WO2025225345A1 - Organic hydride production device, organic hydride production system, and organic hydride production method - Google Patents
Organic hydride production device, organic hydride production system, and organic hydride production methodInfo
- Publication number
- WO2025225345A1 WO2025225345A1 PCT/JP2025/013827 JP2025013827W WO2025225345A1 WO 2025225345 A1 WO2025225345 A1 WO 2025225345A1 JP 2025013827 W JP2025013827 W JP 2025013827W WO 2025225345 A1 WO2025225345 A1 WO 2025225345A1
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- WIPO (PCT)
- Prior art keywords
- cathode
- organic hydride
- anode
- electrode
- electrolyte membrane
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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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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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
-
- 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
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the present invention relates to an organic hydride production apparatus, an organic hydride production system, and an organic hydride production method.
- renewable energy sources such as solar, wind, hydroelectric, and geothermal power to reduce carbon dioxide emissions during the energy generation process.
- One example is a system that uses electricity derived from renewable energy to perform water electrolysis to produce hydrogen.
- Organic hydride systems are also attracting attention as an energy carrier for the large-scale transport and storage of hydrogen derived from renewable energy.
- an organic hydride production apparatus includes an electrolytic cell having an anode electrode that generates protons from water, a cathode electrode that hydrogenates an organic compound having an unsaturated bond (the material to be hydrogenated), and a diaphragm that separates the anode and cathode electrodes (see, for example, Patent Document 1).
- protons are generated by the oxidation of water at the anode electrode, and these protons migrate to the cathode electrode side via the diaphragm, where the material to be hydrogenated is hydrogenated by the protons, thereby producing an organic hydride.
- the organic hydride production apparatus described above can generate protons and hydrogenate the material to be hydrided in a single process. This simplifies the organic hydride production process compared to organic hydride production using a two-stage process in which hydrogen is produced by water electrolysis or other methods and the material to be hydrided is chemically hydrogenated in a reactor at a plant or other facility. It also increases the efficiency of organic hydride production. Furthermore, since the high-pressure vessel for storing hydrogen, which is required when producing hydrogen by water electrolysis or other methods, can be omitted, significant reductions in facility costs are expected.
- the present invention was made in light of these circumstances, and one of its objectives is to provide an organic hydride manufacturing apparatus that can prevent heat generation beyond the temperature range that can occur during normal operation.
- An organic hydride manufacturing apparatus for solving the problems includes an electrolytic cell having an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anode fluid and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, wherein the liquid level of the anode fluid in the anode chamber is equal to or higher than the height of the upper end surface of the cathode electrode.
- An organic hydride production system as an aspect of the present invention that solves the problems includes an organic hydride production apparatus and a power supply device, wherein the organic hydride production apparatus has an electrolyte membrane and an electrolytic cell having an anode chamber disposed on one side of the electrolyte membrane and accommodating an anolyte and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, and the liquid level of the anolyte in the anode chamber is equal to or higher than the height of an upper end surface of the cathode electrode.
- An aspect of the present invention that solves the problems is an organic hydride production method that produces an organic hydride using an organic hydride production apparatus that includes an electrolytic cell having an electrolyte membrane, an anode chamber that is arranged on one side of the electrolyte membrane and contains an anolyte and an anode electrode, and a cathode chamber that is arranged on the other side of the electrolyte membrane and contains a cathode electrode, and the liquid level of the anolyte in the anode chamber is adjusted to be equal to or higher than the height of the upper end surface of the cathode electrode.
- FIG. 1 is a schematic diagram showing an example of an organic hydride manufacturing apparatus according to this embodiment.
- FIG. 2 is a schematic diagram showing an example of the structure of the electrolytic cell in the organic hydride manufacturing apparatus according to this embodiment.
- FIG. 3 is a graph showing the results of the temperature profile in Example 1.
- FIG. 4 is a graph showing the results of the temperature profile in Comparative Example 1.
- An organic hydride manufacturing apparatus (hereinafter sometimes referred to as "the present embodiment") has an electrolytic cell including an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anolyte and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, and may also include other components as necessary.
- the organic hydride production method of the present embodiment is a method for producing an organic hydride using an organic hydride production apparatus including an electrolytic cell having an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anode fluid and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, and is a method for adjusting the liquid level of the anode fluid in the anode chamber to be equal to or higher than the height of the upper end surface of the cathode electrode, and may include other processes as necessary.
- FIG. 1 is a schematic diagram showing an example of an organic hydride production apparatus according to this embodiment.
- the organic hydride production apparatus 1 mainly comprises an electrolytic cell 2, a power supply 4, an anolyte supply device 6, a catholyte supply device 8, and a control device 10.
- the electrolytic cell 2 hydrogenates the material to be hydrogenated, which is a dehydrogenated form of an organic hydride, by an electrochemical reduction reaction to produce the organic hydride.
- Fig. 2 is a schematic diagram showing an example of the structure of the electrolytic cell in the organic hydride manufacturing apparatus according to this embodiment. As shown in Fig. 2, the electrolytic cell 2 has an anode electrode 12, a current collector 13, a cathode electrode 14, an anode chamber 16, a cathode chamber 18, and an electrolyte membrane 20.
- the anode electrode 12 oxidizes water in the anolyte to generate protons.
- the anode electrode 12 may include an anode catalyst layer.
- the anode catalyst layer may be disposed so as to be in contact with the electrolyte membrane 20.
- the anode catalyst contained in the anode catalyst layer is not particularly limited and can be selected appropriately depending on the purpose. Examples include metals such as iridium (Ir), ruthenium (Ru), and platinum (Pt), or oxides of these metals.
- the anode catalyst may be dispersed and supported on an electronically conductive substrate, or may be coated on it.
- the substrate There are no particular restrictions on the substrate and it can be selected appropriately depending on the purpose, but it is preferable that it is made of a material whose main component is a metal such as titanium (Ti) or stainless steel (SUS).
- the substrate may take the form of, for example, a woven or nonwoven sheet, mesh, a porous sintered body, a foam molded body (foam), or expanded metal.
- the current collector 13 is placed so as to be in contact with the anode electrode 12. There are no particular restrictions on the structure of the current collector 13 as long as it is electrically conductive, but it is preferable that it does not impede the supply of water to the anode electrode 12 or the flow of anode fluid within the anode chamber, and it may have a porous structure.
- the current collector 13 is preferably elastic and can be tightly adhered to the anode electrode 12.
- the current collector 13 may be attached to the tip of an elastic body such as a spring and pressed firmly against the anode electrode 12 to ensure close contact, or the current collector 13 itself may be made of an elastic material and pressed against the anode electrode 12 to ensure close contact.
- the anode electrode 12 is housed in the anode chamber 16.
- the anode chamber 16 is defined, for example, by the electrolyte membrane 20, an end plate 22a, and a spacer 24a.
- the end plate 22a is a plate made of a metal such as stainless steel or titanium, and is installed on the side of the anode electrode 12 opposite the electrolyte membrane 20.
- the end plate 22a has a groove-shaped flow path on the main surface facing the anode electrode 12. The anolyte supplied to the anode chamber 16 passes through this flow path to the anode electrode 12, and is then discharged from the anode chamber 16 through this flow path.
- the spacer 24a is a frame-shaped sealing material placed between the electrolyte membrane 20 and the end plate 22a.
- the space in the anode chamber 16 excluding the anode electrode 12 and the current collector 13 forms a flow path for the anode fluid.
- the end plate 22a is provided with a first anode opening 26 and a second anode opening 28 that connect the inside and outside of the anode chamber 16.
- the first anode opening 26 is a so-called supply port that supplies anolyte to the anode chamber 16.
- the second anode opening 28 is a so-called discharge port that discharges anolyte from the anode chamber 16.
- the location of the first anode opening 26 is not limited to the surface of the end plate 22a facing the anode electrode 12 shown in Figures 1 and 2; it is preferable to provide it at the bottom of the anode chamber 16, and it may also be provided on the bottom surface of the anode chamber 16.
- the second anode opening 28 is preferably located at the top of the anode chamber 16, and more preferably at a position higher than the height of the upper end surface 14a of the cathode electrode 14.
- the amount of anolyte supplied to the anode chamber 16 is adjusted so that the liquid level of the anolyte in the anode chamber 16 is equal to or higher than the upper end surface 14a of the cathode electrode 14.
- This configuration prevents heat generation that significantly exceeds the temperature range that can occur during normal operation of the organic hydride production apparatus 1.
- the "temperature range that can occur during normal operation” refers to the surface temperature range that can occur for the cathode electrode 14 or cathode catalyst layer in the organic hydride production apparatus 1 during normal operation; specifically, a temperature above 0°C and below 100°C, the boiling point of water.
- anode fluid level height refers to the height relative to the bottom surface of the anode chamber 16, as indicated by the symbol H A in Fig. 2.
- the “height of the upper end surface 14a of the cathode electrode” refers to the height relative to the bottom surface of the anode chamber 16, as indicated by the symbol H B in Fig. 2.
