Furthermore, the honeycomb type hydrogen production apparatus according to (1) to (3), (8) , (11) to (13) has means for supplying fuel and an oxidant to the hydrogen production cell. In addition, in the case of (12) , there is a discharge control means for taking out electric energy from the hydrogen production cell. In the case of (13) , electric energy is applied to the hydrogen production cell. For the electrolysis. In the case of (11) , the discharge control means for taking out electric energy from the hydrogen production cell and the open circuit without the electrolysis means for applying electric energy to the hydrogen production cell. The honeycomb-type hydrogen production apparatuses (1) to (3) and (8) include the honeycomb-type hydrogen production apparatuses (11) to (13) . Furthermore, these hydrogen production apparatuses monitor the voltage of the hydrogen production cell and / or the generation amount of gas containing hydrogen, and supply or concentration of fuel and oxidant, and electric energy to be extracted (in the case of (12) above ) ) Or applied electric energy (in the case of (13) above ) .
Further, in the present invention, an electric vehicle (fuel cell vehicle) is not limited to a vehicle that obtains the driving force of a vehicle with only a fuel cell, but includes a hybrid car that uses another power source in combination.

The honeycomb type hydrogen production apparatus of the present invention can reform the fuel at a temperature much lower than the conventional reforming temperature of room temperature to 100 ° C. or less, and therefore requires less energy for reforming. In addition to shortening the time required for start-up, the fuel cell power generation device using the hydrogen production device, the electric vehicle and submarine equipped with the fuel cell power generation device, and the hydrogen supply system using the hydrogen production device It is possible to eliminate the need for a heat insulating material for shutting off the heat generated by the quality device, and to easily supply the gas containing hydrogen generated from the hydrogen production device to the fuel cell without cooling. Play.
In addition, nitrogen in the air is not mixed in the gas containing hydrogen, or the amount is very small, and no CO is contained, so a gas with a relatively high hydrogen concentration can be obtained and a CO removal step is unnecessary. The effect that it is.
In addition, since a large number of reaction tubes are combined in a honeycomb shape and no separator is used, the hydrogen production apparatus can be made compact.
The honeycomb type hydrogen production apparatus of the present invention can generate hydrogen without supplying electric energy to the hydrogen production cell from the outside, but even when it has a means for taking out electric energy, Even when a means for applying is provided, hydrogen can be generated.
In the case where a means for taking out electric energy is provided, the electric energy can be used effectively.
Even when a means for applying electric energy from the outside is provided, by supplying a small amount of electric energy from the outside to the hydrogen production cell, it is possible to generate more hydrogen than the supplied electric energy.
Furthermore, in any case, it is possible to control the process by monitoring the voltage of the hydrogen production cell and / or the generation amount of gas containing hydrogen, and the hydrogen production apparatus can be made compact. There exists an effect that the cost of an apparatus, a fuel cell power generator, an electric vehicle, a submarine, and a hydrogen supply system can be reduced.

The best mode for carrying out the present invention will be exemplified below.
In particular, the honeycomb-type hydrogen production apparatus of the present invention is basically novel, and what is described below is merely one embodiment, and the present invention is not limited thereby.

The present inventors have developed a hydrogen production apparatus (Japanese Patent Application No. 2004-367992) that uses a cell having the same structure as a conventional direct methanol fuel cell to decompose a fuel containing organic matter and produce a gas containing hydrogen. In addition, an independent hydrogen production system (Japanese Patent Application No. 2005-151125), a fuel cell power generation device (Japanese Patent Application No. 2005-151124), an electric vehicle (Japanese Patent Application No. 2005-096955), a hydrogen supply system (Japanese Patent Application No. 2005-096956) and a submarine (Japanese Patent Application No. 2005-096957) were developed.
All of the hydrogen production apparatuses in the above invention use an oxidation electrode separator provided with a flow channel for flowing an oxidant. However, without using a separator, an oxidant is provided on the oxidation electrode side. It has been found that hydrogen is generated by providing a region where supply is insufficient, and the invention of a hydrogen production apparatus and the like (Japanese Patent Application No. 2005-164145) has been completed. The present invention relates to an improved invention. .

An example of a honeycomb type hydrogen production apparatus of the present invention (hereinafter abbreviated as “hydrogen production apparatus”) is shown in FIG. This hydrogen production apparatus has a hydrogen production cell (10) in which a large number of reaction tubes are combined in a honeycomb shape, an auxiliary machine for operating the hydrogen production apparatus, and a means for extracting a gas containing hydrogen.
A hydrogen production cell (10) shown in FIG. 1 (a) includes a fuel electrode (12) and a fuel electrode (12) on one side surface (inner side surface) of inner and outer surfaces of a cylindrical diaphragm (11) as shown in FIG. 1 (b). A cell is formed by combining a number of reaction tubes each provided with an oxidation electrode (14) on the other side surface (outer surface) in a honeycomb shape.
Alternatively, the inner side surface and the outer side surface may be interchanged, and an oxidation electrode may be provided on the inner side surface of the cylindrical diaphragm, and a fuel electrode may be provided on the outer side surface of the cylindrical diaphragm.
The hydrogen production cell (10) includes a flow path (13) for supplying a fuel (methanol aqueous solution) containing organic matter and water to the fuel electrode (12) together with the reaction tube, and an oxidation electrode (14). ) Is provided with a flow path (15) for supplying an oxidizing agent (air).

As an auxiliary machine for operating the hydrogen production apparatus, a fuel pump (16) for supplying a methanol aqueous solution to the fuel electrode (12) and an air blower (17) for supplying air to the oxidation electrode (14) are provided.
The flow path (13) in the fuel electrode is connected by a conduit via a fuel pump (16) and a flow rate adjustment valve (18), and the flow path (15) in the oxidation electrode is adjusted with the air blower (17). They are connected by a conduit via a valve (19).
The fuel (100% methanol) is stored in the fuel tank (20), transferred from there to the fuel adjustment tank (21), and mixed with water in the fuel adjustment tank (21). For example, about 3% methanol It is adjusted to an aqueous solution and supplied to the fuel electrode (12).

In the hydrogen production apparatus configured as described above, when electric energy is supplied to the fuel pump (16) and the air blower (17) and moved, and the flow rate adjustment valve (18) is opened, methanol is driven by the fuel pump (16). When the aqueous solution is supplied from the fuel adjustment tank (21) to the fuel electrode (12) through the flow path (13) and the flow rate adjustment valve (19) is opened, the air is blown to the flow path (15) by the air blower (17). And supplied to the oxidation electrode (14).
As a result, a reaction as described later occurs between the fuel electrode and the oxidation electrode (air electrode), and a gas containing hydrogen is generated from the fuel electrode (12) side.

The amount of gas containing hydrogen is determined by providing a voltage regulator (22) for monitoring the voltage (open circuit voltage or operating voltage) of the hydrogen production cell (10), and supplying and concentration of fuel and air, and the electricity to be taken out. It can be adjusted by controlling the energy or applied electrical energy.
Further, when a cell is formed by combining a large number of tubular reaction tubes in a honeycomb shape, as shown in FIGS. 1 (c) and (d), a conductor is connected from the fuel electrode (12) and the oxidation electrode (14). It is preferable to monitor the voltage of the hydrogen production cell (10) by drawing out and measuring the potential.
As shown in FIG. 1 (c), the fuel electrodes (12) of the reaction tubes combined in a honeycomb shape may be integrated to draw out a conducting wire, or in a honeycomb shape as shown in FIG. 1 (d). Conductors may be drawn individually from the fuel electrode (12) of the reaction tube and collected.
The generated hydrogen-containing gas is taken out from the hydrogen production cell (10), passed through a gas-liquid separator (23), separated into hydrogen-containing gas and unreacted methanol aqueous solution, and part or all of the unreacted methanol aqueous solution. Is circulated by a circulation means comprising a conduit (24) returning to the fuel adjustment tank (21). In some cases, water may be supplied from outside the system.

