WO2007116734A1 - エネルギー供給システム及び水素生成物質 - Google Patents
エネルギー供給システム及び水素生成物質 Download PDFInfo
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- WO2007116734A1 WO2007116734A1 PCT/JP2007/056384 JP2007056384W WO2007116734A1 WO 2007116734 A1 WO2007116734 A1 WO 2007116734A1 JP 2007056384 W JP2007056384 W JP 2007056384W WO 2007116734 A1 WO2007116734 A1 WO 2007116734A1
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- hydrogen
- water
- supply system
- energy supply
- unit
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/60—Preparation of carbonates or bicarbonates in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- the present invention relates to an energy supply system and a hydrogen producing material.
- FIG. 1 is a block diagram showing an example of a conventional energy supply system.
- the conventional energy supply system 101 comprises a fuel cell 104 as an energy generating device, a hydrogen tank 102 and an oxygen tank 103.
- the fuel cell 104 is supplied with hydrogen from the hydrogen tank 102 via the pipe 111 and oxygen from the oxygen tank 103 via the pipe 112.
- the fuel cell 104 generates heat as well as power based on hydrogen and oxygen.
- the fuel cell 104 discharges the exhaust (water vapor) through the pipe 113
- the energy supply system 101 suppress emissions as much as possible, and reuse reusable ones as much as possible.
- the energy supply system 101 is used in an enclosed space 110 such as underwater, underground, space facilities, or transportation means, the requirement is particularly remarkable.
- the hydrogen tank 102 generates hydrogen by the reaction of metal and water, it is conceivable to circulate the water vapor in the exhaust to the hydrogen tank 102 through the pipe 113a.
- a fuel cell power generation system is disclosed in Japanese Patent Application Laid-Open No. 2003-317786.
- This fuel cell power generation system generates a hydrogen by the reaction of a hydrogen generating substance (P) and water (W) with a fuel cell (2) which generates electricity using hydrogen as fuel and generates the hydrogen.
- the hydrogen generator (4) to be supplied to the fuel cell (2) and the water generated by the operation of the fuel cell (2) are received, and the water is used as reaction water in the hydrogen generator (4).
- a water supply device (7) for supplying water for supplying water.
- the hydrogen generator generates hydrogen by supplying water to a hydrogen generating material (eg, Mg alloy particles).
- a hydrogen generating material eg, Mg alloy particles.
- Japanese Patent Laid-Open No. 2002-208425 discloses a fuel cell fuel reformer.
- This fuel reformer is a fuel reformer that produces hydrogen from fuel and steam.
- Fuel reforming catalyst layer filled with catalyst for steam reforming of fuel reforming fuel gas supply means for introducing reforming fuel gas including fuel and steam into the fuel reforming catalyst layer, steam reforming A reformed fuel gas exhausting means for discharging the hydrogen main component gas generated by the fuel reforming catalyst layer from the fuel reforming catalyst layer, and the fuel reforming catalyst layer to absorb carbon dioxide contained in the reformed fuel
- a metal oxide layer provided downstream of the The metal oxide layer is, for example, a magnesium oxide layer.
- the magnesium oxide layer reacts with carbon dioxide to produce magnesium carbonate. That is, carbon dioxide can be recovered without being released to the atmosphere.
- a fuel cell system is disclosed in Japanese Patent Laid-Open No. 2002-373690.
- the fuel cell system comprises a fuel cell, a hydrogen storage device, a third flow path, and a radiator.
- the hydrogen storage device is provided in a second flow passage branched from a first flow passage communicating the hydrogen supply device and the fuel cell, and accommodates a hydrogen storage alloy.
- the third channel circulates the cooling water of the fuel cell.
- the radiator is provided in the middle of the third flow path.
- the hydrogen storage alloy absorbs and does not release hydrogen when the fuel cell system stops before warming up. Have sex.
- the hydrogen storage device is installed to exchange heat with the cooling water downstream of the third flow path radiator.
- a means for detecting the temperature of the cooling water downstream of the radiator in the third flow path, and the hydrogen storage alloy force when the detected cooling water temperature reaches the operation upper limit temperature of the fuel cell And means for controlling to lower In this fuel cell system, the flow path of the fuel cell cooling water and the flow path of the water to the hydrogen storage alloy are the same.
- Japanese Patent Laid-Open No. 2002-80202 discloses a fuel cell fuel gas generation system.
- the fuel gas generation system injects water from the injector to hydrolyze the metal hydride to produce hydrogen while supplying finely pulverized metal hydride into the reactor.
- the water supplied is the water produced by the fuel cell.
- the water tank for hydrolysis can be omitted or downsized, and the whole system can be downsized.
- the waste heat of the fuel cell may be supplied to the reactor to thermally decompose the metal hydride, or the heat generated during hydrolysis may be used to thermally decompose another metal hydride.
- This fuel cell system may use the heat of the fuel cell cooling water for hydrogen production.
- the fuel cell cooling water itself is not used for hydrogen production.
- An object of the present invention is to provide an energy supply system and a hydrogen-producing substance that can suppress emissions and reuse as much as possible.
- Another object of the present invention is to provide an energy supply system and a hydrogen-producing substance capable of suppressing an increase in the concentration of carbon dioxide in a closed space (or a finite space).
- Still another object of the present invention is to provide an energy supply system and a hydrogen-producing substance capable of suppressing emissions and reusing as much as possible in a closed space.
- Another object of the present invention is to provide an energy supply system and a hydrogen-producing substance capable of stably producing and supplying a necessary amount of hydrogen in an enclosed space regardless of operating conditions. .
- the energy supply system of the present invention comprises a hydrogen supply unit in which a hydrogen-producing substance and water react to generate hydrogen and a hydroxide compound, and a hydrogen supply unit.
- An energy generating unit is provided which generates energy from hydrogen supplied from the oxygen source and oxygen supplied from the oxygen supplying unit.
- a processing unit in which water is produced by the reaction of a hydroxylated compound generated in the hydrogen supply unit and a gas containing at least carbon dioxide.
- a separation unit may be provided in which the carbonic acid compound and water generated in the processing unit are separated.
- the hydrogen generating material is Mg, Ni, Fe, V, Mn,
- the water-soluble film may contain a material that dissolves by contact with water.
- the water-soluble film is an aqueous epoxy resin, an aqueous urethane resin, an aqueous acrylic resin, an aqueous polyester resin, an aqueous acrylic silicone resin, an aqueous fluorine resin,
- aqueous silica 'organic hybrid polymers it is possible to include at least one material selected from the group consisting of caustic.
- the hydrogen supply unit may be provided with a temperature control unit that controls the temperature of the hydrogen generation material.
- the energy supply system described above may include water amount adjustment means for controlling the amount of water in the hydrogen supply unit.
- the above-mentioned energy supply system may be provided with pressure adjusting means for controlling the pressure in the hydrogen supply unit.
- the hydrogen supply unit includes a hydrogen generation material supply unit that supplies a hydrogen generation material to the inside!
- the above energy supply system may include a heat exchange unit that controls the temperature of water and hydrogen.
- the heat exchange unit uses oxygen to generate water and hydrogen. You may control the temperature of
- the hydrogen-producing substance of the present invention comprises particles that release hydrogen by reaction with water, and a water-soluble film that covers the surface of the particles.
- the particles may contain a material having the property of releasing hydrogen in a hydrolysis reaction.
- particles are Mg, Ni, Fe, V, Mn, Ti, Cu, Ag, Ca
- the water-soluble film may contain a material that dissolves in contact with water.
- the water-soluble film is an aqueous epoxy resin, an aqueous urethane resin, an aqueous acrylic resin, an aqueous polyester resin, an aqueous acrylic silicone resin, an aqueous fluorine resin. And at least one material selected from fat and aqueous silica 'organic hybrid polymers.
- the method for producing a hydrogen-producing substance of the present invention (a) particles that release hydrogen by reaction with water are treated with the first method so that the oxide film on the surface disappears.
- the method further comprises the steps of: placing a reducing atmosphere under the conditions; and (b) placing the particles in an acid atmosphere under the second condition so as to form an oxide film on part of the surface.
- the particles may contain a material having a property of releasing hydrogen by a hydrolysis reaction.
- the particles are selected from Mg, Ni, Fe, V, Mn, Ti, Cu, Ag, Ca, Zn, Zr, Co, Cr, Al Force may include at least one selected material.
- the acid atmosphere under the second condition may be controlled by the partial pressure of oxygen to a gas inert to acid.