- the mechanism is as follows:
- an organic hydride production apparatus when an organic hydride production apparatus is in operation, water is oxidized in the anode chamber to generate protons and oxygen gas. Meanwhile, the cathode chamber is filled with a cathode solution containing a substance to be hydrided (e.g., toluene), and much of this toluene adheres to the cathode catalyst layer. If a pinhole occurs in the electrolyte membrane during operation of the organic hydride production apparatus, allowing oxygen gas to leak from the anode to the cathode, the oxygen gas can undergo a combustion reaction with the hydrogen gas and toluene in the cathode chamber.
- a substance to be hydrided e.g., toluene
- the organic hydride production apparatus 1 adjusts the liquid level of the anolyte in the anode chamber 16 to be equal to or higher than the upper surface 14a of the cathode electrode 14.
- the combustion reaction between oxygen gas, hydrogen gas, and toluene that occurs during operation of the organic hydride production apparatus 1 is affected by the dryness of the cathode electrode 14. Therefore, if the cathode electrode 14 is wet with liquid, the combustion reaction can be prevented, and abnormal heat generation can be suppressed.
- the entire cathode electrode 14 can be wetted via the electrolyte membrane 20, preventing the occurrence of a combustion reaction and heat generation that significantly exceeds the temperature range that can occur during normal operation. Furthermore, volatilization of the substance to be hydrided can be suppressed, contributing to improved organic hydride production efficiency.
- a water volume sensor 29 may be provided in the second anode opening 28 and the second anode pipe 42 communicating with the second anode opening 28 as a detector for detecting the amount of anode fluid discharged from the anode chamber 16.
- the water volume sensor 29 detects the flow rate of water flowing through the second anode opening 28 and the second anode pipe 42.
- the water volume sensor 29 may be configured as a known flow meter.
- the amount of anolyte in the anode chamber 16 can be estimated based on the amount of anolyte discharged from the anode chamber 16. That is, the level of the anolyte in the anode chamber 16 can be controlled to be equal to or higher than the upper surface of the cathode electrode 14 based on the amount of anolyte discharged from the anode chamber 16. If the amount of anolyte detected by the detection unit is less than a predetermined amount, the operation of the organic hydride manufacturing apparatus 1 may be stopped. This control may be performed by a control device.
- the "predetermined amount” is not particularly limited, and can be set appropriately depending on the structure and application of the organic hydride manufacturing apparatus 1 so that the level of the anolyte in the anode chamber 16 is equal to or higher than the upper surface of the cathode electrode 14.
- the anode chamber 16 preferably has a gas retention section 17 in the upper part of the anode chamber 16.
- the gas retention section 17 is a space in which gases such as oxygen gas, which are reaction by-products of the anode electrode 12, retain.
- the term "upper part of the anode chamber” is not particularly limited and can be appropriately selected depending on the purpose, and may be, for example, the space between the liquid surface of the anode fluid and the ceiling surface of the anode chamber 16.
- the provision of gas retention section 17 allows gases such as oxygen gas to remain in the upper part of the anode chamber, thereby preventing the gas from lowering the liquid level of the anode fluid.
- the gas can be quickly discharged from second anode opening 28.
- the gas retention section 17 is preferably provided above the height of the upper end surface of the cathode electrode in the anode chamber 16, and more preferably provided at a position higher than the height of the upper end surface of the cathode electrode in the anode chamber 16.
- the cathode electrode 14 hydrogenates the substance to be hydrogenated in the cathode solution with the protons generated at the anode electrode to produce an organic hydride.
- the cathode electrode 14 may include a cathode catalyst layer.
- the cathode catalyst layer may be disposed so as to be in contact with the electrolyte membrane 20.
- the cathode catalyst contained in the cathode catalyst layer is not particularly limited and can be selected appropriately depending on the purpose, and examples include platinum and ruthenium.
- the cathode catalyst may also be supported on a catalyst carrier having a porous structure.
- catalyst carriers include electron-conductive materials such as porous carbon, porous metals, and porous metal oxides.
- the cathode catalyst may be coated with an ionomer.
- a catalyst support carrying the cathode catalyst is coated with an ionomer.
- the ionomer There are no particular restrictions on the ionomer and it can be selected appropriately depending on the purpose. Examples include perfluorosulfonic acid polymers such as Nafion (registered trademark) and Flemion (registered trademark). It is preferable that the ionomer partially coats the cathode catalyst. This allows the three elements required for the electrochemical reaction in the cathode catalyst layer (the substance to be hydrided, protons, and electrons) to be efficiently supplied to the reaction site.
- a diffusion layer may be disposed in contact with the main surface of the cathode catalyst layer opposite the electrolyte membrane 20.
- the diffusion layer uniformly diffuses the liquid substance to be hydrogenated, which is supplied from the outside, into the cathode catalyst layer.
- the organic hydride produced in the cathode catalyst layer is discharged to the outside of the cathode catalyst layer via the diffusion layer.
- the material for the diffusion layer is not particularly limited and can be selected appropriately depending on the purpose, but conductive materials such as carbon or metal are preferred.
- the diffusion layer is preferably in the form of a porous material such as a sintered fiber or particle body, or a foam molded body. Specific examples of diffusion layers include woven carbon fabric (carbon cloth), nonwoven carbon fabric, and carbon paper.
- the cathode electrode 14 is housed in the cathode chamber 18.
- the cathode chamber 18 is defined, for example, by the electrolyte membrane 20, the end plate 22b, and the spacer 24b.
- the end plate 22b is a plate made of a metal such as stainless steel or titanium, and is installed on the side of the cathode electrode 14 opposite the electrolyte membrane 20.
- the end plate 22b has a groove-shaped flow path on the main surface facing the cathode electrode 14. The cathode fluid supplied to the cathode chamber 18 passes through this flow path to the cathode electrode 14, and is discharged from the cathode chamber 18 through this flow path.
- the spacer 24b is a frame-shaped sealing material placed between the electrolyte membrane 20 and the end plate 22b.
- the space in the cathode chamber 18 excluding the cathode electrode 14 forms a flow path for the cathode fluid.
- the end plate 22b is provided with a first cathode opening 30 and a second cathode opening 32 that connect the inside and outside of the cathode chamber 18.
- the first cathode opening 30 is a so-called supply port that supplies cathode fluid to the cathode chamber 18.
- the second cathode opening 32 is a so-called discharge port that discharges cathode fluid from the cathode chamber 18.
- the first cathode opening 30 may be a so-called discharge port that discharges cathode fluid from the cathode chamber 18, and the second cathode opening 32 may be a so-called supply port that supplies cathode fluid to the cathode chamber 18.
- the location of the first cathode opening 30 is not limited to the surface of the end plate 22b facing the cathode electrode 14 shown in Figures 1 and 2; it is preferable to provide it at the bottom of the cathode chamber 18, and it may also be provided on the bottom surface of the cathode chamber 18.
- the location of the second cathode opening 32 is not limited to the surface of the end plate 22b facing the cathode electrode 14 shown in Figures 1 and 2; it is preferable to provide it at the top of the cathode chamber 18, and it may also be provided on the ceiling of the cathode chamber 18.
- Electrode membrane >> The anode chamber 16 and the cathode chamber 18 are separated by an electrolyte membrane 20.
- the electrolyte membrane 20 is sandwiched between the anode electrode 12 and the cathode electrode 14.
- the electrolyte membrane 20 is composed of a solid polymer electrolyte membrane with proton conductivity, which transfers protons from the anode chamber 16 to the cathode chamber 18.
- a solid polymer electrolyte membrane with proton conductivity which transfers protons from the anode chamber 16 to the cathode chamber 18.
- the solid polymer electrolyte membrane can be selected appropriately depending on the purpose, as long as it is a material that conducts protons.
- a fluorine-based ion exchange membrane with sulfonic acid groups can be used.
- Anode fluid is supplied to the anode chamber 16 by an anode fluid supply device 6.
- anode fluid supply device 6 There are no particular restrictions on the anode fluid, and it can be selected appropriately depending on the purpose as long as it contains water. Examples include aqueous sulfuric acid solution, aqueous nitric acid solution, aqueous hydrochloric acid solution, pure water, and ion-exchanged water.
- Cathode chamber 18 is supplied with cathode fluid by cathode fluid supply device 8.
- the cathode fluid contains an organic hydride raw material (material to be hydrided) to be supplied to the cathode electrode 14.
- the cathode fluid does not contain any organic hydride before operation of the organic hydride production apparatus 1 begins, and after operation begins, the organic hydride produced by electrolysis is mixed in, resulting in a mixture of the material to be hydrided and the organic hydride. It is preferable that the material to be hydrided and the organic hydride are liquid at 20°C and 1 atmosphere.
- the substance to be hydrided and the organic hydride are not particularly limited and can be selected appropriately depending on the purpose, as long as they are organic compounds that can add/desorb hydrogen by reversibly causing hydrogenation/dehydrogenation reactions.
- examples include acetone-isopropanol compounds, benzoquinone-hydroquinone compounds, and aromatic hydrocarbon compounds. Of these, aromatic hydrocarbon compounds are preferred from the perspective of transportability during energy transportation.
- Aromatic hydrocarbon compounds are compounds that contain at least one aromatic ring, and examples include benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, and diphenylethane.
- Alkylbenzenes include compounds in which 1 to 4 hydrogen atoms on an aromatic ring are substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, and examples include toluene, xylene, mesitylene, ethylbenzene, and diethylbenzene.
- Alkylnaphthalenes include compounds in which 1 to 4 hydrogen atoms on the aromatic ring are substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, such as methylnaphthalene.
