WO2020240967A1 - 水素システムおよび水素システムの運転方法 - Google Patents
水素システムおよび水素システムの運転方法 Download PDFInfo
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- B01D—SEPARATION
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- B01D53/26—Drying gases or vapours
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/085—Removing impurities
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
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- 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
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- 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
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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
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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
- Y02E60/50—Fuel cells
Definitions
- This disclosure relates to a hydrogen system and a method of operating the hydrogen system.
- Patent Document 1 discloses a water electrolyzer that generates high-pressure hydrogen gas while electrolyzing water.
- the hydrogen gas produced by water electrolysis contains water. Therefore, when storing such hydrogen in a hydrogen storage device such as a tank, if the hydrogen contains a large amount of water, the amount of hydrogen in the hydrogen storage device decreases due to the presence of water in the hydrogen storage device, which is efficient. Not the target.
- the water contained in hydrogen condenses in the hydrogen reservoir. Therefore, it is desired that the water content of hydrogen when stored in the hydrogen reservoir is reduced to, for example, about 5 ppm or less.
- Patent Document 1 a gas-liquid separator for separating hydrogen and water on the path through which hydrogen flows between the water electrolyzer and the hydrogen storage device, and a gas-liquid separator for adsorbing and removing water from hydrogen.
- a hydrogen generation system equipped with an adsorption tower has been proposed.
- Patent Document 2 a system for stably removing water in hydrogen is provided by configuring an adsorption tower for adsorbing and removing water in high-pressure hydrogen gas as a pressure swing adsorption type purifier (PSA). Proposed.
- PSA pressure swing adsorption type purifier
- An object of the present disclosure is to provide, as an example, a hydrogen system and a method for operating a hydrogen system, which can remove water contained in the cathode gas discharged from the cathode of a compressor more efficiently than before.
- protons taken out from the anode fluid supplied to the anode move to the cathode via the electrolyte membrane, and compressed hydrogen is generated.
- One aspect of the hydrogen system operating method of the present disclosure is a step in which protons taken out from the anodic fluid supplied to the anode move to the cathode via an electrolyte membrane to generate compressed hydrogen, and compressed. It comprises a step of moving water from a hydrogen-containing cathode gas through a water permeable membrane to a low pressure liquid filling the containment.
- the hydrogen system of one aspect of the present disclosure and the operation method of the hydrogen system have an effect that the water contained in the cathode gas discharged from the cathode of the compressor can be removed more efficiently than before.
- FIG. 1 is a diagram showing an example of a measuring device for evaluating the water permeability of a water permeable membrane.
- FIG. 2A is a diagram showing an example of the measurement result of LLP of the water permeable membrane.
- FIG. 2B is a diagram showing an example of the measurement result of LVP of the water permeable membrane.
- FIG. 3 is a diagram showing an example of the chemical potential of water in relation to relative humidity.
- FIG. 4 is a diagram showing an example of the hydrogen system of the first embodiment.
- FIG. 5 is a diagram showing an example of the hydrogen system of the first embodiment of the first embodiment.
- FIG. 6 is a diagram showing an example of a hydrogen system according to a third embodiment of the first embodiment.
- FIG. 1 is a diagram showing an example of a measuring device for evaluating the water permeability of a water permeable membrane.
- FIG. 2A is a diagram showing an example of the measurement result of LLP of the water permeable membrane.
- FIG. 2B
- FIG. 7 is a diagram showing an example of a hydrogen system according to a third embodiment of the first embodiment.
- FIG. 8 is a diagram showing an example of a hydrogen system according to a third embodiment of the first embodiment.
- FIG. 9 is a diagram showing an example of the hydrogen system of the second embodiment.
- FIG. 10 is a diagram showing an example of a hydrogen system according to an embodiment of the second embodiment.
- FIG. 11 is a diagram showing an example of a hydrogen system according to an embodiment of the second embodiment.
- FIG. 12 is a diagram showing an example of the hydrogen system of the third embodiment.
- FIG. 13 is a diagram showing an example of the hydrogen system of the fourth embodiment.
- FIG. 14 is a diagram showing an example of a hydrogen system according to an embodiment of the fourth embodiment.
- an electrochemical hydrogen pump using a solid polymer electrolyte membrane which is an example of the above compressor
- hydrogen (H 2 ) in an anode fluid such as a hydrogen-containing gas supplied to the anode is protonated to the cathode.
- Hydrogen is increased in pressure by moving and returning the proton (H + ) to hydrogen (H 2 ) at the cathode.
- the electrolyte membrane has increased proton conductivity under high temperature and high humidification conditions (for example, the temperature and dew point of the hydrogen-containing gas supplied to the electrolyte membrane are about 60 ° C.), and hydrogen in the electrochemical hydrogen pump The efficiency of the compression operation is improved.
- the amount of water in the cathode gas when the high-pressure hydrogen gas (hereinafter referred to as cathode gas) discharged from the cathode of the electrochemical hydrogen pump is stored in the hydrogen reservoir is, for example, about 5 ppm as described above. It is desired to reduce the amount to less than a certain level, but it is often difficult to efficiently remove the water content in such a cathode gas.
- the water content in hydrogen can be adsorbed by a porous adsorbent such as zeolite.
- a porous adsorbent such as zeolite.
- the operating time of the adsorption tower is determined by the amount of water sent to the adsorption tower, it is necessary to increase the size of the adsorption tower when the adsorption tower is used under the condition that the amount of water in hydrogen is large.
- high-pressure hydrogen gas flows in the adsorption tower it is necessary to configure the container of the adsorption tower so that it can withstand high pressure, which may lead to a further increase in size of the adsorption tower.
- Patent Document 2 it is possible to reduce the filling amount of the adsorbent by using a pressure swing adsorption type refiner. However, in this case, there is room for improvement, such as complication of the members constituting the flow path through which hydrogen flows, and the problem that it is necessary to handle hydrogen adsorbed together with water by the adsorbent when the adsorbent is regenerated.
- Patent Document 1 it is proposed to separate the water in the hydrogen gas discharged from the water electrolyzer from the hydrogen gas by a gas-liquid separator, but the gas-liquid separator is provided with the above water permeable film. That has not been considered.
- a water permeable membrane was incorporated into the device and the water permeability of the water permeable membrane was evaluated.
- FIG. 1 is a diagram showing an example of a measuring device for evaluating the water permeability of a water permeable membrane.
- the cell 800 of the measuring device includes a storage unit 800L on the low pressure side, a storage unit 800H on the high pressure side, and a water permeable membrane 805.
- the storage unit 800L and the storage unit 800H are each formed in a columnar shape, and a circular separator and a gas diffusion layer are laminated in a plan view.
- the separator is made of titanium metal
- the gas diffusion layer of the storage portion 800L is made of a titanium powder sintered body
- the gas diffusion layer of the storage portion 800H is made of a titanium fiber sintered body.
- the water permeable membrane 805 is sandwiched by the gas diffusion layers of the storage unit 800L and the storage unit 800H, and a serpentine-like flow path (hereinafter, serpentine) is provided on the main surface of the separator in contact with the gas diffusion layers. Flow path) is formed.
- serpentine a serpentine-like flow path
- Flow path is formed.
- Nafion registered trademark, manufactured by DuPont
- Nafion NRE-212 product name, hereinafter abbreviated as “N212 film”
- Nafion 115 product name, hereinafter abbreviated as “N115 film”
- the cell 800 is provided with end plates on the outside of the separators of the storage unit 800L and the storage unit 800H, and each member of the cell 800 is provided with bolts and screws that penetrate each member of the cell 800.
- the members are fastened together with the end plates.
- a sheathed heater is embedded in each end plate. As a result, the cell 800 can be heated to an appropriate temperature.
- This measuring device is a water permeability (Liquid-vapor permeation; hereinafter, LVP) of the water permeable film 805 from high-pressure water (liquid) to a hydrogen-containing gas in a normal-pressure state, and a normal-pressure state from high-pressure water (liquid). It is configured so that both the water permeability (Liquid-liquid permeation; hereinafter, LLP) of the water permeable film 805 into water (liquid) can be measured.
- LVP water permeability of the water permeable film 805 from high-pressure water (liquid) to a hydrogen-containing gas in a normal-pressure state, and a normal-pressure state from high-pressure water (liquid).
- a manual hydraulic pump 804 capable of applying water pressure from about 2 MPaG to about 100 MPaG is connected to the inflow port (inlet of the serpentine flow path) of the storage portion 800H in the cell 800.
- a two-way valve 903 is connected to the outlet (outlet of the serpentine flow path) of the storage portion 800H of the cell 800.
- the three-way valves 901 and 902 connected to the inflow outlets (entrances and outlets of the serpentine flow path) of the storage portion 800L of the cell 800 are operated.
- the inflow port of the storage unit 800L (the inlet of the serpentine flow path) communicates with the water pipe provided with the water pump 801 and the outlet of the storage unit 800L (the inlet of the serpentine flow path).
- the outlet communicates with a water pipe provided with a balance 806.
- the valves 901 and 902 of the three-way valves 901 and 902 connected to the inflow outlets (the inlet and outlet of the serpentine flow path) of the storage portion 800L of the cell 800 are started.
- the inflow port (inlet of the serpentine flow path) of the storage unit 800L communicates with the hydrogen pipe provided with the mass flow controller 802 and the bubbler 803, and the outlet of the storage unit 800L.
- (Outlet of the serpentine flow path) communicates with a hydrogen pipe provided with a mirror surface type dew point meter 807.
- the above measuring device is an example and is not limited to this example.
- the seeds heater was controlled so that the temperature of the cell 800 was about 50 ° C.
- the hydraulic pump 804 was operated to fill the storage portion 800H of the cell 800 with water, and the two-way valve 903 was closed to seal the outlet of the storage portion 800H.
- the water pump 801 was operated to fill the storage portion 800L of the cell 800 with water, and the inlet of the storage portion 800L was sealed by closing a sealing valve (not shown).
- the operation of the hydraulic pump 804 was controlled so that the water pressure of the water existing in the storage unit 800H was about 2 MPaG.
- the permeation flux (permeation velocity) of water in the water permeation membrane 805 was derived by measuring the amount of water flowing out from the outlet of the storage unit 800L per fixed time with the balance 806.
- the above-mentioned derivation of the permeated flux of water in the water permeable membrane 805 was also performed when the water pressure of the water existing in the storage portion 800H was about 5 MPaG, about 10 MPaG, about 15 MPaG, and about 20 MPaG, respectively. ..
- FIG. 2A is a diagram showing an example of the measurement result of LLP of the water permeable membrane.
- the vertical axis of FIG. 2A shows the permeation flux (mol / m 2 / s) of water in the water permeable membrane 805, and the horizontal axis shows the water pressure (MPaG) of water existing in the storage portion 800H. ..
- FIG. 2A shows the measurement data of LLP for the N212 membrane and the N115 membrane as the water permeable membrane 805.
- FIG. 2A shows the measured values of LLP (black rhombus and white rhombus) of the water permeable film 805 when the temperature of the cell 800 is about 50 ° C., and the water permeable film when the temperature is about 65 ° C.
- the measured values of LLP of 805 (black square and white square) and the measured value of LLP of the water permeable film 805 (black triangle and white triangle) at the same temperature of about 70 ° C. are plotted.
- the above measurement procedure and measurement result are examples, and are not limited to this example.
- the seeds heater was controlled so that the temperature of the cell 800 was about 50 ° C.
- the hydraulic pump 804 was operated to fill the storage portion 800H of the cell 800 with water, and the two-way valve 903 was closed to seal the outlet of the storage portion 800H.
- the mass flow controller 802 was operated, and the water temperature of the bubbler 803 was adjusted so that the storage portion 800L of the cell 800 was filled with a hydrogen-containing gas having a relative humidity of about 38% based on the cell temperature.
- a hydrogen-containing gas having a relative humidity of about 38% is circulated through the storage unit 800L at a desired flow rate (for example, about 500-1000 ml / min), and the dew point of the hydrogen-containing gas flowing out from the outlet of the storage unit 800L is mirrored. It was measured with a formula dew point meter 807.
- the operation of the hydraulic pump 804 was controlled so that the water pressure of the water existing in the storage unit 800H was about 2 MPaG. Then, when the measured value of the mirror dew point meter 807 becomes stable, the dew point of the hydrogen-containing gas flowing out from the outlet of the storage unit 800L is measured by the mirror dew point meter 807 to permeate the water in the water permeation film 805. The dew point (permeation velocity) was derived.
- the above derivation of the permeated flux of water in the water permeable membrane 805 was also performed when the water pressure of the water existing in the storage portion 800H was about 5 MPaG, about 10 MPaG, about 15 MPaG, and about 20 MPaG, respectively. ..
- FIG. 2B is a diagram showing an example of the measurement result of LVP of the water permeable membrane.
- the vertical axis of FIG. 2B shows the permeation flux (mol / m 2 / s) of the water of the water permeation membrane 805, and the horizontal axis shows the water pressure (MPaG) of the water existing in the storage portion 800H. ..
- FIG. 2B shows the measurement data of LVP for the N212 membrane and the N115 membrane as the water permeable membrane 805. Specifically, FIG. 2B shows the measured values of LVP (black rhombus and white rhombus) of the water permeable membrane 805 when the temperature of the cell 800 is about 50 ° C., and the water permeable membrane when the temperature is about 65 ° C. The measured values of LVP of 805 (black and white squares) and the measured values of LVP of water permeable membrane 805 (black and white circles) at the same temperature of about 75 ° C. are plotted.
- LVP black rhombus and white rhombus
- the above measurement procedure and measurement result are examples, and are not limited to this example.
- the LLP water permeation flux of the water permeation membrane 805 is more pressure than the LVP (water permeation flux) of the water permeation membrane 805.
- the dependency was great.
- the LLP water permeation flux of the N212 membrane increases significantly with the increase in the water pressure of the water existing in the storage portion 800H. It was about 2.7 to about 5 times the LVP (permeated flux of water) of N212.