- a hydrogen supply unit in which a hydrogen-producing substance and water react to generate hydrogen and a hydroxide compound, and a hydrogen supply unit
- An energy generating unit that generates energy by hydrogen supplied from the oxygen supply unit and oxygen supplied from the oxygen supplying unit, and a cooling unit including a circulation flow path through which cooling water that cools the energy generating unit flows.
- the circulation channel is provided with a branch channel through which cooling water is supplied from the circulation channel to the hydrogen supply unit based on the amount of hydrogen supplied from the hydrogen supply unit to the energy generation unit.
- a processing unit may be provided that generates water by reacting a hydroxylated compound generated in the hydrogen supply unit with a gas containing at least carbon dioxide.
- a separation unit may be provided in which the carbonic acid compound and water generated in the processing unit are separated.
- FIG. 1 is a configuration diagram showing an example of a conventional energy supply system.
- FIG. 2 is a block diagram showing the configuration of the first embodiment of the energy supply system of the present invention.
- FIG. 3 is a view showing the configuration of the embodiment of the hydrogen-producing substance of the present invention.
- FIG. 4 is a view showing another configuration of the embodiment of the hydrogen-producing substance of the present invention.
- FIG. 5 is a block diagram showing the configuration of a second embodiment of the energy supply system of the present invention.
- FIG. 6 is a block diagram showing the configuration of a third embodiment of the energy supply system of the present invention.
- FIG. 7 is a block diagram showing the configuration of a fourth embodiment of the energy supply system of the present invention.
- FIG. 8 is a block diagram showing the configuration of a fifth embodiment of the energy supply system of the present invention.
- FIG. 9 is a schematic view showing another configuration of the hydrogen supply unit 2.
- FIG. 10 is a block diagram showing a configuration of a sixth embodiment of the energy supply system of the present invention.
- FIG. 11 shows the configuration of the seventh embodiment of the energy supply system of the present invention. Block diagram.
- FIG. 2 is a block diagram showing the configuration of the first embodiment of the energy supply system of the present invention.
- the energy supply system 1 is provided in the enclosed space 10, and includes a hydrogen supply unit 2, an oxygen supply unit 3, a fuel cell 4, a processing unit 5, and a separation unit 6.
- the enclosed space 10 is a facility having a generally closed space as a whole, such as facilities provided in the sea, underground, or space, or transportation means for moving in the sea, underground, or space.
- CO 2 carbon dioxide
- enclosed space 10 carbon dioxide (CO 2) will increase due to equipment and human activity.
- it can be attached fuel
- the energy supply system 1 needs to control emissions and reuse as much as possible.
- the hydrogen supply unit 2 is produced by the reaction of water (H 0) 23 and magnesium (Mg) particles 21 by the following formula:
- Water (H 0) 23 is contained in the exhaust of the fuel cell 4 and supplied from the pipe 13. That water (H 0) 23 is contained in the exhaust of the fuel cell 4 and supplied from the pipe 13. That water (H 0) 23 is contained in the exhaust of the fuel cell 4 and supplied from the pipe 13. That water (H 0) 23 is contained in the exhaust of the fuel cell 4 and supplied from the pipe 13. That water (H 0) 23 is contained in the exhaust of the fuel cell 4 and supplied from the pipe 13. That water (H
- 0) 23 may be liquid water, a mixture of liquid water and steam, or only steam.
- Magnesium (Mg) particles 21 exist inside the hydrogen supply unit 2.
- the generated hydrogen (H 2) is
- Fuel cell 4 is supplied via pipe 11.
- the generated magnesium hydroxide (Mg (OH) 2) 22 precipitates in the water 23 and is treated as a slurry mixed with the water through the pipe 14 and the processing unit 5
- the oxygen supply unit 3 supplies oxygen (O 2) to the fuel cell 4 through the pipe 12.
- Oxygen supply unit 3 supplies oxygen (O 2) to the fuel cell 4 through the pipe 12.
- 3 is not particularly limited, but is, for example, an oxygen cylinder.
- the fuel cell 4 is composed of hydrogen (H 2) from the hydrogen supply unit 2 and oxygen (O 2) from the oxygen supply unit 3.
- the type of the fuel cell 4 is not particularly limited, and is, for example, PEFC (solid polymer fuel cell).
- PEFC solid polymer fuel cell
- other facilities that generate energy using hydrogen may be used.
- a hydrogen gas engine For example, a hydrogen gas engine.
- power electric power when linked with a generator
- heat are generated based on hydrogen and oxygen
- the exhaust is water (steam).
- Power (power) and heat are recovered and used by equipment not shown.
- the processing unit 5 mixes the slurry (magnesium hydroxide (Mg (OH)) 22 + water 23) from the hydrogen supply unit 2 through the pipe 14 with the atmosphere gas (diacid of the sealed space 10 through the pipe 16).
- Carbon (C) magnesium hydroxide (Mg (OH) 22 + water 23) from the hydrogen supply unit 2 through the pipe 14 with the atmosphere gas (diacid of the sealed space 10 through the pipe 16).
- the formed magnesium carbonate (MgCO 3) 24 precipitates in water (H 0) 23 and mixes with water 23
- the combined slurry is supplied to the separation unit 6 through the pipe 15.
- the separator 6 is a carbon in the slurry (magnesium carbonate (MgCO 3) 24 + water (H 0) 23).
- the processing unit 5 solidifies and removes the separated magnesium carbonate 24 and delivers the water 23 to another device for reuse (not shown).
- the reuse is exemplified as water for the hydrogen supply unit 2 and water for the anode of the fuel cell via a water storage device (not shown).
- the energy supply system of the present invention it is used for the treatment of carbon dioxide dioxide which is inevitably generated in the enclosed space 10 rather than discharging hydroxide 22 generated by the production of hydrogen. There is. This eliminates the need to provide a carbon dioxide removal device.
- useful water 23 can be produced by using carbon dioxide dioxide and magnesium hydroxide 22 which are conventionally removed as unnecessary ones. That is, in the enclosed space 10, carbon dioxide While being able to suppress the concentration increase of the element, it becomes possible to suppress and reuse the emissions (carbon dioxide and hydroxide 22).
- magnesium (Mg) particles 21 used for the hydrogen supply unit 2 will be described.
- Magnesium particles 21 are particles containing magnesium (Mg) and release hydrogen by reaction with water. That is, the magnesium particles 21 may be pure magnesium particles, magnesium particles containing impurities, particles of an alloy containing magnesium, or particles containing magnesium as a catalyst metal supported on a catalyst carrier. . Alternatively, the hydrogen-producing substance 21 of the present invention shown below may be used.
- FIG. 3 is a view showing the configuration of an embodiment of the hydrogen-producing substance 21 of the present invention.
- the hydrogen-producing substance 21 of the present invention is, for example, particles 61 of magnesium shown in FIG. 3 (a) (example: pure magnesium particles, magnesium particles containing impurities, particles of magnesium-containing alloy, and catalyst carrier.
- the surface of the catalyst metal-like particles containing magnesium is covered with a water-soluble film 62 as shown in FIG. 3 (b).
- Such a water-soluble coating 62 may be an aqueous epoxy resin, an aqueous urethane resin, an aqueous acrylic resin, an aqueous polyester resin, an aqueous acrylic silicone resin, an aqueous fluorine resin, an aqueous silica 'organic silica, organic silica, organic silicone, It is exemplified as one containing at least one kind of material selected from among materials which dissolve by contact with water, such as liquid polymers.
- the surface of the particles 61 can be prevented from being oxidized by covering with the water-soluble film 62.
- hydrogen can be generated by the reaction with the water 23.
- the ratio of the surface 6 la to which the particles 61 are exposed to the surface 6 lb to which the particles 61 are not exposed controls the generation rate of generated hydrogen. Can be controlled.
- the water-soluble film can not be completely dissolved and remains on the surface, so the hydrogen generation rate can be suppressed compared to the case where all the water-soluble film is dissolved.
- the water-soluble film can not be completely dissolved and remains on the surface, so the hydrogen generation rate can be suppressed as compared with the case where all the water-soluble film is dissolved.
- the surface 61 a and the surface 61 b of the water-soluble film 62 The ratio of hydrogen to hydrogen can be controlled in more detail to more precisely control the rate of hydrogen generation. For example, by lowering the temperature of water, the water-soluble film can not be dissolved completely and remains on the surface, so that the hydrogen generation rate can be suppressed as compared with the case where all the water-soluble film is dissolved.