- the substance to be hydrogenated is preferably at least one of toluene and benzene.
- Nitrogen-containing heterocyclic aromatic compounds such as pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, N-alkylpyrrole, N-alkylindole, and N-alkyldibenzopyrrole can also be used as the substance to be hydrogenated.
- Organic hydrides include the hydrogenated compounds mentioned above, such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and piperidine.
- the electrode reaction at the anode electrode 12 and the electrode reaction at the cathode electrode 14 proceed in parallel.
- Protons produced by the electrolysis of water at the anode electrode 12 are supplied to the cathode electrode 14 via the electrolyte membrane 20.
- Electrons produced by the electrolysis of water are supplied to the cathode electrode 14 via the end plate 22a, the external circuit, and the end plate 22b.
- the protons and electrons supplied to the cathode electrode 14 are used to hydrogenate toluene at the cathode electrode 14. As a result, methylcyclohexane is produced.
- the organic hydride manufacturing apparatus 1 can perform the electrolysis of water and the hydrogenation reaction of the material to be hydrogenated in a single step. This increases the efficiency of organic hydride manufacturing compared to conventional technologies that manufacture organic hydrides using a two-stage process that includes a process for producing hydrogen using water electrolysis or the like, and a process for chemically hydrogenating the material to be hydrogenated in a reactor at a plant or the like. Furthermore, since there is no need for a reactor for chemical hydrogenation or a high-pressure vessel for storing hydrogen produced by water electrolysis or the like, significant reductions in equipment costs can be achieved.
- a side reaction of hydrogen gas generation may occur. As the supply of material to be hydrogenated to the cathode electrode 14 becomes insufficient, this side reaction becomes more likely to occur.
- the anolyte supply device 6 supplies anolyte to the anode chamber 16.
- the anolyte supply device 6 includes an anolyte tank 36, a gas-liquid separator 38, a first anode pipe 40, a second anode pipe 42, a third anode pipe 44, a first anode pump 46, and a second anode pump 48.
- the gas-liquid separation section 38 can be composed of a known gas-liquid separation tank.
- the first anode pump 46 and the second anode pump 48 can be configured with known pumps such as gear pumps or cylinder pumps.
- the anode fluid supply device 6 may also circulate the anode fluid using a fluid delivery device other than a pump.
- the anode fluid tank 36 stores the anode fluid to be supplied to the anode chamber 16.
- the anode fluid tank 36 is connected to the anode chamber 16 by a first anode pipe 40.
- One end of the first anode pipe 40 is connected to the anode fluid tank 36, and the other end is connected to the first anode opening 26.
- a first anode pump 46 is provided midway along the first anode pipe 40.
- the gas-liquid separation unit 38 is connected to the anode chamber 16 by a second anode pipe 42. One end of the second anode pipe 42 is connected to the second anode opening 28, and the other end is connected to the gas-liquid separation unit 38.
- the gas-liquid separation unit 38 is connected to the anode fluid tank 36 by a third anode pipe 44.
- a second anode pump 48 is provided midway along the third anode pipe 44.
- the anode fluid in the anode fluid tank 36 flows through the first anode piping 40 and into the anode chamber 16 from the first anode opening 26.
- the anode fluid is supplied to the anode chamber 16 by upflow and is used for the electrode reaction at the anode electrode 12.
- the anode fluid in the anode chamber 16 flows into the gas-liquid separation unit 38 via the second anode piping 42.
- Oxygen gas is generated by the electrode reaction at the anode electrode 12.
- oxygen gas is mixed into the anode fluid discharged from the anode chamber 16.
- the gas-liquid separation unit 38 separates the oxygen gas in the anode fluid from the anode fluid and discharges it outside the system.
- the second anode pump 48 the anode fluid from which the oxygen gas has been separated is returned to the anode fluid tank 36 via the third anode piping 44.
- the cathode fluid supply device 8 includes a cathode fluid tank 50, a gas-liquid separation unit 52, an oil-water separation unit 54, a gas tank 56, a first cathode pipe 58 to a sixth cathode pipe 72, a first cathode pump 74 to a fourth cathode pump 80, and a first on-off valve 84 to a fourth on-off valve 94.
- the gas-liquid separation section 52 can be composed of a known gas-liquid separation tank.
- the oil-water separation section 54 can be constructed from a known oil-water separation tank.
- the first cathode pump 74 to the fourth cathode pump 80 can be configured with known pumps such as gear pumps or cylinder pumps.
- the cathode fluid supply device 8 may also circulate the cathode fluid using a fluid delivery device other than a pump.
- the first on-off valve 84 to the fourth on-off valve 94 can be constructed using known valves such as solenoid valves or air-operated valves.
- the cathode fluid tank 50 stores the cathode fluid to be supplied to the cathode chamber 18.
- the cathode fluid tank 50 is connected to the cathode chamber 18 by a first cathode piping 58.
- One end of the first cathode piping 58 is connected to the cathode fluid tank 50, and the other end is connected to the first cathode opening 30.
- a first cathode pump 74 and a first on-off valve 84 are provided midway along the first cathode piping 58.
- the first cathode pump 74 is positioned closer to the cathode chamber 18 than the first on-off valve 84.
- the gas-liquid separation unit 52 is connected to the cathode chamber 18 by a second cathode piping 60.
- One end of the second cathode piping 60 is connected to the second cathode opening 32, and the other end is connected to the gas-liquid separation unit 52.
- a second on-off valve 86 is provided midway along the second cathode piping 60.
- the oil-water separation section 54 is connected to the gas-liquid separation section 52 by a third cathode piping 62.
- a second cathode pump 76 and a third on-off valve 88 are provided in the middle of the third cathode piping 62.
- the second cathode pump 76 is positioned closer to the gas-liquid separation section 52 than the third on-off valve 88.
- the oil-water separation section 54 is also connected to the cathode liquid tank 50 by a fourth cathode piping 64.
- a third cathode pump 78 is provided in the middle of the fourth cathode piping 64.
- a fifth cathode piping 66 is also connected to the oil-water separation section 54.
- the fifth cathode piping 66 is connected to the oil-water separation section 54, and the other end is connected to, for example, a drainage tank (not shown).
- a fourth cathode pump 80 and a water volume sensor 96 are provided in the middle of the fifth cathode piping 66.
- the water volume sensor 96 detects the flow rate of water flowing through the fifth cathode pipe 66.
- the water volume sensor 96 can be configured as a known flow meter.
- the gas tank 56 is connected to the cathode chamber 18 by a sixth cathode pipe 72.
- One end of the sixth cathode pipe 72 is connected to the gas tank 56, and the other end is connected to the second cathode opening 32 via the second cathode pipe 60.
- a fourth on-off valve 94 is provided midway along the sixth cathode pipe 72.
- the other end of the sixth cathode pipe 72 is connected to a region of the second cathode pipe 60 closer to the cathode chamber 18 than the second on-off valve 86, and is thereby connected to the second cathode opening 32 via the second cathode pipe 60.
- this configuration is not limited, and the sixth cathode pipe 72 may be connected directly to the second cathode opening 32.
- the cathode fluid supply device 8 can form a first path of the cathode fluid by using a cathode fluid tank 50, a first cathode pipe 58, a cathode chamber 18, a second cathode pipe 60, a gas-liquid separation unit 52, a third cathode pipe 62, an oil-water separation unit 54, and a fourth cathode pipe 64.
- a cathode fluid tank 50 a first cathode pipe 58, a cathode chamber 18, a second cathode pipe 60, a gas-liquid separation unit 52, a third cathode pipe 62, an oil-water separation unit 54, and a fourth cathode pipe 64.
- an upflow of the cathode fluid is formed in the cathode chamber 18.
- the "upflow" of the cathode fluid refers to the flow of the cathode fluid into the cathode chamber 18 from the first cathode opening 30 located below and the discharge of the cathode fluid from the second cathode opening 32 located above.
- a “downflow” may also be used, in which the cathode fluid flows into the cathode chamber 18 from the second cathode opening 32 located above and the discharge of the cathode fluid from the first cathode opening 30 located below.
- the cathode fluid in the cathode fluid tank 50 flows through the first cathode piping 58 and into the cathode chamber 18 from the first cathode opening 30.
- the first on-off valve 84 is open, allowing the cathode fluid to flow from the cathode fluid tank 50 to the first cathode opening 30.
- the cathode fluid is supplied to the cathode chamber 18 by upflow.
- the cathode fluid in the cathode chamber 18 flows into the gas-liquid separation unit 52 via the second cathode piping 60.
- the second on-off valve 86 is open, allowing the flow of cathode fluid from the second cathode opening 32 to the gas-liquid separation unit 52.
- the fourth on-off valve 94 is closed, blocking the flow of cathode fluid from the second cathode opening 32 to the gas tank 56.
- hydrogen gas is generated by a side reaction at the cathode electrode 14.
- hydrogen gas is mixed into the cathode fluid discharged from the cathode chamber 18.
- the gas-liquid separation unit 52 separates the hydrogen gas in the cathode fluid from the cathode fluid and discharges it outside the system.
- the cathode fluid from which hydrogen gas has been separated flows into the oil-water separation section 54 via the third cathode piping 62 by driving the second cathode pump 76.
