JP4578867B2 - Hydrogen storage / supply device and system thereof, distributed power source using the same, and automobile - Google Patents

Description

  The present invention relates to a novel hydrogen storage and supply device that stores hydrogen and supplies hydrogen to a distributed power source such as an automobile or a household fuel cell, a system thereof, a distributed power source using the system, and an automobile.

As global warming due to carbon dioxide and the like becomes serious, hydrogen is attracting attention as an energy source for the next generation instead of fossil fuels. In addition, cogeneration of power generation facilities has attracted attention in order to promote energy saving by effectively using energy and reducing CO ₂ emissions. In recent years, fuel cell power generation systems that generate power using hydrogen have been rapidly developed as a power source for various uses such as automobiles, household power generation facilities, vending machines, and portable devices. A fuel cell generates electricity when hydrogen and oxygen are reacted to form water, and can be used for hot water supply and air conditioning using thermal energy generated at the same time. In addition to fuel cells, internal combustion engines such as microturbines and microengines are also being developed.

  On the other hand, a hydrogen transportation, storage, and supply system that is indispensable for using hydrogen as a fuel has become a major issue. Since hydrogen is a gas at room temperature, it is difficult to store and transport compared to liquids and solids. Moreover, hydrogen is a flammable substance, and there is a risk of explosion when it is mixed with air at a predetermined mixing ratio.

  As disclosed in Patent Document 1, hydrogen is generated by adding water vapor to a hydrocarbon fuel, and this hydrogen is stored in a hydrogen storage alloy and released at start-up, as disclosed in Patent Document 1. A power generation system is shown which is added to fuel, hydrodesulfurized and supplied to a fuel cell.

  In recent years, organic hydride systems using hydrocarbons such as cyclohexane and decalin have attracted attention as a hydrogen storage method that is excellent in safety, transportability, and storage capacity. Since these hydrocarbons are liquid at room temperature, they are excellent in transportability.

  For example, benzene and cyclohexane are cyclic hydrocarbons having the same carbon number, but benzene is an unsaturated hydrocarbon in which the bonds between carbons are double bonds, whereas cyclohexane is a saturated hydrocarbon having no double bonds. Hydrogen. Cyclohexane is obtained by the hydrogenation reaction of benzene, and benzene is obtained by the dehydrogenation reaction of cyclohexane. That is, hydrogen can be stored and supplied by utilizing hydrogenation and dehydrogenation of these hydrocarbons.

  As disclosed in Patent Documents 2 and 3, a method of performing a dehydrogenation reaction by blowing cyclohexane on a high-temperature catalyst layer with an atomizer and separating a product of hydrogen and benzene into a gas and a liquid with a cooler is shown. ing.

JP 7-192746 A JP 2002-274801 A JP 2002-184436 A Applied Catalysis A: General 233, 91-102 (2002)

  However, in order to store and supply hydrogen using a hydrogenation reaction and a dehydrogenation reaction typified by a reaction between benzene and cyclohexane, the reaction efficiency is low, so the reaction efficiency needs to be increased.

  Furthermore, in practical use, the reaction temperature of the dehydration reaction of organic hydrides such as cyclohexane and decalin is as high as 250 ° C. or higher, and heating with a heater does not use part of the power generated in the fuel cell. Doing so will reduce efficiency. Moreover, in the apparatuses disclosed in Patent Documents 2 and 3, the apparatus becomes large.

  An object of the present invention is to provide a small and efficient hydrogen storage / supply device, a system thereof, a distributed power source and an automobile that can store and supply hydrogen at a low temperature.

In a hydrogen storage / supply device that releases or stores hydrogen using a medium that chemically repeats the storage and release of hydrogen,
A planar medium flow path through which the medium flows;
And hydrogen, which are pre-Symbol released, and the planar hydrogen separating means for separating the medium releasing the medium and hydrogen were stored hydrogen,
The released hydrogen, the medium storing hydrogen, and the circulation port through which each of the medium releasing hydrogen flows in or out are formed integrally.
The hydrogen separation means is composed of a composite functional layer in which a catalyst layer is formed on the inner surface of pores formed in a porous resin, and the released hydrogen is converted into a gaseous state with the medium storing hydrogen and the hydrogen. Separating from the discharged medium,
The composite functional layer is provided in contact with the medium flow path;
The medium flow path, have a plurality of injection unit for injecting the medium into the reaction section and the reaction section as a planar structure formed on one surface of the substrate,
The medium flow path, the hydrogen separation unit and the composite functional layer characterized that you have been successively formed.

The present invention relates to a hydrogen storage / supply device that releases or stores hydrogen using a medium that chemically repeats storage and release of hydrogen.
A planar medium flow path through which the medium flows;
A catalyst layer formed in the flow path;
A planar hydrogen separation means for separating the released hydrogen from the medium storing hydrogen and the medium releasing hydrogen;
The released hydrogen, the medium storing hydrogen and the flow outlet through which the medium released hydrogen flows out are formed integrally.
The hydrogen separation means comprises a hydrogen separation membrane that separates the released hydrogen in a gaseous state from the medium storing hydrogen and the medium releasing hydrogen;
The hydrogen separation membrane is formed in contact with the catalyst layer;
The medium flow path, have a plurality of injection unit for injecting the medium into the reaction section and the reaction section as a planar structure formed on one surface of the substrate,
The medium flow path, Rukoto catalyst layer and a hydrogen separating means are sequentially formed,
Alternatively, the hydrogen separation means is a flat plate cooler for cooling the released hydrogen, the medium storing hydrogen, and the medium releasing hydrogen, and the hydrogen released by the cooler is converted into a gas In the state, the medium storing hydrogen and the medium releasing hydrogen are separated from the medium as a liquid,
The cooler is formed adjacent to the surface of the medium flow path;
The medium flow path, have a plurality of injection unit for injecting the medium into the reaction section and the reaction section as a planar structure formed on one surface of the substrate,
The medium flow path, the catalyst layer and the hydrogen separation means is characterized that you have been successively formed.

Further, the flow port of the separated hydrogen, the medium that has released the medium and hydrogen was stored hydrogen is preferably made as outlet or supply opening by the switching means for changing alternately each inflow or outflow .

Hydrogen storage and supply system of the present invention, that the flow path on at least one surface of the high thermal conductivity substrate, a catalyst layer, a spacer, said hydrogen separation unit consisting of hydrogen flow path layer及Pi cooler are successively formed The flow path, the catalyst layer, the hydrogen separation means comprising a hydrogen separation membrane, a spacer, and a hydrogen flow path layer are sequentially formed on at least one surface of the high thermal conductive substrate. Alternatively, the flow path on at least one surface of the high thermal conductivity substrate, the hydrogen separation membrane, a catalyst layer, a fuel injection layer and the fuel injecting the medium in the catalyst layer in which a plurality of through holes were stored disposed hydrogen It is preferable that a fuel storage layer for storing is sequentially formed.

  The hydrogen storage / supply apparatus of the present invention can be used only for hydrogen storage or can be used only for hydrogen supply. In addition, by controlling the anti-wide temperature for each of the dehydrogenation reaction and the hydrogenation reaction, both hydrogen storage and supply functions can be achieved.

  The flow path is in the form of a substrate or a sheet having various planar patterns of a fuel injection part, a reaction part and a diffusion part for injecting the medium storing the hydrogen.

  It is important for the fuel injection portion to uniformly diffuse the fuel into the catalyst layer, and is achieved by the following two methods. The first method is to supply fuel from a flow path pattern in which the fuel injection portion is formed in the same plane as the catalyst layer and the injection port cross section has a curvature. In particular, it is preferably formed in a spray nozzle shape, the nozzle diameter is 1 to 500 μm, and the spray angle is O to 85 °. Secondly, after the fuel is uniformly diffused in the fuel storage layer, the fuel is supplied from the fuel injection layer in which a plurality of through holes are arranged. It is preferable that the hole diameter of the through-hole is reduced from the upper surface to the lower surface, and the hole diameter on the lower surface is O.3 to 300 μm. In either case, the number of flow path patterns and the number of through holes is not limited, and the flow path pattern and the number of through holes are appropriately prepared so that fuel can be uniformly supplied to the catalyst layer.

  The reaction section has a barrier pattern that serves as a barrier for the flow of the medium, the pattern width of the flow path and the wiring gap are each 0.1 to 1000 μm, the flow path pattern is made of metal, It becomes preferable that it becomes a heater by energizing from the above, and that the catalyst layer is a porous film or a porous layer produced by anodic oxidation.

  The hydrogen storage / supply device of the present invention comprises a combustion catalyst layer for burning residual hydrogen of a fuel cell or the medium after dehydrogenation reaction on the surface opposite to the catalyst layer formation side of the high thermal conductivity substrate, and It is preferable that a combustion chamber substrate on which a channel for introducing the residual hydrogen or the medium is formed is sequentially formed.

  As a medium for releasing and storing hydrogen, it is a gas or liquid at room temperature, and is composed of an organic compound or an inorganic compound. Any of these alkyl-substituted products or a mixture of a plurality of them may be used, and an aromatic compound is preferred. The fuel as these media stores hydrogen by adding hydrogen to a double bond between carbons. The hydrogen supply body after hydrogen addition releases hydrogen and returns to the original hydrogen storage body. These media are suitable carriers for hydrogen recycling.

  In the present invention, it is preferable to use a catalyst capable of storing and releasing hydrogen at a lower temperature, and the efficiency of the entire system can be improved. The catalyst includes at least one metal selected from the group consisting of nickel, palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron, which are metal catalysts, and alumina. It is preferably composed of at least one selected from the group consisting of zinc oxide, silica, zirconium oxide and diatomaceous earth, and a combination of a metal catalyst and a basic support is preferable. The basic carrier consists of alumina, zinc oxide and zirconium oxide.

  The basic support is made of a clad material with an aluminum layer on an aluminum or non-metal surface, and a high thermal conductivity substrate. The alumina film formed by anodizing the aluminum surface further expands the pores generated by anodizing. After the treatment, it is preferably formed by boehmite treatment and baking. Furthermore, it is preferable to fill at least one selected from the group consisting of zinc oxide, silica, zirconium oxide and diatomaceous earth into the pores obtained by anodization.

  The hydrogen storage / supply system of the present invention includes a fuel supply unit, a tank unit, a heat exchanger, and the hydrogen storage / supply device described above, and the heat exchanger is discharged from the fuel to be supplied and the hydrogen storage / supply unit. It is preferable to exchange heat with heated waste liquid or heated water discharged from the fuel cell.

  The fuel supply unit is a liquid transport device capable of intermittent liquid feeding, and the tank unit is a movable partition plate that separates and stores hydride as fuel and dehydrogenated product as waste liquid. It is preferable to store the waste liquid.

  A distributed power source and an automobile according to the present invention are a combination of the above-described hydrogen storage / supply system and a generator or a prime mover selected from a fuel cell, a gas turbine, and an internal combustion engine. Supply. In addition, hydrogen is stored and supplied by using the combustion heat generated when unreacted hydrogen discharged from the fuel cell and the hydrogen engine is burned.

  The hydrogen storage / supply device of the present invention has a planar shape of various patterns as a flow path on the above-described high thermal conductive substrate, and a catalyst layer, a spacer, and a hydrogen flow path layer are sequentially stacked and integrated on the top. In addition, a catalyst layer, a cooler or hydrogen separation membrane, a spacer, and a hydrogen channel layer are sequentially stacked and integrated on the upper part of the channel, and a large number of catalyst layers and through holes are arranged on the upper part in the plane. A fuel injection layer, a fuel storage layer for storing the fuel is laminated and integrated, a cooler or a hydrogen separation membrane, a catalyst layer, a fuel injection layer in which a large number of through holes are arranged in a plane, It is preferable to form a microreactor by a thin film forming process in which fuel storage layers for storing fuel are sequentially stacked and integrated.

  Furthermore, the hydrogen storage / supply device of the present invention is provided with a combustion catalyst layer for burning residual hydrogen of the fuel cell or an aromatic compound generated after the dehydrogenation reaction on the lower surface of the high thermal conductivity substrate in the hydrogen storage / supply device described above. It is preferable that a combustion chamber substrate having a flow path for introducing residual hydrogen or an aromatic compound is laminated and integrated under the lower portion. In addition, it is preferable to use hydrogen produced by electric power generated by renewable energy.

  As a hydrogen supplier, organic hydride dehydrogenation is subject to thermodynamic constraints. The dehydration reaction of organic hydride is an endothermic reaction, and the equilibrium shifts to the dehydrogenation side as the partial pressure of hydrogen and the generated aromatic hydrocarbon decreases at a high temperature. Conversely, as the partial pressure of hydrogen or aromatic hydrocarbon increases at low temperatures, the equilibrium shifts to the hydrogenation side, making it difficult to extract hydrogen. Accordingly, hydrogen storage proceeds easily even at low temperatures, but it is difficult to supply hydrogen as a dehydrogenation reaction.

  The conversion is determined by the equilibrium of dehydrogenation and hydrogenation, and at 250 ° C., the thermodynamically calculated conversion of organic hydride is about 30% for methylcyclohexane and about 50% for decalin. In order to proceed the dehydrogenation reaction at a temperature of 250 ° C., it is necessary to control the equilibrium partial pressure. A typical example is a control method using a hydrogen separation membrane, and by removing the produced hydrogen from the reaction system, the hydrogen partial pressure can be reduced and the reaction equilibrium can be shifted in the direction of hydrogen production. . However, the effect is small unless the hydrogen separation membrane and the catalyst are adjacent to each other.

  In addition, the present invention enables high-speed hydrogen generation by forming a catalyst layer directly on a high thermal conductivity substrate to improve thermal conduction in order to suppress a rapid decrease in catalyst layer temperature due to an endothermic reaction during hydrogen generation. ing. Further, the reaction can be performed in a small space, hydrogen can be efficiently separated by the adjacent hydrogen separation membrane, and the equilibrium partial pressure control can be easily performed. In addition, the catalyst is formed on the flow path of the medium reduced to the micron or nano order by coating, etc., and the catalyst is made effective by increasing the surface area / volume ratio of the catalyst layer and increasing the contact efficiency between the organic hydride and the catalyst layer. The reaction rate can be improved.

  When the flow path is large, the liquid portion is thick and the existence ratio of the composite interface is small. By reducing the flow path and increasing the surface area of the liquid, the thickness of the liquid portion is reduced and the abundance ratio of the composite interface can be increased. Moreover, the porous film formed adjacent to the catalyst surface of the catalyst layer or the catalyst layer has pores on the order of nm. As the droplet size of the liquid becomes smaller, the vapor pressure of the liquid increases, and the liquid is easily vaporized even at a low temperature. A combination of a small droplet size channel and pores on the nanometer-size catalyst surface can form a micro composite interface, and the dehydrogenation reaction can proceed efficiently even at low temperatures.

  The present invention is designed to be small and thin by sealing the whole with a sealing material. A part of the sealing material is provided with a fuel supply port and a discharge port that lead to the pattern gap formed on the substrate, and the hydride as the fuel and the dehydrogenated product as the waste liquid are separated by an external movable partition plate. It is connected to a separate fuel tank. The fuel is supplied intermittently using a pump or the like while controlling the supply amount with a mass flow meter or the like. Each member and manufacturing procedure will be described below.

  High thermal conductive substrates include ceramic materials such as aluminum nitride, silicon nitride, alumina, mullite, carbon materials such as graphite sheets, metal and clad materials such as copper, nickel, aluminum, silicon and titanium, heat resistant polymer thin films such as polyimide, and These mixtures can be used, and the value obtained by dividing the thermal conductivity by the film thickness is 1000 or more, more preferably 10,000 or more. The larger the thermal conductivity and the thinner the film thickness, the more effectively the waste heat and combustion heat can be used to heat the catalyst layer.