- An energy supply system for controlling the temperature of water will be described in the second and subsequent embodiments.
- the particles 61 In the hydrogen supply unit 2, magnesium is used as the particles 61 in consideration of the reaction between magnesium hydroxide 22 and carbon dioxide in the processing unit 5.
- the hydrogen-producing substance 21 of the present invention does not limit the particles 61 to magnesium.
- the particles 61 In the case of the above-mentioned processing unit 5, in the case of heat resistance, the particles 61 have a hydrolytic reaction such as Mg ⁇ Ni ⁇ Fe ⁇ V, Mn, Ti ⁇ Cu ⁇ Ag ⁇ Ca ⁇ Zn, Zr ⁇ Co, Cr, Al, etc. And at least one material selected from materials having the property of releasing hydrogen.
- the particles 61 may be particles generally composed of only the material, particles of an alloy containing the material, or particles of the material in the form of a catalytic metal supported on a catalyst carrier.
- the surface of the particles 61 is prevented from being oxidized, hydrogen is generated when the water-soluble film 62 is dissolved by the supplied water, and the water is controlled by controlling the type of the water-soluble film 62 and the film forming conditions. It is possible to control the formation rate of hydrogen and to control the generation rate of hydrogen by controlling the temperature and pressure of the supplied water.
- FIG. 4 is a view showing another configuration of the embodiment of the hydrogen-producing substance 21 of the present invention.
- the particles 61 exemplified by magnesium particles have oxides 63 formed on the surface when stored in an air atmosphere. Therefore, as shown in FIG. 4 (b), in use, the particles 61 are placed in a predetermined reducing atmosphere so that the oxide film 63 on the surface disappears.
- the predetermined reducing atmosphere is, for example, a hydrogen atmosphere, atmospheric pressure, about 300.degree. As a result, the oxide film 63 which has covered the surface is removed by reduction.
- the particles 61 are placed in a predetermined oxidizing atmosphere so as to form an oxide film 63a on a part of the surface.
- the predetermined oxidizing atmosphere is set by the partial pressure of oxygen to the gas inert to oxidation. The higher the partial pressure of oxygen, the more the surface area covered by the oxide film. The lower the oxygen partial pressure, the smaller the surface area covered by the oxide film.
- the oxygen partial pressure is 5% or more and 10% or less
- the rest is composed of a gas inert to oxidation. Atmosphere, atmospheric pressure and room temperature. This makes it possible to control the amount of the acid film 63a covering the surface, so that the rate of hydrogen generation can be controlled.
- the particle 61 is magnesium, and when the restriction of the processing unit 5 is not present, the particle 61 is Mg, Ni, Fe, V, Mn, Ti, Cu, Ag , Ca, Zn, Zr, Co, Cr, Al, etc., preferably including at least one material selected from materials having the property of releasing hydrogen in a hydrolysis reaction.
- the hydrogen supply unit 2 When the energy supply system 1 is activated, the hydrogen supply unit 2 is supplied with water 23 from a water storage device (not shown) and from the pipe 13 after activation. Then, hydrogen and magnesium hydroxide 22 are generated by the reaction of water 23 and magnesium particles 21.
- the hydrogen supply unit 2 supplies hydrogen to the fuel cell 4 through the pipe 11 and the slurry in which magnesium hydroxide 22 and water 23 are mixed through the pipe 14 to the processing unit 5.
- the oxygen supply unit 3 supplies oxygen to the fuel cell 4 via the pipe 12.
- the fuel cell 4 generates power and heat from the hydrogen from the hydrogen supply unit 2 and the oxygen from the oxygen supply unit 3.
- water (steam) is generated as an exhaust and discharged to piping 13.
- the processing unit 5 is supplied with a slurry (a magnesium hydroxide 22 + water 23) supplied via a pipe 14 and carbon dioxide via a pipe 16. Then, water 23 and magnesium carbonate 24 are formed by the reaction of hydroxyl group magnesium 22 and its carbon dioxide in the slurry.
- the processing unit 5 supplies the slurry in which the magnesium carbonate 24 and the water 23 are mixed to the separation unit 6 through the pipe 15.
- the separation unit 6 separates the slurry (magnesium carbonate 24 + water 23) supplied via the pipe 15 into magnesium carbonate 24 and water 23.
- the separation unit 6 solidifies and removes the magnesium carbonate 24 and delivers the water 23 to another device for reuse. For example, it is stored in the above-mentioned not-shown water storage device and reused at startup.
- a pump or a valve for controlling the flow of fluid may be provided in the middle of each pipe, if necessary.
- FIG. 5 is a block diagram showing the configuration of a second embodiment of the energy supply system of the present invention.
- the energy supply system la is provided in the enclosed space 10, and a hydrogen supply unit 2, an oxygen supply unit 3, a fuel cell 4, a processing unit 5, a separation unit 6, a heat exchange unit 7, a temperature sensor 31, 32, a liquid level gauge 33, flow control valves 41, 42, 43, and a control valve 45 are provided.
- the piping 17, the piping 13, and the piping 11 a pass through.
- a cooling heat medium having a controlled flow rate flows through the flow control valve 41.
- water (steam) discharged from the fuel cell 4 and supplied to the hydrogen supply unit 2 flows.
- the pipe 11 a is delivered to the hydrogen supply unit 2 power pipe 11, and a part of the hydrogen whose flow rate is controlled flows through the flow control valves 42 and 43 (the rest pass through the 1 lb pipe).
- the heat exchange unit 7 cools (condenses) water (steam: high temperature) supplied to the hydrogen supply unit 2 through the pipe 13 by heat exchange with the cooling heat medium (low temperature) passing through the pipe 17 Do. By condensing into liquid water, it is possible to control the amount of hydrogen generation in the hydrogen supply unit 2 more easily.
- the flow control valve 41 controls the flow rate of the cooling heat medium (example: PID control) to obtain the temperature of the water 23 in the pipe 13. It can be cooled to the desired temperature.
- the cooling heat medium lower temperature
- the enclosed space 10 when the enclosed space 10 is in contact with the sea or a river, it is exemplified by seawater or water of a river.
- oxygen for the fuel cell 4 needs to be raised to the operating temperature when supplied to the fuel cell 4, such oxygen can also be used.
- the pipe 12 is connected to the pipe 17 and all or part of the oxygen flowing through the pipe 12 is branched to the pipe 17. In that case, it is not necessary to procure a cooling heat medium from the outside of the system of the enclosed space 10, and the energy supply system can be simplified and its autonomy can be realized. It can be enhanced. Or, even if there is a shortage of cooling heat medium, it can be stored in seawater or river water.
- the control (for example, PID control) of the flow control valve 41 based on the temperature T1 described above is performed by a control device (not shown).
- the reaction of the magnesium particles 21 and the water 23 in the hydrogen supply unit 2 can be controlled by supplying the water 23 of the piping 13 to a desired temperature and supplying the water 23 to the hydrogen supply unit 2.
- the controller calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4, and the water in the hydrogen supply unit 2 based on the amount of hydrogen. It is possible to control the amount of hydrogen (production rate) produced at a desired temperature.
- the heat exchange unit 7 cools the hydrogen (high temperature) supplied to the fuel cell 4 through the pipe 11 a to a predetermined temperature by heat exchange with the cooling heat medium (low temperature) passing through the pipe 17.
- another pipe 17 '(not shown) through which the cooling heat medium (low temperature) passes may be used.
- the flow control valves 42 and 43 are linked to flow the flow rate of hydrogen flowing through the pipe 1 la and the pipe 1 lb
- the ratio of hydrogen flow rate of piping 11a to hydrogen flow rate of piping 11a is determined by controlling (example: PID control), hydrogen at the inlet of fuel cell 4 and predetermined temperature (example: fuel cell 4 is PEFC If the temperature is about 80 ° C).
- the hydrogen supply unit 2 is basically the same as that of the first embodiment. However, the difference is that a level gauge 33 and a pipe 18 are provided, and the pipe 18 is connected to a control valve 45.
- the liquid level meter 33 measures the liquid level of the water 23 of the hydrogen supply unit 2.
- the control valve 45 delivers water 23 to another (example: water storage device (not shown)) via the pipe 18.