- the third on-off valve 88 is in an open state, allowing the cathode fluid to flow from the gas-liquid separation section 52 to the oil-water separation section 54.
- the oil-water separation unit 54 separates the water in the cathode fluid from the cathode fluid.
- the separated water is discharged to the drain tank via the fifth cathode piping 66 by driving the fourth cathode pump 80.
- the amount of water separated from the cathode fluid by the oil-water separation unit 54 in other words, the amount of water discharged from the cathode chamber 18, is detected by a water volume sensor 96.
- the cathode fluid from which the water has been separated is returned to the cathode fluid tank 50 via the fourth cathode piping 64 by driving the third cathode pump 78.
- each electrolytic cell 2 is aligned, for example, so that the anode chambers 16 and cathode chambers 18 are aligned in the same direction, and adjacent electrolytic cells 2 are stacked with a current-carrying plate sandwiched between them. This electrically connects each electrolytic cell 2 in series.
- the current-carrying plate is made of a conductive material such as metal.
- the electrolytic cells 2 may be connected in parallel, or a combination of series and parallel connections may be used.
- the power supply 4 is a DC power supply that supplies power to the electrolytic cell 2.
- a predetermined electrolysis voltage is applied between the anode electrode 12 and the cathode electrode 14 of the electrolytic cell 2, causing an electrolysis current to flow.
- the power supply 4 receives power from a power supply device 34 and supplies power to the electrolytic cell 2 .
- the power supply device 34 is a power supply device that supplies DC power to the power supply 4 of the organic hydride manufacturing apparatus 1, and includes at least one of a first power supply device 341 and a second power supply device 342. It may also include a power conversion unit that converts the output voltage of the first power supply device 341 to a predetermined voltage.
- the first power supply device 341 can be, for example, a power generation device that generates electricity from renewable energy sources. Specific examples include wind power generation devices, solar power generation devices, hydroelectric power generation devices, geothermal power generation devices, wave power generation devices, temperature difference power generation devices, and biomass power generation devices.
- the power conversion unit converts the output voltage of the first power supply device 341 to a predetermined voltage.
- a DC/DC converter is used as the power conversion unit.
- the power conversion unit converts the voltage using a transformer, rectifies it using a bridge-type diode, smooths it using a smoothing electrolytic capacitor, and supplies the power to the electrolytic cell 2 from the output terminal.
- the power conversion unit may also convert the output voltage of the second power supply device 342 to a predetermined voltage.
- the second power supply device 342 may be, for example, a storage battery or a thermal power plant that burns fossil fuels such as natural gas and coal.
- the power of the second power supply device 342 may be used as a secondary power when the power supplied from the first power supply device 341 is insufficient.
- the organic hydride manufacturing apparatus 1 can stably operate by supplying power from the second power supply device 342 to the electrolytic cell 2 in addition to the power from the first power supply device 341.
- the second power supply device 342 is configured as a storage battery, the second power supply device 342 can be charged by receiving power from the first power supply device 341, thereby reducing CO2 emissions from the power supply device 34.
- the second power supply device 342 may supply power to the power source 4 independently of the first power supply device 341.
- the second power supply device 342 may supply power to the power source unit 22 under control of the control device 10.
- the power supply device 34 may also be equipped with a storage battery, store the power generated by at least one of the first power supply device 341 and the second power supply device 342, and supply power from the storage battery to the organic hydride manufacturing apparatus 1 as needed.
- the control device 10 controls the supply of power from the power source 4 to the electrolytic cell 2.
- the potentials of the anode electrode 12 and the cathode electrode 14 are controlled by the control device 10.
- the control device 10 is realized as a hardware configuration by elements and circuits such as a computer CPU and memory, and as a software configuration by a computer program, etc., but in Figure 1 it is depicted as a functional block realized by the cooperation of these. It will naturally be understood by those skilled in the art that these functional blocks can be realized in various ways by combining hardware and software.
- the control device 10 receives at least one of a signal indicating the voltage of the electrolytic cell 2, a signal indicating the potential of the anode electrode 12, and a signal indicating the potential of the cathode electrode 14 from a detection unit 98 provided in the electrolytic cell 2.
- the detection unit 98 can detect the potential of each electrode and the voltage of the electrolytic cell 2 using a known method.
- the detection unit 98 includes, for example, a known voltmeter.
- a reference electrode is provided on the electrolyte membrane 20.
- the reference electrode is maintained at a reference electrode potential.
- the reference electrode is a reversible hydrogen electrode (RHE).
- One terminal of the detection unit 98 is connected to the reference electrode, and the other terminal is connected to the electrode to be detected, thereby detecting the electrode potential relative to the reference electrode.
- the detection unit 98 detects the voltage of the electrolytic cell 2
- one terminal of the detection unit 98 is connected to the anode electrode 12, and the other terminal is connected to the cathode electrode 14, thereby detecting the potential difference between the two electrodes, i.e., the voltage.
- the detection unit 98 sends a signal indicating the detection result to the control device 10.
- the detection unit 98 includes a current detection unit that detects the current flowing between the anode electrode 12 and the cathode electrode 14.
- the current detection unit is configured, for example, with a known ammeter. The current value detected by the current detection unit is input to the control device 10.
- the control device 10 may previously store information on the current-voltage characteristics (IV characteristics) of the electrolytic cell 2. If the control device 10 stores information on the IV characteristics, this information may be updateable as needed.
- the IV characteristics of the electrolytic cell 2 are determined by factors such as the catalyst composition of each electrode, the type of diffusion layer and substrate, the type of electrolyte membrane 20, the flow path structure of the anolyte and catholyte in the electrolytic cell 2, and the dimensions of each part, and can be measured and determined in advance.
- control device 10 receives a signal indicating the amount of power supplied from the power supply device 34, thereby determining the amount of power that can be supplied to the electrolytic cell 2 from the power source 4, and can calculate the voltage value to be applied to the electrolytic cell 2 from the IV characteristics, i.e., control the value of the current flowing through the electrolytic cell 2.
- the control device 10 controls the anode fluid supply device 6 and the cathode fluid supply device 8. Specifically, the control device 10 controls the operation of the first anode pump 46, the second anode pump 48, and the first cathode pump 74 to the fourth cathode pump 80. The control device 10 also controls the opening and closing of the first on-off valve 84 to the fourth on-off valve 94. The control device 10 also receives signals indicating the detection results from the water volume sensor 29 and the water volume sensor 96.
- the hydrogenation reaction of the material to be hydrogenated occurs as the main reaction, and a hydrogen generation reaction may occur as a side reaction.
- the occurrence of side reactions leads to a decrease in the faradaic efficiency of the organic hydride production apparatus 1.
- protons accompanied by water, may move from the anode electrode 12 side to the cathode electrode 14 side, causing water to accumulate in the cathode chamber 18.
- water inhibits the flow of the material to be hydrogenated if a large amount of water accumulates in the cathode chamber 18, the amount of material to be hydrogenated supplied to the reaction site of the cathode electrode 14 decreases, making it easier for side reactions to proceed.
- hydrogen gas generated in side reactions also inhibits the flow of the material to be hydrogenated, making side reactions even more likely to occur. Therefore, it is preferable to discharge the hydrogen gas and water remaining in the cathode chamber 18 from the cathode chamber 18.
- an organic hydride manufacturing system 3 includes an organic hydride manufacturing apparatus 1 and a power supply device 34. Note that a description of the components of the organic hydride manufacturing system 3 that overlap with those of the above-described (organic hydride manufacturing apparatus) will be omitted.
- the organic hydride production system 3 includes an organic hydride production apparatus 1 and, as a power supply device 34, at least one of a first power supply device that supplies electricity derived from renewable energy to the power supply of the organic hydride production apparatus 1, and a second power supply device that supplies electricity derived from fossil fuels to the power supply of the organic hydride production apparatus 1.
- the organic hydride production system 3 includes the organic hydride production apparatus 1 described above and a first power supply device 341. As a result, the organic hydride production system 3 can efficiently produce organic hydride by producing organic hydride in the organic hydride production apparatus 1 using electricity derived from renewable energy supplied from the first power supply device 341.
- the organic hydride production system 3 can produce organic hydride using electricity derived from renewable energy generated by the first power supply device 341, thereby reducing the consumption of fossil fuels and CO 2 emissions associated with hydrogen production.
- the organic hydride production system 3 supplies the electrolytic cell 2 with power generated by the second power supply device 342, thereby enabling stable operation of the organic hydride production apparatus 1. This allows the organic hydride production system 3 to stably produce organic hydride in the organic hydride production apparatus 1.
- the organic hydride production device 1 when the power supply device 34 supplies power from the first power supply device 341, i.e., power generated by the first power supply device 341, to the electrolytic cell 2 of the organic hydride production device 1, the organic hydride production device 1 operates, and when power from the first power supply device 341 is not supplied to the electrolytic cell 2, the organic hydride production device 1 may stop operating.
- operation refers to the time when the organic hydride production apparatus 1 is producing organic hydride, which is its main purpose. Therefore, even when the organic hydride production apparatus 1 is not operating, power may be supplied to the organic hydride production apparatus 1 from the second power supply device 342.