  The present invention uses waste heat of a high-temperature system such as a fuel cell and combustion heat of unreacted gas, and can transfer the heat to the catalyst layer faster. In particular, the dehydrogenation reaction is an endothermic reaction. As the reaction proceeds, the temperature of the catalyst decreases and the reaction rate decreases. However, the use of the above-described high thermal conductive substrate can prevent the catalyst temperature from decreasing.

In particular, the case of pattern formation by a nanoprint process will be described below. For example, Si, SiO ₂ , SiC, Fe, Al, Al ₂ O ₃ etc. with fine irregularities on the surface are used as a mold, and the shape is transferred by pressing it on a resin thin film, and resin protrusions Can be produced. A photolithography technique and an etching technique generally used in a semiconductor manufacturing process can be applied to the uneven processing of the mold. Examples of the material for the resin thin film include thermoplastic or photocurable resins such as cycloolefin polymer, polymethyl methacrylate, polystyrene, polycarbonate, and polypropylene. The resin protrusion produced by the nanoprint process has a diameter or side of 0.01 to 100 μm and a height of 0.5 to 100 μm. A catalyst carrier can be formed on the surface of fine resin protrusions by a sol-gel method. Thereafter, a nanoscale Ni pattern can be formed by electroless Ni plating or the like. Finally, the resin is dissolved and removed, and a catalyst layer is prepared by supporting a catalyst metal on a catalyst carrier. By using the Ni pattern as a heater, the catalyst layer can be directly heated, and a decrease in the catalyst temperature can be prevented.

  After forming the catalyst carrier, Pd and Ag layers are formed on the surface of the catalyst carrier by electroless plating. Finally, the resin is dissolved and removed, and the catalyst metal is supported on the catalyst carrier, thereby separating the catalyst layer and hydrogen. A layer structure with adjacent film layers can be formed. The partial pressure of hydrogen generated by the reaction can be reduced, and as a result, the reaction rate can be improved. In addition, the Pd-Ag film produced by electroless plating or sputtering is deposited conformally with respect to the concavo-convex shape, and the concavo-convex shape is maintained. The hydrogen separation membrane side can be used as a hydrogen circulation port.

  A nanoscale Ni pattern can be formed on the mold used for nanoprinting by electroless Ni plating or the like. A catalyst layer can be formed on the formed pattern surface in the same manner as described above.

  Next, the catalyst layer will be described. The catalyst layer may be formed directly on the aforementioned pattern or may be formed on the hydrogen separation membrane side. In any case, the catalyst layer is composed of a metal catalyst and a metal catalyst support material, and the metal material includes Ni, Pd, Pt, Rh, Ir, Re, Ru, Mo, W, V, Os, Cr, Co, Fe Such metals and their alloy catalysts can be used. The method for producing the catalyst material is not particularly limited, such as a coprecipitation method or a thermal decomposition method.

  As the catalyst support material, activated carbon, carbon nanotubes, silica, alumina, alumina silicate such as zeolite, and the like can be used. In the case of a dehydrogenation reaction at 200 ° C. or lower, basic oxides such as alumina, zinc oxide, silica, zirconium oxide and diatomaceous earth can be used. Moreover, what compounded them can be used. The catalyst carrier can be formed by a solution process such as a sol-gel method, plating, or anodization, or a dry process such as a vapor deposition method, a sputtering method, or a CVD method.

  When using a clad material with an aluminum layer on an aluminum or non-aluminum surface, a porous alumina produced by anodization on the aluminum surface can be directly produced, and the high thermal conductivity substrate and the catalyst carrier are in close contact. And heat conductivity are favorable and more preferable. After anodizing the aluminum surface and then enlarging the pores produced by anodization, boehmite treatment, when the fired film is used as a carrier, the surface area of the carrier is increased compared to the case where only anodization is performed, This is a more preferable form because the amount of catalyst supported can be increased.

  In addition, another catalyst carrier such as a basic oxide can be filled in the porous pores generated by anodic oxidation, and the acidity of the carrier surface and the adsorption ability to the fuel can be adjusted.

  Examples of the clad material provided with an aluminum layer on the non-aluminum metal surface include Mg, Cr, Mo, W, Mn, Fe, Co, Ni, Ti, Zr, V, Cu, Ag, Zn, Bi, Sn, Pb and An aluminum layer is formed on the surface of a single metal or alloy plate made of Sb or the like, a metal plywood obtained by polymerizing a plurality of metal plates, or a sponge-like metal plate, etc. by non-water plating, pressure bonding, vapor deposition, or bumping. Can be used.

  In the anodic oxidation method, for example, phosphoric acid, chromic acid, oxalic acid, sulfuric acid aqueous solution or the like can be used as the electrolytic solution, but phosphoric acid, chromic acid, or oxalic acid aqueous solution is preferable in order to avoid catalyst poisoning. The pore diameter and film thickness of the porous layer formed by anodization can be appropriately set according to conditions such as applied voltage, processing temperature, and processing time. The pore diameter is preferably 10 nm to 300 nm, and the film thickness is preferably 5 to 300 μm. The temperature of the anodizing treatment solution is preferably 0 to 50 ° C, particularly 30 to 40 ° C. The treatment time for this anodic oxidation varies depending on the treatment conditions and the film thickness to be formed. For example, when a 4% by weight oxalic acid aqueous solution is used as the electrolyte, the treatment bath temperature is 30 ° C., and the applied voltage is 40 V, the treatment time is 7 hours. By doing so, an anodized layer of 100 μm can be formed.

  The surface of the anodized film is treated with an acidic aqueous solution in which phosphoric acid or oxalic acid is dissolved, and the formed pores are enlarged, followed by boehmite treatment. For example, in the case of phosphoric acid, the concentration of the acidic aqueous solution is preferably 5 to 20% by weight, and the treatment is performed at 10 to 30 ° C. for 10 minutes to 3 hours until the pore diameter is appropriately expanded. After completion of the anodization, the pores can be expanded by immersing in an anodizing bath for a predetermined time. The boehmite treatment is performed at 50 ° C. to 200 ° C. in water having a pH of 6 or more, preferably 7 or more, dried and then fired. The treatment time of the boehmite treatment varies depending on the pH and treatment temperature, but is preferably 5 minutes or more. For example, when treating in water of pH 7, it is treated for about 2 hours. Firing is for forming γ-alumina and is performed at 300 to 550 ° C. for 0.5 to 5 hours.

  The spacer is mounted on the upper part of the catalyst layer, and when used as a hydrogen supply device, it serves as a flow layer for generated hydrogen, and when used as a hydrogen storage device, it serves as a hydrogen supply port. The spacer has a structure in which a groove is cut in a plane or a through-hole is formed in a direction perpendicular to the substrate, and a hydrogen separation membrane is provided on one side of the spacer. A porous material can also be used as the spacer material. Porous materials include ceramic materials such as aluminosilicates such as silica, alumina, and zeolite, laminated metal processed into mesh, carbon fiber, woven fibers such as alumina, heat resistant materials such as fluororesin and polyimide Can be used.

  Materials for hydrogen flow path include flow path processing such as metal materials such as stainless steel, titanium, aluminum, nickel and silicon, carbon-based materials such as glassy carbon and porous carbon, and ceramic materials such as glass, alumina and cordierite. If possible. The metal material can be produced by cutting or press molding. For carbon-based materials, sulfuric acid is poured between layers such as natural graphite, heated to 700 to 800 ° C., and then expanded, followed by press molding, artificial graphite, carbon particles, carbon nanotubes, carbon nanofibers, carbon nanohorns, etc. It can be obtained by injection-molding or compression-molding a thermosetting resin such as a phenol resin, a furan resin, or a polyimide resin and then carbonizing and firing in a vacuum or in an inert gas atmosphere.

  The hydrogen separation means separates the produced hydrogen from the medium storing hydrogen and the medium releasing hydrogen, and includes separation using a hydrogen separation membrane, adsorption separation, and cooling separation. In both cases, gaseous hydrogen and the medium are separated inside the hydrogen storage and supply device, the equilibrium state is moved in the direction of dehydrogenation, and hydrogen can be produced at a low temperature. Hydrogen separation membranes include heat-resistant polymers such as porous polyimide, alumina silicates such as zeolite, oxides such as silica, zirconia, and alumina, and Pd, Pd-Ag, V, Nb, Zr, Ta, Ni A film of hydrogen storage metal such as -Zr can be used. Also, the above materials may be used in combination, such as forming a Pd—Ag film on the surface of the porous polyimide piece. A V-based metal film is preferably used as the metal film. A film in which Mo, Co, Ni or the like is alloyed with V metal has excellent hydrogen permeation performance even at a low temperature of 250 ° C. or lower. These films are preferably made as thin as possible with a thickness of 3 μm or less because the hydrogen permeation rate decreases as the film thickness increases. In the case of using a thicker membrane, the hydrogen permeation rate can be increased by setting the pressure on the hydrogen permeation side to be lower than the pressure on the reaction side.

  These hydrogen separation membranes can be formed using film forming methods such as a rolling method, a solution method, a vapor deposition method, and a sputtering method. In the solution method, coating can be performed by a dipping method, a spin coating method, a spray method, or the like, and a fine particle dispersion or the like can also be used as the coating solution. For the metal film, a plating process can be used, and the film can be formed by electroless plating or electroplating.

  When porous polyimide is used as a hydrogen separation membrane, a porous polyimide having a skin layer on one surface and having voids or sponge-shaped pores can be used. The porous polyimide film is a film in which pores having a pore diameter of 0.01 μm or more exist uniformly throughout the film, and the evaluation of the pore diameter distributed in the film is measured by a nitrogen adsorption method or the like. The skin layer is a relatively dense layer having pores of several nm formed in the very vicinity of the surface of the porous polyimide film, and exhibits hydrogen separation ability. On the other hand, catalyst particles can also be supported in voids and sponge-like holes. As a method for supporting the catalyst in the porous pores, the porous polyimide is immersed in a catalyst dispersion or vacuumed, and then dried and fixed, or immersed in a precursor solution such as chloroplatinic acid, and then vacated with a reducing agent. There is a method of depositing particles inside the pores.

  For production of the porous polyimide, biphenyltetracarboxylic acid (sBPDA) can be used as the aromatic tetracarboxylic dianhydride, and paraphenylenediamine (PPD) and 4,4′diaminodiphenyl ether (DDE) can be used as the aromatic diamine. Examples of the solvent include N-methylpyrrolidone and Y-butyrolactone as long as they can dissolve the polymer.

  As a method for forming the porous layer, there are various film forming methods such as a wet coagulation method, a dry coagulation method, and a stretching method. The wet coagulation method is preferable because an open-cell porous membrane can be obtained. In the wet coagulation method, a film-forming stock solution (dope) in which a resin and additives are dissolved in a solvent is prepared, and this is applied (cast) on a substrate such as copper to be immersed in the coagulation solution to replace the solvent, The resin is solidified (gelled), and then the coagulation liquid and the like are removed by drying to obtain a porous layer.

  The dope in the wet coagulation method is preferably applied in a temperature range of -20 to 40 ° C. The coagulation liquid may be any one that is compatible with the solvent without dissolving the resin used. Water, alcohols such as methanol, ethanol and isopropyl alcohol, and a mixed solution thereof are used, and water is particularly often used. The temperature of the coagulation liquid at the time of immersion is not particularly limited. Preferably, it is the temperature range of 0-50 degreeC.

  The polymer concentration of the film-forming stock solution is preferably in the range of 5 to 25 parts by weight. In particular, in order to obtain a porous molded body having superior strength, the polymer concentration is 7 parts by weight or more and has a high porosity. In order to obtain a molded product, the amount is preferably 20 parts by weight or less. If the concentration is too high, the viscosity becomes too high and handling becomes difficult, and if the concentration is too low, a porous film cannot be formed.

  An inorganic substance such as lithium nitrate or an organic substance such as polyvinyl pyrrolidone can be added for controlling the pore shape and the pore diameter. The concentration of the additive is preferably 1 to 10 parts by weight in the solution. When lithium nitrate is added, the replacement speed of the solvent and the coagulating liquid is high, and a finger void structure (structure having a void in a finger shape) can be formed in the sponge structure. When an additive such as polyvinyl pyrrolidone that slows the coagulation speed is added, a porous layer having a sponge structure uniformly spread can be obtained.

  The dope is applied to a certain thickness, soaked in a coagulating liquid such as water, solidified, or left to solidify in a water vapor atmosphere, and then soaked in water. Become. After forming the porous layer, the porous layer is taken out from the coagulation liquid and dried. The drying temperature is not particularly limited. Drying at 200 ° C. or lower is desirable. The formed porous layer is finally heat-treated at 200 to 500 ° C., and the precursor (polyamic acid) is heated and closed to be polyimide.

  By the above means, a porous body having a high porosity of about 30 to 85% can be formed on a substrate such as copper. Preferably, the pore diameter is 1.0 μm or less and the porosity is 30% or more, more preferably the pore diameter is 0.5 μm or less and the porosity is 40 to 70%. Within this range, the pores are sufficiently uniformly distributed throughout the polyimide film.

  The porous polyimide membrane functions not only as a hydrogen separation membrane but also as a catalyst carrier. Catalysts can be supported in the pores of the porous membrane, and the gasified fuel and the fuel liquefied by capillary condensation coexist in the pores. Can be formed. In addition, since the skin layer functioning as a hydrogen separation membrane is adjacent, the produced hydrogen can be immediately separated to reduce the hydrogen partial pressure, and the dehydrogenation reaction can proceed efficiently.

A catalyst carrier integrated with a hydrogen separation membrane can be used. For example, a case where a clad material in which an aluminum layer is provided on the surface of a Pd—Ag metal is used will be described below. After the surface of the aluminum is processed, the entire aluminum layer is made an anodized oxide film. In order to reduce the thickness of the Al ₂ O ₃ barrier film at the Al ₂ O ₃ / Pd—Ag interface formed at that time, the electrolysis voltage is lowered in the latter half of the anodizing treatment. Subsequently, the underlying Ag—Pd metal surface is exposed by removing only the Al ₂ O ₃ barrier film. Finally, a hydrogen separation membrane integrated catalyst can be obtained by supporting Pt in an Al ₂ O ₃ membrane. Similarly, when Zr is used, a hydrogen separation membrane-integrated catalyst can be produced, Zr itself functions as a hydrogen separation membrane, and an oxide film can be formed on the Zr surface, which is a more preferable form.

  For hydrogen separation by adsorption separation, a material capable of adsorbing a hydrogen storage medium such as composite oxides such as alumina, silica, titania and zirconia, zeolite and activated carbon is used. These materials are used as a catalyst carrier, and once adsorb and separate the hydrogen storage medium produced on the metal catalyst. The adsorbed hydrogen storage medium is quickly desorbed and discharged from the reactor after hydrogen is discharged from the reactor.

  The adsorption / desorption of the hydrogen storage body is performed by a cycle by temperature or a cycle by pressure. The cycle by temperature will be described below. With the catalyst in the reactor set to a predetermined reaction temperature, a hydrogen supplier is supplied to the catalyst. The hydrogen supply body undergoes a dehydrogenation reaction on the catalyst surface, and hydrogen and a hydrogen storage body are generated. At this time, the dehydrogenation reaction is an endothermic reaction, the temperature of the catalyst is lowered, the produced hydrogen storage body is adsorbed on the catalyst carrier, and the hydrogen is discharged out of the reactor as it is and separated from the hydrogen gas. When the dehydrogenation reaction is completed, when the temperature of the catalyst returns to a predetermined temperature, the hydrogen storage body adsorbed on the catalyst carrier is desorbed and discharged out of the reactor. As described above, by utilizing the endothermic reaction of the dehydrogenation reaction, a temperature cycle can be created, and hydrogen separation can be performed by adsorption and desorption of the hydrogen storage body. In addition, since there is a time difference between the discharge of the hydrogen and the hydrogen storage body, it is preferable to inject the hydrogen supply body into the reactor by a pulse.