- the hydrogen supply unit 2 can control the reaction between the magnesium particles 21 and the water 23 based on the liquid level of the water 23 measured by the liquid level meter 33. That is, based on the liquid level of the water 23 measured by the liquid level meter 33, the control valve 45 is controlled so that the amount of water 23 supplied and accumulated in the hydrogen supply unit 2 becomes a desired amount (example : PID control).
- the control of the control valve 45 (example: PID control) based on the liquid level of the water 23 is performed by a control device (not shown).
- a control device (not shown).
- the controller calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4, and based on the amount of hydrogen, the level gauge 33 It is possible to control the amount of hydrogen (generation rate) generated by setting the liquid level of water 2 3 to be measured to the desired liquid level
- the sealed space 10, the oxygen supply unit 3, the fuel cell 4, the processing unit 5, and the separation unit 6 are the same as in the first embodiment, and thus the description thereof is omitted.
- the same action and effect as those of the first embodiment can be obtained.
- the temperature of water in the pipe 13 can be controlled to a desired temperature. This makes it possible to control the reaction between magnesium particles 21 and water 23 to control the amount of hydrogen produced (generation rate).
- the delivery amount of water 23 by the control valve 45 the liquid level of the water 23 can be controlled to a desired liquid level. As a result, it is possible to control the reaction between the magnesium particles 21 and the water 23 to control the amount of generated hydrogen (the generation rate).
- the hydrogen can be at a predetermined temperature at the inlet of the fuel cell 4 (example: the fuel cell 4 is PEFC In the case of (about 80 ° C) can be.
- magnesium (Mg) particles used for the hydrogen supply unit 2 are the same as those of the first embodiment including the descriptions of FIG. 3 and FIG. 4, and thus the description thereof is omitted.
- the hydrogen supply unit 2 is supplied with water 23 from the water storage device (not shown) at the start of the energy supply system la and from the pipe 13 after the start. Then, hydrogen and magnesium hydroxide 22 are generated by the reaction of water 23 and magnesium particle 21. At this time, when the energy supply system la is started, the amount of water 23 is controlled to a desired amount by controlling the control valve 45 based on the liquid level of the water 23 to control the amount of water 23 reacting with the magnesium particles 21. Control. Thereby, it is possible to control the amount of generated hydrogen (generation rate).
- the water supplied to the hydrogen supply unit 2 is controlled to a desired temperature by the control of the flow control valve 41 based on the temperature of the water 23.
- the amount (production rate) of hydrogen to be produced can be controlled.
- the hydrogen supply unit 2 supplies hydrogen to the fuel cell 4 through the pipe 11 and the slurry in which the hydroxide hydroxide 22 and the water 23 are mixed through the pipe 14 to the processing unit 5.
- the oxygen supply unit 3 supplies oxygen to the fuel cell 4 through the pipe 12. At this time, hydrogen is supplied to the fuel cell 4 at a predetermined temperature by control of the flow control valves 42 and 43 based on the temperature T 2. As a result, the thermal efficiency of the fuel cell 4 can be improved, and the operation can be performed more properly.
- the fuel cell 4 generates power and heat from the hydrogen from the hydrogen supply unit 2 and the oxygen from the oxygen supply unit 3. In addition, water (water vapor) is generated as an exhaust and discharged to the piping 13.
- the processing unit 5 is supplied with a slurry (a magnesium hydroxide 22 + water 23) supplied via a pipe 14 and carbon dioxide via a pipe 16. Then, water 23 and magnesium carbonate 24 are formed by the reaction of hydroxide magnesium and 22 carbon dioxide in the slurry.
- the processing unit 5 supplies the slurry in which the magnesium carbonate 24 and the water 23 are mixed to the separation unit 6 through the pipe 15.
- the separation unit 6 separates the slurry (magnesium carbonate 24 + water 23) supplied via the pipe 15 into magnesium carbonate 24 and water 23.
- the separation unit 6 solidifies and removes the magnesium carbonate 24 and delivers the water 23 to another device for reuse. For example, it is stored in the above-mentioned not-shown water storage device and reused at startup.
- control the temperature of water 23 in piping 13 in heat exchange section 7 By controlling the amount of water 23 in the hydrogen supply unit 2, it is possible to control the reaction between the magnesium particles 21 and the water 23 to control the amount of hydrogen (generation rate) to be generated. Further, by controlling the flow rate of hydrogen flowing through the pipe 11 a and the pipe l i b in cooperation with the flow control valves 42 and 43, the hydrogen can be brought to a predetermined temperature at the inlet of the fuel cell 4.
- the temperature control of the water 23 of the pipe 13 in the heat exchange unit 7 and the control of the amount of the water 23 in the hydrogen supply unit 2 are performed! It is also possible to do one or the other. Also in that case, the same effect can be obtained.
- FIG. 6 is a block diagram showing the configuration of a third embodiment of the energy supply system of the present invention.
- the energy supply system lb is provided in the enclosed space 10, and comprises a hydrogen supply unit 2, an oxygen supply unit 3, a fuel cell 4, a processing unit 5, a separation unit 6, a liquid level gauge 33, a temperature sensor 37, and a control valve 45. Do.
- the hydrogen supply unit 2 is basically the same as that of the first embodiment. However, it differs in that a heat exchange pipe 25, a liquid level gauge 33, a temperature sensor 37, and a pipe 18 are provided, and a control valve 45 is connected to the pipe 18.
- a heat medium flows through the heat exchange pipe 25.
- the heat medium exchanges heat with the magnesium particles 21 and the water 23 of the hydrogen supply unit 2.
- the heat medium is heated or cooled based on the temperature T3 of the temperature sensor 37 in a heat medium temperature control unit (not shown) to control the temperature.
- the hydrogen supply unit 2 controls the reaction by controlling the temperature T3 of the magnesium particles 21 and the water 23 by heat exchange between the temperature-controlled heat medium and the magnesium particles 21 and the water 23. be able to. That is, based on the temperature T3 of the temperature sensor 37, the temperature of the heat medium is controlled such that the magnesium particles 21 and the water 23 have a desired temperature (example:
- Control of the temperature of the heat medium based on the temperature T3 of the magnesium particles 21 and the water 23 is performed by a control device (not shown).
- a control device (not shown)
- the controller calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4, and based on the amount of hydrogen, the magnesium particles 21 and the hydrogen supply unit It is possible to control the amount of hydrogen (generation rate) generated by setting the temperature of the water 23 in 2 to a desired temperature.
- the level gauge 33 measures the level of the water 23 of the hydrogen supply unit 2.
- the control valve 45 delivers the water 23 to another (example: water storage device (not shown)) via the pipe 18.
- the hydrogen supply unit 2 can control the reaction between the magnesium particles 21 and the water 23 based on the liquid level of the water 23 measured by the liquid level meter 33. That is, based on the liquid level of the water 23 measured by the liquid level meter 33, the control valve 45 is controlled so that the amount of the water 23 supplied and accumulated in the hydrogen supply unit 2 becomes a desired amount (example: PID Control.
- the control (example: PID control) of the control valve 45 based on the level of the water 23 is performed by a control device (not shown).
- a control device not shown
- the controller calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4, and based on the amount of hydrogen, the level gauge 33
- the amount of hydrogen (generation rate) generated by setting the liquid level of water 2 3 is measured to the desired liquid level
- the sealed space 10, the oxygen supply unit 3, the fuel cell 4, the processing unit 5, and the separation unit 6 are the same as in the first embodiment, and thus the description thereof is omitted.
- the same action and effect as those of the first embodiment can be obtained.
- the temperature of the heat medium of the pipe 25 it is possible to control the reaction between the magnesium particles 21 and the water 23 to control the amount of hydrogen (generation rate) to be generated.
- the liquid level of the water 23 can be controlled to a desired liquid level by controlling the delivery amount of the water 23 by the control valve 45.
- the magnesium (Mg) particles used in the hydrogen supply unit 2 are the same as those in the first embodiment including the descriptions in FIG. 3 and FIG. 4, and thus the description thereof is omitted.
- the hydrogen supply unit 2 is supplied with water 23 from the water storage device (not shown) at the start of the energy supply system lb and from the piping 13 after the start. Then, hydrogen and magnesium hydroxide 22 are generated by the reaction of water 23 and magnesium particle 21. At this time, by controlling the control valve 45 based on the liquid level of the water 23, the amount of the water 23 is controlled to a desired amount, and the amount of the water 23 reacting with the magnesium particles 21 is controlled. In addition, the temperature of the magnesium particles 21 and the water 23 is controlled by controlling the temperature of the heat medium of the pipe 25. At least one of these can control the amount of hydrogen produced (generation rate).