- the LLP permeated flux of water of the N212 membrane reached about 0.15 (mol / m 2 / s).
- VVP vapor-vapor permeation
- the LLP of the water permeable membrane 805 is higher than that of the LVP of the water permeable membrane 805. Means to be.
- the above-mentioned measurement data of LLP and LVP of the water permeable film 805 and the report of the above non-patent document show that when the water pressure of the water existing in the storage portion 800H increases to a predetermined pressure, the LLP of the water permeable film 805 Means that it is higher than the LVP and VVP of the water permeable film 805.
- a cathode gas flow path provided on one of the main surfaces of the water permeable film and the water permeable film, in which the compressed hydrogen is generated, and the cathode gas discharged from the cathode of the compressor flows, and water. It comprises a first remover, which is provided on the other main surface of the permeable membrane, contains a housing filled with a liquid having a pressure lower than that of the cathode gas, and removes water contained in the cathode gas.
- the hydrogen system of this embodiment can remove water contained in the cathode gas discharged from the cathode of the compressor more efficiently than before. Specifically, by filling the accommodating portion provided on the other main surface of the water permeable film with a liquid having a pressure lower than that of the cathode gas, the water permeable membrane has a water permeable film as compared with the case where the accommodating portion is filled with the low pressure gas. The permeation flux of water can be increased.
- the effect of the hydrogen system of this embodiment is that when the water pressure of water increases to a predetermined pressure, the LLP of the water permeable membrane becomes higher than the LVP of the water permeable membrane, FIGS. 2A and 2B. It is also verified from the measurement data of.
- the first remover may be provided with a discharge path for discharging the liquid in the accommodating portion.
- the accommodating portion may be a flow path through which a liquid flows.
- the temperature of the liquid may be lower than the temperature of the cathode gas flowing into the first remover. ..
- the temperature of the liquid may be lower than the dew point of the cathode gas flowing into the first remover.
- the first remover since the temperature of the liquid is lower than the temperature of the cathode gas flowing into the first remover, the first remover is moved by heat exchange between the cathode gas and the liquid through the water permeable film. The cathode gas is cooled as it passes through.
- the first remover when the temperature of the liquid is lower than the dew point of the cathode gas flowing into the first remover, condensed water is likely to be generated from the water vapor in the cathode gas. Then, the high-pressure condensed water in contact with the water-permeable membrane can efficiently permeate the low-pressure liquid in contact with the water-permeable membrane through the water-permeable membrane.
- the process of adsorbing the water vapor to the water permeable film and the water permeating the water permeable film can be a rate-determining condition for the water permeability of the water permeable film.
- the high-pressure condensed water condensed from the cathode gas is recovered from the cathode gas as liquid water through the water permeable film, the above process does not exist, so that the water permeable film is compared with the former case. It is considered that it is possible to increase the permeation flux of the water in the water, and as a result, the water in the cathode gas can be efficiently removed in the first remover.
- the liquid may contain water in any one of the first to fourth aspects of the hydrogen system.
- the hydrogen system of this embodiment is contained in the cathode gas discharged from the cathode of the compressor by using water having a large heat capacity and being easily available as the liquid in the accommodating portion of the first remover. It is possible to easily and effectively remove the water.
- the liquid in the housing of the first remover is not limited to such water.
- a liquid having a high molecular weight and not passing through the pores of the water permeable membrane and containing a hydroxyl group forming a hydrogen bond Since the molecular weight of water is small, water passes through the pores of various films, but for some reason, the cathode gas flow path (high pressure) and the liquid flow path (low pressure) of the first remover By reversing the magnitude relationship of the pressure, even if water is mixed into the cathode gas through the water permeable film, it does not have an adverse effect other than increasing the amount of water in the cathode gas.
- the hydrogen system of the sixth aspect of the present disclosure is for supplying the liquid discharged from the first remover to the first remover again in any one of the first to fifth aspects of the hydrogen system.
- a recycling channel may be provided.
- the liquid discharged from the first remover when hydrogen in the cathode gas permeates the water permeable membrane, the liquid discharged from the first remover may contain hydrogen.
- the hydrogen system of this embodiment can alleviate such inconvenience by recycling the liquid discharged from the first remover through the recycling flow path.
- the liquid contains water
- the anode fluid is a hydrogen-containing gas
- the first removal may be provided to supply the liquid discharged from the vessel to the hydrogen-containing gas supplied to the anode.
- the hydrogen system of this embodiment supplies the water discharged from the first remover through the supply path to the hydrogen-containing gas, and uses the water for humidifying the hydrogen-containing gas supplied to the anode of the compressor. can do. Further, hydrogen dissolved in water can be moved from the anode of the compressor to the cathode and compressed.
- the water permeable membrane may be a polymer membrane containing a sulfonic acid group.
- the hydrogen system of this embodiment can effectively exert the function of removing the water contained in the cathode gas discharged from the cathode of the compressor in the first remover.
- the hydrogen system of the ninth aspect of the present disclosure does not have to energize the water permeable membrane in any one of the hydrogen systems of the first to eighth aspects.
- the water permeable film is composed of a proton conductive electrolyte film
- electrodes containing a substance (for example, platinum) that promotes an electrochemical hydrogen oxidation reaction and a hydrogen generation reaction are provided on both sides of the water permeable film.
- a current is passed between the electrodes of the water permeable film, protons move in the water permeable film according to the current, and for example, low-pressure liquid (for example, water) may be electrolyzed in the water permeable film.
- low-pressure liquid for example, water
- the hydrogen system according to the tenth aspect of the present disclosure is the first hydrogen system according to any one of the first to ninth aspects, in a flow path through which the liquid flows in the first remover (hereinafter referred to as a liquid flow path). Perforated structure may be provided. Further, in the hydrogen system of the eleventh aspect of the present disclosure, in any one of the first to tenth aspects, a second porous structure is provided in contact with the water permeable membrane in the cathode gas flow path. It may be provided.
- the pressure difference between the cathode gas flow path (high pressure) and the liquid flow path (low pressure) of the first remover causes The water permeable film is deformed in the direction of blocking the liquid flow path.
- the water permeable membrane may come into contact with the member of the first remover constituting the liquid flow path. Then, the flow of the liquid in the liquid flow path may become difficult, but in the hydrogen system of this embodiment, since the first porous structure is provided in the liquid flow path, such a problem is alleviated.
- the water that has permeated the water permeable membrane can be efficiently drained to the outside of the first remover together with the liquid in the liquid flow path through the pores of the first porous structure.
- the flow of the cathode gas in the main cathode gas flow path tends to become a laminar flow.
- the water in the cathode gas flows along with the cathode gas, for example, the water in the cathode gas existing at a position away from the water permeable film has a low probability of coming into contact with the water permeable film. That is, in this case, the water permeating the water permeable membrane may be limited to the water in the cathode gas flowing along the vicinity of the main surface of the water permeable membrane.
- the flow of the cathode gas in the main cathode gas flow path is forcibly changed in a random direction by providing the second porous structure in the cathode gas flow path. Can be done.
- water in the cathode gas existing at various positions in the cathode gas flow path can come into contact with the water permeable membrane.
- the probability that the water in the cathode gas and the water permeable film come into contact with each other is higher than in the case where the second porous structure is not provided in the cathode gas flow path.
- the high pressure water that comes into contact with the water permeable film due to the differential pressure between the cathode gas flow path (high pressure) and the liquid flow path (low pressure) of the first remover.
- it can efficiently permeate a low-pressure liquid in contact with the water-permeable film through the water-permeable film. This makes it possible to promote the removal of water contained in the cathode gas in the first remover.
- the cathode gas can easily pass through the gap between the second porous structure and the water permeable membrane. Then, for example, when the size of the void changes depending on the magnitude of the differential pressure between the cathode gas flow path (high pressure) and the liquid flow path (low pressure) of the first remover, the flow state of the cathode gas changes to the cathode. It changes in the gas flow path. This affects the water permeability of the water permeable membrane, which makes it difficult to stably remove the water contained in the cathode gas.
- the contact interface between the two can be kept stable, so that the above problems can be alleviated.
- the hydrogen system of this embodiment by providing the second porous structure in contact with the water permeable film, the second porous structure heats for cooling the cathode gas flowing through the cathode gas flow path. Functions as a conductor. Therefore, the cathode gas is effectively cooled when the cathode gas passes through the cathode gas flow path. As a result, the hydrogen system of this embodiment generates condensed water from the water vapor in the cathode gas as compared with the case where the second porous structure is not provided in contact with the water permeable membrane in the first remover. Can be promoted.
- the hydrogen system of the twelfth aspect of the present disclosure is a laminate in which the compressor includes a cell including a cathode, an electrolyte membrane, and an anode in any one of the hydrogen systems of the first to eleventh aspects.
- the remover may be laminated integrally with the laminated body.
- the hydrogen system of this embodiment can simplify the system configuration by stacking the compressor and the first remover.
- a high pressure cathode gas flows. Therefore, if the compressor and the first remover are provided separately, a high-rigidity end plate for fixing the compressor and the first remover is often required.
- the end plate used for the compressor and the first remover can be shared. Therefore, in the hydrogen system of this embodiment, by laminating the first remover integrally with the above-mentioned laminate, for example, the end plate used for the compressor and the first remover can be shared. , The system configuration is simplified.
- U liq_338 U 0 liq_338 + ⁇ ⁇ [P (z) -P STD ]
- ⁇ is “1.990 J mol -1 atm -1 ”
- P (z) is the pressing force on water
- P STD is the normal pressure
- the permeation of water in the water permeable membrane is caused by the difference in chemical potential on both sides of the water permeable membrane. Therefore, even if gas is supplied to the region on the low pressure side of the water permeable membrane with full humidification (relative humidity: 100%), the region on the high pressure side of the water permeable membrane remains until the chemical potentials on both sides of the water permeable membrane become equal.
- Water permeation driving force acts on the water permeation membrane in the direction of decreasing relative humidity. For example, in the example shown in FIG. 3, a water permeation driving force acts on the water permeable membrane until the relative humidity in the region of 20 MPaG of the water permeable membrane reaches H1.
- a gas having a relative humidity of less than 100% in the normal pressure region of the water permeable membrane when a gas having a relative humidity of less than 100% in the normal pressure region of the water permeable membrane is supplied, the relative humidity in the region of 20 MPaG of the water permeable membrane is lower than that of H1 described above.
- a water permeation driving force acts on the water permeable membrane.
- H2 H2 ⁇ H1
- the hydrogen system of the thirteenth aspect of the present disclosure was devised based on such a finding, and in the hydrogen system of the first to twelfth aspects, the first surface of the water permeable film is the first.
- a second remover may be provided in which the cathode gas that has passed through the remover of 1 is circulated, and a gas having a lower chemical potential of water vapor contained in the gas than the cathode gas is circulated on the other main surface.
- the low pressure side of the water permeable membrane is filled with a liquid (for example, water), so that the water permeable membrane can be understood from the data of the chemical potential with a relative humidity of 100% in FIG.
- a liquid for example, water
- the water permeable membrane can be understood from the data of the chemical potential with a relative humidity of 100% in FIG.
- a second remover is used to circulate a gas having a lower chemical potential of water vapor contained in the gas than the cathode gas on the other main surface of the water permeable membrane. ..
- the hydrogen system of this embodiment can reduce the water content of the cathode gas to a low concentration as compared with the case where the water content in the cathode gas is removed only by the first remover.
- the hydrogen system of the 14th aspect of the present disclosure includes a third remover including an adsorbent for removing water in the cathode gas that has passed through the first remover in the hydrogen systems of the first to twelfth aspects. You may.
- the water content in the cathode gas that has passed through the first remover is easily removed by using the adsorbent of the third remover by the above configuration.
- the hydrogen system of this embodiment can reduce the amount of water adsorbed by the adsorbent per unit time as compared with the case where the first remover does not remove the water in the cathode gas. Then, even if the filling amount of the adsorbent in the third remover is reduced, the water adsorption performance of the adsorbent of the third remover can be appropriately maintained for a desired period, so that the third remover can be removed. It is possible to reduce the size and cost of the vessel.
- the method of operating the hydrogen system according to the fifteenth aspect of the present disclosure includes a step in which protons taken out from the anodic fluid supplied to the anode move to the cathode via an electrolyte membrane to generate compressed hydrogen, and a compression. It comprises a step of moving water from the hydrogen-containing cathode gas to a low-pressure liquid filling the housing through a water-permeable membrane.
- the operation method of the hydrogen system of this embodiment can remove the water contained in the cathode gas discharged from the cathode of the compressor more efficiently than before.
- the details of the action and effect of the operation method of the hydrogen system of the present embodiment are the same as those of the hydrogen system of the first aspect, and thus the description thereof will be omitted.
- the method of operating the hydrogen system of the 16th aspect of the present disclosure may include a step of discharging the liquid in the accommodating portion in the method of operating the hydrogen system of the 15th aspect.
- the accommodating portion may be a flow path through which a liquid flows.
- the temperature of the liquid may be lower than the temperature of the cathode gas in any one of the methods of operating the hydrogen system according to the fifteenth to the seventeenth aspects.
- the high-pressure condensed water condensed from the cathode gas discharged from the cathode of the compressor is efficiently removed by using the water permeable membrane.
- the liquid may contain water in the method of operating the hydrogen system according to any one of the 15th to 18th aspects.
- the operation method of the hydrogen system of this embodiment uses water having a large heat capacity and being easily available as the liquid in the accommodating portion to remove the water contained in the cathode gas discharged from the cathode of the compressor. It can be done easily and effectively.
- FIG. 4 is a diagram showing an example of the hydrogen system of the first embodiment.
- the hydrogen system 200 includes an electrochemical hydrogen pump 100 and a first remover 300.
- the electrochemical hydrogen pump 100 is an apparatus in which protons (H + ) taken out from the anode fluid supplied to the anode AN are transferred to the cathode CA via the electrolyte membrane 11 to generate compressed hydrogen.