  The pressure cycle is performed in a state where valves are provided at the fuel injection portion of the reactor and the outlet of the reactive organism, and the timing of opening and closing of each is optimized. After the hydrogen supply body is injected into the reactor in pulses, the valves of the injection section and the discharge section are closed, the pressure inside the reactor is increased, and the hydrogen storage body is adsorbed on the catalyst carrier and separated from the hydrogen. Next, the valve inside the outlet is opened and the gas inside the reactor is discharged. At this time, a vacuum pump may be connected to forcibly discharge the adsorbate.

  The above-mentioned hydrogen separation by adsorption separates hydrogen and the hydrogen storage body by a cycle based on temperature or pressure, but it is more effective to separate the hydrogen with a hydrogen separation membrane using a hydrogen separation membrane and to separate the hydrogen storage body by adsorption. Thus, equilibrium control can be performed and low-temperature hydrogen supply can be performed. Thus, by separating hydrogen and products by adsorption, the equilibrium condition of the reaction can be set to the dehydrogenation side, and hydrogen can be efficiently generated at a low temperature.

  The hydrogen separation by cooling is a means for separating hydrogen by changing the phase of only the medium to a liquid by cooling the gaseous hydrogen heated by the heat transferred from the high thermal conductive substrate and the medium with a cooler. is there. The cooled liquid medium is supplied again to the high-temperature catalyst layer. On the other hand, hydrogen is removed from the system via the hydrogen flow path, so the equilibrium moves in the direction of the dehydrogenation reaction, and hydrogen is efficiently generated at a low temperature. It becomes possible to do.

  In the present invention, a plurality of hydrogen storage / supply devices in which the above-described members are stacked and integrated can be collectively formed on a large area scale and then cut into a single hydrogen storage / supply device. It is.

  The outer periphery of the hydrogen storage / supply device needs to be sealed. When sealing, there are a method in which each member is sandwiched between metal plates and the periphery is bolted and a method in which sealing is performed with a sealing material. As the sealing material, metal, ceramics, glass, a resin material, or the like can be used as long as hydrogen or fuel liquid can be prevented from leaking. Sealing can be performed using a coating or a melting method. Alternatively, when a material used in circuit mounting such as sand is used, a mounting process such as reflow can be used.

  The hydrogen storage / supply device of the present invention is designed to be small and thin by sealing the whole with a sealing material. Part of the sealing material is provided with a fuel supply port and a discharge port leading to the fuel storage layer, and a fuel tank that separates and stores the hydride as fuel and the dehydrogenated product as waste by an external movable partition plate It is connected to. The fuel is supplied using a pump or the like while controlling the supply amount with a mass flow meter or the like.

  The supply of the medium to the hydrogen storage / supply device may be carried out by directly injecting it with a pump and piping outside the reactor, or a hydrogen supply unit may be built in the present device. When the medium injection part is built in, there are a method of injecting from the same plane as the catalyst layer and a method of injecting in the direction perpendicular to the catalyst layer. When injecting from the same plane, the injection portion is directly formed on the substrate on which the catalyst layer is formed. Any method that can uniformly inject in a plane may be used. A method is used in which the medium can be supplied uniformly, such as injecting at a wide angle in the form of a spray nozzle, or forming and injecting many injection ports. On the other hand, in the case of injecting in the vertical direction, the substrate having many holes is used as an injection part and laminated on the catalyst layer. If necessary, a spacer may be inserted between the injection part and the catalyst layer.

  In the case of injecting in the vertical direction, the fuel supplied from the fuel tank can be introduced into the fuel storage layer in the hydrogen storage / supply device and temporarily stored. The fuel storage layer is always filled with fuel, and if fuel is further supplied to the fuel storage layer by a pressure pump, the fuel that cannot be stored in the storage layer, that is, the fuel supplied to the storage layer is fueled. Via the through hole of the injection layer, it is uniformly dropped or injected and supplied into the surface of the catalyst layer arranged in the lower layer. The through hole has a reduced shape from the upper surface to the lower surface, and functions as a spray nozzle. The hole diameter on the lower surface is preferably 0.3 to 300 μm, and the smaller the nozzle diameter, the finer droplets can be obtained and the fuel can be uniformly supplied to the catalyst.

  Materials used for the fuel injection layer include thermosetting resins such as polyimide, fluorinated resin, and silicon resin that are excellent in chemical resistance and heat resistance, and glass such as silica, alumina, mullite, and cordierite. Ceramics, copper, aluminum, iron and the like can be used. When the through hole is formed, it can be formed by mechanical processing such as etching or sand blasting. For example, when forming a through hole in copper, after forming a resist having a large number of holes on the copper surface by photolithography, spray etching is performed for a predetermined time with an iron chloride solution or the like only on the resist-formed surface. Since the etching progresses isotropically, the copper cross section after the etching process has an elliptical shape and is reduced from the etched surface to the back surface. Similarly, when forming a through hole in glass, a through hole in which the hole is reduced can be formed by forming a resist on the glass surface and sandblasting for a predetermined time.

  The catalyst layer disposed below the fuel injection layer is a catalyst in which a recess is provided in the catalyst layer corresponding to each hole of the through hole, and the fuel supplied from each through hole is present in a minute space of the corresponding recess. By making it react by, reaction can be advanced more efficiently.

  When the hydrogen storage / supply device of the present invention is combined with a fuel cell or the like, it is appropriately installed at a location where waste heat can be effectively used. At that time, the catalyst can be efficiently heated by placing the high thermal conductivity substrate of the hydrogen storage / supply device in close contact with the portion where the waste heat of the fuel cell is generated. Specifically, for example, when combined with a polymer electrolyte fuel cell, the heat exchanger housing surface that exchanges heat of waste heat generated from the stack is an example of the portion where waste heat is generated. In household fuel cells, water is distributed to heat exchangers for the production of hot water, but the organic hydride, which is the fuel, is also distributed to cool the fuel cell stack and protect the electrolyte membrane from heat damage. Can be preheated. For humidification of the air supplied to the fuel cell, use of hot water obtained by heat exchange or water vapor generated by power generation is used. In a fuel cell for automobiles, water vapor generated by power generation is sufficient to humidify the air supplied to the fuel cell. Therefore, fuel is circulated through the heat exchanger to preheat the fuel. Further, as a part where waste heat is generated, in the case of an automobile fuel cell, a compressor used for supplying air to the cathode electrode can be mentioned.

  When a combustion chamber layer for burning unreacted hydrogen is provided on the lower surface of the high thermal conductive substrate, it is not particularly necessary to place it in close contact with the fuel cell. For example, in the case of a conventional fuel gas for home use by city gas reforming, the hydrogen utilization rate of the fuel cell is 80%, and the rest is burned and used as a heat source of about 600 ° C. for the reformer. When the hydrogen storage / supply device of the present invention is used, the reaction temperature required for hydrogen generation is lower than that of the reformer, so that the hydrogen utilization efficiency of the fuel cell can be improved.

  A conventional hydrogen supply device requires many accessories such as a sprayer, cylinder, piston, and cooler. The overall size of the device is larger, and a heater is used. However, since the overall efficiency of the hydrogen storage / supply device of the present invention has a microreactor structure and is small and thin, it is exhausted from its waste heat or from a fuel cell, a hydrogen engine, etc. Combustion heat obtained by burning unreacted hydrogen gas can be used effectively and is highly efficient.

  The present invention can produce a power generation system connected to a fuel cell, etc., can perform a dehydrogenation reaction of organic hydride at 250 ° C. or less, can be downsized, and waste heat of fuel cell or unreacted If the combustion heat obtained by burning the hydrogen gas is used, the load on the heater to be heated can be reduced, so that the system efficiency can be improved. The waste heat temperature of phosphoric acid type fuel cells is 150 to 220 ° C, and the waste heat temperature of solid polymer fuel cells is 80 to 150 ° C. Utilizing the waste heat or combustion heat obtained by burning unreacted gas Thus, the hydrogen storage / supply device can be operated efficiently.

  The hydrogenation reaction to aromatic hydrocarbons as hydrogen storage is an exothermic reaction, and it is advantageous that the hydrogen partial pressure is high. The hydrogenation reaction to aromatic hydrocarbons is easier than the dehydrogenation reaction, and hydrogen can be efficiently stored using the apparatus of the present invention.

The waste heat that can be used in the hydrogen storage / supply device is not limited to the fuel cell, and waste heat from high-temperature systems such as turbines and engines can also be used. The waste heat of the turbine and engine is 300 ° C. or higher, and hydrogen storage and supply can be performed without using a heater. In addition to the fuel cell, the hydrogen obtained from the hydrogen supply device may be generated by, for example, burning hydrogen and using a turbine or an engine. Furthermore, the present hydrogen storage / supply system can be used in a large-scale power generation system such as a conventional thermal power plant or nuclear power plant. In addition, by constructing the power generation system as described above, energy efficiency is improved, CO ₂ can be reduced, and global warming can be prevented.

  When combining hydrogen storage / supply devices with solid oxide fuel cells and molten carbonate fuel cells, the waste heat temperatures obtained are 1000 ° C and 600-700 ° C, respectively. In terms of material and reaction efficiency, it is difficult. That is, in terms of material, sealing is incomplete due to differences in heat-resistant temperature and thermal expansion of each member, which is not preferable in terms of fuel and hydrogen leakage. In terms of reaction efficiency, if the reaction temperature is too high, the fuel is vaporized, and the gas-liquid solid composite interface cannot be efficiently used, and there are side reactions such as thermal decomposition of the fuel and carbon deposition on the catalyst layer. It is not preferable in that it progresses. Therefore, when combining a hydrogen storage / supply device with a solid oxide fuel cell or a molten carbonate fuel cell, use a heater by placing the hydrogen supply device in an appropriate location or by installing a heat exchanger. Without using, it is preferable to utilize the waste heat lowered to a desired temperature. When combined with a solid oxide fuel cell or a molten carbonate fuel cell, only the waste heat is sufficient, but when a combustion chamber layer for burning unreacted hydrogen is provided on the lower surface of the high thermal conductive substrate, As in the case of the molecular fuel cell, it is not particularly necessary to place it in close contact with the fuel cell.

  ADVANTAGE OF THE INVENTION According to this invention, the storage and supply of hydrogen at low temperature is possible, and a small and efficient hydrogen storage / supply device, its system, a distributed power source using the system, and an automobile can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail by way of specific examples, but the present invention is not limited to the following examples.

  FIG. 1 is a schematic diagram showing a hydrogen storage / supply system using a home-use distributed power source and a hydrogen vehicle as examples of grid power and renewable power generation according to the present invention. The hydrogen storage / supply device of this embodiment functions as a part of this system. The house 1000 includes a solar cell 1001 installed on a roof or the like, a system power 1002, a water electrolysis device 1003, a hydrogen storage / supply device 1004, and a fuel cell system 1005. The automobile 1008 is equipped with a hydrogen storage / supply device 1009 and a fuel cell system 1010. Electricity generated by renewable energy power generation such as the solar cell 1001 is converted into alternating current via the inverter 1006. The converted electricity is used in household electrical equipment 1007 or not used in electrical equipment 1007, and when surplus power is generated, the converted electricity is supplied to water electrolysis device 1003.

  In the water electrolysis apparatus 1003, hydrogen and oxygen are generated by electrolysis of water. The generated hydrogen is sent to the hydrogen storage / supply device 1004, and the hydrogenated aromatic compound dehydrogenated by the hydrogen storage / supply device 1004 can be hydrogenated and regenerated into fuel.

Electric power can be divided into peak power corresponding to daytime load fluctuations and base power for supplying constant basic power day and night. The power generation system shown in FIG. 1 is a power generation system that supplies peak power corresponding to daytime load fluctuations, and base power uses grid power 1002 of an electric power company or the like. The grid power 1002 also preferably uses renewable energy to reduce CO ₂ . Not only solar power generation but also many renewable energies such as wind power, geothermal, ocean temperature difference, tidal power, and biomass can be used. Solar power can only be generated during the day, while other renewable energy can be generated at night. In the case of a thermal power plant or the like, power generation is temporarily stopped in order to reduce fuel consumption at night, because the amount of power used is drastically reduced compared to the daytime. On the other hand, since renewable energy does not incur fuel costs, there is no problem even if power is supplied as long as power can be generated at night. However, since there is a high possibility of surplus power at night when the usage is low, hydrogen is produced using the generated surplus power for water electrolysis, and organic hydride is produced using the hydrogen storage / supply devices 1004 and 1009 of the present invention. Stores hydrogen as Hydrogen stored as an organic hydride is provided as fuel for the fuel cell shown in FIG. Power generation from renewable energy during the day is actively supplied as the peak power of the system.

  The automobile 1008 supplies the hydrogen generated by the hydrogen storage / supply device 1009 from the organic hydride as fuel to the fuel cell system 1010, generates electric power, and runs by a motor. The automobile 1008 also includes a water electrolysis device 1003 as in the case of a household distributed power source, and can start up the hydrogen supply / storage device 1009 with nighttime power to store hydrogen as an organic hydride.

  2 is an external view of the hydrogen storage / supply device of the present invention, FIG. 3 is a perspective view showing the internal structure of FIG. 2, and FIG. 4 is a cross-sectional view showing the internal structure. The hydrogen storage / supply device 1 of the present example is a high thermal conductive substrate 2 made of sintered AlN (thermal conductivity: 250 W / mK), a Cu channel protrusion 3, and a catalyst layer made of 5 wt% Pt / alumina catalyst. 4, a medium flow path 5 formed by a gap between protrusions, a spacer 6, a hydrogen flow path 8, a cooler 13, and a sealing material 9. A part of the sealing material 9 is provided with a fuel supply port 10, a discharge port 11, and a hydrogen flow port 12 that lead to a pattern gap formed on the high thermal conductive substrate 2, and hydrogen that is a fuel in a movable partition plate. It is connected to a fuel tank that separates and stores the dehydrogenated product and the dehydrogenated product as waste liquid (not shown). The medium serving as the fuel was supplied using a pressurizing pump capable of intermittent control while controlling the flow rate with a mass flow meter.

  The organic hydride fuel as a medium passes through the medium flow path 5 in the recess, and a dehydrogenation reaction proceeds while contacting the catalyst layer 4 formed on the pattern surface, thereby generating hydrogen. The generated hydrogen is separated from the fuel and the generated aromatic hydrocarbon by the cooler 13, passes through the hydrogen flow path 8, passes through the hydrogen circulation port 12, and is supplied to an external fuel cell or the like. In the case of hydrogen storage, hydrogen passes through the hydrogen flow port 12, contacts the catalyst layer 4 from the hydrogen flow path 8 through the spacer 6, hydrogenates the aromatic hydrocarbon compound supplied from the flow path 5, and exits from the flow path 5 outlet. Organic hydride can be obtained.