- the hydrogen supply unit 2 supplies hydrogen to the fuel cell 4 through the pipe 11 and the slurry in which the hydroxide hydroxide 22 and the water 23 are mixed through the pipe 14 to the processing unit 5.
- the oxygen supply unit 3 supplies oxygen to the fuel cell 4 through the pipe 12.
- the fuel cell 4 generates power and heat from the hydrogen from the hydrogen supply unit 2 and the oxygen from the oxygen supply unit 3.
- water (steam) is generated as an exhaust and discharged to piping 13.
- the processing unit 5 is supplied with a slurry (a magnesium hydroxide 22 + water 23) supplied via a pipe 14 and carbon dioxide via a pipe 16. Then, water 23 and magnesium carbonate 24 are formed by the reaction of hydroxyl group magnesium 22 and its carbon dioxide in the slurry.
- the processing unit 5 supplies the slurry in which the magnesium carbonate 24 and the water 23 are mixed to the separation unit 6 through the pipe 15.
- the separation unit 6 separates the slurry (magnesium carbonate 24 + water 23) supplied via the pipe 15 into magnesium carbonate 24 and water 23.
- the separation unit 6 solidifies and removes the magnesium carbonate 24 and delivers the water 23 to another device for reuse. For example, it is stored in the above-mentioned not-shown water storage device and reused at startup.
- the same function and effect as those of the first embodiment can be obtained.
- the reaction between the magnesium particles 21 and the water 23 is controlled to generate the amount of hydrogen ( It is possible to control the generation rate).
- the temperature control of the magnesium particles 21 and the water 23 by the heat medium and the control of the amount of the water 23 in the hydrogen supply unit 2 are also performed by shifting. It is good to do as well. Also in that case, the same effect can be obtained.
- FIG. 7 is a block diagram showing the configuration of a fourth embodiment of the energy supply system of the present invention.
- the energy supply system lc is provided in the enclosed space 10, and the hydrogen supply unit 2, the oxygen supply unit 3, the fuel cell 4, the processing unit 5, the separation unit 6, the water storage unit 8, the liquid level meter 33, and the liquid level meter 35 , Control valve 47, pump 52 equipped.
- the water storage section 8 is supplied with water (H20) contained in the exhaust gas of the fuel cell 4 through the pipe 13. Then, the water is supplied to the hydrogen supply unit 2 by the pump 52 connected to the pipe 55.
- the water storage unit 8 is provided with a control valve 47 via a liquid level gauge 35 and a pipe 19, and when the liquid level gauge 35 detects that the internal water 23 has exceeded a predetermined amount, the control valve 47 Open and send out the water 23 inside to another (example: water storage unit (not shown)) via piping 19.
- the hydrogen supply unit 2 is basically the same as that of the first embodiment. However, the difference is that the fuel cell 4 has a liquid level gauge 33 in that the exhaust gas (water) is not directly received but is received via the pipe 55 after being temporarily stored in the water storage unit 8.
- the liquid level meter 33 measures the liquid level of the water 23 of the hydrogen supply unit 2.
- the hydrogen supply unit 2 can control the reaction between the magnesium particles 21 and the water 23 based on the liquid level of the water 23 measured by the liquid level meter 33. That is, based on the liquid level of the water 23 measured by the liquid level meter 33, the pump 52 is controlled so that the amount of water 23 supplied and accumulated in the hydrogen supply unit 2 becomes a desired amount (example: PID control). For example, the delivery rate (flow rate) of the water 23 is controlled by the number of revolutions of the pump 52 and the on / off of the pump 52.
- the control (example: PID control) of the pump 52 based on the level of the water 23 is performed by a controller (not shown).
- a controller not shown
- the controller calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4 and measures it with the liquid level meter 33 based on the amount of hydrogen.
- the closed space 10, the oxygen supply unit 3, the fuel cell 4, the processing unit 5, and the separation unit 6 are the same as in the first embodiment, and thus the description thereof is omitted.
- the same function and effect as those of the first embodiment can be obtained.
- the reaction between the magnesium particles 21 and the water 23 is controlled.
- magnesium (Mg) particles 21 used in the hydrogen supply unit 2 are the same as those in the first embodiment including the descriptions in FIG. 3 and FIG. 4, and thus the description thereof is omitted.
- the hydrogen supply unit 2 is supplied with the water 23 from the water storage unit 8 both at the time of start-up and after the start of the energy supply system lc. Then, hydrogen and magnesium hydroxide 22 are produced by the reaction of water 23 and magnesium particles 21. At this time, by controlling the pump 52 based on the liquid level of the water 23, the amount of water 23 is controlled to a desired amount, and the amount of water 23 reacting with the magnesium particles 21 is controlled. As a result, the amount of generated hydrogen (production rate) can be controlled.
- the hydrogen supply unit 2 supplies hydrogen to the fuel cell 4 through the pipe 11 and the slurry in which the hydroxide hydroxide 22 and the water 23 are mixed through the pipe 14 to the processing unit 5.
- the oxygen supply unit 3 supplies oxygen to the fuel cell 4 through the pipe 12.
- the fuel cell 4 generates power and heat from the hydrogen from the hydrogen supply unit 2 and the oxygen from the oxygen supply unit 3.
- water (steam) is generated as an exhaust and discharged to piping 13.
- the processing unit 5 is supplied with a slurry (a magnesium hydroxide 22 + water 23) supplied via a pipe 14 and carbon dioxide via a pipe 16. And, the hygroscopic mug in the slurry Water 23 and magnesium carbonate 24 are formed by the reaction of Nesium 22 with its carbon dioxide.
- the processing unit 5 supplies the slurry in which the magnesium carbonate 24 and the water 23 are mixed to the separation unit 6 through the pipe 15.
- the separation unit 6 separates the slurry (magnesium carbonate 24 + water 23) supplied via the pipe 15 into magnesium carbonate 24 and water 23.
- the separation unit 6 solidifies and removes the magnesium carbonate 24 and delivers the water 23 to another device for reuse. For example, it is stored in the above-mentioned not-shown water storage device and reused at startup.
- the same function and effect as those of the first embodiment can be obtained.
- the reaction between the magnesium particles 21 and the water 23 can be controlled to control the amount of generated hydrogen (the generation rate). Become.
- FIG. 8 is a block diagram showing the configuration of a fifth embodiment of the energy supply system of the present invention.
- the energy supply system Id is provided in the enclosed space 10, and a hydrogen supply unit 2, an oxygen supply unit 3, a fuel cell 4, a processing unit 5, a separation unit 6, a heat exchange unit 7, a temperature sensor 31, 32, a liquid level gauge 33, a pressure gauge 34, flow control valves 41, 42, 43, a control valve 45, pressure control valves 44, 46, and a pressure pump 51.
- the hydrogen supply unit 2 is basically the same as that of the second embodiment. However, a pressure gauge 34 is provided, a pressure pump 51 is connected to the pipe 13, and a pressure control valve 44 is connected to the pipe 11.
- the pressure gauge 34 measures the pressure of the hydrogen supply unit 2.
- the pressurizing pump 51 boosts the pressure of the water 23 supplied from the fuel cell 4 to a desired pressure, and supplies it to the hydrogen supply unit 2.
- the pressure control valve 44 reduces the pressure of hydrogen supplied from the hydrogen supply unit 2 to the operating pressure of the fuel cell 4 and supplies the fuel cell 4 via the pipes l la and l ib.
- a pressure control valve 46 is provided in a pipe 56 for bypassing the pressure pump 51 and is opened as necessary.
- the hydrogen supply unit 2 can control the reaction between the magnesium particles 21 and the water 23 based on the pressure of the hydrogen supply unit 2 measured by the pressure gauge 34. That is, it measures with pressure gauge 34 Based on the pressure of the hydrogen supply unit 2, the pressure pump 51 is controlled (example: PID control) so that the pressure of the water 23 supplied and accumulated in the hydrogen supply unit 2 becomes a desired pressure.
- PID control example: PID control
- the control of the pressure pump 51 based on the pressure of the hydrogen supply unit 2 is performed by a control device (not shown).
- a control device not shown.
- control device calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4, and the hydrogen measured by the pressure gauge 34 based on the amount of hydrogen. It is possible to control the amount of hydrogen (production rate) generated by setting the pressure of the supply unit 2 to a desired pressure.
- the same function and effect as those of the second embodiment can be obtained.