- the anode fluid for example, hydrogen-containing gas, water, or the like can be used.
- the electrochemical hydrogen pump 100 may have any configuration as long as it is an electrochemical compression device using an electrolyte membrane 11.
- the electrochemical hydrogen pump 100 has an anode gas introduction path 29 for supplying the hydrogen-containing gas to the anode AN and an anode gas lead-out path 31 for discharging the hydrogen-containing gas from the anode AN.
- a cathode gas lead-out path 26 for discharging the cathode gas from the cathode CA is provided.
- the cathode gas is, for example, a high-pressure hydrogen-containing gas containing water vapor discharged from the cathode CA.
- the first remover 300 is provided on one main surface of the water permeable film 115 and the water permeable film 115, and a flow path through which the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 flows (hereinafter, cathode).
- the water content in the cathode gas includes the liquid water contained in the cathode gas.
- the water removed by the first remover 300 includes, for example, condensed water condensed from the cathode gas.
- This condensed water is generated in the flow path from the cathode CA of the electrochemical hydrogen pump 100 to the first remover 300 in the cathode gas lead-out path 26, or in the cathode gas flow path 114 in the first remover 300. Will be done.
- the first remover 300 may have any configuration as long as it is a film-type remover capable of removing water contained in the cathode gas.
- the first remover 300 includes a cathode gas flow path 114, a flow path 113 through which a low-pressure liquid flows (hereinafter, liquid flow path 113), and these flow paths 113, 114.
- a water permeable membrane 115 provided between the two may be provided. That is, in this case, the liquid flow path 113 corresponds to the above-mentioned accommodating portion.
- Other examples of the containment section will be described in the fourth embodiment.
- the first remover 300 has a cathode gas lead-out path 26 for flowing the cathode gas through the cathode gas flow path 114, and a liquid introduction path 111 and a liquid lead-out path for passing the liquid through the liquid flow path 113. 112 and are provided.
- the water permeable membrane 115 may have any structure as long as it has low permeability of hydrogen (H 2 ) in the cathode gas and allows water in the cathode gas to permeate.
- the water permeable membrane 115 may be composed of a polymer membrane containing a sulfonic acid group.
- the water permeable membrane 115 can be provided with a function of permeating not only the liquid water in the cathode gas but also water vapor. Since the sulfonic acid group of the polymer membrane can exhibit hydrophilicity, a water path can be formed in the polymer membrane. Therefore, the hydrogen system 200 of the present embodiment effectively exerts the function of removing the water contained in the cathode gas discharged from the cathode of the electrochemical hydrogen pump 100 in the first remover 300 by the above configuration. Can be done.
- the temperature of the liquid flowing into the first remover 300 is lower than the temperature of the cathode gas flowing into the first remover 300.
- the temperature of the liquid flowing into the first remover 300 is lower than the dew point of the cathode gas flowing into the first remover 300. Therefore, in the hydrogen system 200 of the present embodiment, a cooler (not shown) may be provided at an appropriate position in the liquid introduction path 111.
- the following operations may be performed by, for example, a controller arithmetic circuit (not shown) reading a control program from the controller storage circuit. However, it is not always essential to perform the following operations on the controller. The operator may perform some of the operations. Further, the operation of the hydrogen system 200 when a hydrogen-containing gas is used as the anode fluid will be described below.
- a low-pressure hydrogen-containing gas is supplied to the anode AN of the electrochemical hydrogen pump 100, and the voltage of the voltage applyer (not shown in FIG. 4) is applied to the electrochemical hydrogen pump 100.
- the protons taken out from the hydrogen-containing gas supplied to the anode AN move to the cathode CA via the electrolyte membrane 11 to generate compressed hydrogen (hydrogen compression operation).
- hydrogen molecules are separated into hydrogen ions (protons) and electrons by an oxidation reaction (formula (1)). Protons are conducted in the electrolyte membrane 11 and move to the cathode catalyst layer.
- the hydrogen generated by the cathode CA of the electrochemical hydrogen pump 100 is compressed by the cathode CA as a cathode gas containing water vapor.
- the cathode gas can be compressed by the cathode CA by increasing the pressure loss of the cathode gas lead-out path 26 by using a flow rate regulator (not shown).
- the flow rate regulator include a back pressure valve and a regulating valve provided in the cathode gas lead-out path 26.
- the cathode gas is discharged from the cathode CA of the electrochemical hydrogen pump 100 to the outside of the electrochemical hydrogen pump 100 through the cathode gas lead-out path 26.
- the first remover 300 a step of moving water from the compressed hydrogen-containing cathode gas to a low-pressure liquid filling the liquid flow path 113 via the water permeable membrane 115 is performed.
- the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 flows through one main surface of the water permeable membrane 115. Therefore, in the first remover 300, the operation of removing the water contained in the cathode gas is performed by circulating a liquid having a pressure lower than that of the cathode gas on the other main surface of the water permeable membrane 115.
- the above-mentioned water includes liquid water contained in the cathode gas.
- This water includes, for example, condensed water condensed from the cathode gas.
- This condensed water is generated in the flow path from the cathode CA of the electrochemical hydrogen pump 100 to the first remover 300 in the cathode gas lead-out path 26, or in the cathode gas flow path 114 in the first remover 300. Will be done. Further, the temperature of the liquid flowing into the first remover 300 may be lower than the temperature of the cathode gas flowing into the first remover 300.
- the method of operating the hydrogen system 200 and the hydrogen system 200 of the present embodiment can remove water contained in the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 more efficiently than before. Specifically, by circulating a low-pressure liquid on the other main surface of the water-permeable film 115, the permeation flux of water in the water-permeable film 115 can be reduced as compared with the case where a low-pressure gas is circulated on this main surface. Can be high.
- the effect of the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment is that when the water pressure of water increases to a predetermined pressure, the LLP of the water permeable film is compared with the LVP of the water permeable film. It is also verified from the measurement data of FIGS. 2A and 2B that the pressure becomes higher.
- high-pressure condensed water condensed from the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 is efficiently used with the water permeable film 115. Will be removed.
- the temperature of the liquid flowing into the first remover 300 is lower than the temperature of the cathode gas flowing into the first remover 300, between the cathode gas and the liquid via the water permeable film 115.
- the cathode gas is cooled when the cathode gas passes through the first remover 300.
- the first remover 300 when the temperature of the liquid flowing into the first remover 300 is lower than the dew point of the cathode gas flowing into the first remover 300, the water vapor in the cathode gas is condensed water. Is likely to occur.
- the high-pressure condensed water in contact with the water-permeable membrane 115 can efficiently permeate the low-pressure liquid in contact with the water-permeable membrane 115 through the water-permeable membrane 115.
- the process of adsorbing the water vapor to the water permeable film 115, the water permeable film 115 It is considered that the evaporation process of the permeated water can be a rate-determining condition for the water permeability of the water permeation film 115.
- the first remover 300 can efficiently remove the water in the cathode gas.
- the effect of the hydrogen system 200 and the operation method of the hydrogen system 200 of the present embodiment as described above is that when the water pressure of water increases to a predetermined pressure, the LLP of the water permeable film becomes the LVP and VVP of the water permeable film. It is also verified from the measurement data of FIGS. 2 and 3 and the reports of non-patent documents that the pressure is higher than that of the above.
- the hydrogen system 200 is provided with, for example, a temperature detector that detects the temperature of the electrochemical hydrogen pump 100, a pressure detector that detects the pressure of the cathode gas compressed by the cathode CA of the electrochemical hydrogen pump 100, and the like. You may be.
- the hydrogen system 200 includes a valve for opening and closing the anode gas introduction path 29, the anode gas lead-out path 31, the cathode gas lead-out path 26, the liquid introduction path 111, and the liquid lead-out path 112 at appropriate positions. It may be provided.
- the electrochemical hydrogen pump 100 has a dead end in which the entire amount of hydrogen (H 2 ) in the hydrogen-containing gas supplied to the anode AN through the anode gas introduction path 29 is compressed by the cathode CA without providing the anode gas lead-out path 31.
- the structure may be adopted.
- the hydrogen-containing gas may be, for example, pure hydrogen gas or a gas having a lower hydrogen concentration than pure hydrogen gas.
- the latter hydrogen-containing gas may be, for example, a hydrogen gas generated by electrolysis of water or a reformed gas containing hydrogen.
- FIG. 5 is a diagram showing an example of the hydrogen system of the first embodiment of the first embodiment.
- the hydrogen system 200 includes an electrochemical hydrogen pump 100, a first remover 300, a recycling flow path 140, a supply path 130, and a hydrogen source 700.
- electrochemical hydrogen pump 100 and the first remover 300 are the same as the hydrogen system 200 of the first embodiment, the description thereof will be omitted.
- the liquid flowing through the first remover 300 contains water.
- the method of operating the hydrogen system 200 and the hydrogen system 200 of the present embodiment is to use water having a large heat capacity and easily available as the liquid flowing through the first remover 300, thereby using the electrochemical hydrogen pump 100. Moisture contained in the cathode gas discharged from the cathode CA can be easily and effectively removed.
- the liquid flowing through the first remover 300 is not limited to such water.
- the anode fluid supplied to the anode AN of the electrochemical hydrogen pump 100 is a hydrogen-containing gas from the hydrogen source 700.
- the hydrogen-containing gas generated by the hydrogen source 700 include a reforming gas generated by a reforming reaction such as methane gas, and a hydrogen gas generated by electrolysis of water.
- the recycling flow path 140 is a flow path for supplying the water discharged from the first remover 300 to the first remover 300 again.
- the supply path 130 is a flow path for supplying the water discharged from the first remover 300 to the hydrogen-containing gas supplied to the anode AN of the electrochemical hydrogen pump 100. That is, in this example, the liquid lead-out path 112 branches into the recycling flow path 140 and the supply path 130 at a branching portion, and the downstream end of the recycling flow path 140 is connected to the liquid introduction path 111, so that the supply path The downstream end of 130 is connected to the anode gas introduction path 29.
- the hydrogen system 200 of FIG. 5 may be provided with a flow rate controller (not shown) that controls the flow rate of water flowing through the recycling flow path 140 and the supply path 130.
- the flow rate controller may have any configuration as long as it can control the flow rate of such water.
- Examples of the flow rate controller include a flow rate control valve.
- Such a flow rate control valve may be, for example, a three-way valve with a controllable flow rate ratio provided at a connection portion (the above-mentioned branch portion) between the recycling flow path 140 and the supply path 130, or a three-way switching. It may be a valve.
- the flow rate control valve may be a two-way valve whose valve opening degree can be controlled, which is provided on either one or both of the supply path 130 and the recycling flow path 140, and is turned on and off. It may be a valve.
- a cooler (not shown) for cooling the water flowing through the recycling flow path 140 may be provided.
- the cooler may have any configuration as long as it is a device having a cooling function for cooling the water.
- the cooler may be, for example, an air-cooled cooler or a cooler using a coolant.
- the former cooler includes, for example, a cooling fan, cooling fins, and the like.
- the latter cooler includes, for example, a flow path member through which the coolant flows.
- the coolant for example, cooling water, antifreeze, etc. can be used.
- hydrogen in the cathode gas permeates the water permeable membrane 115
- hydrogen may be contained in the water discharged from the first remover 300.
- the water discharged from the first remover 300 is discharged to the outside, it is necessary to appropriately perform post-treatment of hydrogen dissolved in the water.
- the method of operating the hydrogen system 200 and the hydrogen system 200 of the present embodiment can alleviate such inconvenience by recycling the water discharged from the first remover 300 through the recycling flow path 140. it can.
- the water discharged from the first remover 300 is supplied to the hydrogen-containing gas through the supply path 130, and the water is supplied to the hydrogen-containing gas by an electrochemical hydrogen pump. It can be used to humidify the hydrogen-containing gas supplied to the 100 anode AN. Further, hydrogen dissolved in water can be moved from the anode AN of the electrochemical hydrogen pump 100 to the cathode CA and compressed.
- the operation method of the hydrogen system 200 and the hydrogen system 200 of this embodiment may be the same as that of the first embodiment except for the above-mentioned features.
- the liquid flow path 113 in the first remover 300 is provided with the first porous structure, and the cathode gas flow path 114 in the first remover 300. It is the same as the hydrogen system 200 of the first embodiment except that the second porous structure is provided so as to be in contact with the water permeable film 115.
- the first porous structure may be provided in the liquid flow path 113 in the first remover 300 so as to be in contact with the water permeable membrane 115 of the first remover 300.
- the first porous structure can suppress the displacement and deformation of the water permeable film 115 generated by the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300.
- High rigidity is desirable.
- the first porous structure may be made of metal.
- the second porous structure made of metal may be, for example, a metal sintered body. Examples of the metal sintered body include a metal powder sintered body made of stainless steel or titanium, a metal fiber sintered body, and the like.
- the second porous structure is suitable for displacement and deformation of the water permeable membrane 115 generated by the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300. It is desirable to have elasticity to follow.
- the second porous structure may be composed of an elastic body containing carbon fibers. Examples of such an elastic body include carbon felt on which carbon fibers are laminated.
- the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300 The water permeable film 115 is deformed in the direction of blocking the liquid flow path 113 due to the differential pressure of. For example, due to such a differential pressure, the water permeable membrane 115 may come into contact with the member of the first remover 300 constituting the liquid flow path 113. Then, the flow of the liquid in the liquid flow path 113 may become difficult.
- the first porous structure is provided in the liquid flow path 113. The problem is alleviated. The water that has permeated the water permeable membrane 115 can be efficiently drained to the outside of the first remover 300 together with the liquid in the liquid flow path 113 through the pores of the first porous structure.
- the first porous structure is not provided so as to be in contact with the water permeable membrane 115, for example, the first removal is performed at the edge portion of the member of the first remover 300 constituting the liquid flow path 113. Bending stress on the water permeable membrane 115 based on the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the vessel 300 may occur. Then, the water permeable membrane 115 may be damaged by such bending stress.