The hydrogen generation reaction mechanism in the hydrogen production apparatus of the present invention is estimated as follows.
In the region of sufficient supply of oxidant (oxygen) provided on the oxidation electrode (air electrode) side (hereinafter referred to as “discharge region”), the following discharge reaction in a fuel cell, that is, as shown in FIG. Furthermore, the reaction (A) occurs on the fuel electrode side, and the reaction (B) occurs on the air electrode side. FIG. 2 shows a longitudinal section of a partial region of the wall of the reaction tube used in the hydrogen production apparatus of the present invention, and the same applies to FIGS. 3 and 4.
(A) CH ₃ OH + H ₂ O → 6H ⁺ + 6e ⁻ + CO ₂
(B) 6H ⁺ + 6e ⁻ + 3 / 2O ₂ → 3H ₂ O

On the other hand, when a proton conductive solid electrolyte membrane such as Nafion is used, a crossover phenomenon in which CH ₃ OH permeates from the fuel electrode to the air electrode side is known, and supply of oxygen provided on the air electrode side is insufficient. In the region (hereinafter referred to as “hydrogen generation region”), the reaction (B) does not occur, and the crossover methanol is electrolytically oxidized and the reaction (D) occurs, as shown in FIG. On the side, the hydrogen generation reaction (C) occurs.
(C) 6H ⁺ + 6e ⁻ → 3H ₂
(D) CH ₃ OH + H ₂ O → 6H ⁺ + 6e ⁻ + CO ₂

In the case of the hydrogen production apparatus of the invention according to claim 14 of the present application (hereinafter referred to as “open circuit conditions”), e ⁻ generated by the reactions (A) and (D) is not supplied to the counter electrode through the external circuit. From the above, the movement of H ⁺ and e ⁻ produced by the reaction (A) at the fuel electrode to the air electrode and the movement of H ⁺ and e ⁻ produced by the reaction (D) at the air electrode to the fuel electrode are apparent. It is thought that it was canceled.
That is, as shown in FIG. 4, H ⁺ and e ⁻ generated by the reaction (A) in the discharge region on the fuel electrode side move to the hydrogen generation region on the same fuel electrode side, and the reaction (C) occurs. On the other hand, hydrogen is generated, while H ⁺ and e ⁻ generated by the reaction (D) in the hydrogen generation region on the air electrode side move to the same discharge region on the air electrode side, and the reaction (B) Presumed to be awake.
Assuming that the reactions (A) and (C) proceed on the fuel electrode and the reactions (B) and (D) proceed on the oxidation electrode, the following reactions are established as a whole.
2CH ₃ OH + 2H ₂ O + 3 / 2O ₂ → 2CO ₂ + 3H ₂ O + 3H ₂
The theoretical efficiency of this reaction is 59% (3 mol hydrogen exotherm / 2 mol methanol exotherm).

In the case of a hydrogen production apparatus (hereinafter referred to as “discharge condition”) of the invention according to claim 15 of the present invention having “a means for taking out electric energy to the outside using the fuel electrode as a negative electrode and the oxidation electrode as a positive electrode”. It is thought that hydrogen is generated by a mechanism similar to the hydrogen generation mechanism under conditions. However, unlike the case of the open circuit condition, it is necessary to maintain the electrical neutral condition of the entire cell by moving H ⁺ corresponding to the discharge current from the fuel electrode to the air electrode. It is considered that the reaction (A) proceeds faster than the reaction (B) than the reaction (D) at the air electrode.

Also in the case of the hydrogen production apparatus (hereinafter referred to as “charging condition”) of the invention according to claim 16 of the present invention having “a means for applying electric energy from the outside with the fuel electrode as a cathode and the oxidation electrode as an anode”. It is thought that hydrogen is generated by a mechanism similar to the hydrogen generation mechanism under circuit conditions. However, unlike the case of the open circuit condition, it is necessary to maintain the electrical neutral condition of the entire cell by moving H ⁺ corresponding to the electrolysis current from the air electrode to the fuel electrode. It is considered that the reaction (C) proceeds faster (more) than the reaction (B) at the air electrode than the reaction (B) at the air electrode.

When producing the hydrogen production apparatus of the present invention, first, as shown in FIG. 1 (b), a tubular diaphragm (11) is provided, and fuel is provided on one of the inner and outer surfaces of the tubular diaphragm. A reaction tube having an electrode (12) and an air electrode (14) on the other side is prepared.
The method for producing the reaction tube as shown in FIG. 1B is not limited. First, a gas diffusion layer with a fuel electrode catalyst and a gas diffusion layer with an air electrode catalyst are hot-pressed on both sides of the electrolyte membrane. After manufacturing a flat plate MEA (membrane-electrode assembly) similar to the conventional one, the flat plate MEA is rolled into a cylindrical shape, the end portions of the electrolyte membrane are overlapped, and the overlapped portion is heat-sealed. A cylindrical MEA in which one of the fuel electrode and the air electrode is on the inner side and the other is on the outer side is manufactured, and the inside of the cylindrical MEA can be reinforced with a plastic tube having a hole to form a reaction tube.
As another manufacturing method, instead of the gas diffusion layer with the fuel electrode catalyst layer, a carbon tube having a fuel electrode catalyst layer provided on the outer peripheral surface is prepared, and an electrolyte layer (diaphragm) is formed on the surface of the fuel electrode catalyst layer. A method of forming a reaction tube by forming an air electrode catalyst layer on the surface of the electrolyte layer (diaphragm) and winding a carbon felt as a gas diffusion layer around the surface of the air electrode catalyst layer can also be employed.

In order to provide the air electrode (14) with a region where the supply of oxidant (air) is insufficient, a mask (as shown in FIG. 5) is formed on a part of the gas diffusion layer of the air electrode (gas diffusion layer of the reaction tube). 14M) is preferably provided (masking is performed).
FIG. 5 is a vertical cross-sectional view of the tube wall of the reaction tube corresponding to the right portion of the vertical cross-sectional view of the reaction tube shown in FIG. 1B, and the same applies to FIGS.
Further, as shown in FIG. 6, even if a mask (12M) is provided on a part of the gas diffusion layer (MEA gas diffusion layer) of the fuel electrode (12), it is slight as shown in a reference example described later. Generates hydrogen. This is because by masking part of the fuel electrode, diffusion of methanol and water to the air electrode side increases through the electrolyte in the part that is not masked, and the air electrode of methanol and water in the masked part. As a result, on the air electrode side where methanol has diffused, oxygen is consumed by oxidation of methanol, and a region where oxygen is insufficient on the air electrode side is formed, whereas methanol diffuses. On the air electrode side that was not there, oxygen was not consumed, but a region where oxygen was sufficiently present on the air electrode side was formed, and the same effect as masking part of the air electrode side was achieved. Can be thought of.

When masks (12M) and (14M) are respectively provided in part of the gas diffusion layers of the fuel electrode (12) and the air electrode (14), hydrogen is generated as shown in the reference examples and comparative examples described later. It may or may not occur.
As shown in FIG. 7, when a mask is provided on a part of the gas diffusion layer of the fuel electrode (12) and the air electrode (14) so as to face the same position, hydrogen is not generated. This is because the hydrogen generation region is formed by providing a mask (14M) in a part of the gas diffusion layer of the air electrode (14), but the mask (12M) is formed in the corresponding region of the fuel electrode (12). Since it is provided, it is considered that methanol for the reaction (D) is not diffused and the hydrogen generation reaction (C) does not occur.
As shown in FIG. 8, when a mask is provided in a part of the gas diffusion layer of the fuel electrode (12) and the air electrode (14) so as not to face the opposite position, hydrogen is not generated. This is because a mask (12M) is provided in the discharge region of the fuel electrode (12), no methanol is supplied, the reaction (A) does not occur, and H ⁺ and e ⁻ are not generated. ^{This is because +} and e ⁻ are not supplied from the discharge region to the hydrogen generation region, and the hydrogen generation reaction (C) does not occur.
As shown in FIG. 9, masks (12M) and (14M) are opposed to a part of the gas diffusion layers of the fuel electrode (12) and the air electrode (14), and only a part of the masks (12M) and (14M) are opposed to each other. In the case of providing a half-shift, a discharge region (1) and a hydrogen generation region (2) are formed, a discharge reaction occurs in the region (1), and a hydrogen generation reaction occurs in the region (2). So hydrogen is generated.

Although the shape of the masking (mask) is not limited, it can be formed in a band shape as shown in FIG. Masking may be performed in spots.
The amount of gas containing hydrogen can be adjusted by appropriately setting the size, number, etc. of the spot-like masks, such as the width, interval, number, etc. of the strip-like masks.
A resin such as an epoxy resin can be used as the masking material.
Further, as a masking means, it is possible to carry out simply by impregnation into the gas diffusion layer, coating, screen printing, sticking of a seal and the like.
In addition to masking as described above, oxidation may be performed by means such as forming a gas diffusion layer in a dense manner, combining gas diffusion layers with different materials, or forming irregularities on the surface of the gas diffusion layer. By making the electrode gas diffusion layer non-uniform, a region where the supply of the oxidizing agent is insufficient can be provided on the oxidation electrode side.

  As the diaphragm (11) of the reaction tube in the hydrogen production apparatus of the invention, a proton conductive solid electrolyte membrane used as a polymer electrolyte membrane in a fuel cell can be used. As the proton conductive solid electrolyte membrane, a perfluorocarbon sulfonic acid membrane having a sulfonic acid group such as a Nafion membrane manufactured by DuPont is preferable.

The fuel electrode and the oxidation electrode (air electrode) are preferably electrodes having electrical conductivity and catalytic activity. For example, a catalyst and PTFE resin supported on a carrier made of carbon powder or the like in a gas diffusion layer. It can be prepared by applying and drying a catalyst paste containing a binder such as Nafion solution and a substance for imparting ionic conductivity such as Nafion solution.
The gas diffusion layer is preferably made of carbon paper subjected to water repellent treatment.
Any fuel electrode catalyst can be used, but a catalyst in which a platinum-ruthenium alloy is supported on carbon powder is preferable.
Any air electrode catalyst can be used, but one in which platinum is supported on carbon powder is preferable.