  The manufacturing method will be described below. A Cu film having a thickness of 100 μm was formed on a 50 mm × 50 mm, 1 mm thick AlN high thermal conductive substrate 2 by sputtering and electroplating, and then a channel protrusion 3 was formed by etching. In order to prevent corrosion of the channel protrusion 3, the surface thereof was plated with gold. Subsequently, a Pt particle mixed alumina sol was applied thereon and baked at 450 ° C. for 1 hour to form a catalyst layer 4. As the flow path protrusion 3, a protrusion having a straight shape from the fuel supply port to the discharge port having a pattern width and a gap of both 100 μm and a height of 20 μm was formed. The thickness of the catalyst layer 4 is 0.5 μm, and has an uneven shape reflecting the shape of the flow path protrusion 3. On the other hand, an alumina ceramic having a thickness of 100 μm was used as the spacer 6. These are laminated with the uneven SUS304 / Ti hydrogen flow path 8, the substrate on which the catalyst layer 4 is formed, and the cooler 13, and the fuel supply port 10, the discharge port 11, and the hydrogen flow port 12 are provided. Was sealed with a glass sealing material 9. The fuel supply port 10 and the discharge port 11 communicate with each other on the same plane as shown in FIG.

  The hydrogen storage / supply device of this example has a size of 70 mm × 70 mm and a thickness of 7 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the high thermal conductive substrate 2 side was in contact with it, and was heated to 250 ° C. 1-Methyldecahydronaphthalene was used as the fuel and was supplied into the apparatus to perform a dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 25 seconds, which was 18 L / min per gram of Pt. As described above, in the hydrogen storage / supply device of this example, the catalyst was efficiently heated and the reaction proceeded by configuring the external heat source to the catalyst layer with the high thermal conductivity substrate. In the present embodiment, the fuel flow path 5 has a straight shape, but may have a planar shape shown in FIG.

  FIG. 5 is a plan view showing a planar structure composed of various patterns of the medium flow path. Various patterns are formed as the medium flow path 5 on the surface of the high thermal conductive substrate 2. Since the pattern gap is used as a flow path for fuel or the like, the pattern is designed to be a continuous pattern from the fuel inlet to the outlet. There are no particular limitations on the number of fuel inlets and outlets, as long as an appropriate flow rate can be supplied. Preferably, the plane pattern of the medium flow path 5 includes at least one pattern of a fuel injection part 2003, a reaction part 2004, and a diffusion part 2005 as shown in FIG. A catalyst is applied to the surface. In the drawing, the portions shown in black are protrusions, and the white portions are the medium flow paths 5.

  In addition, the pattern of the reaction unit 2004 is provided with a pattern having a protrusion that becomes a barrier when fuel flows from the upstream side near the fuel supply port toward the downstream side near the waste liquid discharge port, and some fuel contacts the barrier. Then, the catalytic reaction proceeds, and a part of the process is repeated in which the fuel passes through the slit between the barriers and comes into contact with the next barrier. The fuel efficiently contacts the catalyst surface within the catalyst layer surface, thereby improving the reaction efficiency and increasing the hydrogen supply rate. The optimum pattern is designed so that the fuel is uniformly supplied in the plane by adjusting the flow resistance of the liquid and changing the barrier pattern length according to the properties such as the boiling point and viscosity of the fuel to be used.

  The barrier pattern length indicates the length of the pattern in the in-plane vertical direction with respect to the fuel flow direction. In the case of using a fuel having a large liquid flow resistance, the barrier pattern length is made small, and the pattern shape is designed so that the fuel is easily supplied downstream as shown in FIG. The barrier pattern shape is not particularly limited, and examples thereof include a square shape and a circular shape. Moreover, you may arrange | position combining the barrier pattern of a different pattern length, and the barrier pattern of a different shape from upstream to downstream. Further, in the case of a rectangular barrier pattern, the barrier pattern may be arranged at an angle with respect to the fuel flow direction. If the barrier height is large, the catalyst supporting area can be increased. In addition, since heat transfer is slower in the upper part of the barrier than in the lower part, heat distribution occurs in the barrier. As a result, a large number of gas-liquid solid composite interfaces are formed, and the reaction efficiency can be improved.

  In the pattern formation, mechanical processing such as cutting and pressing, and soft lithography such as etching, plating, and nanoprinting process can be used to form a finer pattern. Further, a dry process such as vapor deposition or sputtering may be used.

  The pattern material is not particularly limited, but a material suitable for etching and plating processes such as Ni, Cr and Cu can be easily manufactured and is preferable. Furthermore, corrosion of the produced pattern can be prevented by applying Au plating thereon.

  Further, a pattern having protrusions may be used as the heater wire. For example, in the case of a hydrogen storage / supply device integrated with a fuel cell, the catalyst can be heated by applying an electric current to the heater wire from the outside at the start-up when no waste heat is generated.

  FIG. 6 is a diagram showing the shape of the fuel injection part of the hydrogen supply / storage device of this embodiment. The fuel injection part 2003 is formed in a spray nozzle shape as shown in FIG. 6, and a nozzle having a nozzle diameter 2001 of 1 to 500 μm and a spray angle 2002 of 0 to 85 ° can be used.

  As described above, according to this embodiment, it is possible to provide a small and efficient hydrogen storage / supply device and system for storing hydrogen and supplying hydrogen to a distributed power source such as an automobile or a household fuel cell.

Comparative Example 1

  FIG. 7 is an external view of the hydrogen storage / supply device of this comparative example. FIG. 8 is a cross-sectional view showing the internal structure. A hydrogen storage / supply device 501 using a stainless steel pipe 511 having a diameter of 15 mm, a length of 50 mm, and a plate thickness of 2 mm was produced. As shown in FIG. 8, the inside of the device is a honeycomb structure 512, a palladium tube 502 having a diameter of 10 mm × a length of 50 mm and a thickness of 80 μm, and 5 g% Pt / activated carbon catalyst 10 g applied inside the palladium tube 502, The catalyst layer 503 is provided. A fuel supply port 504, a fuel discharge port 505, and a hydrogen extraction port 506 were connected to the hydrogen storage / supply device 501. A fuel tank 507 and a waste liquid tank 508 were connected to the fuel supply port 504 and the fuel discharge port 505, respectively. The fuel was fed by a pump 509. A heater (not shown) prepared with the hydrogen storage / supply device 501 as an external heat source was installed around it and heated to 250 ° C. Methylcyclohexane was supplied as the fuel, and methylcyclohexane was dehydrogenated. As a result, the amount of hydrogen generated was 2 L / min per gram of Pt. The hydrogen storage / supply device 501 has a wide fuel flow path, insufficient gasification of fuel, a gas-liquid solid composite interface is not well formed on the catalyst layer surface, and a hydrogen separation membrane is not adjacent to the catalyst layer. Since it was provided on the outer periphery and hydrogen could not be immediately separated to reduce the hydrogen partial pressure, the conversion rate of the dehydrogenation reaction was low.

  FIG. 9 is an external view of the hydrogen storage / supply device of the present embodiment, FIG. 10 is its internal structure, and FIG. 11 is its sectional view. This embodiment is an example in which a hydrogen separation membrane is used as the hydrogen separation means of the hydrogen storage / supply device used in the hydrogen storage / supply system of the first embodiment. Similar to the first embodiment, the hydrogen storage / supply device 21 of the present embodiment includes a high thermal conductive substrate 22, a Cu pattern 23, a catalyst layer 24, a fuel passage 25 in the pattern gap, a spacer 26, and a hydrogen composed of a Pd—Ag film. A separation membrane 27, a hydrogen channel 28, and a sealing material 29 are included. A part of the sealing material is provided with a fuel supply port 30, a discharge port 31, and a hydrogen circulation port 32 that lead to a pattern gap formed on the substrate, and a hydride that is a fuel by an external movable partition plate and It is connected to a fuel tank that separates and stores the dehydrogenated product that is a waste liquid (not shown). The supply of fuel is the same as in Example 1, and the organic hydride fuel passes through the flow path 25 of the recesses between the patterns, and the dehydrogenation reaction proceeds while contacting the catalyst layer 24 to generate hydrogen. The generated hydrogen is separated from the fuel and the generated aromatic hydrocarbon through the hydrogen separation membrane 27, and then pure hydrogen is discharged to the spacer 26, passes through the hydrogen flow path 28, passes through the hydrogen circulation port 32, and is externally supplied. Supplied to. In the case of hydrogen storage, hydrogen passes through the hydrogen flow port 32, contacts the catalyst layer 24 from the hydrogen flow path 28 through the spacer 26 and the hydrogen separation membrane 27, and hydrogenates the aromatic hydrocarbon compound supplied from the flow path 25. Organic hydride can be obtained from the outlet of the channel 25.

FIG. 12 is a flowchart showing a method for manufacturing the hydrogen storage / supply device of this embodiment. A Cu film having a thickness of 100 μm was formed on a 50 × 50 mm ² , 1 mm thick AlN high thermal conductive substrate 22 by sputtering and electroplating, and then a metal pattern 23 was formed by etching. The surface was plated with gold to prevent corrosion of the pattern. Subsequently, a Pt particle mixed alumina sol was applied thereon and baked at 450 ° C. for 1 hour to form a catalyst layer 24. As a pattern, a straight line from the fuel supply port to the discharge port having a pattern width and a gap of 100 μm was formed. The thickness of the catalyst layer 24 is 0.5 μm, and has an uneven shape reflecting the shape of the pattern 23. On the other hand, a 100 μm thick alumina ceramic was used as the spacer 26, and a 2 μm Pd—Ag alloy film was formed on one side thereof by sputtering to form a hydrogen separation film 27. These are laminated with the uneven SUS304 / Ti hydrogen flow path 28 and the substrate on which the catalyst layer is formed, and a fuel supply port 30, a discharge port 31 and a hydrogen flow port 32 are provided, and the other outer periphery is sealed with glass. Material 29.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 4 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the AlN high thermal conductivity substrate side was in contact with it and heated to 250 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 20 L / min of hydrogen per gram of Pt. Thus, it can be said that the hydrogen storage / supply device of the present invention can be efficiently utilized by efficiently heating the catalyst by configuring the external heat source to the catalyst layer with the high thermal conductivity substrate. In addition, by providing a hydrogen separation membrane, the cooler can be removed, the configuration of the hydrogen supply device can be simplified, and the generated hydrogen can be promptly separated, resulting in de-equilibrium in the hydrogenation direction, resulting in efficiency even at low temperatures. The effect that the reaction proceeds well was obtained. The same effect was obtained even when Ni-Zr amorphous alloy, Zr metal, or porous polyimide with sputtered Ag-Pd metal on the surface was used as the hydrogen separation membrane. This embodiment also has the same effect as that of the first embodiment.

  The present embodiment is a hydrogen storage / supply device manufactured by changing the medium flow path width of the second embodiment. Using a hydrogen storage / supply device manufactured under each condition, observation was made on whether or not the fuel liquid could be fed and the hydrogen production rate was measured. When the medium flow path width was 0.01 to 10 μm, the nanoprint process was used. When the medium flow width was 50 to 5000 μm, the photolithographic process was used as in Example 2. The nanoprint process is described below. A thin film made of polymethyl methacrylate having a molecular weight of 2500 was applied on a silicon substrate by spin coating. The thickness of the thin film is 5 μm. Next, each of the silicon molds having irregularities at intervals of 0.01, 0.05, 0.1, and 10 μm on the surface was pressed into a thin film. The mold was pulled up vertically to form resin protrusions. The resin protrusion pattern was a straight line from the fuel supply port 10 to the discharge port 11. The height of the protrusion was 10 μm. Subsequently, electroless copper plating, electrolytic copper plating, and gold plating were applied to the surface of the fine resin protrusions, and the resin protrusions were dissolved and removed. Pt particle mixed alumina sol was applied on the surface of the prepared copper flow path pattern. Finally, the catalyst layer was formed by baking at 450 degreeC for 1 hour.

  Table 1 shows the results of measuring whether or not the liquid can be fed and the hydrogen generation rate of the hydrogen storage and supply device manufactured by changing the width of the medium flow path. The hydrogen production rate was measured at 250 ° C. by supplying 1-methyldecahydronaphthalene as a fuel into the apparatus. The fuel supply pulse interval was 20 seconds. When the medium flow path width was 0.01 and 0.05 μm, the liquid could not be fed when the fuel was supplied. When the internal flow path pattern was observed, it was considered that the pattern was broken and the flow path resistance was high, and the liquid could not be fed. In the case of 0.1 μm or more, the liquid can be fed and the hydrogen generation rate was measured. As a result, when the medium flow path width was 10 μm, the maximum hydrogen generation rate was 23 L / min per 1 g of Pt. When the medium flow path width was increased to 2000 and 5000 μm, the hydrogen generation rate was significantly reduced. The area where the convex part of the flow path pattern is in contact with the hydrogen separation membrane is too large, hindering the mass transfer of fuel to the catalyst layer existing in the convex part and the rapid mass transfer of the generated hydrogen. This is probably because the separation membrane cannot be used effectively. This embodiment also has the same effect as that of the first embodiment.

This example uses a 20 μm-thick polyimide sheet (thermal conductivity: 0.6 W / mK) in place of AlN of Example 2 as a high thermal conductive substrate, and produced hydrogen storage according to the manufacturing method of Example 2. -It is a supply device. This hydrogen storage / supply device has a size of 70 × 70 mm ² and a thickness of 3 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the high thermal conductive substrate side was in contact with it and heated to 250 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 25 seconds, and it was possible to continuously generate 17 L / min of hydrogen per gram of Pt. Since the thermal conductivity is slightly smaller than in Example 2, it is necessary to set the pulse interval longer, and as a result, the hydrogen generation rate is reduced, but the catalyst is efficiently heated, and the generated hydrogen is reduced. Separation was possible quickly, and the reaction was de-equilibrated in the hydrogenation direction, and the reaction proceeded efficiently even at low temperatures.

  The present example is a hydrogen storage / supply device manufactured using the 100 μm graphite sheet (500 W / mK) instead of the AlN of Example 2 as a high thermal conductive substrate according to the manufacturing method of Example 2. This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 3 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the high thermal conductive substrate side was in contact with it and heated to 250 ° C. Methylcyclohexane was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 10 seconds, and it was possible to continuously generate 19 L / min of hydrogen per gram of Pt. Thus, in the hydrogen storage / supply device of the present invention, the catalyst is efficiently heated and the generated hydrogen can be promptly separated by configuring the external heat source to the catalyst layer with a high thermal conductive thin film. The effect of allowing the reaction to proceed efficiently even at low temperatures was obtained by de-equilibrium in the hydrogenation direction.

FIG. 13 is a perspective view of the hydrogen storage / supply device of the present embodiment, and FIG. 14 is a cross-sectional view showing its internal structure.
This embodiment is an example in which the fuel injection port is formed on the same plane. A 1 mm thick pure aluminum (thermal conductivity: 250 W / mK) high thermal conductive substrate 62 is used instead of AlN in the second embodiment, and a metal pattern is formed. As shown in FIG. 5B, a fuel injection part having a spray shape, a reaction part having a barrier pattern, and a diffusion part as shown in FIG.

  FIG. 15 is a flowchart showing a method for manufacturing the hydrogen storage / supply device according to the present embodiment based on the manufacturing method according to the second embodiment. Patterning formation on the aluminum surface was performed by the following procedure. The aluminum substrate 62 was immersed in a 4 wt% NaOH aqueous solution to remove the natural oxide layer, and then a resist was applied. Next, after developing using the photomask which has a spray nozzle shape and a barrier pattern, it developed. Subsequently, etching was performed with an FeCl 3 / HCl aqueous solution, and finally, post-treatment was performed using an aqueous NaOH solution and 10 wt% HNO 3. As the projection pattern 63 made of a metal, 100 stages of 100 μm × 300 μm arranged at intervals of 300 μm were formed. The spray nozzle diameter and angle were 300 μm and 45 °, respectively. The fuel injection part, the reaction part, and the diffusion part all had a pattern thickness of 100 μm.