- the hydrogen system 200 of the present embodiment is provided with the first porous structure in contact with the water permeable membrane 115, Such problems are alleviated.
- the liquid can easily pass through the gap between the second porous structure and the water permeable membrane 115. ..
- the liquid flow state is changed in the liquid flow path 113. Change.
- This affects the water permeability of the water permeable membrane 115, which makes it difficult to stably remove the water contained in the cathode gas.
- the contact interface between the two can be kept stable, so that the above problems can be alleviated. Will be done.
- the flow of the cathode gas in the main cathode gas flow path 114 tends to be laminar.
- the water in the cathode gas flows along with the cathode gas, for example, the water in the cathode gas existing at a position away from the water permeable film 115 has a low probability of coming into contact with the water permeable film 115. That is, in this case, the water permeating the water permeable membrane 115 may be limited to the water in the cathode gas flowing along the vicinity of the main surface of the water permeable membrane 115.
- the flow of the cathode gas in the cathode gas flow path 114 is forcibly randomized by providing the second porous structure in the cathode gas flow path 114. You can change the direction. In this case, there is a possibility that water in the cathode gas existing at various positions in the cathode gas flow path 114 can come into contact with the water permeable membrane 115. As a result, in the hydrogen system 200 of the present embodiment, there is a higher probability that the water in the cathode gas and the water permeable membrane 115 come into contact with each other as compared with the case where the second porous structure is not provided in the cathode gas flow path 114. Become.
- the water permeable film 115 is formed by the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300.
- the high-pressure water in contact can efficiently permeate the low-pressure liquid in contact with the water-permeable film 115 through the water-permeable film 115. Thereby, the removal of the water contained in the cathode gas can be promoted in the first remover 300.
- the cathode gas can easily pass through the gap between the second porous structure and the water permeable membrane. .. Then, for example, when the size of the void changes depending on the magnitude of the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300, the flow of the cathode gas The state changes in the cathode gas flow path 114. This affects the water permeability of the water permeable membrane 115, which makes it difficult to stably remove the water contained in the cathode gas. However, in the hydrogen system 200 of the present embodiment, by providing the second porous structure in contact with the water permeable membrane 115, the contact interface between the two can be kept stable, so that the above problems are alleviated. Will be done.
- the second porous structure is provided so as to be in contact with the water permeable film 115, so that the second porous structure cools the cathode gas flowing through the cathode gas flow path 114. Acts as a thermal conductor for. Therefore, the cathode gas is effectively cooled when the cathode gas passes through the cathode gas flow path 114.
- the hydrogen system 200 of the present embodiment has a second porous structure from water vapor in the cathode gas as compared with the case where the second porous structure is not provided in contact with the water permeable membrane 115 in the first remover 300. The generation of condensed water can be promoted.
- the rigidity of the first porous structure can be appropriately ensured by forming the first porous structure with a metal material. Then, the water permeable membrane 115 is less likely to be deformed by the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure), so that the water permeable membrane 115 is between the first porous structure and the water permeable membrane 115.
- the contact interface and the contact interface between the second porous structure and the water permeable membrane 115 can be stably maintained. As a result, the hydrogen system 200 of this embodiment can stabilize the removal of water contained in the cathode gas.
- the second porous structure by forming the second porous structure with an elastic material, elastic deformation of the second porous structure can be appropriately caused. As a result, even if a differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300 is generated, the second porous structure and the water permeable membrane 115 The contact interface between them can be kept stable.
- the flow path member when the water permeable membrane 115 is deformed in the direction of blocking the liquid flow path 113 due to the generation of the above differential pressure, or the member constituting the cathode gas flow path 114 (hereinafter, the flow path member) is deformed outward. If this is the case, it is difficult to stably maintain the contact interface between the second porous structure and the water permeable membrane 115. Then, as described above, since the water permeability of the water permeable membrane 115 is affected, it becomes difficult to stably remove the water contained in the cathode gas.
- the second porous structure by forming the second porous structure with an elastic material, the second porous structure is made with respect to the above deformation of the water permeable membrane 115 and the above deformation of the flow path member.
- the elastic deformation of the second porous structure can be followed in a direction that maintains contact between the structure and the water permeable membrane 115.
- the second porous structure in the case of accommodating the second porous structure in the recess of the flow path member, the second porous structure is previously provided by the amount corresponding to the deformation of the water permeable membrane 115 and the flow path member. It may be compressed and accommodated in the recess of the flow path member.
- the hydrogen system 200 of this embodiment may be the same as the hydrogen system 200 of the first embodiment of the first embodiment or the first embodiment except for the above-mentioned features.
- FIG. 6 (Third Example) 6, 7 and 8 are diagrams showing an example of the hydrogen system of the third embodiment of the first embodiment.
- the electrochemical hydrogen pump 100 and the first remover 300 are integrally configured.
- FIG. 6 shows a vertical cross section including a straight line passing through the center of the hydrogen system 200, the center of the cathode gas passage manifold 50, and the center of the cathode gas lead-out manifold 51 in a plan view.
- FIG. 7 shows a vertical cross section including a straight line passing through the center of the hydrogen system 200, the center of the anode gas introduction manifold 40, and the center of the anode gas lead-out manifold 41 in a plan view.
- FIG. 8 shows a vertical cross section including a straight line passing through the center of the hydrogen system 200, the center of the liquid introduction manifold 60, and the center of the liquid delivery manifold 61 in a plan view.
- the hydrogen system 200 includes a hydrogen pump unit 100A of at least one electrochemical hydrogen pump 100.
- a plurality of hydrogen pump units 100A may be laminated on the electrochemical hydrogen pump 100. That is, in the examples shown in FIGS. 6, 7 and 8, one hydrogen pump unit 100A is shown, but the number of hydrogen pump units 100A is not limited to this example.
- the number of hydrogen pump units 100A can be set to an appropriate number based on operating conditions such as the amount of hydrogen compressed by the cathode CA of the electrochemical hydrogen pump 100.
- the hydrogen pump unit 100A includes an electrolyte membrane 11, an anode AN, a cathode CA, a cathode separator 16, an anode separator 17, and an insulator 21.
- a membrane CCM Catalyst Coated Membrane
- a catalyst layer in which the anode catalyst layer and the cathode catalyst layer are integrally bonded to the electrolyte membrane 11 is often used.
- the anode AN is provided on one main surface of the electrolyte membrane 11.
- the anode AN is an electrode including an anode catalyst layer and an anode gas diffusion layer.
- the above-mentioned membrane CCM with a catalyst layer is used as the electrolyte membrane 11
- the above-mentioned anode gas diffusion layer is provided on the main surface of the anode catalyst layer bonded to the membrane CCM with a catalyst layer.
- An annular seal member (not shown) is provided so as to surround the anode catalyst layer, and the anode catalyst layer is appropriately sealed with such a seal member.
- the cathode CA is provided on the other main surface of the electrolyte membrane 11.
- the cathode CA is an electrode including a cathode catalyst layer and a cathode gas diffusion layer.
- the above-mentioned cathode gas diffusion layer is provided on the main surface of the cathode catalyst layer bonded to the membrane CCM with a catalyst layer.
- An annular sealing member is provided so as to surround the periphery of the cathode catalyst layer, and the cathode catalyst layer is appropriately sealed by such a sealing member.
- the electrolyte membrane 11 is sandwiched between the anode AN and the cathode CA so that the anode catalyst layer and the cathode catalyst layer are in contact with each other.
- the cell containing the cathode CA, the electrolyte membrane 11 and the anode AN is referred to as a membrane-electrode assembly (hereinafter, MEA: Membrane Electrode Assembly), and the electrochemical hydrogen pump 100 includes the cathode CA, the electrolyte membrane 11 and the anode AN. , It may be a laminated body including at least one or more cells.
- the electrolyte membrane 11 has proton conductivity.
- the electrolyte membrane 11 may have any structure as long as it has proton conductivity.
- examples of the electrolyte membrane 11 include, but are not limited to, a fluorine-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane.
- Nafion registered trademark, manufactured by DuPont
- Aciplex registered trademark, manufactured by Asahi Kasei Corporation
- the like can be used as the electrolyte membrane 11.
- the anode catalyst layer is provided on one main surface of the electrolyte membrane 11.
- the anode catalyst layer includes, but is not limited to, platinum as the catalyst metal.
- the cathode catalyst layer is provided on the other main surface of the electrolyte membrane 11.
- the cathode catalyst layer includes, but is not limited to, platinum as the catalyst metal.
- Examples of the catalyst carrier of the cathode catalyst layer and the anode catalyst layer include, but are not limited to, carbon black, carbon powder such as graphite, and conductive oxide powder.
- the cathode catalyst layer and the anode catalyst layer fine particles of the catalyst metal are supported on the catalyst carrier in a highly dispersed manner. Further, in order to increase the electrode reaction field, a hydrogen ion conductive ionomer component is generally added to these cathode catalyst layer and anode catalyst layer.
- the cathode gas diffusion layer is provided on the cathode catalyst layer. Further, the cathode gas diffusion layer is made of a porous material and has conductivity and gas diffusivity. Further, it is desirable that the cathode gas diffusion layer has elasticity so as to appropriately follow the displacement and deformation of the constituent members generated by the differential pressure between the cathode CA and the anode AN during the operation of the electrochemical hydrogen pump 100.
- a member made of carbon fiber is used as the cathode gas diffusion layer.
- a porous carbon fiber sheet such as carbon paper, carbon cloth, or carbon felt may be used. It is not necessary to use a carbon fiber sheet as the base material of the cathode gas diffusion layer.
- a sintered body of metal fibers made of titanium, a titanium alloy, stainless steel or the like, a sintered body of metal powder made of these materials, or the like may be used.
- the anode gas diffusion layer is provided on the anode catalyst layer. Further, the anode gas diffusion layer is made of a porous material and has conductivity and gas diffusivity. Further, it is desirable that the anode gas diffusion layer has high rigidity capable of suppressing displacement and deformation of constituent members generated by the differential pressure between the cathode CA and the anode AN during the operation of the electrochemical hydrogen pump 100.
- a member made of a thin plate of a titanium powder sintered body is used as the anode gas diffusion layer, but the present invention is not limited to this. That is, as the base material of the anode gas diffusion layer, for example, a sintered body of metal fibers made of titanium, a titanium alloy, stainless steel or the like, or a sintered body of metal powder made of these materials can be used. Further, as the base material of the anode gas diffusion layer, for example, expanded metal, metal mesh, punching metal and the like can be used.
- the anode separator 17 is a member provided on the anode gas diffusion layer of the anode AN.
- the cathode separator 16 is a member provided on the cathode gas diffusion layer of the cathode CA.
- a recess is provided in the central portion of each of the cathode separator 16 and the anode separator 17.
- a cathode gas diffusion layer and an anode gas diffusion layer are housed in each of these recesses.
- the hydrogen pump unit 100A is formed by sandwiching the above MEA between the cathode separator 16 and the anode separator 17.
- a serpentine-shaped anode gas flow path including a plurality of U-shaped folded portions and a plurality of linear portions shown.
- an anode gas flow path is an example and is not limited to this example.
- the anode gas flow path may be composed of a plurality of linear flow paths.
- annular and flat plate-shaped insulator 21 provided so as to surround the MEA in a plan view is sandwiched between the conductive cathode separator 16 and the anode separator 17. As a result, a short circuit between the cathode separator 16 and the anode separator 17 is prevented.
- the hydrogen system 200 is provided on the anode feeding plate 22A provided on the anode separator 17 of the hydrogen pump unit 100A and on the cathode separator 16 of the hydrogen pump unit 100A.
- the cathode feeding plate 22C and the voltage applyer 102 are provided.
- the voltage applyer 102 is a device that applies a voltage between the anode catalyst layer and the cathode catalyst layer. Specifically, the high potential of the voltage applicator 102 is applied to the anode catalyst layer, and the low potential of the voltage applicator 102 is applied to the cathode catalyst layer.
- the voltage applyer 102 may have any configuration as long as a voltage can be applied between the anode catalyst layer and the cathode catalyst layer.
- the voltage applyer 102 may be a device that adjusts the voltage applied between the anode catalyst layer and the cathode catalyst layer.
- the voltage applyer 102 includes a DC / DC converter when connected to a DC power source such as a battery, a solar cell, or a fuel cell, and when connected to an AC power source such as a commercial power source. , AC / DC converter.
- the voltage applied between the anode catalyst layer and the cathode catalyst layer and the voltage applied between the anode catalyst layer and the cathode catalyst layer flow so that the electric power supplied to the hydrogen pump unit 100A becomes a predetermined set value. It may be a power type power source whose current is adjusted.
- the low potential side terminal of the voltage applyer 102 is connected to the cathode feeding plate 22C, and the high potential side terminal of the voltage applyer 102 is connected to the anode feeding plate 22A. It is connected.
- the cathode feeding plate 22C is in electrical contact with the cathode separator 16
- the anode feeding plate 22A is in electrical contact with the anode separator 17.
- the anode feeding plate 22A is unilateral in the stacking direction of these members.
- the cathode feeding plate 22C is in electrical contact with the anode separator 17 located at the end of the member, and the cathode feeding plate 22C is in electrical contact with the cathode separator 16 located at the other end in the stacking direction of these members.
- a pair of upper and lower firsts provided so as to sandwich the hydrogen pump unit 100A via each of the anode feeding plate 22A and the cathode feeding plate 22C.
- a first removal unit 300A of the removal device 300 of the above is provided.
- each of the pair of upper and lower first removers 300 includes a first remover unit 300A having the same configuration.
- the first removal unit 300A includes a water permeable membrane 115, a first porous structure 113A, a second porous structure 114A, a separator 18, a separator 19, and an insulator 20.