  In the hydrogen production apparatus configured as described above, when a fuel containing an organic substance such as a methanol aqueous solution is supplied to the fuel electrode, and an oxidizing agent such as air, oxygen, or hydrogen peroxide is supplied to the oxidation electrode (air electrode), Under the conditions, a gas containing hydrogen is generated in the fuel electrode.

In the hydrogen production apparatus of the present invention, since the amount of gas containing hydrogen tends to depend on the voltage between the fuel electrode and the oxidation electrode (air electrode), any of open circuit conditions, discharge conditions, and charging conditions can be used. In this case, the amount of gas containing hydrogen can be adjusted by adjusting the voltage (open circuit voltage or operating voltage) between the fuel electrode and the oxidation electrode (air electrode).
In the case of the open circuit condition, as shown in the examples, hydrogen is generated at an open circuit voltage of 400 to 600 mV. Therefore, by adjusting the open circuit voltage within this range, the gas containing hydrogen is reduced. The amount of generation can be adjusted.

Open circuit voltage or operating voltage and / or the amount of gas containing hydrogen (hydrogen generation rate) can be adjusted by adjusting the supply amount of oxidant (air, oxygen, etc.), adjusting the concentration of oxidant, It can adjust by adjusting the supply amount of the fuel containing, and adjusting the density | concentration of the fuel containing organic substance.
In addition to the above, in the case of discharge conditions, the electrical energy extracted to the outside is adjusted (by adjusting the current to be extracted to the outside, and further by using a power source capable of constant voltage control, a so-called potentio stud. In the case of charging conditions, by adjusting the voltage to be taken out, it is applied by adjusting the applied electric energy (adjusting the applied current, and further using a power source capable of constant voltage control, a so-called potentio stud. The operating voltage and / or the amount of gas containing hydrogen can be adjusted.

In the hydrogen production apparatus of the present invention, the fuel containing organic matter can be decomposed at 100 ° C. or lower, so that the operating temperature of the hydrogen production apparatus can be made 100 ° C. or lower. The operating temperature is preferably 30 to 90 ° C. By adjusting the operating temperature in the range of 30 to 90 ° C., the open circuit voltage or operating voltage and / or the amount of gas containing hydrogen can be adjusted as shown in the following examples.
In the conventional reforming technique that required operation at 100 ° C. or higher, water becomes water vapor, fuel containing organic substances is gasified, and hydrogen is separated even if hydrogen is generated under such conditions. The present invention is advantageous in this respect because it is necessary to use a separate means.
However, when a fuel containing organic matter is decomposed at a temperature of 100 ° C. or higher, there are the above disadvantages, but the present invention denies operating the hydrogen production apparatus of the present invention at a temperature slightly exceeding 100 ° C. is not.

  In view of the presumed principle, the fuel containing organic matter may be any liquid or gaseous fuel that permeates the proton-conductive diaphragm and is electrochemically oxidized to generate protons. Methanol, ethanol, ethylene glycol Liquid fuels containing alcohols such as 2-propanol, aldehydes such as formaldehyde, carboxylic acids such as formic acid, and ethers such as diethyl ether are preferred. Since the fuel containing an organic substance is supplied together with water, a solution containing alcohol and water, among which an aqueous solution containing methanol is preferable. In addition, the aqueous solution containing methanol as an example of the fuel described above is a solution containing at least methanol and water, and the concentration thereof can be arbitrarily selected in a region where a gas containing hydrogen is generated.

  As the oxidizing agent, a gaseous or liquid oxidizing agent can be used. As the gaseous oxidant, a gas containing oxygen or oxygen is preferable. The oxygen concentration of the gas containing oxygen is particularly preferably 10% or more. As the liquid oxidant, a liquid containing hydrogen peroxide is preferable.

  In the present invention, since the fuel input to the hydrogen production apparatus is consumed once in the apparatus and decomposed into hydrogen is low, it is possible to increase the conversion rate to hydrogen by providing a fuel circulation means. preferable.

  The hydrogen production apparatus of the present invention includes means for extracting a gas containing hydrogen from the fuel electrode side and recovers hydrogen, but it is also preferable to recover carbon dioxide. Since it operates at a temperature as low as 100 ° C. or less, a carbon dioxide absorption part that absorbs carbon dioxide contained in a gas containing hydrogen can be provided by simple means.

Next, an example of a package type fuel cell power generation device which is an embodiment of a fuel cell power generation device to which the hydrogen production apparatus of the present invention is applied will be described. The hydrogen production apparatus described above is connected to a fuel cell, and a gas containing hydrogen produced by the hydrogen production apparatus is supplied to the fuel cell.
As shown in FIG. 11, the basic configuration of the fuel cell power generator of the present invention is to supply hydrogen and an oxidant to generate power, and to supply hydrogen to the fuel cell (30). Hydrogen production cell (10) for producing gas containing, power conversion device (36) for converting DC power generated by the fuel cell (30) into predetermined power, control device (37) for controlling the entire power generation device, and fuel Auxiliary equipment such as a pump (16) and an air blower (17) is built in at least the package (38).
In the fuel cell power generation apparatus of the present invention, the hydrogen production cell (10) constituting the hydrogen production apparatus is operated at a low temperature. Therefore, unlike the conventional fuel reformer, the control apparatus (37) is used for hydrogen production. It is possible to place it close to the cell (10). Moreover, the heat insulating material for protecting the control device (37) from the heat generated by the hydrogen production cell (10) can be eliminated.

In this figure, the fuel tank (20) and the fuel adjustment tank (21) are built in the package, but fuel (methanol aqueous solution) may be supplied from the outside of the package without incorporating them. Only the fuel adjustment tank (21) may be incorporated in the package.
The hydrogen-containing gas generated from the hydrogen production cell (10) can be directly supplied to the fuel cell (30). However, a hydrogen tank (25) for storing the gas containing hydrogen is provided, 25) to the fuel cell (30).
Furthermore, it is preferable to provide a gas-liquid separator (23) for separating the gas containing hydrogen and the unreacted methanol aqueous solution and to circulate the unreacted methanol aqueous solution to the hydrogen production cell (10). In addition, you may provide the gas-liquid separator (27) which isolate | separates produced | generated water and unreacted methanol aqueous solution from exhaust air.
Although not shown, a backup battery can be provided in addition to these.

As shown in FIG. 12, the hydrogen production apparatus used in the fuel cell power generation apparatus of the present invention has a hydrogen production cell (10) and an auxiliary machine for operating the hydrogen production apparatus.
The structure of the hydrogen production cell (10) has a fuel electrode (12) on one surface of the diaphragm (11), and a flow path for supplying fuel (methanol aqueous solution) containing organic matter and water to the fuel electrode (12). (13), an oxidation electrode (14) provided on the other surface of the diaphragm (11), and a flow path (15) for supplying an oxidizing agent (air) to the oxidation electrode (14) It is.

A fuel pump (16) for supplying a methanol aqueous solution to the fuel electrode (12) is provided as an auxiliary machine for operating the hydrogen production apparatus. The flow path (13) in the fuel electrode is connected by a conduit via a fuel pump (16) and a flow rate adjusting valve (18).
The fuel (100% methanol) is stored in the fuel tank (20), transferred from there to the fuel adjustment tank (21), and mixed with water in the fuel adjustment tank (21). For example, about 3% methanol It is adjusted to an aqueous solution and supplied to the fuel electrode (12).

Similarly, an air blower (17) can be provided as an auxiliary device to supply air directly to the oxidation electrode (14), but in this figure, air is supplied to the fuel cell (30) by the air blower (17). In addition, unreacted air (exhaust air) discharged from the fuel cell (30) is used.
When oxygen is supplied from the oxidant storage device instead of air to the fuel cell (30), unreacted oxygen (oxygen off-gas) discharged from the fuel cell (30) is used.
Here, by sending exhaust air or oxygen off-gas discharged from the air electrode of the fuel cell (30) to the hydrogen production cell (10), an air blower for the hydrogen production cell (10) becomes unnecessary. The flow path (15) in the oxidation electrode (14) of the hydrogen production cell (10) is connected to the air blower (17) via the flow path (35) in the air electrode (34) of the fuel cell (30). Yes.
Furthermore, since this exhaust air or oxygen off gas has a temperature (about 80 ° C.) that is substantially the same as the operating temperature of the fuel cell (30), the heat of the exhaust air or oxygen off gas is heated in the hydrogen production cell (10). It can be used as a heat source.
When two or more hydrogen production apparatuses are used in combination, the exhaust gas discharged from the other hydrogen production cell (10) is supplied as air to the oxidation electrode (14) of one hydrogen production cell (10). Air can be used.

A stand-alone hydrogen production system can be configured by obtaining from the fuel cell the electric energy supplied to the fuel pump (16) and the air blower (17), which are auxiliary machines for operating the hydrogen production apparatus.
As the fuel cell, the fuel cell (30) can be used, and a part of the electric energy obtained from the fuel cell (30) can be supplied to an auxiliary machine for operating the hydrogen production apparatus. A methanol fuel cell may be provided to supply electric energy obtained from the fuel cell.