  The hydrogen storage / supply device 61 has a size of 70 mm × 70 mm and a thickness of 4 mm. This apparatus was placed on a ceramic heater prepared as an external heat source so that the high thermal conductive substrate 62 side was in contact with it, and heated to 250 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 21 L / min of hydrogen per gram of Pt. As described above, in the hydrogen storage / supply device of the present invention, the catalyst is efficiently heated by configuring the external heat source to the catalyst layer with the high thermal conductive thin film. Further, the presence of barriers in the spray nozzle-shaped fuel injection part and the catalyst reaction part allowed the supplied 1-methyldecahydronaphthalene to uniformly and efficiently contact the catalyst layer, thereby improving the frequency factor. In addition, the generated hydrogen can be promptly separated, and the hydrogen is de-equilibrated in the direction of hydrogenation, so that the reaction proceeds efficiently even at low temperatures.

  In this example, a 1 mm thick pure aluminum plate (thermal conductivity: 250 W / mK) was used as a high thermal conductive substrate, and after forming flow path protrusions having a planar pattern made of the same metal as in Example 6, the aluminum surface was formed. This is a hydrogen storage and supply device that has been anodized, expanded in pore size, and boehmite treated. It produced according to the manufacturing method of Example 6. Anodization, pore enlargement, and boehmite treatment on the aluminum surface were performed in the following procedure.

  The patterned aluminum substrate was electropolished in an 85 wt% phosphoric acid aqueous solution at 60 ° C. and a current density of 20 A / dm 2 for 4 minutes. Next, it was anodized in a 4 wt% oxalic acid aqueous solution at 30 ° C. and an applied voltage of 40 V for 7 hours to form a 100 μm porous alumina layer only on the patterned surface. Next, the treated substrate was immersed in a 5 wt% phosphoric acid aqueous solution at 30 ° C. for 30 minutes to enlarge the pores. Next, as boehmite treatment, it was immersed in boiling water for 2 hours and then baked at 450 ° C. Finally, the catalyst was supported using 5 wt% platinum colloid made of Tanaka Kikinzoku.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 4 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the high thermal conductive substrate side was in contact with it and heated to 250 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 22 L / min of hydrogen per gram of Pt.

  In the hydrogen storage / supply device of this example, the catalyst was efficiently heated by configuring the external heat source to the catalyst layer with a high thermal conductive thin film. Further, the presence of barriers in the spray nozzle-shaped fuel injection part and the catalyst reaction part allowed the supplied 1-methyldecahydronaphthalene to uniformly and efficiently contact the catalyst layer, thereby improving the frequency factor. In addition, since a large amount of platinum catalyst could be supported in a large number of pores formed on the surface of the barrier pattern by a series of anodizing treatments, the reaction rate was improved. In addition, the generated hydrogen can be promptly separated, and the hydrogen is de-equilibrated in the direction of hydrogenation, so that the reaction proceeds efficiently even at low temperatures.

  In addition, the hydrogen storage / supply device of this example was provided with valves at the fuel inlet and outlet to vary the pressure. In the pressure cycle, the hydrogen supply body is pulsed into the reactor, the valves in the injection section and the discharge section are closed, the pressure in the reactor is increased, and then the valve in the discharge port is opened and the gas in the reactor is opened. Was discharged. As a result, it was possible to continuously generate 30 L / min of hydrogen per gram of Pt. After the hydrogen supply body is injected into the reactor in pulses, the valves of the injection section and the discharge section are closed, the pressure inside the reactor is increased, and the hydrogen storage body is adsorbed on the catalyst carrier and separated from the hydrogen. Further, the hydrogen partial pressure inside the reactor is increased, the hydrogen permeation rate of the hydrogen separation membrane is increased, and the hydrogen separation capability can be improved. Thus, by the pressure fluctuation inside the reactor, the separation efficiency between hydrogen and the hydrogen storage body is improved, and the hydrogen production rate can be further improved.

  In this example, a pure aluminum plate (thermal conductivity: 250 W / mK) having a thickness of 1 mm was used as a high thermal conductive substrate, and after forming channel protrusions having a planar pattern as in Example 6, the aluminum surface was anodized. This is a hydrogen storage / supply device in which pore expansion and boehmite treatment are performed, and another basic oxide is filled in the pores. It produced according to the manufacturing method of Example 7. The filling of the basic oxide into the pores formed by anodic oxidation was performed according to the following procedure. Aluminum isopropoxide (20 g) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in hot water (80 g) at 80 ° C., and a predetermined amount of zinc nitrate manufactured by Wako Pure Chemical Industries, Ltd. was added to prepare a sol. After applying the sol to a boehmite-treated substrate, nitric acid (5 mL) was added dropwise to gelate, dried at 120 ° C. for 5 hours, and treated at 450 ° C. for 2 hours. Finally, the catalyst was supported using 5 wt% platinum colloid made of Tanaka Kikinzoku.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 4 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the high thermal conductive substrate side was in contact with it and heated to 250 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 23 L / min of hydrogen per gram of Pt.

  In the hydrogen storage / supply apparatus of this example, the catalyst was efficiently heated in the same manner as in Example 7, and 1-methyldecahydronaphthalene was able to improve the frequency factor uniformly and efficiently in contact with the catalyst layer. . Adsorption with 1-methyldecahydronaphthalene is achieved by filling the second basic oxide and a large amount of platinum catalyst into a large number of pores formed on the surface of the barrier pattern by a series of anodizing treatments. The reaction rate was improved. In addition, the generated hydrogen can be promptly separated, and the hydrogen is de-equilibrated in the direction of hydrogenation, so that the reaction proceeds efficiently even at low temperatures.

  FIG. 16 is a perspective view of the hydrogen storage / supply device of this embodiment, and FIG. 17 is a sectional view thereof. Similar to the first embodiment, the hydrogen storage / supply device 101 of the present embodiment includes a high thermal conductive substrate 102, a catalyst layer 104, a fuel flow path 105, a hydrogen separation membrane 107 made of a Pd-Ag film, a hydrogen flow path 103, and an upper lid 108. , Composed of a sealing material 109. A part of the sealing material 109 is provided with a fuel supply port, a discharge port, and a hydrogen circulation port that lead to a fuel flow path formed on the substrate, and a hydride and waste liquid as fuel by an external movable partition plate. It connects with the fuel tank which isolate | separates and stores the dehydrogenation thing which is (not shown). The fuel was supplied using a pressure pump capable of intermittent control while controlling the flow rate with a mass flow meter. The organic hydride fuel undergoes a dehydrogenation reaction while passing through the fuel flow path 105 in the recess and contacting the catalyst layer 104 to generate hydrogen. The produced hydrogen is separated from the fuel and the produced aromatic hydrocarbon through the hydrogen separation membrane 107, and then pure hydrogen is supplied to the outside through the hydrogen flow path 103 and the hydrogen circulation port. In the case of hydrogen storage, hydrogen passes through the hydrogen passage and the hydrogen passage and the hydrogen separation membrane 107 to contact the catalyst layer 104, hydrogenates the aromatic hydrocarbon compound supplied from the fuel passage 105, and fuel passage 105. Organic hydride can be obtained from the exit.

  FIG. 18 is a flowchart showing a method for manufacturing the hydrogen storage / supply device of this embodiment. A thin film 110 made of polymethyl methacrylate having a molecular weight of 2500 was applied on an AlN high thermal conductive substrate 102 having a thickness of 50 mm × 50 mm and a thickness of 1 mm by spin coating. The thickness of the thin film 110 is 5 μm. Next, a silicon mold 111 having irregularities formed on the surface was pressed onto the thin film 110. The mold was pulled up vertically to form a resin protrusion 112. As the barrier pattern, a straight line from the fuel supply port to the discharge port having a pattern width and a gap of 500 nm was formed. The height of the pattern was 10 μm. Subsequently, a Pt particle mixed alumina sol was applied onto the surface of the fine resin protrusion 112. Thereafter, a 3 μm Ag—Pd film was formed on the surface by sputtering. Finally, the hydrogen separation membrane 107 and the catalyst layer 104 were formed by baking at 450 ° C. for 1 hour. As a post-treatment, the remaining polymethyl methacrylate component was removed with a solvent. The catalyst layer 104 and the hydrogen separation membrane 107 maintained the uneven shape of the originally formed resin protrusion 112, and the catalyst layer side was used as the fuel channel 105 and the hydrogen separation membrane side was used as the hydrogen channel 103. A 300 μm thick upper cover made of SUS304 was laminated on the upper surface of the hydrogen separation membrane 107, and a fuel supply port, a discharge port, and a hydrogen circulation port were provided, and the other outer periphery was sealed with glass.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 3 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the AlN high thermal conductivity substrate side was in contact with it and heated to 250 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 24 L / min of hydrogen per gram of Pt.

  In this example, an effect of efficiently heating the catalyst was obtained by configuring the external heat source to the catalyst layer with a high thermal conductivity substrate. In addition, by forming a pattern by the nanoprint method, it was possible to increase the height of the barrier and increase the amount of catalyst supported even though the pattern was very fine. In addition, since heat transfer is slower in the upper part of the barrier than in the lower part, heat distribution occurs in the barrier, and a large number of gas-liquid solid composite interfaces are formed, improving the reaction efficiency. Furthermore, the presence of a hydrogen separation membrane formed along the shape of the catalyst layer enabled the rapid separation of the generated hydrogen, which resulted in de-equilibrium in the hydrogenation direction and the effect that the reaction proceeded efficiently even at low temperatures. . In addition, since the hydrogen separation membrane is formed in a concavo-convex shape, the concave portion can be used as it is as a hydrogen flow path, and a simpler hydrogen storage / supply device can be produced.

  FIG. 19 is a perspective view of the hydrogen storage / supply device of the present embodiment, and FIG. 20 is a sectional view showing the internal structure thereof. As shown in the figure, AlN (thermal conductivity: 250 W / mK) high thermal conductive substrate 42, Ni channel protrusion 43, catalyst layer 44 made of Pt / activated carbon catalyst sheet, fuel channel 45, spacer 46, Pd-Ag A hydrogen separation membrane 47 made of a membrane, a hydrogen channel 48 and a sealing material 49 are included. A part of the sealing material is provided with a raw material supply port 50 and a discharge port 51 leading to a pattern gap formed on the substrate, and hydride as a fuel and dehydrogenation as a waste liquid by an external movable partition plate. It is connected to a fuel tank that separates and stores the chemicals (not shown). A pump capable of intermittent control was used for fuel supply. The organic hydride fuel undergoes a dehydrogenation reaction while being in contact with the catalyst layer 44 through the channel 45 of the recess between the patterns, and hydrogen is generated. The generated hydrogen is separated from the fuel and the generated aromatic hydrocarbon through the hydrogen separation membrane 47, and then pure hydrogen is discharged to the spacer 46, passes through the hydrogen flow path 48, passes through the hydrogen circulation port 52, and is externally supplied. Supplied to. In the case of hydrogen storage, hydrogen passes through the hydrogen flow port 52, contacts the catalyst layer 44 from the hydrogen channel 48 through the spacer 46 and the hydrogen separation membrane 47, and hydrogenates the aromatic hydrocarbon compound supplied from the channel 45. Organic hydride can be obtained from the outlet of the channel 45.

  FIG. 21 is a flowchart showing the method for manufacturing the hydrogen storage / supply device of this embodiment. A Ni film having a thickness of 100 μm was formed on a 50 mm × 50 mm, 1 mm thick AlN high thermal conductive substrate 42 by sputtering and electroplating, and then a channel protrusion 43 was formed by etching. Both the channel protrusion width and the gap are 100 μm, and the shape is uneven. On the other hand, 100 μm thick alumina ceramics was used as the spacer 46, and a 2 μm Pd—Ag alloy film was formed on one side thereof as a hydrogen separation film 47 by sputtering, and then a Pt / activated carbon catalyst sheet 44 was pressure bonded. These were laminated with the uneven SUS / Ti hydrogen flow path 48 and the patterned substrate, and the fuel supply port 50, the discharge port 51, and the hydrogen flow port portion 52 were provided, and the other outer periphery was glass-sealed.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 4 mm. An electrode was attached to the Ni channel protrusion 43 in the apparatus, and the Pt / activated carbon catalyst sheet was directly heated to 250 ° C. using the channel protrusion 43 as a heater. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 25 seconds, and it was possible to continuously generate 18 L / min of hydrogen per gram of Pt.

  Also in this example, the catalyst layer is efficiently heated by the heater disposed immediately below, and the hydrogen separation membrane is adjacent to the catalyst layer, so that the produced hydrogen can be promptly separated and desorbed in the hydrogenation direction. As a result, the effect of allowing the reaction to proceed efficiently even at a low temperature was obtained. Moreover, the heat source at the time of starting is securable by using the metal pattern which comprises a flow path as a heater.

  In this example, a catalyst composed of a metal catalyst and a support material was studied for dehydrogenation from organic hydride as a catalyst material having high activity even at low temperatures.

(Carrier material)
Activated carbon, Al ₂ O ₃ , ZnO, ZrO ₂ , and diatomaceous earth were used as the catalyst support material. A commercially available product was used except for Al ₂ O ₃ . The activated carbon used was Vulcan manufactured by cabot, diatomaceous earth, ZnO, and ZrO ₂ manufactured by Wako Pure Chemical Industries. For Al ₂ O _3, aluminum isopropoxide (20 g) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in hot water (80 g) at 80 ° C., nitric acid (5 mL) was added dropwise to gelate, dried at 120 ° C. for 5 hours, and then 450 ° C. And processed for 2 hours.

The composite carrier material was prepared as follows. Al ₂ O ₃ complex oxide is made by dissolving Wako Pure Chemicals Aluminum Isopropoxide (20 g) in hot water (80 g) at 80 ° C., adding predetermined amounts of zinc nitrate and zirconyl nitrate, and adding nitric acid (5 mL) dropwise. after gelation, dried for 5 hours at 120 ° C., for 2 hours at _{450 ℃, 2wt% ZnO- Al 2} O 3, 2wt% ZrO 2 - were prepared Al ₂ O _3.
For diatomaceous earth, a predetermined amount of an aqueous solution of zinc nitrate and zirconyl nitrate is impregnated and added to diatomaceous earth, dried at 120 ° C. for 5 hours and then treated at 450 ° C. for 2 hours to produce 2 wt% ZnO-diatomaceous earth, 2 wt% ZrO ₂ -diatomaceous earth. .

(Metal catalyst support)
Tanaka Kikinzoku Pt colloid (2 nm, 4 wt%) was used as the metal catalyst. The metal catalyst loading operation was performed as follows. A predetermined amount of Pt colloid and a support material were weighed so that the amount of metal supported was 5 wt% with respect to the catalyst. The Pt colloid was then diluted with methoxyethanol and impregnated into the support material. After drying at 80 ° C. for 20 minutes, a metal-added catalyst was produced by treatment in a He stream at 400 ° C. for 3 hours.

(Evaluation of desorption characteristics of carrier materials)
The decalin and naphthalene desorption properties were investigated using a GC-mass (SHIMAZU GC6500) equipped with a thermal decomposition apparatus. A quartz tube in a thermal decomposition apparatus was filled with 0.03 mL of catalyst, and 1 μL of 10 wt% naphthalene-added decalin solution was injected with a syringe at a He flow rate of 10 mL / min to adsorb naphthalene and decalin to the support material. Next, the temperature was gradually raised, and the desorption temperature of naphthalene and decalin was examined. The results of the desorption characteristics are shown in Table 2.