- the pressure of the water in the pipe 13 with the pressurizing pump 51, the pressure of the water 23 in the hydrogen supply unit 2 can be controlled to a desired pressure. This makes it possible to control the reaction between the magnesium particles 21 and the water 23 to control the amount (generation rate) of hydrogen produced.
- magnesium (Mg) particles 21 used in the hydrogen supply unit 2 are the same as those in the second embodiment including the descriptions in FIG. 3 and FIG. 4, and thus the description thereof is omitted.
- the hydrogen supply unit 2 is supplied with water 23 from the water storage device (not shown) at the start of the energy supply system Id and from the pipe 13 after the start. Then, hydrogen and magnesium hydroxide 22 are generated by the reaction of water 23 and magnesium particle 21. At this time, at the start of the energy supply system Id, the amount of water 23 is controlled to a desired amount by control of the control valve 45 based on the liquid level of the above-mentioned (second embodiment). Control the amount of water 23 that reacts with particles 21. Thereby, it is possible to control the amount of generated hydrogen (production rate).
- the control of the flow control valve 41 based on the temperature of the water 23 of the above (second embodiment) The supplied water 23 is controlled to a desired temperature, and the control of the pressure pump 51 based on the pressure of the hydrogen supply unit 2 controls the water 23 of the hydrogen supply unit 2 to a desired pressure. These control the reaction between the water 23 and the magnesium particles 21. Thereby, the amount (production rate) of hydrogen to be produced can be controlled.
- the hydrogen supply unit 2 supplies hydrogen to the fuel cell 4 through the pipe 11 and the slurry in which the hydroxide hydroxide 22 and the water 23 are mixed through the pipe 14 to the processing unit 5.
- the oxygen supply unit 3 supplies oxygen to the fuel cell 4 through the pipe 12. At this time, hydrogen is supplied to the fuel cell 4 at a predetermined temperature by control of the flow control valves 42 and 43 based on the temperature T 2. As a result, the thermal efficiency of the fuel cell 4 can be improved, and the operation can be performed more properly.
- the fuel cell 4 generates power and heat from the hydrogen from the hydrogen supply unit 2 and the oxygen from the oxygen supply unit 3. In addition, water (water vapor) is generated as an exhaust and discharged to the piping 13.
- the processing unit 5 is supplied with a slurry (hydroxic acid magnesium 22 + water 23) supplied via the pipe 14 and carbon dioxide via the pipe 16. Then, water 23 and magnesium carbonate 24 are formed by the reaction of hydroxyl group magnesium 22 and its carbon dioxide in the slurry.
- the processing unit 5 supplies the slurry in which the magnesium carbonate 24 and the water 23 are mixed to the separation unit 6 through the pipe 15.
- the separation unit 6 separates the slurry (magnesium carbonate 24 + water 23) supplied via the pipe 15 into magnesium carbonate 24 and water 23.
- the separation unit 6 solidifies and removes the magnesium carbonate 24 and delivers the water 23 to another device for reuse. For example, it is stored in the above-mentioned not-shown water storage device and reused at startup.
- the pressure of the water 23 of the hydrogen supply unit 2 is controlled to a desired pressure by controlling the pressure of the water of the pipe 13 with the pressure pump 51 to control the amount of generated hydrogen (the generation rate). It becomes possible.
- temperature control of water 23 of piping 13 in heat exchange unit 7 water
- the control of the amount of water 23 and the pressure control of the water 23 in the element supply unit 2 may be performed by displacing! /, But displacing may also be performed. Also in that case, the same effect can be obtained.
- FIG. 9 is a schematic view showing another configuration of the hydrogen supply unit 2.
- the hydrogen supply unit 2 includes a particle supply unit 9, a particle supply mechanism 47, and a hydrogen generation unit 2 a, and a control valve 45 is connected via a liquid level gauge 36 and a pipe 18.
- the hydrogen generation unit 2 a stores the water 23 supplied from the pipe 13.
- the liquid level meter 36 detects the liquid level 23a of the water of the hydrogen generation unit 2a.
- the control valve 45 is opened when the liquid level reaches a predetermined height or more, and delivers the water 23 inside to another (example: water storage device (not shown)) through the pipe 18.
- the particle supply unit 9 holds the magnesium particles 21.
- the particle supply mechanism 47 is exemplified by a feeder, and supplies magnesium particles 21 of the particle supply unit 9 to the hydrogen generation unit 2a.
- the control device (not shown) calculates the amount of hydrogen that needs to be generated based on the power generated by the fuel cell 4. Then, based on the amount of hydrogen, the particle supply mechanism 47 is controlled to deliver the desired amount of magnesium particles 21 to the hydrogen generator 2a.
- the hydrogen generator 2a generates necessary amounts of hydrogen and magnesium hydroxide 22 by the reaction between the delivered magnesium particles 21 and the stored water 23.
- the hydrogen generation unit 2 a delivers the hydrogen to the fuel cell 4 and the hydroxide 22 to the processing unit 5.
- the magnesium particles 21 are supplied to the water 23 rather than the water 23 supplied to the magnesium particles 21, the supplied magnesium particles 21 can surely contribute to the reaction. Thereby, control of the amount of hydrogen generation can be performed more accurately.
- FIG. 10 is a block diagram showing the configuration of a sixth embodiment of the energy supply system of the present invention.
- the energy supply system le is provided in the enclosed space 10, and the hydrogen supply unit 2, the oxygen supply unit 3, the fuel cell 4, the heat exchange unit 7, the temperature sensors 31, 32, the liquid level meter 33, the flow control valve 41, 42, 43, 73, 74, control valves 45, 48, cooling unit 90 are provided.
- the piping 17, the piping 13, the piping 81, and the piping 11a pass through.
- a cooling heat medium whose flow rate is controlled flows to the flow control valve 41.
- water (steam) discharged from the fuel cell 4 and supplied to the hydrogen supply unit 2 flows.
- the pipe 81 is supplied from the cooling unit 90 to cool the fuel cell 4, and water (refrigerant) having passed through the fuel cell 4 flows.
- the pipe 11a is delivered from the hydrogen supply unit 2 to the pipe 11, and the flow control valves 42 and 43 flow a part of the hydrogen whose flow rate is controlled (the rest pass through the pipe l ib).
- the heat medium for cooling the piping 17 cools the fluid passing through the piping 13, the piping 81, and the piping 11a.
- the heat exchange unit 7 cools (condenses) water (steam: high temperature) supplied to the hydrogen supply unit 2 via the pipe 13 by heat exchange with the cooling heat medium (low temperature) passing through the pipe 17 Do.
- Control of the amount of hydrogen generation in the hydrogen supply unit 2 can be more easily performed by condensing it into liquid water and further controlling the temperature.
- the flow control valve 41 controls the flow rate of the cooling heat medium (example: PID control).
- the temperature of water 23 can be cooled to the desired temperature.
- cooling heat medium lower temperature
- the enclosed space 10 when the enclosed space 10 is in contact with the sea or a river, it is exemplified by seawater or water of a river.
- oxygen for the fuel cell 4 needs to be raised to the operating temperature when supplied to the fuel cell 4, such oxygen can also be used.
- the pipe 12 is connected to the pipe 17, and all or part of the oxygen flowing through the pipe 12 is branched to the pipe 17. In that case, it is not necessary to prepare the cooling heat medium from outside the system of the enclosed space 10, and the energy supply system can be simplified and its autonomy can be improved. Or, even if there is a shortage of cooling heat medium, it can be stored in seawater or river water.
- the control of the flow control valve 41 based on the temperature T1 described above is performed by a control device (not shown).
- the reaction of the magnesium particles 21 and the water 23 in the hydrogen supply unit 2 can be controlled by supplying the water 23 of the piping 13 to a desired temperature and supplying the water 23 to the hydrogen supply unit 2.
- the controller calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4, and the water in the hydrogen supply unit 2 based on the amount of hydrogen. It is possible to control the amount of hydrogen (production rate) produced at a desired temperature.
- Heat exchange unit 7 further cools hydrogen (high temperature) supplied to fuel cell 4 through pipe 11 a to a predetermined temperature by heat exchange with a cooling heat medium (low temperature) passing through pipe 17. Do. In this case, another pipe 17 '(not shown) through which the cooling heat medium (low temperature) passes may be used.