In the hydrogen production apparatus configured as described above, when electric energy is supplied to the fuel pump (16) and the air blower (17) and moved, and the flow rate adjustment valve (18) is opened, methanol is driven by the fuel pump (16). When the aqueous solution is supplied from the fuel adjustment tank (21) to the fuel electrode (12) through the flow path (13) and the flow rate adjustment valve (19) is opened, the air is blown to the fuel cell (30) by the air blower (17). Through the channel (15) and supplied to the oxidation electrode (14).
As a result, a reaction as described later occurs between the fuel electrode and the oxidation electrode (air electrode), and a gas containing hydrogen is generated from the fuel electrode (12) side.

In addition, the amount of gas containing hydrogen is determined by providing a voltage regulator (22) for monitoring the voltage (open circuit voltage or operating voltage) of the hydrogen production cell (10), Adjustment can be made by controlling the electrical energy to be extracted or applied.
The generated hydrogen-containing gas is passed through a gas-liquid separator (23) to be separated into a hydrogen-containing gas and an unreacted methanol aqueous solution, and the hydrogen-containing gas is stored in a hydrogen tank (25).
Part or all of the separated unreacted methanol aqueous solution is circulated back to the fuel adjusting tank (21) through the conduit (24). In some cases, water may be supplied from outside the system.

Since the exhaust air discharged from the hydrogen production apparatus contains unreacted methanol aqueous solution that has permeated from the fuel electrode due to the crossover phenomenon with the generated water, this exhaust air is separated from the gas-liquid separator ( 27) The produced water and the unreacted methanol aqueous solution are separated through 27), carbon dioxide is removed by the carbon dioxide removing device (28), and then discharged into the atmosphere.
Part or all of the separated product water and the unreacted methanol aqueous solution are circulated back to the fuel adjustment tank (21) through the conduit (29).

Hydrogen stored in the hydrogen tank (25) is supplied to the hydrogen electrode (32) of the fuel cell (30) via the flow rate adjusting valve (26), and the air blower (17) is supplied to the air electrode (34). ) Through the flow rate adjustment valve (19), the reaction of the formula [1] occurs on the hydrogen electrode side, and the reaction of the formula [2] occurs on the air electrode side. 3] occurs, water (steam) is generated, and electricity (DC power) is generated.
_{^{H 2 → 2H + + 2e -}} ··· [1]
2H ⁺ + 2e ⁻ + (1/2) O ₂ → H ₂ O (2)
H ₂ + (1/2) O ₂ → H ₂ O (3)

  As the fuel cell (30), any fuel can be used as long as the fuel is hydrogen, but a polymer electrolyte fuel cell (PEFC) capable of operating at a low temperature of 100 ° C. or lower is preferable. As the polymer electrolyte fuel cell, a fuel cell stack in which a plurality of well-known single cells are stacked can be employed. One unit cell includes a solid polymer electrolyte membrane (31) such as Nafion (trademark of DuPont), a hydrogen electrode (32) and an air electrode (34) which are diffusion electrodes sandwiching the membrane from both sides, and further sandwiching them from both sides. Two separators are provided. Concavities and convexities are formed on both surfaces of the separator, and gas flow paths (33) and (35) in the single cell are formed between the sandwiched hydrogen electrode and air electrode. Among these, in the gas flow path in the single cell (33) formed with the hydrogen electrode, the supplied hydrogen gas is on the other hand, the gas flow path in the single cell (35) formed with the air electrode (35). ), Air flows respectively.

  The power generation of the fuel cell (30) involves heat generation. In the case of the above polymer electrolyte fuel cell (PEFC), the polymer electrolyte membrane exhibits proton conductivity in a water-containing state, so that the polymer electrolyte membrane dries with the heat generation of the fuel cell, and the water content decreases. Then, the internal resistance of the fuel cell increases and the power generation capacity decreases. Therefore, in order to prevent the polymer electrolyte membrane from drying, it is necessary to cool the fuel cell and maintain it at an appropriate operating temperature (about 80 ° C.). On the other hand, in the hydrogen production apparatus, as shown in the examples described later, the higher the temperature, the higher the hydrogen generation efficiency. Therefore, the heat generation of this fuel cell is used for heating the hydrogen production apparatus by providing heat exchange means. Is preferred.

Conventionally, in order to keep the polymer electrolyte membrane in a wet state, the reformed gas and / or reaction air has been humidified and then supplied to the fuel cell body. However, the hydrogen production apparatus used in the present invention is an organic substance and A gas containing hydrogen is taken out from the fuel electrode side for supplying water-containing fuel (methanol aqueous solution or the like). Since hydrogen is humidified, a humidifier can be dispensed with. Furthermore, since the gas containing hydrogen generated from the hydrogen production cell (10) is not as hot as the reformed gas produced by the conventional reformer, it can be supplied to the fuel cell (30) without cooling. it can.
Moreover, as a fuel supplied to a fuel cell, the case where only the hydrogen which generate | occur | produced from the hydrogen production cell (10) is supplied, and the case where the methanol aqueous solution containing hydrogen is supplied are considered. When supplying an aqueous methanol solution containing hydrogen, the gas-liquid separator (23) is unnecessary.

The DC power generated by the fuel cell (30) is introduced into the power converter (36), boosted by the DC / DC converter, or converted to AC power by the DC / AC inverter and output. In addition, the DC power stabilized by the auxiliary converter is used as a drive power source for auxiliary devices such as the fuel pump (16) and the air blower (17), and the AC power is used as a drive power source for electrical equipment in the home. Used.
In these series of power generation operations, the control device (37) includes a voltage regulator (22), a fuel cell (30), a power converter (36), a fuel pump (16), an air blower ( 17) Control the operation of auxiliary equipment such as.

The fuel cell power generator as described above can be mounted on an electric vehicle or a submarine.
The basic configuration of the electric vehicle according to the present invention includes a fuel cell that generates power by supplying hydrogen and an oxidant, a hydrogen production device that produces a gas containing hydrogen to be supplied to the fuel cell, and the fuel cell. And a motor driven by the electricity generated in the above.
FIG. 13 shows an example of a system flow of the fuel cell system in the electric vehicle of the present invention.

A basic configuration of a submarine according to the present invention includes a fuel cell that generates power by supplying hydrogen and an oxidant, a hydrogen production apparatus that produces a gas containing hydrogen to be supplied to the fuel cell, and the fuel cell. And a propulsion device driven by electricity generated in
FIG. 14 shows an example of a system flow of the fuel cell system in the submarine according to the present invention.

In the fuel cell power generator shown in FIG. 10 mounted on the electric vehicle or the submarine of the present invention, as described above, the hydrogen production cell (10) constituting the hydrogen production apparatus is operated at a low temperature. Unlike the case of the fuel reforming apparatus, the control apparatus (37) can be disposed near the hydrogen production cell (10). Moreover, a heat insulating material for protecting the control device (37) from the heat generated by the hydrogen production cell (10) can be eliminated.
In this figure, the fuel tank (20) and the fuel adjustment tank (21) are mounted on an electric vehicle or a submersible, but fuel (methanol aqueous solution) may be supplied from the outside without mounting them. Alternatively, only the fuel adjustment tank (21) may be mounted on an electric vehicle or a submarine.

  In the case of an electric vehicle, the DC power generated in the fuel cell is converted into AC power by the DC / AC inverter as described above, supplied to the motor that is the power source of the electric vehicle, and the motor is driven to generate the DC power. Torque is transmitted to the axle by gears to drive the wheels and drive the car.

In the case of a submarine, as the propulsion device, for example, a well-known means including a motor and a propeller for propulsion mounted on a rotation shaft of the motor can be adopted. The DC power generated in the fuel cell is converted into AC power by the DC / AC inverter as described above, supplied to the motor that is the power source of the submarine, and is driven by the motor and mounted on the rotating shaft of the motor. The propeller for propulsion is driven to rotate.
The electricity generated in the fuel cell is also supplied to pre-search sonars, projectors, observation equipment, and the like.

  Whether it is an electric vehicle or a submarine, it is preferable to provide an electrical energy storage device to store electricity generated by the fuel cell. Electricity generated in the fuel cell is supplied to the motor and the electric energy storage device according to the load of the motor and the amount of electricity stored in the electric energy storage device by using the control device. Specifically, for example, during acceleration, when the motor load is large, electricity from the fuel cell and the electrical energy storage device is supplied to the motor. During deceleration, braking, etc., regenerative electric power obtained from the motor is supplied to the electrical energy storage device. As the electric energy storage device, for example, a secondary battery, an electric double layer capacitor, or the like can be used.

Moreover, a hydrogen supply system can be comprised by connecting the hydrogen production apparatus of this invention with a hydrogen storage means, and supplying the gas containing the hydrogen manufactured with the hydrogen production apparatus to the hydrogen storage means.
When the hydrogen storage means is a hydrogen storage container mounted on an electric vehicle (fuel cell vehicle), hydrogen supply means for supplying hydrogen to the hydrogen storage container, hydrogen supply And a hydrogen production apparatus for producing a gas containing hydrogen to be supplied to the means.
FIG. 15 shows an example of a system flow of the hydrogen supply system of the present invention.