Table 2

(Catalyst performance evaluation)
The conversion rate from decalin to naphthalene was examined using GC-mass (GC6500 manufactured by SHIMAZU) equipped with a thermal decomposition apparatus. 0.03 mL of Pt-supported catalyst is packed in a quartz tube in the thermal decomposition apparatus, and 1 μL of decalin is injected 10 times at intervals of 1 minute with a syringe at 220 ° C. and 250 ° C. in a He flow rate of 10 mL / min. The naphthalene conversion rate of decalin was examined from the peak area ratio of GC-mass of 138 (decalin) and 128 (naphthalene). The results of the catalyst performance evaluation are shown in Table 3. The conversion values in the table are the 10th data.
Table 3

As can be seen from Table 3, by adding ZnO or ZrO ₂ , the conversion rate at 220 ° C. and 250 ° C. is improved over activated carbon and alumina. As a result of examining the desorption characteristics in Table 1, ZnO and ZrO ₂ have lower desorption temperatures of naphthalene and decalin than those of activated carbon and alumina. This is because the addition of a basic oxide such as ZnO or ZrO _{2 to} alumina lowers the desorption temperature of naphthalene, so that the catalyst surface can be easily regenerated, and the conversion rate is improved over activated carbon or alumina. As described above, it is effective to make the support material basic, and it is effective to add ZnO and ZrO ₂ .

In this embodiment, a hydrogen storage / supply device capable of supplying hydrogen at a lower temperature of 150 to 200 ° C. is produced. Compared with the apparatus of Example 10, the configuration of the catalyst used was different, and a 2 wt% ZrO ₂ -Al ₂ O ₃ catalyst thin film was used instead of the Pt / activated carbon catalyst sheet, and the catalyst was prepared according to the production method of Example 10. .

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 4 mm. An electrode was attached to the Ni metal pattern in the apparatus, and the catalyst layer was directly heated to 150 ° C. using the metal pattern as a heater. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, hydrogen could be continuously generated even at a lower temperature of 150 to 200 ° C. Thus, the hydrogen storage / supply apparatus of the present invention can generate hydrogen even at 200 ° C. or lower. When restarting DSS operation, such as fuel cells and gas turbines, there is no heat source, so the hydrogen generator heater must be heated to about 250 ° C until the fuel cell is operated to some extent.

In this embodiment, since hydrogen can be generated from 150 ° C., at the time of restart, the heater is heated to 150 ° C., and hydrogen is first generated. The generated hydrogen is not used for the fuel cell, but is first used for heating the hydrogen generator. When the hydrogen generator reaches 250 ° C., sufficient hydrogen supply becomes possible, and hydrogen supply to the fuel cell is started. As described above, since hydrogen can be generated even at a low temperature of 150 ° C., the heater power consumption at the start can be reduced, and the efficiency at the start of the power supply can be improved. In addition, since the hydrogen generator is heated with hydrogen without burning dehydrogenated compounds, no CO ₂ is emitted.

  FIG. 22 is a perspective view of the hydrogen storage / supply device of the present invention that is movable at a low temperature, and FIG. 23 is a sectional view thereof. The hydrogen storage / supply device 81 of the present embodiment relates to a hydrogen storage / supply device that can operate at 150 to 200 ° C. in addition to the hydrogen storage / supply device manufactured in the twelfth embodiment.

  Compared with the apparatus of Example 5, the metal pattern was changed to a copper pattern and the composite functional layer 84 having two functions of a catalyst layer and a hydrogen separation membrane was provided. The composite functional layer 84 is a porous polyimide film having void-shaped pores. The film thickness and porosity of the porous polyimide used were 20 μm and 65%, respectively. A 5 nm thick skin layer is present on the surface of the porous polyimide membrane adjacent to the spacer, and functions as a hydrogen separation membrane. In order to improve the hydrogen permeation selectivity, an Ag—Pd film was formed on the skin layer surface by sputtering. A catalyst is supported in the void-shaped holes. The organic hydride fuel is supplied to the composite functional layer 84 through the recessed channel 85 between the patterns. In the pores, the gasified fuel and the fuel liquefied by capillary condensation coexist, so that many gas-liquid solid composite interfaces are formed on the entire surface of the film.

  In addition, the presence of a skin layer and an Ag-Pd membrane that function as hydrogen separation membranes makes it possible to immediately separate the produced hydrogen and reduce the hydrogen partial pressure, thus promoting the dehydrogenation reaction efficiently. Can be made. The produced hydrogen is immediately discharged to the spacer 86 through the skin layer, separated from the fuel and the produced aromatic hydrocarbon, and pure hydrogen is taken out to the outside. The obtained pure hydrogen passes through the hydrogen flow path 88 formed on the composite functional layer 84 and supplies hydrogen to the outside. In the case of hydrogen storage, hydrogen passes from the hydrogen flow path 88 through the spacer 86, contacts the catalyst in the composite functional layer 84, hydrogenates the aromatic hydrocarbon compound supplied from the flow path 85, and organic hydride from the flow path 85 outlet. Can be obtained.

FIG. 24 is a flowchart showing the method for manufacturing the hydrogen storage / supply device of this embodiment. A porous polyimide sheet with a copper foil thickness of 100 μm was obtained by electroplating a porous polyimide sheet with a copper foil having a structure of 50 μm × 50 mm copper foil of 18 μm and a porous polyimide layer of 20 μm. Next, a copper pattern 83 was formed by etching, and gold plating was applied thereon to prevent corrosion. Both the pattern width and the gap of the pattern are set to 100 μm, and the shape is uneven. It was immersed in a ZrO ₂ -Al ₂ O ₃ catalyst dispersion and then dried to immobilize the catalyst in the pores of the porous polyimide. Finally, a 2 μm Ag—Pd film was formed on the surface of the skin layer by sputtering to obtain a composite functional layer 84 in which the fuel flow path 85 was formed. A composite functional layer 84 in which a fuel channel 85 is formed, a graphite sheet 82 having a thickness of 50 × 50 mm ² , a 100 μm thickness, a fluorine resin having a thickness of 100 μm, a spacer 86, and a hydrogen channel 88 made of a fluorine resin having an uneven groove. The fuel supply port 90, the discharge port 91, and the hydrogen circulation port portion 92 were provided, and the other outer periphery was sealed with a thermosetting polyimide resin.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 0.5 mm. This apparatus was placed on a ceramic heater prepared as an external heat source so that the graphite sheet side was in contact with it, and heated to 150 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, hydrogen could be generated even at 150 ° C.

  In this example, a large number of composite interfaces can be formed on the surface of the low-temperature active catalyst fixed in the porous pores, and the skin layer and the Ag-Pd membrane function as a hydrogen separation membrane. Hydrogen can be promptly separated and de-equilibrated in the direction of dehydrogenation. As a result, the reaction can proceed efficiently even at low temperatures. Further, although not particularly limited to the constituent materials, the present hydrogen storage / supply device is very thin and flexible, and can be attached in close contact with the curved surface portion. This embodiment is a hydrogen generator that is effective for supplying hydrogen by using waste heat of a generator for mobile devices such as a fuel cell, a turbine, and an engine.

The composite functional film is not limited to the above example, and can be manufactured using a metal and a clad material that can form a flow path processing and oxide film on the surface. An example using Zr as a metal will be described. After processing the flow path by etching on the Zr surface, an oxide film was formed by anodic oxidation. At that time, in order to reduce the thickness of the ZrO ₂ barrier film at the ZrO ₂ / Zr interface, the electrolytic voltage was lowered in the latter half of the anodizing treatment. Thereafter, only the ZrO ₂ barrier layer at the ZrO ₂ / Zr interface was selectively etched to expose the Zr metal surface. Finally, a composite functional film was obtained by supporting a Pt colloid solution in a ZrO ₂ film. Similarly, 1-methyldecahydronaphthalene was used as the fuel and was supplied into the apparatus, and dehydrogenation reaction was performed at 150 ° C. As a result, hydrogen could be generated even at 150 ° C. The Zr metal integrated with the catalyst layer functions as a hydrogen separation membrane, and the produced hydrogen can be promptly separated, de-equilibrated in the direction of dehydrogenation, and the effect that the reaction proceeds efficiently even at low temperatures was obtained.

  FIG. 25 is a perspective view of the hydrogen storage / supply device of the present invention, and FIG. 26 is a sectional view thereof. The hydrogen storage / supply device 121 of this example includes an AlN (thermal conductivity: 250 W / mK) high thermal conductivity substrate 122, a Ni pattern 123, a hydrogen separation membrane 127 made of a Pd-Ag membrane, and 5 wt% in a porous polyimide membrane. It comprises a catalyst layer 124 on which a Pt / alumina catalyst is supported, a fuel injection layer 126 having a number of through holes formed in the surface, a fuel storage layer 128, and a sealing material 129. A part of the sealing material 129 is provided with a fuel supply port, a discharge port, and a hydrogen circulation port leading to the fuel storage layer 128, and a hydride as a fuel and a dehydrogenated product as a waste liquid by an external movable partition plate. Is connected to a fuel tank (not shown).

  The fuel was supplied using a pressure pump capable of intermittent control while controlling the flow rate with a mass flow meter. The fuel supplied from the fuel tank is introduced into the fuel storage layer 128 in the hydrogen storage / supply device and temporarily stored. The fuel storage layer 128 is always filled with fuel. If fuel is further supplied to the fuel storage layer 128 by a pressure pump, the fuel storage layer 128 cannot be stored in the storage layer 128, that is, the amount supplied to the fuel storage layer 128. The fuel is uniformly dropped or injected into the surface of the catalyst layer 124 disposed in the lower layer through the through hole 131 of the fuel injection layer 126. While the supplied fuel is in contact with the catalyst layer 124, a dehydrogenation reaction proceeds to generate hydrogen. The generated hydrogen is separated from the fuel and the generated aromatic hydrocarbon through the hydrogen separation membrane 127, and then pure hydrogen is supplied to the outside through the metal pattern gap 125 and through the hydrogen circulation port. The hole diameter on the lower surface is 0.3 to 300 μm, and the smaller the nozzle diameter, the finer droplets can be obtained.

  Materials used for the fuel injection layer 126 include thermosetting resins that can be injection-molded with excellent chemical resistance and heat resistance, such as polyimide, fluorinated resin, and silicon resin, and glass such as silica, alumina, mullite, and cordierite. Further, ceramics, copper, aluminum, iron and the like can be used. When the through hole is formed, it is not particularly limited, but it can be formed by mechanical processing such as etching or sand blasting. For example, when forming a through hole in copper, after forming a resist having a large number of holes on the copper surface by photolithography, spray etching is performed for a predetermined time with an iron chloride solution or the like only on the resist-formed surface. Since the etching proceeds isotropically, the copper cross-section after the etching process has a U-shape that is half of an ellipse as shown in FIG. Become. Similarly, when forming a through hole in glass, a through hole in which the hole is reduced can be formed by forming a resist on the glass surface and sandblasting for a predetermined time.

A method for manufacturing the hydrogen storage / supply device of this embodiment will be described below. After a 50 μm thick Ni film was formed on a 50 mm × 50 mm, 1 mm thick AlN high thermal conductive substrate 122 by sputtering and electroless plating, a metal pattern 123 was formed by etching. The surface was plated with gold to prevent pattern corrosion. On the other hand, a 50 mm × 50 mm size porous polyimide sheet having a thickness of 50 μm is immersed in a ZrO ₂ -Al ₂ O ₃ catalyst dispersion and then dried to fix the catalyst in the pores of the porous polyimide, thereby forming a catalyst layer. 124 was obtained. The porous polyimide sheet had void-shaped pores and had a porosity of 65%. An Ag—Pd film 127 having a thickness of 3 μm was formed on the skin layer surface of the porous polyimide sheet by sputtering. On the other hand, a resist in which holes having diameters of 300 μm were arranged at a pitch of 500 μm was laminated on one surface of 1 mm thick glass. The fuel injection layer 126 was formed by subjecting the resist surface to sandblasting with alumina fine particles for a predetermined time at an injection pressure of 0.2 MPa, and then removing the resist. In addition, the hole diameter on the back surface side with respect to the sandblasted surface was reduced and was 150 μm. As the fuel storage layer 128, an alumina ceramic having an inner size of 40 × 40 mm ² and a depth of 1 mm was used. These members were laminated, a fuel supply port, a discharge port, and a hydrogen circulation port were provided, and the other outer periphery was glass-sealed.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 4 mm. This apparatus was installed on a ceramic heater prepared as an external heat source so that the AlN high thermal conductivity substrate side was in contact with it and heated to 250 ° C. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 20 L / min of hydrogen per gram of Pt.

  As described above, by configuring the external heat source to the catalyst layer with the high thermal conductivity substrate, the catalyst is efficiently heated and can be used efficiently. In addition, by supplying fuel uniformly from the fuel injection layer having a large number of fine pore diameters to the catalyst layer, a large number of gas-liquid solid composite interfaces were formed in the catalyst layer, and the reaction could proceed efficiently. In addition, by providing a hydrogen separation membrane, it was possible to quickly separate the generated hydrogen, which resulted in de-equilibrium in the hydrogenation direction, and as a result, the effect that the reaction proceeded efficiently even at low temperatures was obtained.

  FIG. 28 is a perspective view of the hydrogen storage / supply device of the present invention, and FIG. 29 is a sectional view thereof. This embodiment is an improvement of the hydrogen storage / supply device of Embodiment 2, and a combustion catalyst layer for burning residual hydrogen discharged from a fuel cell or an aromatic compound generated after a dehydrogenation reaction on the lower surface of a high heat conductive substrate. Obtained by burning unreacted hydrogen or aromatic compound by placing and laminating a combustion chamber substrate in which a flow path for introducing the residual hydrogen or aromatic compound is formed in the lower part thereof This is a hydrogen storage and supply device that uses combustion heat to perform dehydration and hydrogenation of organic hydrides.

  The hydrogen storage / supply device 141 of this embodiment includes an AlN (thermal conductivity: 250 W / mK) high thermal conductive substrate 142, a channel protrusion 143 made of Cu, a catalyst layer 144 made of 5 wt% Pt / alumina catalyst, a pattern gap A fuel flow path 145, a spacer 146, a hydrogen separation membrane 147 made of a Pd-Ag film, a hydrogen flow path 148, a combustion chamber layer 150 provided with a combustion catalyst layer 151, a combustion chamber groove 152, and a sealing material 149. The A part of the sealing material is provided with a fuel supply port, a discharge port, a hydrogen circulation port, a flow path for introducing residual hydrogen or an aromatic compound that leads to a pattern gap formed on the substrate, and an external movable type A partition plate is connected to a fuel tank (not shown) that separates and stores hydride as fuel and dehydrogenation as waste liquid. The fuel was supplied using a pressure pump capable of intermittent control while controlling the flow rate with a mass flow meter.

  The organic hydride fuel passes through the fuel flow path 145 in the recesses between the patterns, and proceeds with the dehydrogenation reaction while contacting the catalyst layer 144 to generate hydrogen. The generated hydrogen is separated from the fuel and the generated aromatic hydrocarbon through the hydrogen separation membrane 147, and then pure hydrogen is discharged to the spacer 146, passes through the hydrogen flow path 148, and passes through the hydrogen circulation port to the outside. Supplied. In the case of hydrogen storage, the hydrogen passes through the hydrogen flow port 148, passes through the spacer 146 and the hydrogen separation membrane 147, contacts the catalyst layer 144, and hydrogenates and flows the aromatic hydrocarbon compound supplied from the flow channel 145. Organic hydride can be obtained from the exit of the path 145.