- the organic hydride production system 3 can efficiently produce organic hydrides directly from renewable energy and other energy sources using the material to be hydrided, without passing through hydrogen gas, as an energy carrier for transporting and storing energy-derived hydrogen. Therefore, the organic hydride production system 3 can be effectively used as a device for producing energy carriers used for transporting and storing electricity generated by the first power supply device 341 and the second power supply device 342.
- the organic hydride production system 3 can be used to transport and store renewable energy via organic hydrides, allowing for efficient use of renewable energy without waste. Therefore, the organic hydride production system 3 can be suitably used for producing energy carriers for transporting and storing renewable energy.
- Example 1 Preparation of cathode-electrolyte membrane composite> A cathode catalyst layer was spray-coated onto one side of an N117 (manufactured by Chemours, thickness 180 ⁇ m) electrolyte membrane to obtain a cathode-electrolyte membrane composite. Specifically, ionomer Nafion® dispersion DE2020 (manufactured by Chemours) was added to PtRu/C catalyst TEC61E54 (manufactured by Tanaka Kikinzoku Kogyo K.K., catalytic metal 54 wt %, Pt:Ru ratio (molar ratio) 1:2) powder.
- the weight ratio of ionomer Nafion® dispersion DE2020 (manufactured by Chemours) to the carbon weight in the catalyst was added so that the weight ratio after drying was 1:2. Thereafter, a solvent (a mixture of 1-propanol and water) was added as necessary to prepare an ink. The resulting ink was sprayed onto N117 so that the total weight of Pt and Ru in the catalyst was 1.0 mg/ cm2 per electrode area of the cathode-electrolyte membrane composite. The solvent component in the ink was then dried at 80°C to obtain a cathode catalyst layer.
- a solvent a mixture of 1-propanol and water
- a cathode diffusion layer SIGRACET® 39BC (manufactured by SGL Carbon) cut to fit the electrode surface was laminated to the surface of the cathode catalyst layer.
- a sheathed T thermocouple manufactured by Hayashi Denko Co., Ltd., D-ST6T-10-300 was inserted between the cathode catalyst layer and the cathode diffusion layer. The thermocouples were installed at three locations: near the entrance, center, and exit of the cathode chamber. A 0.2 mm diameter through-hole simulating a pinhole was drilled in the center of the N117.
- An aqueous solution of iridium tetrachloride was applied to the obtained anode substrate, and the substrate was subjected to a heat treatment at 550°C in an electric furnace. This process was repeated several times to obtain an anode.
- the anode had an iridium oxide anode electrode catalyst layer formed thereon in an amount of 12 g/ m2 in terms of the amount of Ir metal per electrode area.
- the current collector was an elastic body made of flat springs arranged at a 10 mm pitch, which was made by processing a 0.3 mm thick Ti plate. A small amount of platinum layer was formed on the part of the elastic body that came into contact with the anode.
- An electrolytic cell was fabricated by laminating a cathode-electrolyte membrane composite, an anode spacer (EPDM rubber sheet), an anode, a current collector, and an end plate (gold-plated SUS plate, 1.0 mm thick) in this order, and pressing the layers together to form an intimate contact.
- the thickness of the anode spacer i.e., the gap between the electrolyte membrane and the anode, was 0.05 mm.
- Figure 3 shows the temperature profile on the surface of the cathode catalyst layer during electrolysis operation of the organic hydride production equipment described above.
- Example 1 the liquid level of the anode fluid in the anode chamber was higher than the height of the upper surface of the cathode electrode, and the cathode electrode was kept constantly wet with the anode fluid, thereby suppressing an increase in cell temperature.
- Comparative Example 1 An organic hydride manufacturing apparatus was fabricated in the same manner as in Example 1, except that the amount of the anolyte in the anode chamber was adjusted so that the liquid level was lower than the height of the upper end surface of the cathode electrode, and the temperature profile was measured. The results are shown in Figure 4.
- Comparative Example 1 the liquid level of the anode fluid in the anode chamber was lower than the height of the upper surface of the cathode electrode, so part of the cathode electrode was dry. A combustion reaction occurred between oxygen gas leaking through a pinhole in the electrolyte membrane, toluene adhering to the cathode electrode, and hydrogen gas filled in the cathode chamber.
- This embodiment may be specified by the following items.
- [Item 2] 2.
- the organic hydride manufacturing apparatus (1) according to item 1 or 2 wherein the anode chamber (16) has a detection unit (29) that detects the anolyte discharged from the anode chamber (16).
- the detection unit (29) is a flow meter. [Item 6] 5.
- the organic hydride manufacturing apparatus (1) according to item 4 wherein, when the amount of the anolyte detected by the detection unit (29) is less than a predetermined amount, control is performed to stop operation of the organic hydride manufacturing apparatus (1).
- the anode chamber (16) has a second anode opening (28) provided at a position higher than the height of the upper end surface of the cathode electrode (14).
- the apparatus comprises an organic hydride manufacturing apparatus (1) and a power supply device (34),
- the organic hydride manufacturing apparatus (1) includes an electrolytic cell (2) having an electrolyte membrane (20), an anode chamber (16) disposed on one side of the electrolyte membrane (20) and containing an anolyte and an anode electrode (12), and a cathode chamber (18) disposed on the other side of the electrolyte membrane (20) and containing a cathode electrode (14);
- the organic hydride production system (3) has a liquid level of the anolyte in the anode chamber (16) that is equal to or higher than the height of the upper end surface of the cathode electrode (14).
- the power supply device (34) comprises at least one of a first power supply device (341) that supplies electricity derived from renewable energy to a power source of the organic hydride production apparatus, and a second power supply device (342) that supplies electricity derived from fossil fuels to the power source of the organic hydride production apparatus.
- the power supply device (34) comprises at least one of a first power supply device (341) that supplies electricity derived from renewable energy to a power source of the organic hydride production apparatus, and a second power supply device (342) that supplies electricity derived from fossil fuels to the power source of the organic hydride production apparatus.
- the method for producing an organic hydride includes adjusting the liquid level of the anolyte in the anode chamber (16) to be equal to or higher than the height of the upper end surface of the cathode electrode (14).
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Abstract
Description
本発明は、有機ハイドライド製造装置、有機ハイドライド製造システム、及び有機ハイドライド製造方法に関する。 The present invention relates to an organic hydride production apparatus, an organic hydride production system, and an organic hydride production method.
近年、エネルギー生成過程での二酸化炭素排出量を抑制するために、太陽光、風力、水力、地熱発電などで得られる再生可能エネルギーの利用が期待されている。一例としては、再生可能エネルギー由来の電力で水電解を行って、水素を生成するシステムが考案されている。また、再生可能エネルギー由来の水素を大規模輸送、貯蔵するためのエネルギーキャリアとして、有機ハイドライドシステムが注目されている。 In recent years, there has been growing interest in using renewable energy sources such as solar, wind, hydroelectric, and geothermal power to reduce carbon dioxide emissions during the energy generation process. One example is a system that uses electricity derived from renewable energy to perform water electrolysis to produce hydrogen. Organic hydride systems are also attracting attention as an energy carrier for the large-scale transport and storage of hydrogen derived from renewable energy.
例えば、水からプロトンを生成するアノード電極と、不飽和結合を有する有機化合物(被水素化物)を水素化するカソード電極と、アノード電極及びカソード電極を隔てる隔膜とを有する電解槽を備えた有機ハイドライド製造装置が知られている(例えば、特許文献1参照)。この有機ハイドライド製造装置では、アノード電極において水の酸化によりプロトンが生成され、このプロトンが隔膜を介してカソード電極側に移動し、カソード電極においてプロトンで被水素化物が水素化されることで、有機ハイドライドが製造される。 For example, an organic hydride production apparatus is known that includes an electrolytic cell having an anode electrode that generates protons from water, a cathode electrode that hydrogenates an organic compound having an unsaturated bond (the material to be hydrogenated), and a diaphragm that separates the anode and cathode electrodes (see, for example, Patent Document 1). In this organic hydride production apparatus, protons are generated by the oxidation of water at the anode electrode, and these protons migrate to the cathode electrode side via the diaphragm, where the material to be hydrogenated is hydrogenated by the protons, thereby producing an organic hydride.
上述の有機ハイドライド製造装置によれば、プロトンの生成と被水素化物の水素化とを1段階のプロセスで行うことができる。このため、水電解などで水素を製造し、プラントなどのリアクタで被水素化物を化学水素化する2段階プロセスで有機ハイドライドを製造する場合に比べて、有機ハイドライドの製造工程を簡略化できる。あるいは有機ハイドライドの製造効率を高めることができる。また、水電解などで水素を製造する場合に必要となる水素貯留用の高圧容器を省略できるため、設備コストの大幅な削減が見込まれる。 The organic hydride production apparatus described above can generate protons and hydrogenate the material to be hydrided in a single process. This simplifies the organic hydride production process compared to organic hydride production using a two-stage process in which hydrogen is produced by water electrolysis or other methods and the material to be hydrided is chemically hydrogenated in a reactor at a plant or other facility. It also increases the efficiency of organic hydride production. Furthermore, since the high-pressure vessel for storing hydrogen, which is required when producing hydrogen by water electrolysis or other methods, can be omitted, significant reductions in facility costs are expected.