  Hydrogen supply means for supplying hydrogen to a hydrogen storage container mounted on a fuel cell vehicle includes, for example, a hydrogen booster, a high-pressure hydrogen storage tank, and a hydrogen dispenser.

  As the hydrogen booster, a hydrogen compression pump is generally used, but any device capable of boosting hydrogen can be used. The hydrogen gas pressure at the outlet of the hydrogen booster is desirably increased from the viewpoint of volumetric efficiency, preferably 50 atm (5 MPa) or more, more preferably 100 atm (10 MPa) or more, and even more preferably 200 atm (20 MPa) or more. . Moreover, although it does not specifically limit about an upper limit, 1000 atmospheres (100 Mpa) or less is preferable practically.

  It is preferable to provide a hydrogen storage tank (high pressure hydrogen storage tank) in order to store hydrogen after the hydrogen pressurization step. The form of the high-pressure hydrogen storage tank is not particularly limited as long as it can withstand the pressurized hydrogen, and a known high-pressure hydrogen storage tank that can store high-pressure hydrogen gas as it is can be applied. In addition to the tank, a high-pressure hydrogen storage tank containing a hydrogen storage alloy may be used.

  Hydrogen gas is led from a high-pressure hydrogen storage tank to a hydrogen dispenser. Further, the outlet gas of the hydrogen booster can be directly led to the hydrogen dispenser without passing through the high-pressure hydrogen storage tank. In that case, a pipe for connecting the hydrogen booster and the hydrogen dispenser is provided.

  The hydrogen dispenser supplies hydrogen gas to a hydrogen storage container of a fuel cell vehicle using hydrogen as fuel, and a known dispenser can be used. The hydrogen storage container may be a hydrogen storage container that is still mounted on the fuel cell vehicle. If the container is removable from the fuel cell vehicle, the hydrogen storage container is removed from the fuel cell vehicle. It may be a storage container.

Next, reference examples and examples (hydrogen production examples) of the present invention will be shown, but the catalyst, PTFE, Nafion ratio, etc., the thickness of the catalyst layer, gas diffusion layer, electrolyte membrane, etc. can be appropriately changed. However, the present invention is not limited to the reference examples and examples.
Reference Examples 1 to 4 and Comparative Examples 1 and 2 use a flat MEA (membrane-electrode assembly) to provide a hydrogen production cell (flat cell) in which an air supply shortage region is provided on the air electrode side. ) Shows an example of producing hydrogen under open circuit conditions.

(Reference Example 1)
A hydrogen production cell was prepared as follows.
That is, a proton conductive electrolyte membrane (Nafion 115) manufactured by DuPont is used as the electrolyte, and carbon paper (manufactured by Toray) is immersed in a 5% concentration polytetrafluoroethylene dispersion in the air electrode, followed by firing at 360 ° C. Applying an air electrode catalyst paste prepared by mixing an air electrode catalyst (platinum-supported carbon: Tanaka Kikinzoku), PTFE fine powder and 5% Nafion solution (Aldrich) on one side A gas diffusion layer with catalyst was constructed. Here, the weight ratio of the air electrode catalyst, PTFE, and Nafion was 65%: 15%: 20%. The catalyst amount of the air electrode thus produced was 1 mg / cm ² in terms of platinum.

Furthermore, the fuel electrode catalyst paste was prepared by mixing the water repellent treatment of carbon paper using the same method, and further mixing the fuel electrode catalyst (platinum ruthenium-supported carbon: made by Tanaka Kikinzoku), PTFE fine powder and 5% Nafion solution on one side. Was applied to form a gas diffusion layer with a fuel electrode catalyst. Here, the weight ratio of the fuel electrode catalyst, PTFE, and Nafion was 55%: 15%: 30%. The catalyst amount of the fuel electrode thus produced was 1 mg / cm ² in terms of platinum-ruthenium.

The electrolyte membrane, the gas diffusion layer with an air electrode catalyst, and the gas diffusion layer with a fuel electrode catalyst were joined by hot pressing at 140 ° C. and 10 MPa to prepare an MEA. The effective electrode area of the MEA produced in this manner was 60.8 cm ² (length 80 mm, width 76 mm). The thicknesses of the catalyst layers of the air electrode and the fuel electrode and the gas diffusion layers of the air electrode and the fuel electrode after fabrication were approximately the same at about 30 μm and 170 μm, respectively.

  By applying an epoxy resin only on the air electrode gas diffusion layer of the MEA produced as described above, as shown in FIGS. 5 and 10, eight strip masks having a width of 5 mm were provided at intervals of 5 mm. The MEA produced in this way is provided with an air electrode side end plate provided with an air inlet and an air outlet on the air electrode side via silicon rubber, and a fuel inlet and a fuel outlet on the fuel electrode side. A fuel electrode-side end plate provided with a silicon rubber is stacked and sandwiched, and a space is provided so that air is supplied to the surface of the air electrode so that fuel is supplied to the surface of the fuel electrode. Was provided. Further, in order to prevent leakage of fuel and air, packing made of silicon rubber is provided around the fuel electrode and the air electrode. Moreover, in order to measure the electric potential of each electrode, the stainless steel foil which touches an electrode was inserted between the said packing and MEA.

The hydrogen production cell thus prepared was installed in a hot air circulation type electric furnace, the cell temperature (operating temperature) was 50 ° C., the air flow rate was 10 to 50 ml / min on the air electrode side, and 1 M on the fuel electrode side. A methanol aqueous solution (fuel) was flowed at a flow rate of 5.0 ml / min, and the voltage difference (open voltage) between the fuel electrode and the air electrode at that time and the amount of gas generated on the fuel electrode side were measured.
An underwater displacement method was used to measure the amount of gas generated. In addition, the hydrogen concentration in the generated gas was analyzed by gas chromatography to determine the hydrogen production rate.
The results are shown in Table 1.

As shown in Table 1, generation of hydrogen was confirmed from the fuel electrode side of the cell by reducing the air flow rate. Further, when the relationship between the air flow rate and the cell open circuit voltage (OCV) was examined, it was found that the cell open circuit voltage tended to decrease as the air flow rate decreased.
The hydrogen generation rate (hydrogen generation amount) tended to depend on the open circuit voltage, and it was found that hydrogen was generated at an open circuit voltage of 400 to 600 mV. Moreover, the peak of the hydrogen production rate was observed around 500 mV.

(Reference Example 2)
As shown in FIGS. 6 and 10, by applying an epoxy resin only on the fuel electrode gas diffusion layer of the MEA, as in Reference Example 1, except that eight strip masks with a width of 5 mm are provided at intervals of 5 mm. A hydrogen production cell was prepared, and the amount of gas generated on the fuel electrode side was measured as in Reference Example 1.
The results are shown in Table 2.

  As shown in Table 2, by reducing the air flow rate, it was confirmed that a small amount of hydrogen was generated from the fuel electrode side of the cell in the vicinity of an open circuit voltage of 500 mV.

(Comparative Example 1)
By applying an epoxy resin on the gas diffusion layers of the fuel electrode and air electrode of the MEA, as shown in FIG. 7 and FIG. 10, eight strip masks having a width of 5 mm are opposed to the same position at intervals of 5 mm. A hydrogen production cell was prepared in the same manner as in Reference Example 1 except that the gas generation amount generated on the fuel electrode side was measured in the same manner as in Reference Example 1.
The results are shown in Table 3.

As shown in Table 3, generation of hydrogen was not confirmed from the fuel electrode side of the cell even when the air flow rate was reduced.
This is because, as described above, the hydrogen generation region of the fuel electrode is masked, and methanol diffusion for the hydrogen generation reaction cannot be performed.

(Comparative Example 2)
By applying an epoxy resin on the gas diffusion layers of the fuel electrode and air electrode of the MEA, as shown in FIGS. 8 and 10, eight strip masks having a width of 5 mm are provided at the fuel electrode at intervals of 5 mm. A hydrogen production cell was prepared in the same manner as in Reference Example 1 except that six were provided so as not to face the opposite positions, and the amount of gas generated on the fuel electrode side was measured in the same manner as in Reference Example 1.
The results are shown in Table 4.

As shown in Table 4, even if the air flow rate was reduced, generation of hydrogen was not confirmed from the fuel electrode side of the cell.
As described above, this is because the region where the discharge reaction of the fuel electrode should occur is masked, and methanol cannot be supplied for the discharge reaction.

(Reference Example 3)
Using the MEA produced in another lot, a hydrogen production cell was produced in the same manner as in Reference Example 1, and the amount of gas generated on the fuel electrode side was measured in the same manner as in Reference Example 1.
The results are shown in Table 5.

As shown in Table 5, generation of hydrogen was confirmed from the fuel electrode side of the cell at a slightly higher air flow rate than in Reference Example 1. Further, when the relationship between the air flow rate and the open circuit voltage of the cell was examined, it was found that when the air flow rate was decreased, the cell open circuit voltage tended to decrease accordingly.
The hydrogen generation rate (hydrogen generation amount) tended to depend on the open circuit voltage, and it was found that hydrogen was generated at an open circuit voltage of 400 to 600 mV. Moreover, the peak of the hydrogen production rate was observed around 470 mV.