  Hydrogen supply to the combustion chamber substrate 150 was performed while controlling the flow rate with a mass flow meter. The hydrogen storage / supply device 141 of this example was produced according to Example 2. Note that a 5 wt% Pt / alumina catalyst was applied as the combustion catalyst 151 on the lower surface of the high thermal conductive substrate 142. Further, a 10 mm thick alumina ceramic was used as the combustion chamber substrate 150, and a combustion chamber groove 152 having a width of 500 μm and a depth of 2 mm was formed on the surface thereof. Each member was laminated | stacked, the fuel supply port, the discharge port, the hydrogen distribution port, the residual hydrogen introduction port, and the combustion gas discharge port part were provided, and the other outer periphery was glass-sealed.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 15 mm. Hydrogen was supplied to the residual hydrogen inlet and heated to 250 ° C. while controlling the temperature with a thermocouple provided in a part of the high thermal conductive substrate. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 20 L / min of hydrogen per gram of Pt.

  In this way, by configuring the external heat source to the catalyst layer with the high thermal conductivity substrate, the catalyst is heated by efficiently using the combustion heat of hydrogen generated in the combustion substrate provided in the lower portion of the high thermal conductivity substrate. be able to. In addition, by providing a hydrogen separation membrane, it was possible to quickly separate the generated hydrogen, which resulted in de-equilibrium in the hydrogenation direction, and as a result, the effect that the reaction proceeded efficiently even at low temperatures was obtained.

  30 is a perspective view of the hydrogen storage / supply device of the present invention, and FIG. 31 is a cross-sectional view thereof. The hydrogen storage / supply apparatus of the present embodiment is an improvement of the hydrogen storage / supply apparatus of Embodiment 14, and the residual hydrogen discharged from the fuel cell or the aromatic compound generated after the dehydrogenation reaction is formed on the lower surface of the high thermal conductive substrate. A combustion catalyst layer is provided, and a combustion chamber substrate in which a flow path for introducing residual hydrogen or an aromatic compound is formed is disposed under the combustion catalyst layer, and the unreacted hydrogen or aromatic compound is formed by stacking them. This is a hydrogen storage and supply device that uses the combustion heat obtained by combustion to perform dehydration and hydrogenation of organic hydrides.

  The hydrogen storage / supply device 161 of this example includes an AlN (thermal conductivity: 250 W / mK) high thermal conductive substrate 162, a channel protrusion 163 made of Ni, a hydrogen separation membrane 167 made of a Pd-Ag membrane, and a porous polyimide membrane. A catalyst layer 164 carrying a 5 wt% Pt / alumina catalyst therein, a fuel injection layer 166 having a number of through holes formed in the surface, a fuel storage layer 168, a combustion catalyst layer 171, and a combustion chamber groove 172 are provided. It is composed of a combustion chamber substrate 170 and a sealing material 179. A part of the sealing material is provided with a fuel supply port leading to the fuel storage layer 168, a discharge port and a hydrogen circulation port, a flow path for introducing residual hydrogen or an aromatic compound, and the fuel is separated by an external movable partition plate. Is connected to a fuel tank (not shown) that separates and stores the hydride that is the waste liquid and the dehydrogenated product that is the waste liquid.

The fuel was supplied using a pressure pump capable of intermittent control while controlling the flow rate with a mass flow meter. The fuel supplied from the fuel tank is introduced into the fuel storage layer 168 in the hydrogen storage / supply device 161 and temporarily stored. The fuel storage layer 168 is always filled with fuel, and when fuel is further supplied to the fuel storage layer 168 by a pressurizing pump, the fuel storage layer 168 cannot be stored in the fuel storage layer 168, that is, supplied to the fuel storage layer 168. min of fuel through the through hole of the fuel injection layer 16 6, are uniformly dropped or injection-supplied to the arrangement catalyst layer 164 plane in the lower layer. While the injected fuel is in contact with the catalyst layer 164, the dehydrogenation reaction proceeds to generate hydrogen. The generated hydrogen is separated from the fuel and the generated aromatic hydrocarbon through the hydrogen separation membrane 167, and then pure hydrogen is supplied to the outside through the metal pattern gap 165 and through the hydrogen circulation port. The hole diameter is 0.3 to 300 μm on the lower surface, and the smaller the nozzle diameter, the finer droplets can be obtained.

  Materials used for the fuel injection layer 166 include thermosetting resins such as polyimide, fluorinated resin, and silicon resin that can be injection-molded with excellent chemical resistance and heat resistance, and glass such as silica, alumina, mullite, and cordierite. Further, ceramics, copper, aluminum, iron and the like can be used. When the through hole is formed, it is not particularly limited, but it can be formed by mechanical processing such as etching or sand blasting. For example, when forming a through hole in copper, after forming a resist having a large number of holes on the copper surface by photolithography, spray etching is performed for a predetermined time with an iron chloride solution or the like only on the resist-formed surface. Since the etching progresses isotropically, the copper cross section after the etching process has an elliptical shape and is reduced from the etched surface to the back surface. Similarly, when forming a through hole in glass, a through hole in which the hole is reduced can be formed by forming a resist on the glass surface and sandblasting for a predetermined time. Hydrogen was supplied to the combustion chamber substrate 170 while controlling the flow rate with a mass flow meter.

The hydrogen storage / supply device 161 of this example was produced in accordance with Example 14. Note that a 5 wt% Pt / alumina catalyst was applied as the combustion catalyst 171 on the lower surface of the high thermal conductive substrate 162. Further, a 10 mm thick alumina ceramic was used as the combustion chamber substrate 170, and a combustion chamber groove 172 having a width of 500 μm and a depth of 2 mm was formed on the surface thereof. Each member was laminated | stacked, the fuel supply port, the discharge port, the hydrogen distribution port, the residual hydrogen introduction port, and the combustion gas discharge port part were provided, and the other outer periphery was glass-sealed. A 50 μm thick Ni film was formed on a 50 × 50 mm ² , 15 mm thick AlN high thermal conductive substrate 162 by sputtering and electroless plating, and then a metal channel protrusion 163 was formed by etching. The surface was plated with gold to prevent corrosion of the pattern. On the other hand, a 50 × 50 mm ² size 50 μm thick porous polyimide sheet is immersed in a ZrO ₂ —Al ₂ O ₃ catalyst dispersion and then dried to fix the catalyst in the pores of the porous polyimide. Layer 164 was obtained.

The porous polyimide sheet had void-shaped pores and had a porosity of 65%. An Ag-Pd film having a thickness of 3 μm was formed on the skin layer surface of the porous polyimide sheet by sputtering. On the other hand, a resist in which holes having diameters of 300 μm were arranged at a pitch of 500 μm was laminated on one surface of 1 mm thick glass. The fuel injection layer 166 was formed by subjecting the resist surface to sandblasting with alumina fine particles for a predetermined time at an injection pressure of 0.2 MPa, and then removing the resist. In addition, the hole diameter on the back surface side with respect to the sandblasted surface was reduced and was 150 μm. The spacer 26 was made of alumina ceramic having a thickness of 100 μm, and the fuel storage layer 168 was made of alumina ceramic having an inner dimension of 40 × 40 mm ² and a depth of 1 mm. These members were laminated, and a fuel supply port, a discharge port, a hydrogen circulation port, a residual hydrogen introduction port, and a combustion gas discharge port were provided, and the other outer periphery was sealed with glass.

  This hydrogen storage / supply device has a size of 70 mm × 70 mm and a thickness of 15 mm. Hydrogen was supplied to the residual hydrogen inlet and heated to 250 ° C. while controlling the temperature with a thermocouple provided in a part of the high thermal conductive substrate. 1-methyldecahydronaphthalene was used as the fuel and supplied into the apparatus for dehydrogenation reaction. As a result, the hydrogen generation rate was maximized when the fuel supply pulse interval was 20 seconds, and it was possible to continuously generate 21 L / min of hydrogen per gram of Pt.

  In this way, by configuring the external heat source to the catalyst layer with the high thermal conductivity substrate, the catalyst is heated by efficiently using the combustion heat of hydrogen generated in the combustion substrate provided in the lower portion of the high thermal conductivity substrate. be able to. In addition, by supplying fuel uniformly from the fuel injection layer having a large number of fine pore diameters to the catalyst layer, a large number of gas-liquid solid composite interfaces were formed in the catalyst layer, and the reaction could proceed efficiently. In addition, by providing a hydrogen separation membrane, it was possible to quickly separate the generated hydrogen, which resulted in de-equilibrium in the hydrogenation direction, and as a result, the effect that the reaction proceeded efficiently even at low temperatures was obtained.

  FIG. 32 is a configuration diagram of a power generation system in which the solid polymer fuel cell and the hydrogen storage / supply device of Example 13 are integrated, FIG. 33 is a sectional view thereof, and FIG. 34 is a top view. This is an example in which an organic hydride system is utilized more efficiently by integrating the hydrogen storage / supply device created in Example 13 with a fuel cell. Since the hydrogen storage / supply device of Example 13 can be driven at 150 to 200 ° C., a solid polymer fuel cell can be used as an integrated fuel cell.

  Nine hydrogen storage / supply devices 300 prepared in Example 13 and three in parallel were mounted on both sides of the polymer electrolyte fuel cell 200. The hydrogen storage and supply system 202 disposed in the upper and lower portions of the fuel cell stack 201 includes a hydrogen storage / supply device 300, a housing 203, a heat insulating material 204, a sealing material 205, a hydrogen flow path 206, a fuel flow path 207, and a sealing material. It is composed of a heater current cable 208 incorporated therein. The fuel flow path 207 can be used as a fuel supply and waste liquid discharge flow path, and the organic hydride as fuel is preheated with waste heat generated from the fuel cell stack 201 while passing through the fuel flow path 207. The The hydrogen storage / supply device 300 and the fuel cell stack 201 are covered with a heat insulating material 204, and are configured to thoroughly prevent thermal diffusion, thereby greatly improving the efficiency of using fuel cell waste heat.

  FIG. 35 is a flowchart for supplying the hydrogen generated from the fuel supply to the fuel cell. The fuel is sent from the fuel tank to the hydrogen storage / supply device via the preheating fuel passage. Therefore, the generated hydrogen passes through the hydrogen flow path 207 and is sent to the fuel electrode in the fuel cell stack 201. On the other hand, the produced aromatic compound is sent to the fuel tank.

  The fuel tank must store both organic hydride as fuel and dehydrogenated aromatic compound as waste liquid. It is easiest to use two tanks, but the volume is doubled. Therefore, a tank 400 that can store both fuel and waste liquid in one tank was manufactured.

  FIG. 36 is a block diagram of an integrated fuel / waste liquid storage tank. As shown in the figure, a movable partition plate 401 is installed inside the tank so that fuel and waste liquid can be divided into upper and lower parts and stored in the tank. The lower part is a fuel space 402 and the upper part is a waste liquid space 403. First, in order to store fuel in an empty tank, fuel is injected into the fuel space 402 from the lower fuel circulation port 404, the partition plate 401 is raised, and the tank is filled with fuel. Next, when power is supplied by supplying hydrogen, the fuel is supplied from the fuel space 402 to the hydrogen supply device by being sucked by the pump from the fuel circulation port 404 in the fuel space 402. Waste liquid generated after the dehydrogenation reaction passes through the waste liquid circulation port 405 and is stored in the waste liquid space 403 at the upper part of the tank. When the fuel is supplied, the partition plate 401 descends, so that a space is created in the upper part, and the waste liquid can easily enter the tank. Furthermore, there is almost no difference between the density of the organic hydride fuel and the density of the aromatic compound as the waste liquid, so that there is no problem in volume replacement.

  When hydrogen is supplied and the fuel is exhausted and the fuel tank is filled with the waste liquid, for example, recovery by a tank truck and supply of fuel are performed. A pipe is connected to the fuel supply port of the tank truck and the waste liquid circulation port 405 to perform recovery and fuel supply. In the operation of recovery and fuel supply, if the fuel supply is performed by a pump, the partition plate 401 rises, so that the waste liquid is naturally injected into the waste liquid tank of the tank truck. The tank truck also has a movable partition inside, and stores fuel and waste liquid separately. The upper part is the waste liquid space and the lower part is the fuel space so that the waste liquid can be collected smoothly and smoothly when the fuel is supplied.

  If the tank as described above is used, the tank can be used efficiently, and the recovery of the waste liquid and the supply of fuel can be performed smoothly.

  In the power generation system of FIG. 32, 1-methyldecahydronaphthalene was used as the fuel to supply power into the apparatus to generate power. As a result, it was possible to continuously generate 1 kW of power. Thus, the power generation system of the present invention can effectively use the waste heat of the fuel cell, and can efficiently use the organic hydride system. In addition, since it can continuously generate 1 kW, it could be used as an automobile or a home-use distributed generator.

FIG. 37 is an external view of a system combining a polymer electrolyte fuel cell and a hydrogen storage / supply device, and FIG. 38 is a flowchart of the system. Hydrogen storage of Example 17, an example in which improved delivery system provided a heat exchanger 603 between the hydrogen storage and supply system 601 created on the stack housing 602 as in Example 13 of a polymer electrolyte fuel cell System. Between the stack housing 602 and the heat exchanger 603 heat-insulating material is provided.

The organic hydride as a fuel is circulated by pressure pump 605 to the heat exchanger 603. Also, the heat exchanger 603 circulating hot waste generated from water vapor and hydrogen storage and supply system 601 generated from the fuel cell stack 602. As a result, the fuel can be preheated by the waste heat of the water vapor and the high-temperature waste liquid, and at the same time, the fuel cell stack 602 can be cooled to protect the electrolyte membrane from heat damage. The preheated fuel is supplied to the hydrogen storage / supply device 601. In order to bring the hydrogen storage / supply device 601 to a desired temperature, the heater is heated using a part of the electric power generated by the fuel cell stack 602. Waste produced by the reaction is introduced into the heat exchanger 603, the generated hydrogen through the cooler 609, and supplied to the fuel cell stack 602. On the other hand, the air supplied to the fuel cell stack 602 via a blower, further via a humidifier utilizing water vapor discharged from the heat exchanger 603, is supplied to the fuel cell stack 602.

  In the power generation system of FIG. 37, 1-methyldecahydronaphthalene was used as a fuel to supply power into the apparatus to generate power. As a result, it was possible to continuously generate 1 kW of power. As described above, the power generation system of the present invention can effectively utilize the waste heat of the high-temperature waste liquid generated from the water vapor and hydrogen storage / supply device generated from the fuel cell, and can efficiently use the organic hydride system. it can. In addition, since it can continuously generate 1 kW, it could be used as an automobile or a home-use distributed generator.

FIG. 39 is an external view of a power generation system in which a solid polymer fuel cell and a hydrogen storage / supply device incorporating a combustion chamber substrate are combined, and FIG. 40 is a flowchart of the system. This is an example in which the hydrogen storage and supply system of Example 17 is improved, and heat is generated between the stack housing 702 of the polymer electrolyte fuel cell and the hydrogen storage / supply device 701 built in the combustion chamber substrate 711 created in Example 15. it is a system in which a exchanger 703. Incidentally, the heat insulating material is provided between the stack housing 702 and the heat exchanger 703.