本発明者らは、従来の有機ハイドライド製造装置について鋭意検討を重ねた結果、従来の有機ハイドライド製造装置においては、有機ハイドライド製造装置の通常稼働時になり得る温度範囲を超えた発熱の抑制については考慮されておらず、改良の余地があることを見出した。 As a result of extensive research into conventional organic hydride production equipment, the inventors have discovered that conventional organic hydride production equipment does not take into consideration the suppression of heat generation that exceeds the temperature range that can occur during normal operation of the organic hydride production equipment, and that there is room for improvement.
本発明はこうした状況に鑑みてなされたものであり、その目的の1つは、通常稼働時になり得る温度範囲を超えて発熱することを抑制することができる有機ハイドライド製造装置を提供することにある。 The present invention was made in light of these circumstances, and one of its objectives is to provide an organic hydride manufacturing apparatus that can prevent heat generation beyond the temperature range that can occur during normal operation.
課題を解決する本発明の態様としての有機ハイドライド製造装置は、電解質膜と、電解質膜の一方側に配され、アノード液及びアノード電極を収容するアノード室と、電解質膜の他方側に配され、カソード電極を収容するカソード室と、を有する電解槽を備え、アノード室内のアノード液の液面高さは、カソード電極の上端面の高さ以上である。
課題を解決する本発明の態様としての有機ハイドライド製造システムは、有機ハイドライド製造装置と、電力供給装置と、を備え、有機ハイドライド製造装置は、電解質膜と、電解質膜の一方側に配され、アノード液及びアノード電極を収容するアノード室と、電解質膜の他方側に配され、カソード電極を収容するカソード室と、を有する電解槽を有し、アノード室内の前記アノード液の液面高さは、前記カソード電極の上端面の高さ以上である。
課題を解決する本発明の態様としての有機ハイドライド製造方法は、電解質膜と、電解質膜の一方側に配され、アノード液及びアノード電極を収容するアノード室と、電解質膜の他方側に配され、カソード電極を収容するカソード室と、を有する電解槽を備える有機ハイドライド製造装置を用いて、有機ハイドライドを製造する有機ハイドライド製造方法であって、アノード室内のアノード液の液面高さは、カソード電極の上端面の高さ以上に調整する。
An organic hydride manufacturing apparatus according to one aspect of the present invention for solving the problems includes an electrolytic cell having an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anode fluid and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, wherein the liquid level of the anode fluid in the anode chamber is equal to or higher than the height of the upper end surface of the cathode electrode.
An organic hydride production system as an aspect of the present invention that solves the problems includes an organic hydride production apparatus and a power supply device, wherein the organic hydride production apparatus has an electrolyte membrane and an electrolytic cell having an anode chamber disposed on one side of the electrolyte membrane and accommodating an anolyte and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, and the liquid level of the anolyte in the anode chamber is equal to or higher than the height of an upper end surface of the cathode electrode.
An aspect of the present invention that solves the problems is an organic hydride production method that produces an organic hydride using an organic hydride production apparatus that includes an electrolytic cell having an electrolyte membrane, an anode chamber that is arranged on one side of the electrolyte membrane and contains an anolyte and an anode electrode, and a cathode chamber that is arranged on the other side of the electrolyte membrane and contains a cathode electrode, and the liquid level of the anolyte in the anode chamber is adjusted to be equal to or higher than the height of the upper end surface of the cathode electrode.
本発明の態様によれば、通常稼働時になり得る温度範囲を超えて発熱することを抑制することができる有機ハイドライド製造装置を提供することができる。 According to this aspect of the present invention, it is possible to provide an organic hydride manufacturing apparatus that can prevent heat generation exceeding the temperature range that can occur during normal operation.
(有機ハイドライド製造装置、及び有機ハイドライド製造方法)
本発明の実施形態(以下「本実施形態」と称することがある。)に係る有機ハイドライド製造装置は、電解質膜と、電解質膜の一方側に配され、アノード液及びアノード電極を収容するアノード室と、電解質膜の他方側に配され、カソード電極を収容するカソード室と、を有する電解槽を有し、必要に応じて、その他の部材を有していてもよい。
本実施形態の有機ハイドライド製造方法は、電解質膜と、電解質膜の一方側に配され、アノード液及びアノード電極を収容するアノード室と、電解質膜の他方側に配され、カソード電極を収容するカソード室と、を有する電解槽を備える有機ハイドライド製造装置を用いて、有機ハイドライドを製造する有機ハイドライド製造方法であって、アノード室内のアノード液の液面高さを、カソード電極の上端面の高さ以上に調整する方法であって、必要に応じて、その他の工程を有していてもよい。
(Organic hydride production apparatus and organic hydride production method)
An organic hydride manufacturing apparatus according to an embodiment of the present invention (hereinafter sometimes referred to as "the present embodiment") has an electrolytic cell including an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anolyte and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, and may also include other components as necessary.
The organic hydride production method of the present embodiment is a method for producing an organic hydride using an organic hydride production apparatus including an electrolytic cell having an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anode fluid and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, and is a method for adjusting the liquid level of the anode fluid in the anode chamber to be equal to or higher than the height of the upper end surface of the cathode electrode, and may include other processes as necessary.
ここで、本実施形態の有機ハイドライド製造装置及び有機ハイドライド製造方法の一実施形態について図面を参照して説明する。
実施形態は、発明を限定するものではなく例示であって、実施形態に記述されるすべての特徴やその組み合わせは、必ずしも発明の本質的なものであるとは限らない。各図面に示される同一又は同等の構成要素、部材、処理には、同一の符号を付するものとし、適宜重複した説明は省略する。また、各図に示す各部の縮尺や形状は、説明を容易にするために便宜的に設定されており、特に言及がない限り限定的に解釈されるものではない。また、本明細書又は請求項中に「第1」、「第2」などの用語が用いられる場合には、この用語はいかなる順序や重要度を表すものでもなく、ある構成と他の構成とを区別するためのものである。また、各図面において実施形態を説明する上で重要ではない部材の一部は省略して表示する。
Here, an embodiment of an organic hydride manufacturing apparatus and an organic hydride manufacturing method according to the present embodiment will be described with reference to the drawings.
The embodiments are illustrative and do not limit the invention, and all features and combinations thereof described in the embodiments are not necessarily essential to the invention. The same or equivalent components, parts, and processes shown in each drawing are designated by the same reference numerals, and redundant descriptions are omitted where appropriate. The scale and shape of each part shown in each drawing are set for convenience to facilitate explanation and should not be interpreted as limiting unless otherwise specified. Furthermore, when terms such as "first" and "second" are used in this specification or claims, these terms do not represent any order or importance, but are intended to distinguish one configuration from another. Furthermore, some components that are not important for explaining the embodiments are omitted from each drawing.
図1は、本実施形態に係る有機ハイドライド製造装置の一例を示す模式図である。図1に示すように、有機ハイドライド製造装置1は、主な構成として電解槽2と、電源4と、アノード液供給装置6と、カソード液供給装置8と、制御装置10とを備える。 FIG. 1 is a schematic diagram showing an example of an organic hydride production apparatus according to this embodiment. As shown in FIG. 1, the organic hydride production apparatus 1 mainly comprises an electrolytic cell 2, a power supply 4, an anolyte supply device 6, a catholyte supply device 8, and a control device 10.
<電解槽>
電解槽2は、有機ハイドライドの脱水素化体である被水素化物を電気化学還元反応により水素化して、有機ハイドライドを生成する。図2は、本実施形態に係る有機ハイドライド製造装置における電解槽の構造の一例を示す模式図である。図2に示すように、電解槽2は、アノード電極12と、集電体13と、カソード電極14と、アノード室16と、カソード室18と、電解質膜20とを有する。
<Electrolytic cell>
The electrolytic cell 2 hydrogenates the material to be hydrogenated, which is a dehydrogenated form of an organic hydride, by an electrochemical reduction reaction to produce the organic hydride. Fig. 2 is a schematic diagram showing an example of the structure of the electrolytic cell in the organic hydride manufacturing apparatus according to this embodiment. As shown in Fig. 2, the electrolytic cell 2 has an anode electrode 12, a current collector 13, a cathode electrode 14, an anode chamber 16, a cathode chamber 18, and an electrolyte membrane 20.
<<アノード電極>>
アノード電極12は、アノード液中の水を酸化してプロトンを生成する。アノード電極12には、アノード触媒層が含まれていてもよい。例えば、アノード触媒層は、電解質膜20に接するように配されていてもよい。
<<Anode electrode>>
The anode electrode 12 oxidizes water in the anolyte to generate protons. The anode electrode 12 may include an anode catalyst layer. For example, the anode catalyst layer may be disposed so as to be in contact with the electrolyte membrane 20.
アノード触媒層に含まれるアノード触媒としては、特に制限はなく目的に応じて適宜選択することができ、例えば、イリジウム(Ir)、ルテニウム(Ru)、白金(Pt)などの金属、又はこれらの金属酸化物などが挙げられる。 The anode catalyst contained in the anode catalyst layer is not particularly limited and can be selected appropriately depending on the purpose. Examples include metals such as iridium (Ir), ruthenium (Ru), and platinum (Pt), or oxides of these metals.