- the flow control valves 42 and 43 are linked and the flow rate of hydrogen flowing through the pipe 11 a and the pipe l ib
- the ratio of hydrogen flow rate in piping 1 la to hydrogen flow rate in piping 1 lb is determined by controlling (example: PID control), hydrogen is set to a predetermined temperature at the inlet of fuel cell 4 (example: fuel cell 4 is PEFC) In the case of (about 80 ° C).
- the control (for example, PID control) of the flow control valves 42 and 43 based on the above-mentioned temperature T2 is a control device.
- Heat exchange unit 7 further heats the water (high temperature) supplied from cooling unit 90 through cooling pipe 81 to cool fuel cell 4 through heat exchange with cooling heat medium (low temperature) passing through cooling pipe 17. Cooling. The cooled water is returned to the cooling unit 90 through the flow control valve 73, the pipe 82 and the pipe 18 during the normal operation of the fuel cell 4.
- the cooled water is supplied to the hydrogen supply unit 2 through the flow rate control valve 74 and the pipe 83 when the operating condition of the fuel cell 4 is a predetermined operating condition.
- the predetermined operating condition is an operating condition in which the hydrogen supply unit 2 can not generate an amount of hydrogen necessary for the operation of the fuel cell 4 due to a shortage of water.
- the fuel cell is not generating electricity, such as when the fuel cell 4 is activated, the exhaust gas does not contain water.
- the amount of exhaust water is too small. Even in such a case, since the water for cooling the fuel cell 4 is diverted, the fuel cell 4 can be operated without causing the shortage of water and hence the shortage of hydrogen.
- the operation state of the fuel cell 4 can be determined, for example, by measuring the output (current, voltage) of the fuel cell. Measured with a measuring instrument (not shown), the magnitude of the absolute value and the fluctuation per unit time are determined by a control unit (not shown) exemplified by a computer and compared with a reference value to determine can do. For example, when the absolute value of the output (current, voltage) of the fuel cell is smaller than a predetermined reference value, it is determined that the fuel cell 4 is stopped. it can. For example, if the fluctuation per unit time of the output (current, voltage) of the fuel cell is larger on the plus side than a predetermined reference value, it can be judged that a rapid load fluctuation is occurring.
- the control unit controls the flow control valves 73 and 74 to supply an amount of water suitable for the operating condition from the piping 81. It is branched and supplied to the hydrogen supply unit 2.
- the amount of water suitable for the operation condition may be a predetermined amount (stored in the control unit) which is set in advance during the start-up time, or a predetermined amount with time. It is conceivable to increase the flow rate at a rate (stored by the control unit). In addition, if it is a sudden load fluctuation, for example, it is conceivable to flow at a predetermined flow rate (stored in the control unit) proportional to the fluctuation per unit time of the output (current, voltage) of the fuel cell. These controls are executed by the program of the control unit.
- the hydrogen supply unit 2 is basically the same as that of the first embodiment. However, it differs in that a level gauge 33, a piping 18, and a piping 14 are provided, and control valves 45 and 48 are connected to the pipings 18 and 14, respectively.
- the liquid level meter 33 measures the liquid level of the water 23 of the hydrogen supply unit 2.
- the control valve 45 delivers the water 23 of the hydrogen supply unit 2 to the cooling unit 90 through the pipe 18.
- the control valve 48 sends the magnesium hydroxide 22 of the hydrogen supply unit 2 to another (example: processing unit 5) through the pipe 14.
- the hydrogen supply unit 2 can control the reaction between the magnesium particles 21 and the water 23 based on the liquid level of the water 23 measured by the liquid level meter 33. That is, based on the liquid level of the water 23 measured by the liquid level meter 33, the control valve 45 is controlled so that the amount of water 23 supplied and accumulated in the hydrogen supply unit 2 becomes a desired amount (example : PID control). However, the control valve 48 may be used.
- the control (example: PID control) of the control valve 45 (or the control valve 48) based on the liquid level of the water 23 is performed by a control device (not shown).
- a control device (not shown).
- the control device calculates the amount of hydrogen that needs to be generated based on the electric power generated by the fuel cell 4, and is measured by the level gauge 33 based on the amount of hydrogen. It is possible to control the amount of hydrogen (production rate) generated by setting the liquid level of water 23 to the desired liquid level.
- the cooling unit 90 circulates the water for cooling the fuel cell 4 using the circulation channels of the pipe 81, the flow control valve 73, the pipe 82, and the pipe 18. At that time, the heat generated by the fuel cell 4 provided in the middle of the pipe 81 is taken away by the water flowing in the pipe 81. The heat quantity is taken away by the heat exchanger 7 provided in the middle of the pipe 81. As described above, the water for cooling is supplied to the hydrogen supply unit 2 via the flow control valve 74 and the pipe 83 connected in the middle of the pipe 81 according to the operation state of the fuel cell 4.
- the cooling unit 90 includes, for example, a cooling water storage unit 70, a cooling water circulation pump 71, and a cooling water heat exchanger 72.
- the cooling water storage unit 70 stores water 70 a for cooling the fuel cell 4.
- the cooling water circulation pump 71 circulates the water 70a in the circulation flow path. The amount of water circulated in the circulation channel is controlled by a controller (not shown).
- the cooling water heat exchange 72 cools the water 70 a with a refrigerant (eg, seawater) flowing through the pipe 84.
- a refrigerant eg, seawater
- the sealed space 10, the oxygen supply unit 3, and the fuel cell 4 are the same as in the first embodiment, and thus the description thereof will be omitted.
- the flow control valve 41 controls the flow rate of the cooling heat medium, whereby the temperature of water in the pipe 13 can be controlled to a desired temperature.
- the temperature of water in the pipe 13 can be controlled to a desired temperature.
- the hydrogen can be supplied to the inlet of the fuel cell 4 at a predetermined temperature (example: fuel cell 4 is PEFC If the temperature is about 80 ° C).
- magnesium (Mg) particles used for the hydrogen supply unit 2 are the same as those of the first embodiment including the descriptions of FIG. 3 and FIG. 4, and thus the description thereof is omitted.
- the control unit When the energy supply system le is activated, the control unit (not shown) opens the flow control valve 74 and starts controlling the flow rate of water supplied to the hydrogen supply unit 2. At the same time, the control unit operates the cooling water circulation pump 71 of the cooling unit 90. As a result, the water 70 a whose flow rate is controlled is supplied as the water 23 to the hydrogen supply unit 2 through the pipe 81, the flow control valve 74 and the pipe 83.
- the hydrogen supply unit 2 generates hydrogen and magnesium hydroxide 22 whose flow rate is controlled by the reaction of the water 23 whose flow rate is controlled and the magnesium particles 21.
- the control unit controls the flow control valves 42 and 43 of the pipe 11 and supplies hydrogen from the hydrogen supply unit 2 to the fuel cell 4.
- oxygen is supplied from the oxygen supply unit 3 to the fuel cell 4 through the pipe 12.
- the fuel cell 4 generates electric power and heat by the reaction of hydrogen and oxygen.
- the control unit (not shown) detects the generation of electric power, the flow control valve 73 is also opened to start cooling of the fuel cell 4 while controlling the flow rate. Water generated by the reaction starts to be supplied to the hydrogen supply unit 2 through the pipe 13.
- the control unit (not shown) closes the flow control valve 74 after the start of the energy supply system le.
- the water 70 a from the cooling unit 90 is used only for cooling the fuel cell 4.
- the hydrogen supply unit 2 is supplied with the water 23 from the pipe 13 and generates hydrogen and magnesium hydroxide 22 by the reaction of the water 23 and the magnesium particles 21.
- the control unit controls the amount of water 23 to a desired amount by controlling the control valve 45 based on the liquid level of the water 23, and Control the amount of water 23 that reacts with Nesium particles 21. Thereby, the amount (generation rate) of hydrogen to be generated can be controlled.
- the control of the flow control valve 41 based on the temperature of the water 23 controls the water supplied to the hydrogen supply unit 2 to a desired temperature. Control the reaction with particles 21. Thereby, it is possible to control the amount of generated hydrogen (production rate).
- the control unit delivers the slurry in which the magnesium hydroxide 22 and the water 23 are mixed via the pipe 14 to the outside by the control valve 48.
- the fuel cell 4 generates power and heat from the hydrogen from the hydrogen supply unit 2 and the oxygen from the oxygen supply unit 3.
- water (steam) is generated as an exhaust and discharged to piping 13.
- hydrogen is supplied to the fuel cell 4 at a predetermined temperature by control of the flow control valves 42 and 43 based on the temperature T2. Thereby, the thermal efficiency of the fuel cell 4 can be improved, and the operation can be performed more properly.