- the water permeable membrane 115 may have any structure as long as it has low permeability of hydrogen (H 2 ) in the cathode gas and allows water in the cathode gas to permeate.
- a water permeable membrane 115 for example, a proton conductive polymer membrane capable of permeating protons (H + ) made of the same material as the electrolyte membrane 11 can be used.
- examples of the water permeable membrane 115 include, but are not limited to, a fluorine-based polymer membrane and a hydrocarbon-based polymer membrane that can be used for a proton-conducting polymer membrane.
- the first porous structure 113A is provided in the liquid flow path 113 so as to be in contact with the water permeable membrane 115.
- the first porous structure 113A suppresses the displacement and deformation of the water permeable film 115 generated by the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300. It is desirable that the rigidity is as high as possible.
- the base material of such a first porous structure 113A may be made of, for example, a metal material similar to that of the anode gas diffusion layer.
- the second porous structure 114A is provided in the cathode gas flow path 114 so as to be in contact with the water permeable membrane 115.
- the second porous structure 114A is suitable for displacement and deformation of the water permeable membrane 115 generated by the differential pressure between the cathode gas flow path 114 (high pressure) and the liquid flow path 113 (low pressure) of the first remover 300. It is desirable to have elasticity that follows.
- the base material of such a second porous structure 114A may be made of, for example, a metal material similar to that of the cathode gas diffusion layer.
- the separator 18 is a member provided on the second porous structure 114A.
- the separator 19 is a member provided on the first porous structure 113A.
- a recess is provided in the central portion of each of the separator 18 and the separator 19.
- a second porous structure 114A and a first porous structure 113A are housed in each of these recesses, respectively.
- the recesses of the separator 18 and the separator 19 and the region partitioned by the water permeable membrane 115 constitute each of the cathode gas flow path 114 and the liquid flow path 113 of the first remover 300. To do.
- annular and flat plate-shaped insulator 20 provided so as to surround the MEA in a plan view is sandwiched between the separator 18 and the separator 19.
- the first removal unit 300A may have the same cell structure as the hydrogen pump unit 100A described above.
- the hydrogen system 200 includes an anode insulating plate 23A and an anode end plate 24A, a cathode insulating plate 23C and a cathode end plate 24C, and a fastener 25.
- the anode insulating plate 23A and the anode end plate 24A are provided in this order at one end of the hydrogen pump unit 100A and the first removal unit 300A in the stacking direction.
- the cathode insulating plate 23C and the cathode end plate 24C are provided in this order at the other end in the stacking direction.
- the fastener 25 includes each member of the hydrogen pump unit 100A and each member of the first removal unit 300A, an anode feeding plate 22A, an anode insulating plate 23A, an anode end plate 24A, a cathode feeding plate 22C, a cathode insulating plate 23C and a cathode end. It is a member for fastening the plates 24C in the above-mentioned stacking direction.
- the fastener 25 may have any configuration as long as such members can be fastened in the above-mentioned stacking direction.
- examples of the fastener 25 include bolts and nuts with disc springs.
- the bolt of the fastener 25 may be configured to penetrate only the anode end plate 24A and the cathode end plate 24C, but in the hydrogen system 200 of this embodiment, such bolts are the hydrogen pump unit 100A and the hydrogen pump unit 100A.
- Each member of the first removal unit 300A, the anode feeding plate 22A, the anode insulating plate 23A, the anode end plate 24A, the cathode feeding plate 22C, the cathode insulating plate 23C and the cathode end plate 24C are penetrated.
- the end face of the separator 19 located at one end in the above-mentioned stacking direction and the end face of the separator 18 located at the other end in the above-mentioned stacking direction are respectively subjected to the anode insulating plate 23A and the cathode insulating plate 23C, respectively.
- a desired fastening pressure is applied to the hydrogen pump unit 100A and the first removing unit 300A by the fastener 25 so as to be sandwiched between the anode end plate 24A and the cathode end plate 24C, respectively.
- the hydrogen pump unit 100A and the first removal unit 300A are appropriately held in the laminated state by the fastening pressure of the fastener 25 in the above stacking direction. Since the bolts of the fastener 25 penetrate each member of the electrochemical hydrogen pump 100 and the first removal unit 300A, the movement of each member in the in-plane direction can be appropriately suppressed.
- FIG. 6 a schematic diagram of the flow of the cathode gas is indicated by a thin alternate long and short dash arrow.
- the hydrogen system 200 includes a cathode gas passage manifold 50 and a cathode gas lead-out manifold 51.
- the cathode gas passage manifold 50 is composed of a series of communication holes provided at appropriate positions of each member of the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A and the cathode feeding plate 22C.
- the cathode gas passage manifold 50 communicates with the cathode gas diffusion layer of the cathode CA via the first cathode gas passage path 54 provided in the cathode separator 16 and the second cathode gas passage path provided in the separator 18. It also communicates with the cathode gas flow path 114 via 55.
- the cathode gas lead-out manifold 51 is a communication hole provided at an appropriate position in each member of the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A, the cathode feeding plate 22C, the cathode insulating plate 23C, and the cathode end plate 24C. It is composed of a series. That is, the cathode gas lead-out path 26 (see FIG. 4) is connected to the communication hole of the cathode end plate 24C, whereby the cathode gas lead-out path 26 and the cathode gas lead-out manifold 51 communicate with each other.
- the cathode gas lead-out path 26 may be composed of a pipe through which the cathode gas flows.
- the cathode gas lead-out manifold 51 communicates with the cathode gas flow path 114 via a third cathode gas passage path 56 provided in the separator 18.
- the high-pressure cathode gas compressed by the cathode CA of the electrochemical hydrogen pump 100 has the first cathode gas passage path 54, the cathode gas passage manifold 50, and the second, as shown by the single-point chain line arrow in FIG.
- the cathode gas passage path 55, the cathode gas flow path 114, the third cathode gas passage path 56, and the cathode gas lead-out manifold 51 are circulated in this order.
- the cathode gas is discharged to the outside of the hydrogen system 200 through the cathode gas lead-out path 26.
- the cathode gas passes through the cathode gas flow path 114 of the first removal unit 300A, the water contained in the cathode gas is removed in the first removal unit 300A.
- An annular seal member (not shown) is provided so as to surround the cathode gas passage manifold 50 and the cathode gas lead-out manifold 51 at appropriate positions between the members in a plan view, and the cathode gas passage manifold 50 and the cathode gas lead-out manifold 50 are provided. 51 is properly sealed with such a sealing member.
- FIG. 7 a schematic diagram of the flow of the hydrogen-containing gas is indicated by a thin alternate long and short dash arrow.
- the hydrogen system 200 includes an anode gas introduction manifold 40 and an anode gas lead-out manifold 41.
- the anode gas introduction manifold 40 is a communication hole provided at an appropriate position in each member of the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A, the cathode feeding plate 22C, the anode insulating plate 23A and the anode end plate 24A. It is composed of a series.
- An anode gas introduction path 29 (see FIG. 4) is connected to the communication hole of the anode end plate 24A, whereby the anode gas introduction path 29 and the anode gas introduction manifold 40 communicate with each other.
- the anode gas introduction path 29 may be composed of a pipe through which the hydrogen-containing gas supplied to the anode AN flows.
- the anode gas introduction manifold 40 communicates with the anode gas diffusion layer of the anode AN via the first anode gas passage path 45 provided in the anode separator 17.
- the first anode gas passage path 45 and one end of a serpentine-shaped anode gas flow path (not shown) provided in the anode separator 17 may be connected.
- the anode gas lead-out manifold 41 is a communication hole provided at an appropriate position in each member of the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A, the cathode feeding plate 22C, the cathode insulating plate 23C and the cathode end plate 24C. It is composed of a series.
- An anode gas lead-out path 31 (see FIG. 4) is connected to the communication hole of the cathode end plate 24C, whereby the anode gas lead-out path 31 and the anode gas lead-out manifold 41 communicate with each other.
- the anode gas lead-out path 31 may be composed of a pipe through which hydrogen-containing gas discharged from the anode AN flows.
- the anode gas lead-out manifold 41 communicates with the anode gas diffusion layer of the anode AN via the second anode gas passage path 46 provided in the anode separator 17.
- the second anode gas passage path 46 and the other end of the serpentine-shaped anode gas flow path (not shown) provided in the anode separator 17 may be connected.
- the hydrogen-containing gas from the anode gas introduction path 29 passes through the anode gas introduction manifold 40, the first anode gas passage path 45, the anode AN, and the second anode gas, as shown by the single-point chain line arrow in FIG.
- the path 46 and the anode gas lead-out manifold 41 are circulated in this order.
- the hydrogen-containing gas is discharged to the outside of the hydrogen pump unit 100A through the anode gas lead-out path 31.
- the hydrogen-containing gas passes through the anode AN of the hydrogen pump unit 100A, a part of the hydrogen-containing gas is supplied to the electrolyte membrane 11, so that the hydrogen in the hydrogen-containing gas in the hydrogen pump unit 100A is supplied. Compression is done.
- An annular seal member (not shown) is provided so as to surround the anode gas introduction manifold 40 and the anode gas lead-out manifold 41 at appropriate positions between the members in a plan view, and the anode gas introduction manifold 40 and the anode gas lead-out manifold 41 are provided. 41 is properly sealed with such a sealing member.
- the hydrogen system 200 includes a liquid introduction manifold 60 and a liquid lead-out manifold 61.
- the liquid introduction manifold 60 is a series of communication holes provided at appropriate positions in each member of the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A, the cathode feeding plate 22C, the anode insulating plate 23A, and the anode end plate 24A. It is composed of.
- a liquid introduction path 111 (see FIG. 4) is connected to the communication hole of the anode end plate 24A, whereby the liquid introduction path 111 and the liquid introduction manifold 60 communicate with each other.
- the liquid introduction path 111 may be composed of a pipe through which the cooling water supplied to the liquid flow path 113 flows.
- the liquid introduction manifold 60 communicates with the liquid flow path 113 via the first liquid passage path 65 provided in the separator 19.
- the liquid lead-out manifold 61 is a series of communication holes provided at appropriate positions in the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A, the cathode feeding plate 22C, the cathode insulating plate 23C, and the cathode end plate 24C. It is composed of.
- a liquid lead-out path 112 (see FIG. 4) is connected to the communication hole of the cathode end plate 24C, whereby the liquid lead-out path 112 and the liquid lead-out manifold 61 communicate with each other.
- the liquid lead-out path 112 may be composed of a pipe through which the cooling water discharged from the liquid flow path 113 flows.
- the liquid lead-out manifold 61 communicates with the liquid flow path 113 via the second liquid passage path 66 provided in the separator 19.
- the cooling water from the liquid introduction path 111 is the liquid introduction manifold 60, the first liquid passage path 65, the liquid flow path 113, the second liquid passage path 66, and as shown by the arrow of the alternate long and short dash line in FIG.
- the liquid lead-out manifold 61 is circulated in this order. After that, the cooling water is discharged to the outside of the first removal unit 300A through the liquid lead-out path 112.
- An annular seal member (not shown) is provided so as to surround the liquid introduction manifold 60 and the liquid lead-out manifold 61 at appropriate positions between the members in a plan view, and the liquid introduction manifold 60 and the liquid lead-out manifold 61 are engaged. It is properly sealed with a sealing member.
- the integrated configuration of the above-mentioned electrochemical hydrogen pump 100 and the first remover 300 is an example, and is not limited to this example.
- the hydrogen system 200 of the present embodiment is a laminate in which the electrochemical hydrogen pump 100 includes a cell including a cathode CA, an electrolyte membrane 11, and an anode AN, and is a first remover 300 of the first remover 300.
- the removal unit 300A is integrally laminated with this laminated body.
- the system configuration can be simplified by stacking the hydrogen pump unit 100A and the first removal unit 300A.
- a high-pressure cathode gas flows in the hydrogen pump unit 100A and the first removal unit 300A. Therefore, if the hydrogen pump unit and the first removal unit are provided separately, a high-rigidity end plate for fixing the hydrogen pump unit and the first removal unit is often required.
- the end plates used for the hydrogen pump unit 100A and the first removal unit 300A can be used. Since it can be shared as the anode end plate 24A and the cathode end plate 24C, the system configuration is simplified.
- a pair of first removal units 300A are stacked vertically so as to sandwich the hydrogen pump unit 100A from above and below. There is.
- the hydrogen system 200 of the present embodiment can easily and appropriately suppress an increase in contact resistance between the members of the hydrogen pump unit 100A. The reason for this is as follows.
- the first removal unit is integrally laminated only from below or above the hydrogen pump unit 100A, it is attached to the end plate (anode end plate 24A or cathode end plate 24C) on the side where the first removal unit is not laminated.
- the pressure of the cathode gas compressed by the cathode CA of the hydrogen pump unit 100A acts directly.
- the rigidity of the end plate is not sufficient, the end plate on the side where the first removal unit is not laminated may be deformed so as to bulge outward.
- the elastic deformation of the cathode gas diffusion layer cannot follow such deformation, a gap may be generated between the members of the hydrogen pump unit 100A, and the contact resistance between these members may increase. ..
- the pair of first removal units 300A on the top and bottom are integrally laminated from the lower side and the upper side of the hydrogen pump unit 100A, respectively. Can be mitigated. That is, as shown in FIG. 6, the cathode gas compressed by the cathode CA of the hydrogen pump unit 100A is paired vertically through the first cathode gas passage path 54, the cathode gas passage manifold 50, and the second cathode gas passage path 55. It is supplied to each cathode gas flow path 114 of the first removal unit 300A. Therefore, the gas pressure in these cathode gas flow paths 114 becomes a high pressure substantially equal to the gas pressure in the cathode CA of the hydrogen pump unit 100A.
- the load applied to each member of the hydrogen pump unit 100A by the cathode gas in the cathode gas flow path 114 acts to suppress the deformation (deflection) of these members due to the gas pressure in the cathode CA from above and below. To do.