(Reference Example 4)
By applying an epoxy resin on the gas diffusion layers of the fuel electrode and air electrode of the MEA, as shown in FIGS. 9 and 10, eight strip masks having a width of 5 mm are provided at intervals of 5 mm, and only a part of the mask is provided. A hydrogen production cell was prepared in the same manner as in Reference Example 3 except that the gas was generated so as to face each other, and the amount of gas generated on the fuel electrode side was measured in the same manner as in Reference Example 1.
The results are shown in Table 6.

As shown in Table 6, generation of hydrogen was confirmed from the fuel electrode side of the cell in the vicinity of an open circuit voltage of 500 mV by reducing the air flow rate.
When the mask is shifted, as described above, a discharge region and a hydrogen generation region are formed, and hydrogen is generated.

(Reference Example 5)
Next, instead of masking a part of the gas diffusion layer, a reference example in which the gas diffusion layer of the air electrode is made non-uniform by a combination of different materials and a region where air supply is insufficient is provided on the air electrode side. Show.
On the air electrode side of the electrolyte membrane, a polyimide sheet (air blocking layer) having a width of 10 mm and a carbon paper (air permeable layer: gas diffusion layer with an air electrode catalyst) having a width of 10 mm are alternately arranged as shown in FIG. In the same manner as in Example 1, except that carbon paper (gas diffusion layer with a fuel electrode catalyst) is disposed on the fuel electrode side of the electrolyte membrane and bonded by hot pressing at 140 ° C. and 10 MPa. Was made. The thickness of the polyimide sheet was 130 μm before and after pressing, and the thickness of the carbon paper was 280 μm before pressing and 165 μm after pressing (the polyimide sheet returned to its original state after pressing). The thickness of the catalyst layer of the air electrode and the fuel electrode after pressing was about 30 μm, respectively.
Using the MEA thus produced, a hydrogen production cell was produced in the same manner as in Reference Example 1, and the amount of gas generated on the fuel electrode side was measured in the same manner as in Reference Example 1.
The results are shown in Table 7.

  Even when the gas diffusion layer of the air electrode is made non-uniform by a combination of different materials, as shown in Table 7, by reducing the air flow rate, the hydrogen from the fuel electrode side of the cell near the open circuit voltage of 500 mV. The occurrence of was confirmed.

(Reference Example 6)
Next, instead of masking a part of the gas diffusion layer, a reference example is shown in which the gas diffusion layer of the air electrode is made non-uniform by a combination of density and a region where air supply is insufficient is provided on the air electrode side. .
On the air electrode side of the electrolyte membrane, a thin carbon paper with a width of 10 mm and a thickness of 190 μm (a gas diffusion layer with an air electrode catalyst) and a thick carbon paper with a width of 10 mm and a thickness of 335 μm (a gas diffusion layer with an air electrode catalyst) In addition, a thin carbon paper (gas diffusion layer with a fuel electrode catalyst) having a thickness of 190 μm is disposed on the fuel electrode side of the electrolyte membrane, and hot pressing is performed at 140 ° C. with the same pressing pressure (10 MPa) (simultaneous An MEA was produced in the same manner as in Example 1 except that the joining was performed by pressing. The thickness of the carbon paper, which is the gas diffusion layer of the air electrode, before and after pressing is 190 μm → 165 μm, 335 μm → 185 μm, and is almost the same thickness. Therefore, the density (thin carbon paper → Carbon paper is a combination of sparse, thick carbon paper → dense). The thickness of the catalyst layer of the air electrode and the fuel electrode after pressing was about 30 μm, respectively.
Using the MEA thus produced, a hydrogen production cell was produced in the same manner as in Reference Example 1, and the same as in Reference Example 1 except that the flow rate of air flowing to the air electrode side was in the range of 10 to 90 ml / min. The amount of gas generated on the fuel electrode side was measured using the above conditions.
The results are shown in Table 8.

  Even when the gas diffusion layer of the air electrode is made non-uniform by the combination of density, as shown in Table 8, by reducing the air flow rate, the hydrogen flow from the fuel electrode side of the cell near the open circuit voltage of 500 mV. Occurrence was confirmed. Hydrogen was generated at a slightly higher air flow rate than in Reference Example 5 in which the gas diffusion layer of the air electrode was made non-uniform by a combination of different materials.

(Reference Example 7)
Next, instead of masking a part of the gas diffusion layer, a reference example is shown in which the gas diffusion layer of the air electrode is made uneven by unevenness on the surface, and a region where air supply is insufficient is provided on the air electrode side. .
On the air electrode side of the electrolyte membrane, a thin carbon paper having a width of 10 mm and a thickness of 190 μm (gas diffusion layer with an air electrode catalyst) is arranged with a gap of 10 mm, and on the fuel electrode side of the electrolyte membrane, a thickness of 190 μm is arranged. A thin carbon paper (gas diffusion layer with fuel electrode catalyst) is placed on the entire surface, hot pressed at 140 ° C and a pressure of 10 MPa, and then thick carbon paper with a thickness of 335 µm (gas diffusion with an air electrode catalyst). The MEAs were prepared in the same manner as in Example 1 except that the layers were joined and joined by hot pressing (two-stage pressing) at a pressing pressure of 140 ° C. and 10 MPa. Since the thickness of the carbon paper which is the gas diffusion layer of the air electrode before and after pressing is 190 μm → 140 μm, 335 μm → 215 μm, the unevenness (thin carbon paper → concave, thick carbon paper → convex) as shown in FIG. It is a formed carbon paper. The thickness of the catalyst layer of the air electrode and the fuel electrode after pressing was about 30 μm, respectively.
Using the MEA thus produced, a hydrogen production cell was produced in the same manner as in Reference Example 1, and the same as in Reference Example 1 except that the flow rate of air flowing to the air electrode side was in the range of 10 to 90 ml / min. The amount of gas generated on the fuel electrode side was measured using the above conditions.
The results are shown in Table 9.

  Even when the gas diffusion layer of the air electrode is made uneven due to the unevenness of the surface, as shown in Table 9, by reducing the air flow rate, from the fuel electrode side of the cell near the open circuit voltage of 500 mV, Occurrence was confirmed. Similar to the case of Reference Example 6 in which the gas diffusion layer of the air electrode is made non-uniform by the combination of density, the air diffusion is slightly more than in the case of Reference Example 5 in which the gas diffusion layer of the air electrode is made non-uniform by the combination of different materials. Hydrogen was generated at a high flow rate.

Below, the example in the case of manufacturing hydrogen with the hydrogen manufacturing apparatus (open circuit conditions) of the invention which concerns on Claim 14 of this application is shown.
A hydrogen production cell was prepared as follows.
That is, a proton conductive electrolyte membrane (Nafion 115) manufactured by DuPont is used as the electrolyte, and carbon cloth (manufactured by Nippon Carbon) is immersed in a 5% concentration polytetrafluoroethylene dispersion in the air electrode and then fired at 360 ° C. The air electrode catalyst paste prepared by mixing the air electrode catalyst (platinum-supported carbon: made by Tanaka Kikinzoku), PTFE fine powder and 5% Nafion solution (made by Aldrich) on one side was applied to the air. A gas diffusion layer with an electrode catalyst was constructed. Here, the weight ratio of the air electrode catalyst, PTFE, and Nafion was 65%: 15%: 20%. The catalyst amount of the air electrode thus produced was 1 mg / cm ² in terms of platinum.

Further, a fuel electrode catalyst paste prepared by mixing a carbon cloth with water repellent treatment using the same method and further mixing a fuel electrode catalyst (platinum ruthenium-supported carbon: made by Tanaka Kikinzoku), PTFE fine powder and 5% Nafion solution on one side. Was applied to form a gas diffusion layer with a fuel electrode catalyst. Here, the weight ratio of the fuel electrode catalyst, PTFE, and Nafion was 55%: 15%: 30%. The catalyst amount of the fuel electrode thus produced was 1 mg / cm ² in terms of platinum-ruthenium.

The MEA in which the electrolyte membrane, the gas diffusion layer with the air electrode catalyst, and the gas diffusion layer with the fuel electrode catalyst are joined by hot pressing at 140 ° C. and 10 MPa to form the gas diffusion layer in the center of the electrolyte membrane. Produced. The effective electrode area of the MEA thus produced was 32 cm ² (10 cm × 3.2 cm). The thicknesses of the catalyst layer and gas diffusion layer of the air electrode and the fuel electrode after fabrication were approximately the same at about 30 μm and 170 μm, respectively.