The organic hydride as a fuel is circulated by pressure pump 705 to the heat exchanger 703. Also, the heat exchanger 703 circulating hot waste generated from water vapor and hydrogen storage and supply system 701 generated from the fuel cell stack 702. As a result, the fuel can be preheated by the waste heat of the water vapor and the high-temperature waste liquid, and at the same time, the fuel cell stack can be cooled to protect the electrolyte membrane from heat damage. The preheated fuel is supplied to the hydrogen storage / supply device 701. When the residual hydrogen discharged from the fuel cell stack 702 is introduced into the combustion chamber substrate 711 via the residual hydrogen pipe 712 and hydrogen is burned by the combustion catalyst to bring the hydrogen storage / supply device 701 to a desired temperature. It heats rather than using the combustion heat generated. At that time, hydrogen was supplied to the combustion chamber substrate 711 by controlling the supply amount with a mass flow meter. Waste produced by the reaction is introduced into the heat exchanger 703, the generated hydrogen through the cooler 709, and supplied to the fuel cell stack 702. On the other hand, the air supplied to the fuel cell stack 702 via a blower, further via a humidifier utilizing water vapor discharged from the heat exchanger 703, is supplied to the fuel cell stack 702.

  In the power generation system of FIG. 39, 1-methyldecahydronaphthalene was used as the fuel to supply power into the apparatus to generate power. As a result, it was possible to continuously generate 1 kW of power. As described above, the power generation system of the present invention can effectively utilize the waste heat of the high-temperature waste liquid generated from the water vapor and hydrogen storage / supply device generated from the fuel cell, and can efficiently use the organic hydride system. it can. Moreover, since the residual hydrogen discharged from the fuel cell can be used effectively, the hydrogen utilization efficiency can be improved. In addition, since it can continuously generate 1 kW, it could be used as an automobile or a home-use distributed generator.

BRIEF DESCRIPTION OF THE DRAWINGS The whole block diagram which shows typically the hydrogen storage and supply system which used the renewable energy utilization household private power generation of Example 1 as an example. 1 is an external view of a hydrogen storage / supply device according to Embodiment 1. FIG. 1 is a perspective view illustrating an internal structure of a hydrogen storage / supply device according to Embodiment 1. FIG. 1 is a cross-sectional view of a hydrogen storage / supply device according to Embodiment 1. FIG. The top view of the pattern which shows each flow path of the hydrogen storage and supply apparatus of this invention. The top view of the fuel injection part of the hydrogen storage and supply apparatus of this invention. The perspective view of the hydrogen storage and supply system of the comparative example 1. FIG. The schematic diagram which shows the internal structure of the hydrogen storage and supply apparatus of the comparative example 1. FIG. The external view of the hydrogen storage and supply apparatus of Examples 2-5. The perspective view which shows the internal structure of the hydrogen storage and supply apparatus of Examples 2-5. Sectional drawing of the hydrogen storage and supply apparatus of Examples 2-5. The flowchart which shows the manufacturing method of the hydrogen storage and supply apparatus of Examples 2-5. The perspective view which shows the internal structure of the hydrogen storage and supply apparatus of Examples 6-8. Sectional drawing of the hydrogen storage and supply apparatus of Examples 6-8. The flowchart which shows the manufacturing method of the hydrogen storage and supply apparatus of Examples 6-8. The perspective view which shows the internal structure of the hydrogen storage and supply apparatus of the form of Example 9. FIG. Sectional drawing of the hydrogen storage and supply apparatus of the form of Example 9. FIG. The flowchart which shows the manufacturing method of the hydrogen storage and supply apparatus of the form of Example 9. FIG. The perspective view which shows the internal structure of the hydrogen storage and supply apparatus of the form of Example 10, 12. FIG. Sectional drawing of the hydrogen storage and supply apparatus of the form of Example 10, 12. FIG. The flowchart which shows the manufacturing method of the hydrogen storage and supply apparatus of the form of Example 10, 12. The perspective view which shows the internal structure model of the hydrogen storage and supply apparatus of Example 13. FIG. Sectional drawing of the hydrogen storage and supply apparatus of Example 13. FIG. FIG. 19 is a flowchart showing a method for manufacturing the hydrogen storage / supply device of Example 13. The perspective view which shows the internal structure of the hydrogen storage and supply apparatus of Example 14. FIG. Sectional drawing of the hydrogen storage and supply apparatus of Example 14. FIG. Sectional drawing of the fuel injection layer of the hydrogen storage and supply apparatus of Example 14. FIG. The perspective view which shows the internal structure of the hydrogen storage and supply apparatus of Example 15. FIG. Sectional drawing of the hydrogen storage and supply apparatus of Example 15. The perspective view which shows the internal structure of the hydrogen storage and supply apparatus of Example 16. FIG. Sectional drawing of the hydrogen storage and supply apparatus of Example 16. The block diagram which shows the electric power generation system of Example 17. FIG. Sectional drawing of the electric power generation system of Example 17. FIG. The top view of the electric power generation system of Example 17. FIG. FIG. 18 is a block diagram showing a power generation system of Example 17. The perspective view of an integrated fuel and waste liquid storage tank. The perspective view which shows the whole structure of the electric power generation system of Example 18. FIG. The block diagram which shows the electric power generation system of Example 18. FIG. The block diagram which shows the electric power generation system of Example 19. FIG. 20 is a block diagram showing a power generation system of Example 19. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1000 ... House, 1001 ... Solar cell, 1002 ... System electric power, 1003 ... Water electrolysis apparatus, 1004, 1009 ... Hydrogen storage and supply apparatus, 1005 ... Fuel cell, 1006 ... Inverter, 1007 ... Electric equipment, 1008 ... Car, 1010 ... Fuel cell system, 1, 21, 41, 61, 81, 101, 121, 141, 161, 300, 501, 601, 701 ... Hydrogen storage / supply device 2, 22, 42, 62, 82, 102, 122, 142, 162... High thermal conductive substrate, 3, 23, 43, 63, 83, 123, 143, 163... Channel protrusions, 4, 24, 44, 64, 104, 124, 144, 164. 45, 65, 85, 105, 145, ..., medium flow path, 6, 26, 46, 66, 86, 146 ... spacers, 27, 47, 67, 107, 1 7, 147, 167 ... hydrogen separation membrane, 8, 28, 48, 68, 88, 103, 125, 148, 165 ... hydrogen flow path, 108 ... upper lid, 9, 29, 49, 69, 89, 109, 129, 149, 169 ... Glass sealing material, 10, 30, 50, 90 ... Fuel supply port, 11, 31, 51, 91 ... Fuel discharge port, 12, 32, 52, 92 ... Hydrogen flow port, 13 ... Cooler, DESCRIPTION OF SYMBOLS 80 ... Porous polyimide with copper foil, 84 ... Composite functional layer, 110 ... Thin film, 111 ... Mold, 112 ... Resin protrusion, 126, 166 ... Fuel injection layer, 128, 168 ... Fuel storage layer, 131 ... Through-hole , 150, 170 ... combustion chamber substrate, 151, 171 ... combustion catalyst layer, 152, 172 ... combustion chamber groove, 200 ... solid polymer fuel cell, 201 ... fuel cell stack, 202 ... hydrogen storage and supply system, 203 ... Enclosure 204: heat insulating material, 205: sealing material, 206: hydrogen flow path, 207 ... fuel flow path, 208 ... current cable for heater, 400 ... tank, 401 ... partition plate, 402 ... space for fuel, 403 ... space for waste liquid 404, fuel flow port, 405, waste liquid flow port, 501 ... hydrogen storage and supply device, 502 ... palladium pipe, 503 ... catalyst layer, 504 ... fuel supply port, 505 ... fuel discharge port, 506 ... gas-liquid separator, 507 ... fuel tank, 508 ... waste fluid tank, 509 ... pump, 601, 701 ... hydrogen storage and supply device, 602, 702 ... stack housing, 603 and 703 ... heat exchanger, 604, 704 ... tank, 605,705 ... Pump, 607, 707 ... Fuel piping, 608, 708 ... Waste liquid piping, 609, 709 ... Cooler, 610, 710 ... Hydrogen piping, 711 ... Combustion chamber substrate, 7 12: Residual hydrogen piping.

Claims (28)

In a hydrogen storage / supply device that releases or stores hydrogen using a medium that chemically repeats the storage and release of hydrogen,
A planar medium flow path through which the medium flows;
A planar hydrogen separation means for separating the released hydrogen from the medium storing hydrogen and the medium releasing hydrogen;
The released hydrogen, the medium storing hydrogen and the flow port through which the medium releasing hydrogen flows in or out are formed integrally,
The hydrogen separation means is composed of a composite functional layer in which a catalyst layer is formed on the inner surface of pores formed in a porous resin, and the released hydrogen is converted into a gaseous state with the medium storing hydrogen and the hydrogen. Separating from the discharged medium,
The composite functional layer is provided in contact with the medium flow path;
The medium flow path, have a plurality of injection unit for injecting the medium into the reaction section and the reaction section as a planar structure formed on one surface of the substrate,
The medium flow path, hydrogen storage and supply device according to claim Rukoto hydrogen separation unit and the composite functional layer are sequentially formed. In a hydrogen storage / supply device that releases or stores hydrogen using a medium that chemically repeats the storage and release of hydrogen,
A planar medium flow path through which the medium flows;
A catalyst layer formed in the flow path;
A planar hydrogen separation means for separating the released hydrogen from the medium storing hydrogen and the medium releasing hydrogen;
The released hydrogen, the medium storing hydrogen and the flow port through which the medium releasing hydrogen flows in or out are formed integrally,
The hydrogen separation means comprises a hydrogen separation membrane that separates the released hydrogen in a gaseous state from the medium storing hydrogen and the medium releasing hydrogen;
The hydrogen separation membrane is formed in contact with the catalyst layer;
The medium flow path, have a plurality of injection unit for injecting the medium into the reaction section and the reaction section as a planar structure formed on one surface of the substrate,
The medium flow path, the catalyst layer and the hydrogen separation means hydrogen storage and supply device according to claim is Rukoto are sequentially formed. In a hydrogen storage / supply device that releases or stores hydrogen using a medium that chemically repeats the storage and release of hydrogen,
A planar medium flow path through which the medium flows;
A catalyst layer formed in the flow path;
A hydrogen separation means for separating the released hydrogen from the medium storing hydrogen and the medium releasing hydrogen;
The released hydrogen, the medium storing hydrogen and the flow port through which the medium releasing hydrogen flows in or out are formed integrally,
The hydrogen separation means is a flat plate cooler for cooling the released hydrogen, the medium storing hydrogen, and the medium releasing hydrogen, and the hydrogen released by the cooler is in a gaseous state. Separating the medium storing hydrogen and the medium releasing hydrogen from the medium as a liquid;
The cooler is formed adjacent to the surface of the medium flow path;
The medium flow path, have a plurality of injection unit for injecting the medium into the reaction section and the reaction section as a planar structure formed on one surface of the substrate,
The medium flow path, the catalyst layer and the hydrogen separation means hydrogen storage and supply device according to claim is Rukoto are sequentially formed. 4. The hydrogen storage / supply device according to claim 1, wherein the medium flow path is formed on at least one surface of the high thermal conductive substrate.   5. The switching means according to any one of claims 1 to 4, wherein the flow port alternately changes inflow or outflow of the separated released hydrogen, the medium storing hydrogen, and the medium releasing hydrogen. A hydrogen storage / supply device characterized by being a discharge port or a supply port. In claim 3, the hydrogen to at least one surface of the high thermal conductivity substrate, the medium flow path, the catalyst layer, a spacer, characterized in that are sequentially formed the hydrogen separation unit consisting of hydrogen flow path and a condenser Storage and supply equipment. According to claim 1, and wherein at least one surface of the high thermal conductivity substrate, the medium flow path, the catalyst layer, the hydrogen separation unit consisting of hydrogen separation membrane, that spacer and the hydrogen flow channel layer are sequentially formed Hydrogen storage and supply equipment. In claim 2, the at least one surface of the high thermal conductivity substrate, the hydrogen flow channel, the hydrogen separation membrane, a catalyst layer, a fuel injection for injecting the medium in which a plurality of through-holes were stored disposed hydrogen to said catalyst layer A hydrogen storage / supply device characterized in that a fuel storage layer for sequentially storing a layer and the medium storing hydrogen is formed.   9. The hydrogen storage / supply device according to claim 1, further comprising a diffusion unit in contact with the reaction unit. 9. The hydrogen storage / supply device according to claim 8 , wherein the fuel injection layer is formed on the same plane as the catalyst layer.   11. The hydrogen storage / supply device according to claim 9, wherein the reaction unit has a barrier pattern that serves as a barrier for the flow of the medium.   The hydrogen storage / supply device according to claim 1, wherein the medium flow path has a width and a gap of 0.1 to 1000 μm, respectively.   The hydrogen storage / supply device according to claim 1, wherein the medium flow path is made of metal and serves as a heater when energized from outside.   14. The hydrogen storage / supply device according to claim 2, wherein the catalyst layer is a porous membrane. According to claim 2, burning on the opposite side, the medium was discharged residual water-containing or hydrogen fuel cells for the formation face side of the catalyst layer of the medium flow path formed in the high thermal conductive substrate combustion A hydrogen storage / supply device, wherein a combustion chamber substrate on which a catalyst layer and a flow path for introducing the residual hydrogen or the medium are formed is sequentially formed.   16. The catalyst layer according to claim 1, wherein the catalyst layer is at least selected from the group consisting of nickel, palladium, platinum, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, and iron. A hydrogen storage / supply device comprising a metal catalyst composed of one kind of metal and at least one selected from the group consisting of alumina, zinc oxide, silica, zirconium oxide and diatomaceous earth.   17. The hydrogen storage according to claim 4, wherein the high thermal conductive substrate is a clad material in which an aluminum layer is provided on an aluminum or non-aluminum material surface, and an anodic oxide film is formed on the surface.・ Supply device.   18. The hydrogen storage / supply device according to claim 17, wherein the anodic oxide film is alumina formed by enlarging the surface pores, then boehmite, and then firing.   19. The hydrogen storage / supply device according to claim 18, wherein the surface pores are filled with at least one selected from alumina, zinc oxide, silica, and zirconium oxide.   20. The medium according to any one of claims 1 to 19, wherein the medium from which the hydrogen has been released is any one of acetone, benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl, phenanthrene, and their alkyl substituents. A hydrogen storage and supply device characterized by being a mixture of a plurality of the above. A hydrogen storage / supply device according to any one of claims 1 to 20, a tank section for storing the medium storing the hydrogen and a storage section for storing the medium from which the hydrogen has been released, and a storage section for discharging the hydrogen from the medium. And a hydrogen storage / supply system comprising a supply section for supplying the hydrogen to the fuel cell and a heat exchanger.   The heat exchanger according to claim 21, wherein the heat exchanger has a circulation path for exchanging heat between the medium storing the hydrogen and the medium discharging the hydrogen or the heated water discharged from the fuel cell. Hydrogen storage and supply system. According to claim 21 or 22, wherein the medium storing the hydrogen is liquid, hydrogen storage and supply systems, characterized in that the supply unit is intermittent liquid feeding can liquid transfer device. In any one of claims 21 to 23, wherein the tank section, comprising: the above medium storing the hydrogen in a lower portion, a movable partition plate, each separating storing said medium to release the hydrogen at the top Hydrogen storage and supply system.   25. A distributed power source comprising: the hydrogen storage / supply system according to claim 21; the fuel cell; and one of a prime mover selected from a turbine and an engine.   26. The distributed power source according to claim 25, wherein the heat exchanger uses waste heat of the fuel cell or a prime mover.   An automobile comprising the hydrogen storage / supply system according to any one of claims 21 to 24, the fuel cell, and one of a prime mover selected from a gas turbine and an internal combustion engine.   28. The automobile according to claim 27, wherein the heat exchanger uses waste heat of the fuel cell or a prime mover.

Images