- a gap between the members of the hydrogen pump unit 100A is less likely to occur as compared with the case where the first removal unit 300A is integrally laminated only from below or above the hydrogen pump unit 100A. Therefore, an increase in contact resistance between these members can be easily and appropriately suppressed.
- the water permeable membrane 115 is not energized. That is, due to the presence of the anode insulating plate 23A and the cathode insulating plate 23C, the voltage applied by the voltage applyer 102 is not applied to the water permeable membrane 115.
- the water permeable film 115 is composed of the proton conductive electrolyte film 11, a substance that promotes an electrochemical hydrogen oxidation reaction and a hydrogen generation reaction on both sides of the water permeable film 115 (for example, platinum or the like).
- the hydrogen system 200 of the present embodiment is configured so as not to energize the water permeable membrane 115, so that such a possibility can be reduced.
- the hydrogen system 200 of this embodiment may be the same as the hydrogen system 200 of any of the first embodiment and the first embodiment to the second embodiment except for the above-mentioned features.
- FIG. 9 is a diagram showing an example of the hydrogen system of the second embodiment.
- the hydrogen system 200 includes an electrochemical hydrogen pump 100, a first remover 300, and a second remover 400.
- electrochemical hydrogen pump 100 and the first remover 300 are the same as the hydrogen system 200 of the first embodiment, the description thereof will be omitted.
- the second remover 400 allows the cathode gas that has passed through the first remover 300 to flow through one main surface of the water permeation film 125, and the water vapor contained in the gas rather than the cathode gas flows through the other main surface. It is a device that circulates a gas with low chemical potential. Examples of such a gas include, but are not limited to, dry air.
- the second remover 400 may have any configuration as long as it is a film-type remover capable of removing water contained in the cathode gas.
- the high-pressure cathode gas that has passed through the first remover 300 flows through the flow path 124 (hereinafter referred to as the cathode gas flow path 124), and the low-pressure gas flows through the flow path 124.
- a flow path 123 (hereinafter referred to as a gas flow path 123) and a water permeable film 125 provided between the flow paths 123 and 124 are provided.
- the cathode gas lead-out path 26 for passing the cathode gas through the cathode gas flow path 124, the gas introduction path 121 for passing the gas through the gas flow path 123, and the gas lead-out path 122 and are provided.
- the water permeable membrane 125 may have any structure as long as it has low permeability of hydrogen (H 2 ) in the cathode gas and allows water in the cathode gas to permeate.
- the water permeable membrane 125 may be composed of, for example, a polymer membrane containing a sulfonic acid group similar to the water permeable membrane 115 of the first remover 300.
- the following operations may be performed by, for example, a controller arithmetic circuit (not shown) reading a control program from the controller storage circuit. However, it is not always essential to perform the following operations on the controller. The operator may perform some of the operations. Further, the operation of the hydrogen system 200 when a hydrogen-containing gas is used as the anode fluid will be described below.
- a low-pressure hydrogen-containing gas is supplied to the anode AN of the electrochemical hydrogen pump 100, and the voltage of the voltage applyer (not shown in FIG. 9) is applied to the electrochemical hydrogen pump 100. Then, in the electrochemical hydrogen pump 100, the protons extracted from the hydrogen-containing gas supplied to the anode AN move to the cathode CA via the electrolyte membrane 11, and a hydrogen compression operation is performed in which compressed hydrogen is generated. ..
- Hydrogen generated by the cathode CA of the electrochemical hydrogen pump 100 is compressed by the cathode CA as a cathode gas containing water vapor.
- the cathode gas can be compressed by the cathode CA by increasing the pressure loss of the cathode gas lead-out path 26 by using a flow rate regulator (not shown).
- the flow rate regulator include a back pressure valve and a regulating valve provided in the cathode gas lead-out path 26.
- the cathode gas is discharged from the cathode CA of the electrochemical hydrogen pump 100 to the outside of the electrochemical hydrogen pump 100 through the cathode gas lead-out path 26.
- the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 flows through one main surface of the water permeable membrane 115. Therefore, in the first remover 300, the operation of removing the water contained in the cathode gas is performed by circulating a liquid having a pressure lower than that of the cathode gas on the other main surface of the water permeable membrane 115. At this time, the temperature of the liquid flowing into the first remover 300 may be lower than the temperature of the cathode gas flowing into the first remover 300.
- the cathode gas that has passed through the first remover 300 flows through one main surface of the water permeable membrane 125. Therefore, in the second remover 400, the water content in the cathode gas is removed by passing a gas having a lower chemical potential of water vapor contained in the gas than the cathode gas on the other main surface of the water permeable film 125. The operation is performed.
- the hydrogen system 200 of the present embodiment can remove water in the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 more efficiently than before.
- the effect of removing the water contained in the cathode gas by the first remover 300 is the same as that of the hydrogen system 200 of the first embodiment, and thus the description thereof will be omitted.
- a liquid for example, water
- the cathode gas flow path can be understood from the data of the chemical potential having a relative humidity of 100% in FIG.
- the relative humidity of the cathode gas flowing through 114 There is naturally a limit to the reduction of the relative humidity of the cathode gas flowing through 114. That is, it may be difficult to remove the water content in the cathode gas so that the water content of the cathode gas is reduced to a desired low concentration by using only the first remover 300.
- the hydrogen system 200 of the present embodiment uses the second remover 400 to apply a gas having a lower chemical potential of water vapor contained in the gas to the other main surface of the water permeable membrane 125 than the cathode gas. It is in circulation. As a result, the hydrogen system 200 of the present embodiment can reduce the water content of the cathode gas to a low concentration as compared with the case where the water content in the cathode gas is removed only by the first remover 300.
- the hydrogen system 200 of the present embodiment may be the same as the hydrogen system 200 of any of the first embodiment and the first embodiment to the third embodiment except for the above-mentioned features.
- the hydrogen system 200 of the present embodiment is the same as the hydrogen system 200 of the first embodiment of the first embodiment, in addition to the electrochemical hydrogen pump 100, the first remover 300 and the second remover 400, A recycling channel 140, a supply channel 130 and a hydrogen source 700 (see FIG. 5) may be provided.
- the hydrogen system 200 of the present embodiment has the above-mentioned first porous structure in the gas flow path 123 in the second remover 400, similarly to the hydrogen system 200 of the second embodiment of the first embodiment.
- a sexual structure may be provided, or a second porous structure may be provided in the cathode gas flow path 124 in the second remover 400 so as to be in contact with the water permeable film 125.
- Example 10 and 11 are diagrams showing an example of a hydrogen system according to an embodiment of the second embodiment.
- the electrochemical hydrogen pump 100, the first remover 300, and the second remover 400 are integrally configured.
- FIG. 10 shows a vertical cross section including a straight line passing through the center of the hydrogen system 200, the center of the first cathode gas passing manifold 150A, and the center of the second cathode gas passing manifold 150B in a plan view.
- FIG. 11 shows a vertical cross section including a straight line passing through the center of the hydrogen system 200, the center of the gas introduction manifold 160, and the center of the gas lead-out manifold 161 in a plan view.
- the illustration of the vertical cross section including the straight line passing through the center of the hydrogen system 200, the center of the anode gas introduction manifold, and the center of the anode gas lead-out manifold in a plan view is the third embodiment of the first embodiment.
- the anode gas lead-out manifold 41 is the members of the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A, the cathode feeding plate 22C, the cathode insulating plate 23C, and the cathode end plate.
- the anode gas lead-out manifold is provided with the communication holes of the above members, and each member of the second remover 400. It is composed of a series of communication holes provided in the appropriate places.
- the liquid lead-out manifold 61 is a member of the hydrogen pump unit 100A and the first removal unit 300A, an anode feeding plate 22A, a cathode feeding plate 22C, a cathode insulating plate 23C, and a cathode end plate 24C.
- the liquid outlet manifold, together with the communication holes of the above-mentioned members is configured in the right place of each member of the second remover 400. It is composed of a series of communication holes provided in.
- the configuration of the electrochemical hydrogen pump 100 and the configuration of the first remover 300 of the hydrogen system 200 of this embodiment are the same as those of the hydrogen system 200 of the third embodiment of the first embodiment, and thus the description thereof will be omitted. ..
- the fastening configuration of the electrochemical hydrogen pump 100, the first remover 300 and the second remover 400, the flow path configuration of the hydrogen-containing gas in the electrochemical hydrogen pump 100, and the cooling water in the first remover 300 Since the flow path configuration of the above can be easily understood by referring to the contents described in the third embodiment of the first embodiment, the description thereof will be omitted.
- the hydrogen system 200 includes a second removal unit 400A of the second remover 400.
- one second removal unit 400A is shown in the second remover 400, but the number of the second removal units 400A is shown in this example. Not limited. Further, although the second removal unit 400A is provided between the cathode insulating plate 23C and the upper first removal unit 300A, the arrangement of the second removal unit 400A is not limited to this example. The second removal unit may be provided, for example, between the anode insulating plate 23A and the lower first removal unit 300A.
- the second removal unit 400A includes a water permeable membrane 125, a first porous structure 123A, a second porous structure 124A, a separator 118, a separator 119, and an insulator 120.
- the water permeable membrane 125 may have any structure as long as it has low permeability of hydrogen (H 2 ) in the cathode gas and allows water in the cathode gas to permeate.
- a water permeable membrane 125 for example, a proton conductive polymer membrane capable of permeating protons (H + ) made of the same material as the electrolyte membrane 11 can be used.
- examples of the water permeable membrane 125 include, but are not limited to, a fluorine-based polymer membrane and a hydrocarbon-based polymer membrane that can be used for a proton-conducting polymer membrane.
- the first porous structure 123A is provided in the gas flow path 123 so as to be in contact with the water permeable membrane 125.
- the first porous structure 123A suppresses the displacement and deformation of the water permeable film 125 generated by the differential pressure between the cathode gas flow path 124 (high pressure) and the gas flow path 123 (low pressure) of the second remover 400. It is desirable that the rigidity is as high as possible.
- the base material of such a first porous structure 123A may be made of, for example, a metal material similar to that of the anode gas diffusion layer.
- the second porous structure 124A is provided in the cathode gas flow path 124 so as to be in contact with the water permeable membrane 125.
- the second porous structure 124A is suitable for displacement and deformation of the water permeable membrane 125 generated by the differential pressure between the cathode gas flow path 124 (high pressure) and the gas flow path 123 (low pressure) of the second remover 400. It is desirable to have elasticity that follows.
- the base material of such a second porous structure 124A may be made of, for example, a metal material similar to that of the cathode gas diffusion layer.
- the separator 118 is a member provided on the second porous structure 124A.
- the separator 119 is a member provided on the first porous structure 123A.
- a recess is provided in the central portion of each of the separator 118 and the separator 119.
- a second porous structure 124A and a first porous structure 123A are housed in each of these recesses, respectively.
- the recesses of the separator 118 and the separator 119 and the region partitioned by the water permeable membrane 125 constitute each of the cathode gas flow path 124 and the gas flow path 123 of the second remover 400. To do.
- annular and flat plate-shaped insulator 120 provided so as to surround the MEA in a plan view is sandwiched between the separator 118 and the separator 119.
- the second removal unit 400A may have the same cell structure as the hydrogen pump unit 100A described above.
- FIG. 10 a schematic diagram of the flow of the cathode gas is indicated by a thin alternate long and short dash arrow.
- the hydrogen system 200 includes a first cathode gas passage manifold 150A, a second cathode gas passage manifold 150B, and a cathode gas lead-out manifold 151.
- the first cathode gas passage manifold 150A is composed of a series of communication holes provided at appropriate positions of each member of the hydrogen pump unit 100A and the first removal unit 300A, the anode feeding plate 22A and the cathode feeding plate 22C. ..
- the first cathode gas passage manifold 150A communicates with the cathode gas diffusion layer of the cathode CA via the first cathode gas passage path 54 provided in the cathode separator 16 and the second cathode gas provided in the separator 18. It also communicates with the cathode gas flow path 114 via the passage path 55.
- the second cathode gas passage manifold 150B is a communication hole provided at an appropriate position in each member of the hydrogen pump unit 100A, the first removal unit 300A and the second removal unit 400A, the anode feeding plate 22A and the cathode feeding plate 22C. It is composed of a series of.
- the second cathode gas passage manifold 150B communicates with the cathode gas flow path 114 via the third cathode gas passage path 56 provided in the separator 18, and the fourth cathode gas passage path 57 provided in the separator 118. It also communicates with the cathode gas flow path 124 via.
- the cathode gas lead-out manifold 151 is composed of a series of communication holes provided at appropriate positions on the separator 118 of the hydrogen pump unit 100A, the cathode insulating plate 23C, and the cathode end plate 24C.
- a cathode gas lead-out path 26 (see FIG. 10) is connected to the communication hole of the cathode end plate 24C, whereby the cathode gas lead-out path 26 and the cathode gas lead-out manifold 151 are communicated with each other.
- the cathode gas lead-out path 26 may be composed of a pipe through which the cathode gas flows.
- the cathode gas lead-out manifold 151 communicates with the cathode gas flow path 124 via a fifth cathode gas passage path 58 provided in the separator 118.
- the first cathode gas passage manifold 150A and the cathode gas lead-out manifold are provided so that the center of the first cathode gas passage manifold 150A and the center of the cathode gas lead-out manifold 151 pass on the same straight line.
- 151 is provided via the separator 119 and the insulator 120, but their arrangement is not limited to this example.
- the high-pressure cathode gas compressed by the cathode CA of the electrochemical hydrogen pump 100 has the first cathode gas passage path 54, the first cathode gas passage manifold 150A, as shown by the single-point chain line arrow in FIG.
- the second cathode gas passage path 55, the cathode gas flow path 114, the third cathode gas passage path 56, and the second cathode gas passage manifold 150B are circulated in this order.
- the cathode gas flows through the fourth cathode gas passage path 57, the cathode gas flow path 124, the fifth cathode gas passage path 58, and the cathode gas lead-out manifold 151, and then is discharged to the outside of the hydrogen system 200 through the cathode gas lead-out path 26. Will be done.