From the above MEA, a hydrogen production cell was produced as shown in FIG.
First, the MEA is rounded into a cylindrical shape, a part of the electrolyte membrane at the end is overlapped by about 5 mm, the overlapped part is heat-sealed, and the cylindrical shape with the fuel electrode side on the inside and the air electrode side on the outside An MEA was produced. Its external dimensions were an outer diameter of 12 mm and a length of 120 mm (of which the effective electrode portion was 100 mm).
Next, a PP tube having an outer diameter of 11 mm and a length of 160 mm is inserted into the cylindrical MEA, and the PP tube and the upper and lower electrolyte parts of the cylindrical MEA are fixed by heat fusion or an adhesive. The reaction tube was used. By applying an epoxy resin on the air electrode gas diffusion layer of the reaction tube, as shown in FIGS. 5 and 10, eight strip-shaped masks (14M) having a width of 2 mm were provided at intervals of 2 mm.
The reaction tube thus prepared was inserted into a PP outer tube having an inner diameter of 25 mm and a length of 130 mm, which was further provided with an air inlet and outlet, and the upper and lower portions of the PP tube of the previous reaction tube were the The cell was configured by fixing with a rubber stopper so as to be fixed to the outer tube.

The cell thus prepared was installed in a hot air circulation type electric furnace, and the cell temperature (operating temperature) was 80 ° C., and as shown in FIG. 20, the air was supplied to the air electrode at a flow rate of 20 to 300 ml / min. A 1.0M aqueous methanol solution (fuel) is flowed to the fuel electrode side at a flow rate of 8.0 ml / min, and the voltage difference between the fuel electrode and the air electrode (open voltage) at that time and the amount of hydrogen generated on the fuel electrode side are examined. Went. An underwater displacement method was used to measure the amount of gas generated.
The results are shown in Table 10.

  As shown in Table 10, in the cylindrical cell using the reaction tube of the example, as in the case of the reference example which is a flat plate type cell, the open-circuit voltage is around 500 mV from the fuel electrode side of the cell. Hydrogen evolution was observed.

As described above, the honeycomb type hydrogen production apparatus using the reaction tube of the present invention can produce a gas containing hydrogen by decomposing a fuel containing organic matter at 100 ° C. or lower. Hydrogen can be supplied easily.
Further, the fuel cell power generation apparatus using the honeycomb type hydrogen production apparatus of the present invention does not require any special means for protecting the control device built in the package from the heat generated by the hydrogen production apparatus, and further, the fuel cell Therefore, when used as a mobile power source or an on-site power source, it is extremely advantageous when mounted on an electric vehicle or a submarine.
Furthermore, if the honeycomb type hydrogen production apparatus of the present invention is used, hydrogen can be easily supplied to a hydrogen storage container mounted on an electric vehicle (fuel cell vehicle) and a hydrogen storage tank for supplying hydrogen to the fuel cell vehicle. In addition, even when hydrogen is used as a processing gas or the like when manufacturing a semiconductor device, hydrogen storage means is provided so that hydrogen can be easily supplied to a processing place.

It is the schematic which shows an example of the honeycomb type hydrogen production apparatus of this invention. It is the schematic perspective view and schematic longitudinal cross-sectional view which show an example of the reaction tube of this invention. FIG. 5 is a schematic view showing another example of the honeycomb type hydrogen production apparatus of the present invention (one obtained by integrating the fuel electrodes of reaction tubes combined in a honeycomb shape and drawing out a conducting wire). FIG. 6 is a schematic view showing another example of the honeycomb type hydrogen production apparatus of the present invention (in which conductor wires are individually drawn out from the fuel electrodes of reaction tubes combined in a honeycomb shape). It is the schematic which shows the reaction in the discharge area | region of the fuel electrode and air electrode of the reaction tube used for the honeycomb type hydrogen production apparatus of this invention. It is the schematic which shows the reaction in the hydrogen generation area | region of the fuel electrode and air electrode of the reaction tube used for the honeycomb type hydrogen production apparatus of this invention. It is the schematic which shows the total reaction in the fuel electrode and air electrode of the reaction tube used for the honeycomb type hydrogen production apparatus of this invention. It is a longitudinal cross-sectional view of the tube wall of the reaction tube which shows an example of the reaction tube of this invention which provided the mask in a part of surface of the air electrode. It is a longitudinal cross-sectional view of the tube wall of the reaction tube which shows an example of the reaction tube of this invention which provided the mask in a part of surface of the fuel electrode. It is a longitudinal cross-sectional view of the tube wall of the reaction tube which shows an example of the reaction tube which provided the mask in a part of surface of a fuel electrode and an air electrode so as to oppose the same position. It is a longitudinal cross-sectional view of the tube wall of the reaction tube which shows an example of the reaction tube which provided the mask on a part of surface of a fuel electrode and an air electrode so as not to oppose the opposite position. It is a longitudinal cross-sectional view of the tube wall of the reaction tube which shows an example of the reaction tube of this invention which provided the mask shifted by half so that only a part of mask may oppose a part of surface of a fuel electrode and an air electrode. It is the schematic which shows the width | variety of the mask provided in a part of surface of a fuel electrode and an air electrode, a space | interval, and the number. It is the schematic which shows an example of a structure of the fuel cell power generator of this invention. It is the schematic which shows the relationship between the hydrogen production apparatus and fuel cell in the fuel cell electric power generating apparatus of this invention. It is a figure which shows an example of the system flow of the fuel cell system in the electric vehicle of this invention. It is a figure which shows an example of the system flow of the fuel cell system in the submarine of this invention. It is a figure which shows an example of the system flow of the hydrogen supply system of this invention. It is the schematic which shows the example which made the gas diffusion layer of the air electrode nonuniform by the combination of a different material. It is the schematic which shows the example which made the gas diffusion layer of the air electrode nonuniform by the combination of density. It is the schematic which shows the example which made the gas diffusion layer of the air electrode non-uniform | heterogenous by the unevenness | corrugation of the surface. It is the schematic which shows the preparation procedures of the hydrogen production cell in the Example of this invention. It is the schematic which shows the method of supplying fuel and air to the hydrogen production cell in the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Hydrogen production cell 11 Diaphragm 12 Fuel electrode 12M Mask 13 provided in fuel electrode Flow path 14 for supplying fuel electrode 12 with fuel (methanol aqueous solution) containing organic matter and water Oxidation electrode (air electrode)
14M Mask 15 provided on oxidation electrode Flow path 16 for supplying oxidant (air) to oxidation electrode (air electrode) 14 Fuel pump 17 Air blower 18 Fuel flow rate adjustment valve 19 Air flow rate adjustment valve 20 Fuel tank 21 Fuel adjustment Tank 22 Voltage regulator 23 Gas-liquid separator (separates hydrogen-containing gas and unreacted methanol aqueous solution)
24 Conduit 25 for returning the unreacted aqueous methanol solution to the fuel adjustment tank 21 Hydrogen tank 26 Hydrogen flow rate adjusting valve 27 Gas-liquid separator
28 Carbon Dioxide Removal Device 29 Conduit 30 for Returning Unreacted Methanol Aqueous Solution to Fuel Adjustment Tank 21 Fuel Cell 31 Solid Polymer Electrolyte Membrane 32 Hydrogen Electrode 33 Channel 34 for Supplying Hydrogen to Hydrogen Electrode 32 Air Electrode 35 Air A flow path 36 for supplying air to the air electrode 34 A power converter 37 that converts direct-current power generated by the fuel cell 30 into predetermined power 37 A controller 38 that controls the entire power generator

Claims (47)