- the control unit detects a rapid change (rise) of the load connected to the fuel cell 4, the following operation is performed. That is, the control unit opens the flow control valve 74 according to the magnitude of the load fluctuation, and starts control of the flow rate of water supplied to the hydrogen supply unit 2. As a result, water 70 a whose flow rate is controlled is additionally supplied to the hydrogen supply unit 2.
- the hydrogen supply unit 2 is supplied with the water 70 a from the pipe 81 in addition to the water 23 from the pipe 13, and generates a large amount of hydrogen and magnesium hydroxide 22 by a reaction with magnesium particles 21. can do. Due to this large amount of hydrogen, the fuel cell 4 can generate a sufficient amount of electric power despite the rapid change (rise) of the load. At this time, the flow control valve 73 is open, and the fuel cell 4 is continuously cooled.
- a necessary amount of hydrogen can be stably generated and supplied in the enclosed space regardless of operating conditions such as start-up and sudden change in load.
- FIG. 11 is a block diagram showing the configuration of a seventh embodiment of the energy supply system of the present invention.
- the energy supply system If is provided in the enclosed space 10, the hydrogen supply unit 2, the oxygen supply unit 3, the fuel cell 4, the processing unit 5, the separation unit 6, the heat exchange unit 7, the temperature sensors 31, 32 and the liquid level gauge 33, flow control valves 41, 42, 43, 73, 74, control valves 45, 48, cooling unit 90 Do.
- the present embodiment is different from the sixth embodiment in that the processing unit 5 and the separation unit 6 are added, and the water separated by the separation unit 6 is supplied to the cooling water storage unit 70. .
- processing unit 5 and the separation unit 6 are the same as in the first embodiment etc. except that the water separated in the separation unit 6 is supplied to the cooling water storage unit 70, the explanation thereof will be made. Omit.
- control unit controls the mixed slurry of magnesium hydroxide 22 and water 23 via the pipe 14 and controls the valve 4
- emissions can be suppressed and efficiency can be improved in the energy supply system used in a sealed space.
- efficiency can be improved in the energy supply system used in a sealed space.
- the energy supply system used in the enclosed space it becomes possible to suppress the increase in the concentration of carbon dioxide in the enclosed space.
- the necessary amount of hydrogen can be stably generated and supplied regardless of the operating conditions.
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
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Abstract
Description
Claims
Priority Applications (6)
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KR1020087023685A KR101102683B1 (ko) | 2006-03-28 | 2007-03-27 | 에너지 공급 시스템 및 수소 생성 물질 |
US12/294,831 US20100136441A1 (en) | 2006-03-28 | 2007-03-27 | Energy supplying system and hydrogen-producing material |
JP2008509773A JP5010583B2 (ja) | 2006-03-28 | 2007-03-27 | エネルギー供給システム及び水素生成物質 |
KR1020107024205A KR101102750B1 (ko) | 2006-03-28 | 2007-03-27 | 수소 생성 물질의 제조 방법 |
EP07739822A EP2009727A4 (en) | 2006-03-28 | 2007-03-27 | ENERGY SUPPLY SYSTEM AND SUBSTANCE PRODUCING HYDROGEN |
KR1020107024203A KR101102700B1 (ko) | 2006-03-28 | 2007-03-27 | 수소 생성 물질 |
Applications Claiming Priority (2)
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JP2006-089367 | 2006-03-28 | ||
JP2006089367 | 2006-03-28 |
Publications (1)
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WO2007116734A1 true WO2007116734A1 (ja) | 2007-10-18 |
Family
ID=38581032
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PCT/JP2007/056384 WO2007116734A1 (ja) | 2006-03-28 | 2007-03-27 | エネルギー供給システム及び水素生成物質 |
Country Status (5)
Country | Link |
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US (1) | US20100136441A1 (ja) |
EP (1) | EP2009727A4 (ja) |
JP (1) | JP5010583B2 (ja) |
KR (4) | KR101102750B1 (ja) |
WO (1) | WO2007116734A1 (ja) |
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JP2010509170A (ja) * | 2007-03-20 | 2010-03-25 | ジュンタエ パク | 水素発生用組成物を利用した水素発生装置及び水素発生用組成物 |
JPWO2008136087A1 (ja) * | 2007-04-23 | 2010-07-29 | 三菱重工業株式会社 | エネルギー供給システム |
JP2009217968A (ja) * | 2008-03-07 | 2009-09-24 | Casio Comput Co Ltd | 発電装置及び電子機器 |
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JP2010159192A (ja) * | 2009-01-09 | 2010-07-22 | Toyota Motor Corp | 水素含有金属材状態判定装置及び水素生成装置 |
JP2010198995A (ja) * | 2009-02-27 | 2010-09-09 | Mitsubishi Heavy Ind Ltd | 固体高分子形燃料電池発電システム |
US9434611B2 (en) * | 2009-04-22 | 2016-09-06 | Aquafairy Corporation | Packaged hydrogen-generating agent, manufacturing method therefor, and hydrogen generation method |
US20120058046A1 (en) * | 2009-04-22 | 2012-03-08 | Aquafairy Corporation | Packaged hydrogen-generating agent, manufacturing method therefor, and hydrogen generation method |
JP2011206685A (ja) * | 2010-03-30 | 2011-10-20 | Taiheiyo Cement Corp | 反応制御方法 |
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WO2015093184A1 (ja) * | 2013-12-16 | 2015-06-25 | 皓士 大田 | 水素発生剤及び水素発生方法 |
JP5796150B1 (ja) * | 2013-12-16 | 2015-10-21 | 皓士 大田 | 水素発生剤及び水素発生方法 |
JP2016064937A (ja) * | 2014-09-24 | 2016-04-28 | トナミ運輸株式会社 | 水素発生用固液分離装置及び水素発生触媒の再利用方法 |
JP2017533160A (ja) * | 2015-01-09 | 2017-11-09 | 華南理工大学 | 水素発生材料のCaMg2系合金水素化物およびその調製方法、並びにその応用 |
WO2020110758A1 (ja) * | 2018-11-26 | 2020-06-04 | 株式会社エスイー | 水素発生システム、発電システム、水素発生方法、及び、発電方法 |
KR20210006470A (ko) * | 2018-11-26 | 2021-01-18 | 가부시키가이샤 에스이 | 수소 발생 시스템, 발전 시스템, 수소 발생 방법, 및, 발전 방법 |
JPWO2020110758A1 (ja) * | 2018-11-26 | 2021-02-15 | 株式会社エスイー | 水素発生システム、発電システム、水素発生方法、及び、発電方法 |
KR102268148B1 (ko) | 2018-11-26 | 2021-06-23 | 가부시키가이샤 에스이 | 수소 발생 시스템, 발전 시스템, 수소 발생 방법, 및, 발전 방법 |
US11939217B2 (en) | 2018-11-26 | 2024-03-26 | Se Corporation | Hydrogen generation system, power generation system, hydrogen generation method, and power generation method |
JP2020083716A (ja) * | 2018-11-28 | 2020-06-04 | 株式会社エスイー | 水素化マグネシウムの生成反応の向上を図った水素化マグネシウムを含む水素発生材料を製造する材料製造方法、及び、その材料製造方法で製造された水素化マグネシウムを含む水素発生材料を用いた水素製造方法 |
JP7152638B2 (ja) | 2018-11-28 | 2022-10-13 | 株式会社エスイー | 水素化マグネシウムの生成反応の向上を図った水素化マグネシウムを含む水素発生材料を製造する材料製造方法、及び、その材料製造方法で製造された水素化マグネシウムを含む水素発生材料を用いた水素製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR101102700B1 (ko) | 2012-01-05 |
KR101102750B1 (ko) | 2012-01-05 |
KR20080104161A (ko) | 2008-12-01 |
JPWO2007116734A1 (ja) | 2009-08-20 |
KR20100120318A (ko) | 2010-11-15 |
KR101030362B1 (ko) | 2011-04-20 |
KR101102683B1 (ko) | 2012-01-05 |
EP2009727A1 (en) | 2008-12-31 |
US20100136441A1 (en) | 2010-06-03 |
KR20100120319A (ko) | 2010-11-15 |
JP5010583B2 (ja) | 2012-08-29 |
KR20100120317A (ko) | 2010-11-15 |
EP2009727A4 (en) | 2011-12-14 |
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