- the cathode gas passes through the cathode gas flow path 114 of the first removal unit 300A and the cathode gas flow path 124 of the second removal unit 400A in this order, the first removal unit 300A and the second removal unit 300A Moisture in the cathode gas is removed in the removal unit 400A.
- An annular seal member (not shown) is provided so as to surround the first cathode gas passage manifold 150A, the second cathode gas passage manifold 150B, and the cathode gas lead-out manifold 151 at appropriate positions between the members in a plan view.
- the first cathode gas passage manifold 150A, the second cathode gas passage manifold 150B, and the cathode gas lead-out manifold 151 are appropriately sealed with such a sealing member.
- FIG. 11 a schematic diagram of the gas flow is indicated by a thin alternate long and short dash arrow.
- the hydrogen system 200 includes a gas introduction manifold 160 and a gas lead-out manifold 161.
- the gas introduction manifold 160 is provided at appropriate locations on the hydrogen pump unit 100A, the first removal unit 300A and the second removal unit 400A, the anode feeding plate 22A, the cathode feeding plate 22C, the anode insulating plate 23A and the anode end plate 24A. It is composed of a series of communication holes provided.
- a gas introduction path 121 (see FIG. 9) is connected to the communication hole of the anode end plate 24A, whereby the gas introduction path 121 and the gas introduction manifold 160 communicate with each other.
- the gas introduction path 121 may be composed of a pipe through which the gas supplied to the gas flow path 123 flows.
- the gas introduction manifold 160 communicates with the gas flow path 123 via the first gas passage path 67 provided in the separator 119.
- the gas lead-out manifold 161 is provided at appropriate locations on the hydrogen pump unit 100A, the first removal unit 300A and the second removal unit 400A, the anode feeding plate 22A, the cathode feeding plate 22C, the cathode insulating plate 23C and the cathode end plate 24C. It is composed of a series of communication holes provided.
- a gas lead-out path 122 (see FIG. 9) is connected to the communication hole of the cathode end plate 24C, whereby the gas lead-out path 122 and the gas lead-out manifold 161 are communicated with each other.
- the gas lead-out path 122 may be composed of a pipe through which the gas discharged from the gas flow path 123 flows.
- the gas lead-out manifold 161 communicates with the gas flow path 123 via the second gas passage path 68 provided in the separator 119.
- the gas from the gas introduction path 121 is the gas introduction manifold 160, the first gas passage path 67, the gas flow path 123, the second gas passage path 68, and the gas, as shown by the arrow of the alternate long and short dash line in FIG.
- the lead-out manifold 161 is distributed in this order. After that, the gas is discharged to the outside of the second removal unit 400A through the gas lead-out path 122.
- An annular seal member (not shown) is provided so as to surround the gas introduction manifold 160 and the gas lead-out manifold 161 at appropriate positions between the members in a plan view, and the gas introduction manifold 160 and the gas lead-out manifold 161 are engaged. It is properly sealed with a sealing member.
- the integrated configuration of the above-mentioned electrochemical hydrogen pump 100, the first remover 300, and the second remover 400 is an example, and is not limited to this example.
- the hydrogen system 200 of the present embodiment is a laminate in which the electrochemical hydrogen pump 100 includes a cell including a cathode CA, an electrolyte membrane 11, and an anode AN, and is a first remover 300 of the first remover 300.
- the removal unit 300A and the second removal unit 400A of the second remover 400 are integrally laminated with this laminate.
- the system configuration can be simplified by stacking the hydrogen pump unit 100A, the first removal unit 300A, and the second removal unit 400A.
- a high-pressure cathode gas flows in the hydrogen pump unit 100A and the second removal unit 400A. Therefore, if the hydrogen pump unit and the second removal unit are provided separately, a high-rigidity end plate for fixing the hydrogen pump unit and the second removal unit is often required.
- the end plates used for the hydrogen pump unit 100A and the second removal unit 400A can be used. Since it can be shared as the anode end plate 24A and the cathode end plate 24C, the system configuration is simplified.
- the water permeable membrane 115 and the water permeable membrane 125 are not energized. That is, due to the presence of the anode insulating plate 23A and the cathode insulating plate 23C, the voltage applied by the voltage applyer 102 is not applied to the water permeable membrane 115 and the water permeable membrane 125. The reason for such a configuration is the same as that described in the third embodiment of the first embodiment.
- the hydrogen system 200 of this embodiment is the same as the hydrogen system 200 of any of the first embodiment, the first embodiment-3rd embodiment, and the second embodiment except for the above-mentioned features. You may.
- FIG. 12 is a diagram showing an example of the hydrogen system of the third embodiment.
- the hydrogen system 200 includes an electrochemical hydrogen pump 100, a first remover 300, and a third remover 500.
- electrochemical hydrogen pump 100 and the first remover 300 are the same as the hydrogen system 200 of the first embodiment, the description thereof will be omitted.
- the third remover 500 is a device containing an adsorbent that removes water in the cathode gas that has passed through the first remover 300.
- the third remover 500 may have any configuration as long as it is a remover using such an adsorbent.
- the adsorbent of the third remover 500 may be made of any material as long as it is a material that adsorbs and removes water vapor and the like in the cathode gas. Examples of the adsorbent material include porous materials such as zeolite and silica gel.
- the hydrogen system 200 of the present embodiment simply removes the water content in the cathode gas that has passed through the first remover 300 by using the adsorbent of the third remover 500.
- the hydrogen system 200 of the present embodiment only the water contained in the cathode gas that could not be removed by the first remover 300 may be adsorbed and removed by the adsorbent of the third remover 500.
- the hydrogen system 200 of the present embodiment can reduce the amount of water adsorbed by the adsorbent per unit time as compared with the case where the first remover 300 does not remove the water in the cathode gas. Then, even if the filling amount of the adsorbent in the third remover 500 is reduced, the water adsorption performance of the adsorbent of the third remover 500 can be appropriately maintained for a desired period, and thus the third remover 500 can be maintained. It is possible to reduce the size and cost of the remover 500.
- the hydrogen system 200 of the present embodiment may be provided with a hydrogen reservoir (not shown) for storing the cathode gas (hydrogen) from which water has been removed by the third remover 500.
- a hydrogen reservoir (not shown) for storing the cathode gas (hydrogen) from which water has been removed by the third remover 500.
- the hydrogen storage device include a hydrogen tank.
- the dry cathode gas (hydrogen) stored in the hydrogen reservoir is supplied to the hydrogen consumer in a timely manner.
- the hydrogen consumer include a fuel cell and the like.
- the hydrogen system 200 of the present embodiment is any one of the first embodiment, the first embodiment-3rd embodiment, the second embodiment, and the second embodiment, except for the above-mentioned features. It may be the same as the hydrogen system 200 of.
- the hydrogen system 200 of the present embodiment is the same as the hydrogen system 200 of the first embodiment of the first embodiment, in addition to the electrochemical hydrogen pump 100, the first remover 300, and the third remover 500.
- a recycling channel 140, a supply channel 130 and a hydrogen source 700 may be provided.
- a second remover 400 (see FIG. 9) described in the second embodiment is inserted between the first remover 300 and the third remover 500. It may be provided.
- the hydrogen system 200 of the fourth embodiment is the same as the hydrogen system 200 of the first embodiment except for the configuration of the first remover 301 described below.
- the first remover 301 is provided on one main surface of the water permeable film 115 and the water permeable film 115, and is a flow path through which the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 flows (hereinafter, the cathode).
- the water content in the cathode gas includes liquid water contained in the cathode gas.
- the water removed by the first remover 301 includes, for example, condensed water condensed from the cathode gas.
- This condensed water is generated in the flow path from the cathode CA of the electrochemical hydrogen pump 100 to the first remover 301 in the cathode gas lead-out path 26, or in the cathode gas flow path 114 in the first remover 301. Will be done.
- the first remover 301 may have any configuration as long as it is a film-type remover capable of removing water contained in the cathode gas.
- the first remover 301 has a cathode gas flow path 114, a container 170, a water permeable film 115 provided between the cathode gas flow path 114 and the container 170, and a container 170.
- a discharge path 171 for discharging the liquid in the container may be provided. That is, in this case, the container 170 corresponds to the above-mentioned accommodating portion.
- the discharge path 171 extends so as to communicate with the inside and outside of the container.
- controller arithmetic circuit (not shown) reading a control program from the controller storage circuit.
- controller arithmetic circuit
- the operator may perform some of the operations.
- a low-pressure hydrogen-containing gas is supplied to the anode AN of the electrochemical hydrogen pump 100, and the voltage of a voltage applyer (not shown in FIG. 13) is applied to the electrochemical hydrogen pump 100.
- the protons taken out from the hydrogen-containing gas supplied to the anode AN move to the cathode CA via the electrolyte membrane 11 to generate compressed hydrogen (hydrogen compression operation). Is done. Since such a hydrogen compression operation is the same as that of the first embodiment, detailed description thereof will be omitted.
- the cathode gas flows from the cathode CA of the electrochemical hydrogen pump 100 to the outside of the electrochemical hydrogen pump 100 through the cathode gas lead-out path 26. It is discharged.
- the first remover 301 a step of moving water from the compressed hydrogen-containing cathode gas to a low-pressure liquid in the container 170 via the water permeable membrane 115 is performed.
- the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 flows through one main surface of the water permeable membrane 115. Therefore, in the first remover 301, the operation of removing the water contained in the cathode gas is performed by filling the container 170 provided on the other main surface of the water permeable membrane 115 with a liquid having a pressure lower than that of the cathode gas. ..
- the above-mentioned water includes liquid water contained in the cathode gas.
- This water content includes, for example, condensed water condensed from the cathode gas.
- This condensed water is generated in the flow path from the cathode CA of the electrochemical hydrogen pump 100 to the first remover 301 in the cathode gas lead-out path 26, or in the cathode gas flow path 114 in the first remover 301. Will be done.
- the temperature of the liquid may be lower than the temperature of the cathode gas flowing into the first remover 301.
- a step of discharging the liquid in the container 170 may be performed in the discharge path 171.
- the container 170 When the hydrogen system 200 is in operation, the container 170 may not be filled with liquid and the container 170 may be empty.
- the condensed water moves from the cathode gas into the container 170 via the water permeable membrane 115.
- the inside of the container 170 can be filled with water.
- the method of operating the hydrogen system 200 and the hydrogen system 200 of the present embodiment can remove water contained in the cathode gas discharged from the cathode CA of the electrochemical hydrogen pump 100 more efficiently than before.
- the hydrogen system 200 and the operation method of the hydrogen system 200 of the present embodiment are the first embodiment, the first embodiment of the first embodiment-3rd embodiment, the second embodiment, and the second embodiment. It may be the same as any one of the embodiment and the third embodiment.
- the hydrogen system 200 of the present embodiment includes a second remover 400 (see FIG. 9) described in the second embodiment, a third remover 500 (see FIG. 12) described in the third embodiment, and the like. It may be provided.
- FIG. 14 is a diagram showing an example of a hydrogen system according to an embodiment of the fourth embodiment.
- the electrochemical hydrogen pump 100 and the first remover 301 are integrally configured.
- FIG. 14 shows a vertical cross section including the center of the hydrogen system 200, the center of the drainage manifold 171A, and a straight line passing through in a plan view. Further, in FIG. 14, “top” and “bottom” are taken as shown in the figure, and it is assumed that gravity acts from top to bottom.
- the illustration of the vertical cross section including the center of the hydrogen system 200, the center of the cathode gas passage manifold 50, and the center of the cathode gas lead-out manifold 51 in a plan view is the third embodiment.
- FIG. 6 the illustrated contents of FIG. 6 described in the examples, it can be easily understood and will be omitted.
- the configuration of the electrochemical hydrogen pump 100 of the hydrogen system 200 of this embodiment is the same as that of the hydrogen system 200 of the third embodiment of the first embodiment, the description thereof will be omitted. Further, the fastening configuration of the electrochemical hydrogen pump 100 and the first remover 301, and the flow path configuration of the cathode gas and the hydrogen-containing gas in the electrochemical hydrogen pump 100 have been described in the third embodiment of the first embodiment. The explanation is omitted because it can be easily understood by taking the contents into consideration.
- a pair of upper and lower first removers 301 provided so as to sandwich the hydrogen pump unit 100A via the anode feeding plate 22A and the cathode feeding plate 22C respectively.
- the removal unit 301A of 1 is provided.
- each of the pair of upper and lower first removers 301 includes a first remover unit 301A having the same configuration.
- the first removal unit 301A includes a water permeable membrane 115, a first porous structure 170A, a second porous structure 114A, a separator 18, a separator 19, and an insulator 20.
- the water permeable membrane 115, the second porous structure 114A, the separator 18, and the insulator 20 are the same as those in the third embodiment of the first embodiment, and thus the description thereof will be omitted.
- the region (space) partitioned by the recess of the separator 19 and the water permeable membrane 115 corresponds to the inside of the container 170.
- a first porous structure 170A is provided in this region. Since the configuration of the first porous structure 170A is the same as that of the first porous structure 113A described in the third embodiment of the first embodiment, the description thereof will be omitted.
- the above configuration of the first remover 301 is an example and is not limited to this example. For example, it is not necessary to provide the porous structure in the region partitioned by the recess of the separator 19 and the water permeable membrane 115.
- FIG. 14 a schematic diagram of the flow of water is indicated by a thin alternate long and short dash arrow.
- the hydrogen system 200 includes a drainage manifold 171A.
- the drainage manifold 171A is formed by a series of communication holes provided at appropriate positions of the hydrogen pump unit 100A and the first removal unit 301A, the anode feeding plate 22A, the cathode feeding plate 22C, the anode insulating plate 23A, and the anode end plate 24A. It is configured.