  In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, the fuel cell has a cylindrical diaphragm, and a fuel electrode is formed on one side of the inner and outer surfaces of the cylindrical diaphragm, and an oxidation electrode is formed on the other side. A hydrogen production cell in which a plurality of reaction tubes provided are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidizing agent to the oxidation electrode, and a gas containing hydrogen from the fuel electrode side Characterized in that it comprises means for generating and taking out, and a region where supply of the oxidant is insufficient is provided on the oxidation electrode side by masking only a part of the gas diffusion layer of the oxidation electrode. Honeycomb type hydrogen production equipment.   In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, the fuel cell has a cylindrical diaphragm, and a fuel electrode is formed on one side of the inner and outer surfaces of the cylindrical diaphragm, and an oxidation electrode is formed on the other side. A hydrogen production cell in which a plurality of reaction tubes provided are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidizing agent to the oxidation electrode, and a gas containing hydrogen from the fuel electrode side Characterized in that it comprises means for generating and taking out, and a region where supply of the oxidant is insufficient on the oxidation electrode side is provided by masking only a part of the gas diffusion layer of the fuel electrode. Honeycomb type hydrogen production equipment.   In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, the fuel cell has a cylindrical diaphragm, and a fuel electrode is formed on one side of the inner and outer surfaces of the cylindrical diaphragm, and an oxidation electrode is formed on the other side. A hydrogen production cell in which a plurality of reaction tubes provided are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidizing agent to the oxidation electrode, and a gas containing hydrogen from the fuel electrode side Masking a portion of the gas diffusion layer of both the oxidation electrode and the fuel electrode, and a region where the supply of the oxidant is insufficient on the oxidation electrode side. A honeycomb type hydrogen production apparatus provided by shifting at least a part of masking on both sides facing each other.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 3, wherein the masking is performed in a band shape.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 3, wherein the masking is performed in a spot shape.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 5, wherein the masking is performed by impregnating the gas diffusion layer with a resin or applying a resin to a surface of the gas diffusion layer.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 6, wherein the masking is performed by screen printing.   In a hydrogen production apparatus for decomposing a fuel containing organic matter and producing a gas containing hydrogen, the fuel cell has a cylindrical diaphragm, and a fuel electrode is formed on one side of the inner and outer surfaces of the cylindrical diaphragm, and an oxidation electrode is formed on the other side. A hydrogen production cell in which a plurality of reaction tubes provided are combined in a honeycomb shape, means for supplying a fuel containing organic matter and water to the fuel electrode, means for supplying an oxidizing agent to the oxidation electrode, and a gas containing hydrogen from the fuel electrode side A honeycomb type hydrogen production comprising a means for generating and taking out, and a region where the supply of the oxidant is insufficient is provided on the oxidation electrode side with a non-uniform gas diffusion layer of the oxidation electrode apparatus.   9. The honeycomb type hydrogen production apparatus according to claim 8, wherein the gas diffusion layer of the oxidation electrode is made non-uniform by forming it densely or by combining different materials.   The honeycomb type hydrogen production apparatus according to claim 8 or 9, wherein the gas diffusion layer of the oxidation electrode is made uneven by forming irregularities on the surface.   11. The open circuit having no means for taking out electric energy from a hydrogen production cell constituting the hydrogen production apparatus and means for applying electric energy from the outside to the hydrogen production cell. The honeycomb type hydrogen production apparatus according to claim 1.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 10, further comprising means for taking out electric energy to the outside using the fuel electrode as a negative electrode and the oxidation electrode as a positive electrode.   The honeycomb hydrogen production apparatus according to any one of claims 1 to 10, further comprising means for applying electric energy from the outside with the fuel electrode as a cathode and the oxidation electrode as an anode.   The honeycomb-type hydrogen production apparatus according to any one of claims 1 to 13, wherein a voltage between the fuel electrode and the oxidation electrode is 400 to 600 mV.   The honeycomb type hydrogen according to any one of claims 1 to 14, wherein a generation amount of the gas containing hydrogen is adjusted by adjusting a voltage between the fuel electrode and the oxidation electrode. manufacturing device.   The voltage between the fuel electrode and the oxidation electrode and / or the generation amount of the gas containing hydrogen is adjusted by adjusting the supply amount of the oxidant. The honeycomb type hydrogen production apparatus according to claim 1.   The operating temperature is 100 ° C or lower, The honeycomb type hydrogen production apparatus according to any one of claims 1 to 16.   The organic substance supplied to the fuel electrode is one or more organic substances selected from the group consisting of alcohol, aldehyde, carboxylic acid, and ether. The described honeycomb type hydrogen production apparatus.   The honeycomb type hydrogen production apparatus according to claim 18, wherein the alcohol is methanol.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 19, wherein the oxidizing agent supplied to the oxidation electrode is a gas containing oxygen or oxygen.   The honeycomb-type hydrogen production apparatus according to any one of claims 1 to 20, wherein the diaphragm is a proton conductive solid electrolyte membrane.   The honeycomb type hydrogen production apparatus according to claim 21, wherein the proton conductive solid electrolyte membrane is a perfluorocarbon sulfonic acid solid electrolyte membrane.   The honeycomb-type hydrogen production apparatus according to any one of claims 1 to 22, wherein the fuel electrode catalyst is a platinum-ruthenium alloy supported on carbon powder.   The honeycomb-type hydrogen production apparatus according to any one of claims 1 to 23, wherein the catalyst of the oxidation electrode is a catalyst in which platinum is supported on carbon powder.   The honeycomb-type hydrogen production apparatus according to any one of claims 1 to 24, wherein a circulation means for fuel containing the organic matter is provided.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 25, further comprising a carbon dioxide absorption part that absorbs carbon dioxide contained in the gas containing hydrogen.   A fuel cell is connected to the honeycomb type hydrogen production apparatus according to any one of claims 1 to 26, and electric energy supplied to an auxiliary machine for operating the honeycomb type hydrogen production apparatus is obtained from the fuel cell. A honeycomb type hydrogen production apparatus.   A fuel comprising: connecting the honeycomb-type hydrogen production apparatus according to any one of claims 1 to 27 to a fuel cell; and supplying the fuel cell with a gas containing hydrogen produced by the hydrogen production apparatus. Battery power generator. 28. The honeycomb type hydrogen production apparatus according to any one of claims 14 to 27, wherein means for taking out electric energy from the hydrogen production cell and means for applying electric energy from the outside to the hydrogen production cell. A honeycomb type hydrogen production apparatus that is an open circuit that does not include a honeycomb type hydrogen production apparatus that has means for taking out electrical energy from the fuel electrode as a negative electrode and the oxidation electrode as a positive electrode, and a fuel electrode as a cathode. A honeycomb type hydrogen production apparatus using a combination of two or more honeycomb type hydrogen production apparatuses selected from the group of honeycomb type hydrogen production apparatuses having means for applying electric energy from the outside as an anode is connected to a fuel cell, and the fuel retardant you and supplying a gas containing hydrogen produced in the honeycomb hydrogen generating device to the battery Cell power plant. A fuel cell power generation device, a fuel cell, the honeycomb-type hydrogen production device for producing a gas containing hydrogen to be supplied to the fuel cell, a power conversion device for converting DC power generated by the fuel cell into predetermined power, 30. The fuel cell power generator according to claim 28 or 29 , wherein a control device for controlling the entire power generator is built in at least the package. The fuel cell power generator according to any one of claims 28 to 30, wherein the hydrogen-containing gas produced by the honeycomb-type hydrogen production apparatus is supplied to the fuel cell without cooling.   The oxidant supplied to the oxidation electrode of the honeycomb type hydrogen production apparatus is exhaust gas discharged from the fuel cell or another honeycomb type hydrogen production apparatus or a gas containing unreacted oxygen. The fuel cell power generator according to any one of 28 to 31.   33. The fuel cell power generator according to any one of claims 28 to 32, wherein a heat insulating material for blocking heat generated by the honeycomb type hydrogen production apparatus is not provided.   An electric vehicle comprising the fuel cell power generator according to any one of claims 28 to 33.   A submarine equipped with the fuel cell power generator according to any one of claims 28 to 33.   The honeycomb type hydrogen production apparatus according to any one of claims 1 to 27 is connected to a hydrogen storage means, and a gas containing hydrogen produced by the honeycomb type hydrogen production apparatus is supplied to the hydrogen storage means. Characteristic hydrogen supply system.   The hydrogen supply system according to claim 36, wherein the hydrogen storage means is a hydrogen storage container mounted on an electric vehicle.   In a reaction tube for a hydrogen production cell having a cylindrical diaphragm and a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and an oxidation electrode on the other side, the gas diffusion layer of the oxidation electrode is oxidized A reaction tube for a hydrogen production cell, wherein a region where the supply of the agent is insufficient is provided by masking only a part of the gas diffusion layer of the oxidation electrode.   In a reaction tube for a hydrogen production cell having a cylindrical diaphragm and a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and an oxidation electrode on the other side, the gas diffusion layer of the oxidation electrode is oxidized A reaction tube for a hydrogen production cell, wherein a region where the supply of the agent is insufficient is provided by masking only a part of the gas diffusion layer of the fuel electrode.   In a reaction tube for a hydrogen production cell having a cylindrical diaphragm and a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and an oxidation electrode on the other side, the gas diffusion layer of the oxidation electrode is oxidized The region where the supply of the agent is insufficient is provided by masking a part of the gas diffusion layer on both sides of the oxidation electrode and the fuel electrode, and by shifting at least part of the masking on both opposing sides. A reaction tube for a hydrogen production cell.   The reaction tube for a hydrogen production cell according to any one of claims 38 to 40, wherein the masking is performed in a band shape.   The reaction tube for a hydrogen production cell according to any one of claims 38 to 40, wherein the masking is performed in a spot shape.   43. The reaction tube for a hydrogen production cell according to any one of claims 38 to 42, wherein the masking is performed by impregnating the gas diffusion layer with a resin or applying a resin to a surface of the gas diffusion layer. .   44. The reaction tube for a hydrogen production cell according to any one of claims 38 to 43, wherein the masking is performed by screen printing.   In a reaction tube for a hydrogen production cell having a cylindrical diaphragm and a fuel electrode on one side of the inner and outer surfaces of the cylindrical diaphragm and an oxidation electrode on the other side, the gas diffusion layer of the oxidation electrode is oxidized A reaction tube for a hydrogen production cell, wherein a region where the supply of the agent is insufficient is provided with the gas diffusion layer of the oxidation electrode being non-uniform.   46. The reaction tube for a hydrogen production cell according to claim 45, wherein the gas diffusion layer of the oxidation electrode is made non-uniform by forming it densely or by combining different materials.   47. The reaction tube for a hydrogen production cell according to claim 45 or 46, wherein the gas diffusion layer of the oxidation electrode is made uneven by forming irregularities on the surface.