アノード触媒は、電子伝導性を有する基材に分散担持されていてもよく、コーティングされていてもよい。基材としては、特に制限はなく目的に応じて適宜選択することができるが、チタン(Ti)、ステンレス鋼(SUS)などの金属を主成分とする材料で構成されることが好ましい。また、基材の形態としては、例えば、織布や不織布のシート、メッシュ、多孔性の焼結体、発泡成型体(フォーム)、エキスパンドメタルなどが挙げられる。 The anode catalyst may be dispersed and supported on an electronically conductive substrate, or may be coated on it. There are no particular restrictions on the substrate and it can be selected appropriately depending on the purpose, but it is preferable that it is made of a material whose main component is a metal such as titanium (Ti) or stainless steel (SUS). The substrate may take the form of, for example, a woven or nonwoven sheet, mesh, a porous sintered body, a foam molded body (foam), or expanded metal.
集電体13は、アノード電極12に接するように配置される。集電体13の構造としては、通電性を有するものであれば特に制限はないが、アノード電極12への水の供給や、アノード室内のアノード液の流通を阻害しないものであることが好ましく、多孔質構造としてもよい。集電体13としては、弾性を有し、アノード電極12に強く密着させることが好ましい。例えば、ばねなどの弾性体の先端に集電体13を付着させて、アノード電極12に強く押し当てて密着させる構造としてもよいし、集電体13自体に弾性を持つ材料を用いて、集電体13をアノード電極12に押し当てて密着させる構造としてもよい。 The current collector 13 is placed so as to be in contact with the anode electrode 12. There are no particular restrictions on the structure of the current collector 13 as long as it is electrically conductive, but it is preferable that it does not impede the supply of water to the anode electrode 12 or the flow of anode fluid within the anode chamber, and it may have a porous structure. The current collector 13 is preferably elastic and can be tightly adhered to the anode electrode 12. For example, the current collector 13 may be attached to the tip of an elastic body such as a spring and pressed firmly against the anode electrode 12 to ensure close contact, or the current collector 13 itself may be made of an elastic material and pressed against the anode electrode 12 to ensure close contact.
アノード電極12は、アノード室16に収容される。アノード室16は、例えば、電解質膜20と、エンドプレート22aと、スペーサ24aとによって画成される。 The anode electrode 12 is housed in the anode chamber 16. The anode chamber 16 is defined, for example, by the electrolyte membrane 20, an end plate 22a, and a spacer 24a.
エンドプレート22aは、例えば、ステンレス鋼、チタンなどの金属で構成される板材であり、アノード電極12の、電解質膜20とは反対側に設置される。一例としてのエンドプレート22aは、アノード電極12側を向く主表面に溝状の流路を有する。アノード室16に供給されるアノード液は、この流路を通ってアノード電極12に供給され、この流路を通ってアノード室16から排出される。 The end plate 22a is a plate made of a metal such as stainless steel or titanium, and is installed on the side of the anode electrode 12 opposite the electrolyte membrane 20. As an example, the end plate 22a has a groove-shaped flow path on the main surface facing the anode electrode 12. The anolyte supplied to the anode chamber 16 passes through this flow path to the anode electrode 12, and is then discharged from the anode chamber 16 through this flow path.
スペーサ24aは、電解質膜20とエンドプレート22aとの間に配置される枠状のシール材である。アノード室16におけるアノード電極12及び集電体13を除く空間は、アノード液の流路を構成する。 The spacer 24a is a frame-shaped sealing material placed between the electrolyte membrane 20 and the end plate 22a. The space in the anode chamber 16 excluding the anode electrode 12 and the current collector 13 forms a flow path for the anode fluid.
エンドプレート22aには、アノード室16の内外を連通する第1アノード開口26及び第2アノード開口28が設けられる。 The end plate 22a is provided with a first anode opening 26 and a second anode opening 28 that connect the inside and outside of the anode chamber 16.
第1アノード開口26は、アノード室16にアノード液を供給する、所謂供給口である。第2アノード開口28は、アノード室16からアノード液を排出する、所謂排出口である。 The first anode opening 26 is a so-called supply port that supplies anolyte to the anode chamber 16. The second anode opening 28 is a so-called discharge port that discharges anolyte from the anode chamber 16.
第1アノード開口26が設けられる位置としては、図1~2に示されるアノード電極12に対向するエンドプレート22a面に限られず、アノード室16の下部に設けられることが好ましく、アノード室16の底面に設けられていてもよい。 The location of the first anode opening 26 is not limited to the surface of the end plate 22a facing the anode electrode 12 shown in Figures 1 and 2; it is preferable to provide it at the bottom of the anode chamber 16, and it may also be provided on the bottom surface of the anode chamber 16.
第2アノード開口28が設けられる位置としては、アノード室16の上部に設けられることが好ましく、カソード電極14の上端面14aの高さよりも高い位置に設けられることがより好ましい。 The second anode opening 28 is preferably located at the top of the anode chamber 16, and more preferably at a position higher than the height of the upper end surface 14a of the cathode electrode 14.
有機ハイドライド製造装置1において、アノード室16内に供給されるアノード液量は、アノード室16内のアノード液の液面高さが、カソード電極14の上端面14aの高さ以上となるように調整される。このような構成とすることによって、有機ハイドライド製造装置1の通常稼働時になり得る温度範囲を著しく超えて発熱することを抑制することができる。なお、本明細書における「通常稼働時になり得る温度範囲」とは、有機ハイドライド製造装置1におけるカソード電極14又はカソード触媒層が通常稼働時になり得る表面温度範囲のことであり、具体的には、0℃以上、かつ水の沸点である100℃未満である。 In the organic hydride production apparatus 1, the amount of anolyte supplied to the anode chamber 16 is adjusted so that the liquid level of the anolyte in the anode chamber 16 is equal to or higher than the upper end surface 14a of the cathode electrode 14. This configuration prevents heat generation that significantly exceeds the temperature range that can occur during normal operation of the organic hydride production apparatus 1. Note that in this specification, the "temperature range that can occur during normal operation" refers to the surface temperature range that can occur for the cathode electrode 14 or cathode catalyst layer in the organic hydride production apparatus 1 during normal operation; specifically, a temperature above 0°C and below 100°C, the boiling point of water.
なお、本明細書において、「アノード液の液面高さ」は、図2において符号HAで示される通り、アノード室16の底面を基準としたときの高さである。「カソード電極の上端面14aの高さ」は、図2において符号HBで示される通り、アノード室16の底面を基準としたときの高さである。 In this specification, the "anode fluid level height" refers to the height relative to the bottom surface of the anode chamber 16, as indicated by the symbol H A in Fig. 2. The "height of the upper end surface 14a of the cathode electrode" refers to the height relative to the bottom surface of the anode chamber 16, as indicated by the symbol H B in Fig. 2.
メカニズムは、以下の通りである。 The mechanism is as follows:
一般的に、有機ハイドライド製造装置の稼働に伴い、アノード室では水が酸化されてプロトンが生成されるとともに、酸素ガスが発生する。一方で、カソード室には、被水素化物(例えば、トルエン)を含むカソード液が充填されており、当該トルエンはカソード触媒層上にも多く付着している。有機ハイドライド製造装置の稼働時に、電解質膜にピンホールが生じて酸素ガスがアノードからカソードへリークすると、当該酸素ガスは、カソード室内の水素ガス及びトルエンと燃焼反応を起こし得る。 Generally, when an organic hydride production apparatus is in operation, water is oxidized in the anode chamber to generate protons and oxygen gas. Meanwhile, the cathode chamber is filled with a cathode solution containing a substance to be hydrided (e.g., toluene), and much of this toluene adheres to the cathode catalyst layer. If a pinhole occurs in the electrolyte membrane during operation of the organic hydride production apparatus, allowing oxygen gas to leak from the anode to the cathode, the oxygen gas can undergo a combustion reaction with the hydrogen gas and toluene in the cathode chamber.
有機ハイドライド製造装置1は、上述した通り、アノード室16内のアノード液の液面高さが、カソード電極14の上端面14a高さ以上となるように調整される。有機ハイドライド製造装置1の稼働時に生じる酸素ガスと、水素ガス及びトルエンとの燃焼反応は、カソード電極14の乾燥状態に影響を受けるものであることから、カソード電極14が液体で濡れた状態であれば燃焼反応を防ぎ、結果として異常発熱を抑制することができる。本実施形態においては、アノード室16内のアノード液の液面高さが、カソード電極14の上端面14a高さ以上となるように調整することによって、電解質膜20を介してカソード電極14の全体を濡らすことができ、燃焼反応の発生及び通常稼働時になり得る温度範囲を著しく超えて発熱することを抑制することができる。さらに、被水素化物の揮発を抑制することもでき、有機ハイドライドの製造効率の向上にも寄与する。 As described above, the organic hydride production apparatus 1 adjusts the liquid level of the anolyte in the anode chamber 16 to be equal to or higher than the upper surface 14a of the cathode electrode 14. The combustion reaction between oxygen gas, hydrogen gas, and toluene that occurs during operation of the organic hydride production apparatus 1 is affected by the dryness of the cathode electrode 14. Therefore, if the cathode electrode 14 is wet with liquid, the combustion reaction can be prevented, and abnormal heat generation can be suppressed. In this embodiment, by adjusting the liquid level of the anolyte in the anode chamber 16 to be equal to or higher than the upper surface 14a of the cathode electrode 14, the entire cathode electrode 14 can be wetted via the electrolyte membrane 20, preventing the occurrence of a combustion reaction and heat generation that significantly exceeds the temperature range that can occur during normal operation. Furthermore, volatilization of the substance to be hydrided can be suppressed, contributing to improved organic hydride production efficiency.