- a drainage path 172 is connected to the communication hole of the anode end plate 24A, whereby the drainage path 172 and the drainage manifold 171A are communicated with each other.
- the drainage path 172 may be composed of a pipe through which water drained from the container 170 flows.
- the drainage manifold 171A communicates with the inside of the container 170 via the water passage path 171B provided in the separator 19.
- Such a water passage path 171B may be composed of a communication groove provided on the main surface of the separator 19 that contacts the other main surface side of the water permeable membrane 115.
- An annular sealing member (not shown) is provided so as to surround the drainage manifold 171A at an appropriate position between the members in a plan view, and the drainage manifold 171A is appropriately sealed by such a sealing member.
- the water in the container 170 flows through the water passage path 171B and the drainage manifold 171A in this order as shown by the arrow of the alternate long and short dash line in FIG.
- the water is then drained out of the hydrogen system 200 through the drainage path 172.
- the condensed water condensed from the water vapor in the cathode gas moves into the container 170 via the water permeable film 115.
- the water in the container 170 is sent to the drainage manifold 171A through the water passage path 171B.
- this water flows downward in the drainage manifold 171A due to the action of gravity, and then moves to the drainage path 172.
- the drainage manifold 171A and the water passage path 171B form the discharge passage 171 for discharging the liquid (water) in the container 170.
- the integrated configuration of the above-mentioned electrochemical hydrogen pump 100 and the first remover 301 is an example, and is not limited to this example.
- the hydrogen system 200 of the present embodiment is a laminate in which the electrochemical hydrogen pump 100 includes a cell including a cathode CA, an electrolyte membrane 11, and an anode AN, and is a first remover 301 of the first remover 301.
- the removal unit 301A is integrally laminated with this laminated body.
- the details of the action and effect of the hydrogen system 200 of this embodiment are the same as those of the hydrogen system 200 of the third embodiment of the first embodiment, and thus the description thereof will be omitted.
- the hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment of the first embodiment-3rd embodiment, the second embodiment, the second embodiment, and the third embodiment, except for the above-mentioned features. It may be similar to the hydrogen system 200 of any of the embodiments and the fourth embodiment.
- 1st Embodiment, 1st Example of 1st Embodiment-3rd Example, 2nd Embodiment, 2nd Embodiment, 3rd Embodiment, 4th Embodiment and 4th Embodiment May be combined with each other as long as they do not exclude each other.
- the hydrogen system 200 may include other compressors such as a water electrolyzer.
- One aspect of the present disclosure can be used, for example, in a hydrogen system and a method of operating a hydrogen system, which can remove water contained in the cathode gas discharged from the cathode of a compressor more efficiently than before.
- Electrolyte film 16 Cathode separator 17: Anogas separator 18: Separator 19: Separator 20: Insulator 21: Insulator 22A: Anogas feeding plate 22C: Cone feeding plate 23A: Anodic insulating plate 23C: Cone insulating plate 24A: Anode end Plate 24C: Cathode end plate 25: Fastener 26: Cathode gas lead-out path 29: Anoside gas introduction path 31: Anoside gas lead-out path 40: Anoside gas introduction manifold 41: Anoside gas lead-out manifold 45: First anode gas passage path 46: 2nd anode gas passage path 50: cathode gas passage manifold 51: cathode gas lead-out manifold 54: 1st cathode gas passage path 55: 2nd cathode gas passage path 56: 3rd cathode gas passage path 57: 4th cathode gas passage path 58: Fifth cathode gas passage path 60: Liquid introduction manifold
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Abstract
Description
図1は、水透過膜の水透過性を評価するための測定装置の一例を示す図である。
以下、水透過膜805のLLPの測定手順および測定結果について説明する。
以下、水透過膜805のLVPの測定手順および測定結果について説明する。
図2Aおよび図2Bから理解できるとおり、セル800の全ての温度において、水透過膜805のLLP(水の透過流束)は、水透過膜805のLVP(水の透過流束)に比べて圧力依存性が大きかった。例えば、水透過膜805がN212膜であると、このような傾向が顕著に現れており、N212膜のLLP(水の透過流束)は、収納部800Hに存在する水の水圧の増加とともに大幅に増加して、N212のLVP(水の透過流束)の約2.7~約5倍であった。例えば、セル800の温度が約70℃において、N212膜のLLP(水の透過流束)は、約0.15(mol/m2/s)にも達した。
上記の式において、δは「1.990 J mol-1 atm-1」であり、P(z)は水に対する加圧力であり、PSTDは、常圧である。
以下の実施形態では、上記の圧縮器の一例である電気化学式水素ポンプを備える水素システムの構成および水素システムの運転方法について説明する。
図4は、第1実施形態の水素システムの一例を示す図である。
以下、第1実施形態の水素システム200の動作の一例について図面を参照しながら説明する。
カソード:2H++2e-→H2(高圧) ・・・(2)
電気化学式水素ポンプ100のカソードCAで生成された水素は、水蒸気を含むカソードガスとして、カソードCAで圧縮される。例えば、図示しない流量調整器を用いて、カソードガス導出経路26の圧損を増加させることにより、カソードCAでカソードガスを圧縮することができる。なお、流量調整器として、例えば、カソードガス導出経路26に設けられた背圧弁、調整弁などを挙げることができる。
図5は、第1実施形態の第1実施例の水素システムの一例を示す図である。
本実施例の水素システム200は、第1の除去器300内の液体流路113に、第1の多孔性構造体が設けられること、および、第1の除去器300内のカソードガス流路114に、水透過膜115と接するように第2の多孔性構造体が設けられること以外、第1実施形態の水素システム200と同様である。なお、第1の多孔性構造体は、第1の除去器300の水透過膜115と接するように第1の除去器300内の液体流路113に設けられていてもよい。
図6、図7および図8は、第1実施形態の第3実施例の水素システムの一例を示す図である。本実施例の水素システム200では、電気化学式水素ポンプ100および第1の除去器300が一体的に構成されている。
以下、図面を参照しながら、電気化学式水素ポンプ100の構成の一例を説明する。
以下、図面を参照しながら、第1の除去器300の構成の一例を説明する。
以下、図面を参照しながら、電気化学式水素ポンプ100および第1の除去器300の締結構成の一例を説明する。
以下、図6を参照しながら、電気化学式水素ポンプ100および第1の除去器300におけるカソードガスの流路構成の一例を説明する。なお、図6では、カソードガスの流れの模式図が細い一点鎖線の矢印で示されている。
以下、図7を参照しながら、水素ポンプユニット100AのアノードANに供給するアノード流体が水素含有ガスである場合における水素含有ガスの流路構成の一例を説明する。なお、図7では、水素含有ガスの流れの模式図が細い一点鎖線の矢印で示されている。
以下、図8を参照しながら、第1の除去ユニット300Aの液体流路113に供給する液体が冷却水である場合における冷却水の流路構成の一例を説明する。なお、図8では、冷却水の流れの模式図が細い一点鎖線の矢印で示されている。
[装置構成]
図9は、第2実施形態の水素システムの一例を示す図である。
以下、第2実施形態の水素システム200の動作の一例について図面を参照しながら説明する。
図10および図11は、第2実施形態の実施例の水素システムの一例を示す図である。本実施例の水素システム200では、電気化学式水素ポンプ100、第1の除去器300および第2の除去器400が一体的に構成されている。
以下、図面を参照しながら、第2の除去器400の構成の一例を説明する。
以下、図10を参照しながら、電気化学式水素ポンプ100、第1の除去器300および第2の除去器400におけるカソードガスの流路構成の一例を説明する。なお、図10では、カソードガスの流れの模式図が細い一点鎖線の矢印で示されている。
以下、図11を参照しながら、第2の除去ユニット400Aの気体流路123に供給する気体(例えば、乾燥した空気)の流路構成の一例を説明する。なお、図11では、気体の流れの模式図が細い一点鎖線の矢印で示されている。
図12は、第3実施形態の水素システムの一例を示す図である。
第4実施形態の水素システム200は、以下に説明する第1の除去器301の構成以外は、第1実施形態の水素システム200と同様である。
図14は、第4実施形態の実施例の水素システムの一例を示す図である。本実施例の水素システム200では、電気化学式水素ポンプ100および第1の除去器301が一体的に構成されている。
以下、図面を参照しながら、第1の除去器301の構成の一例を説明する。
以下、図14を参照しながら、第1の除去ユニット301Aの容器170から排出される液体が水である場合における排出路171(排水路)の流路構成の一例を説明する。なお、図14では、水の流れの模式図が細い一点鎖線の矢印で示されている。
16 :カソードセパレーター
17 :アノードセパレーター
18 :セパレーター
19 :セパレーター
20 :絶縁体
21 :絶縁体
22A :アノード給電板
22C :カソード給電板
23A :アノード絶縁板
23C :カソード絶縁板
24A :アノード端板
24C :カソード端板
25 :締結器
26 :カソードガス導出経路
29 :アノードガス導入経路
31 :アノードガス導出経路
40 :アノードガス導入マニホールド
41 :アノードガス導出マニホールド
45 :第1アノードガス通過経路
46 :第2アノードガス通過経路
50 :カソードガス通過マニホールド
51 :カソードガス導出マニホールド
54 :第1カソードガス通過経路
55 :第2カソードガス通過経路
56 :第3カソードガス通過経路
57 :第4カソードガス通過経路
58 :第5カソードガス通過経路
60 :液体導入マニホールド
61 :液体導出マニホールド
65 :第1液体通過経路
66 :第2液体通過経路
67 :第1気体通過経路
68 :第2気体通過経路
100 :電気化学式水素ポンプ
100A :水素ポンプユニット
102 :電圧印加器
111 :液体導入経路
112 :液体導出経路
113 :液体流路
113A :第1の多孔質構造体
114 :カソードガス流路
114A :第2の多孔質構造体
115 :水透過膜
118 :セパレーター
119 :セパレーター
120 :絶縁体
121 :気体導入経路
122 :気体導出経路
123 :気体流路
123A :第1の多孔質構造体
124 :カソードガス流路
124A :第2の多孔質構造体
125 :水透過膜
130 :供給路
140 :リサイクル流路
150A :第1カソードガス通過マニホールド
150B :第2カソードガス通過マニホールド
151 :カソードガス導出マニホールド
160 :気体導入マニホールド
161 :気体導出マニホールド
170 :容器
170A :第1の多孔質構造体
171 :排出路
171A :排水マニホールド
171B :水通過経路
172 :排水経路
200 :水素システム
300 :第1の除去器
301 :第1の除去器
300A :第1の除去ユニット
301A :第1の除去ユニット
400 :第2の除去器
400A :第2の除去ユニット
500 :第3の除去器
700 :水素源
AN :アノード
CA :カソード
Claims (19)
- アノードに供給するアノード流体から取り出されたプロトンが、電解質膜を介してカソードに移動し、圧縮された水素が生成される圧縮器と、
水透過膜、前記水透過膜の一方の主面上に設けられ、前記圧縮器のカソードから排出されるカソードガスが流通するカソードガス流路、および前記水透過膜の他方の主面上に設けられ、前記カソードガスより低圧の液体が満ちている収容部を含み、前記カソードガスに含まれる水分を除去する第1の除去器と、を備える水素システム。 - 前記第1の除去器に前記収容部内の液体を排出する排出路を備える、請求項1に記載の水素システム。
- 前記収容部は、前記液体が流れる流路である、請求項1または2に記載の水素システム。
- 前記液体の温度は、前記第1の除去器に流入する前記カソードガスの温度よりも低い請求項1-3のいずれか1項に記載の水素システム。
- 前記液体が、水を含む請求項1-4のいずれか1項に記載の水素システム。
- 前記第1の除去器から排出された前記液体を、再び前記第1の除去器に供給するためのリサイクル流路を備える、請求項1-5のいずれか1項に記載の水素システム。
- 前記液体は水を含み、前記アノード流体は水素含有ガスであり、前記第1の除去器から排出された前記液体を前記アノードに供給される前記水素含有ガスに供給する供給路を備える、請求項1-4、および6のいずれか1項に記載の水素システム。
- 前記水透過膜が、スルホン酸基を含む高分子膜である請求項1-7のいずれか1項に記載の水素システム。
- 前記水透過膜に通電をしない請求項1-8のいずれか1項に記載の水素システム。
- 前記第1の除去器内の前記液体が流れる流路に、第1の多孔性構造体が設けられる請求項3に記載の水素システム。
- 前記カソードガス流路に、前記水透過膜と接するように第2の多孔性構造体が設けられる請求項1-10のいずれか1項に記載の水素システム。
- 前記圧縮器が、前記カソード、前記電解質膜、および前記アノードを含むセルを備える積層体であり、前記第1の除去器が前記積層体と一体で積層されている請求項1-11のいずれか1項に記載の水素システム。
- 水透過膜の一方の主面に前記第1の除去器を通過した前記カソードガスを流通させ、他方の主面に前記カソードガスよりも、ガス中に含まれる水蒸気の化学ポテンシャルが低い気体を流通させる第2の除去器を備える請求項1-12のいずれか1項に記載の水素システム。
- 前記第1の除去器を通過した前記カソードガス中の水分を除去する吸着材を含む第3の除去器を備える請求項1-13のいずれか1項に記載の水素システム。
- アノードに供給するアノード流体から取り出されたプロトンが、電解質膜を介してカソードに移動し、圧縮された水素が生成されるステップと、
圧縮された水素を含むカソードガスから水分を、水透過膜を介して収容部内に満ちている低圧の液体に移動させるステップと、を備える水素システムの運転方法。 - 前記収容部内の液体を排出するステップを備える、請求項15に記載の水素システムの運転方法。
- 前記収容部は、前記液体が流れる流路である、請求項15または16に記載の水素システムの運転方法。
- 前記液体の温度は、前記カソードガスの温度よりも低い請求項15-17のいずれか1項に記載の水素システムの運転方法。
- 前記液体が、水を含む請求項15-18のいずれか1項に記載の水素システムの運転方法。
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