第2アノード開口28、及び第2アノード開口28に連通する第2アノード配管42には、アノード室16から排出されるアノード液の量を検知する検知部として、水量センサ29が設けられていてもよい。水量センサ29は、第2アノード開口28及び第2アノード配管42内を流れる水の流量を検知する。水量センサ29は、公知の流量計で構成することができる。 A water volume sensor 29 may be provided in the second anode opening 28 and the second anode pipe 42 communicating with the second anode opening 28 as a detector for detecting the amount of anode fluid discharged from the anode chamber 16. The water volume sensor 29 detects the flow rate of water flowing through the second anode opening 28 and the second anode pipe 42. The water volume sensor 29 may be configured as a known flow meter.
水量センサ29を設けることにより、アノード室16から排出されるアノード液の量に応じて、アノード室16内のアノード液量を推定することができる。即ち、アノード室16から排出されるアノード液の量に応じて、アノード室16内のアノード液の液面高さが、カソード電極14の上端面高さ以上となるように制御することができる。検知部によって検知されるアノード液の液量が所定量未満である場合、有機ハイドライド製造装置1の稼働を停止するように制御してもよい。これらの制御は、制御装置によって行われてもよい。ここで当該「所定量」とは、特に制限はなく、有機ハイドライド製造装置1の構造や用途に応じて、アノード室16内のアノード液の液面高さが、カソード電極14の上端面高さ以上となるように適宜設定することができる。 By providing a water volume sensor 29, the amount of anolyte in the anode chamber 16 can be estimated based on the amount of anolyte discharged from the anode chamber 16. That is, the level of the anolyte in the anode chamber 16 can be controlled to be equal to or higher than the upper surface of the cathode electrode 14 based on the amount of anolyte discharged from the anode chamber 16. If the amount of anolyte detected by the detection unit is less than a predetermined amount, the operation of the organic hydride manufacturing apparatus 1 may be stopped. This control may be performed by a control device. Here, the "predetermined amount" is not particularly limited, and can be set appropriately depending on the structure and application of the organic hydride manufacturing apparatus 1 so that the level of the anolyte in the anode chamber 16 is equal to or higher than the upper surface of the cathode electrode 14.
アノード室16は、アノード室16の上部に気体滞留部17を有することが好ましい。気体滞留部17は、アノード電極12の反応副産物である酸素ガスなどの気体が滞留する空間である。本明細書における「アノード室の上部」とは、特に制限はなく目的に応じて適宜選択することができ、例えば、アノード液の液面とアノード室16の天面との間の空間としてもよい。
気体滞留部17を設けると、酸素ガスなどの気体がアノード室の上部に滞留することができるため、当該気体によってアノード液の液面高さが押し下げられることが抑制される。また、第2アノード開口28から気体を速やかに排出することができる。
気体滞留部17は、有機ハイドライド製造過程でアノード室内に気体が生じた場合であっても、アノード液面を適切に調整することができる観点から、アノード室16内のカソード電極の上端面の高さより上方に設けることが好ましく、アノード室16内のカソード電極の上端面の高さより高い位置に設けられることがより好ましい。
The anode chamber 16 preferably has a gas retention section 17 in the upper part of the anode chamber 16. The gas retention section 17 is a space in which gases such as oxygen gas, which are reaction by-products of the anode electrode 12, retain. In this specification, the term "upper part of the anode chamber" is not particularly limited and can be appropriately selected depending on the purpose, and may be, for example, the space between the liquid surface of the anode fluid and the ceiling surface of the anode chamber 16.
The provision of gas retention section 17 allows gases such as oxygen gas to remain in the upper part of the anode chamber, thereby preventing the gas from lowering the liquid level of the anode fluid. In addition, the gas can be quickly discharged from second anode opening 28.
From the viewpoint of being able to appropriately adjust the anode liquid level even if gas is generated in the anode chamber during the organic hydride production process, the gas retention section 17 is preferably provided above the height of the upper end surface of the cathode electrode in the anode chamber 16, and more preferably provided at a position higher than the height of the upper end surface of the cathode electrode in the anode chamber 16.
<<カソード電極>>
カソード電極14は、カソード液中の被水素化物を、アノード電極で生成されたプロトンで水素化して有機ハイドライドを生成する。カソード電極14には、カソード触媒層が含まれていてもよい。例えば、カソード触媒層は、電解質膜20に接するように配されていてもよい。
<<Cathode electrode>>
The cathode electrode 14 hydrogenates the substance to be hydrogenated in the cathode solution with the protons generated at the anode electrode to produce an organic hydride. The cathode electrode 14 may include a cathode catalyst layer. For example, the cathode catalyst layer may be disposed so as to be in contact with the electrolyte membrane 20.
カソード触媒層に含まれるカソード触媒としては、特に制限はなく目的に応じて適宜選択することができ、例えば、白金、ルテニウムなどが挙げられる。また、カソード触媒は、多孔質構造を有する触媒担体に担持されていてもよい。触媒担体としては、例えば、多孔性カーボン、多孔性金属、多孔性金属酸化物などの電子伝導性材料などが挙げられる。 The cathode catalyst contained in the cathode catalyst layer is not particularly limited and can be selected appropriately depending on the purpose, and examples include platinum and ruthenium. The cathode catalyst may also be supported on a catalyst carrier having a porous structure. Examples of catalyst carriers include electron-conductive materials such as porous carbon, porous metals, and porous metal oxides.
カソード触媒は、アイオノマーで被覆されていてもよい。例えば、カソード触媒を担持した状態にある触媒担体がアイオノマーで被覆される。アイオノマーとしては、特に制限はなく目的に応じて適宜選択することができ、例えば、ナフィオン(登録商標)、フレミオン(登録商標)などのパーフルオロスルホン酸ポリマーなどが挙げられる。なお、アイオノマーは、カソード触媒を部分的に被覆していることが好ましい。これにより、カソード触媒層における電気化学反応に必要な3要素(被水素化物、プロトン、及び電子)を、効率的に反応場に供給することができる。 The cathode catalyst may be coated with an ionomer. For example, a catalyst support carrying the cathode catalyst is coated with an ionomer. There are no particular restrictions on the ionomer and it can be selected appropriately depending on the purpose. Examples include perfluorosulfonic acid polymers such as Nafion (registered trademark) and Flemion (registered trademark). It is preferable that the ionomer partially coats the cathode catalyst. This allows the three elements required for the electrochemical reaction in the cathode catalyst layer (the substance to be hydrided, protons, and electrons) to be efficiently supplied to the reaction site.
カソード触媒層の、電解質膜20とは反対側の主表面に接するように拡散層を配置してもよい。拡散層は、外部から供給される液状の被水素化物をカソード触媒層に均一に拡散させる。また、カソード触媒層で生成される有機ハイドライドは、拡散層を介してカソード触媒層の外部へ排出される。 A diffusion layer may be disposed in contact with the main surface of the cathode catalyst layer opposite the electrolyte membrane 20. The diffusion layer uniformly diffuses the liquid substance to be hydrogenated, which is supplied from the outside, into the cathode catalyst layer. In addition, the organic hydride produced in the cathode catalyst layer is discharged to the outside of the cathode catalyst layer via the diffusion layer.
拡散層の材質としては、特に制限はなく目的に応じて適宜選択することができるが、カーボンや金属などの導電性材料が好ましい。拡散層の態様としては、繊維若しくは粒子の焼結体、発泡成型体といった多孔質体であることが好ましい。拡散層の具体例としては、カーボンの織布(カーボンクロス)、カーボンの不織布、カーボンペーパーなどが挙げられる。 The material for the diffusion layer is not particularly limited and can be selected appropriately depending on the purpose, but conductive materials such as carbon or metal are preferred. The diffusion layer is preferably in the form of a porous material such as a sintered fiber or particle body, or a foam molded body. Specific examples of diffusion layers include woven carbon fabric (carbon cloth), nonwoven carbon fabric, and carbon paper.
カソード電極14は、カソード室18に収容される。カソード室18は、例えば、電解質膜20と、エンドプレート22bと、スペーサ24bとによって画成される。 The cathode electrode 14 is housed in the cathode chamber 18. The cathode chamber 18 is defined, for example, by the electrolyte membrane 20, the end plate 22b, and the spacer 24b.
エンドプレート22bは、例えば、ステンレス鋼、チタンなどの金属で構成される板材であり、カソード電極14の、電解質膜20とは反対側に設置される。一例としてのエンドプレート22bは、カソード電極14側を向く主表面に溝状の流路を有する。カソード室18に供給されるカソード液は、この流路を通ってカソード電極14に供給され、この流路を通ってカソード室18から排出される。 The end plate 22b is a plate made of a metal such as stainless steel or titanium, and is installed on the side of the cathode electrode 14 opposite the electrolyte membrane 20. As an example, the end plate 22b has a groove-shaped flow path on the main surface facing the cathode electrode 14. The cathode fluid supplied to the cathode chamber 18 passes through this flow path to the cathode electrode 14, and is discharged from the cathode chamber 18 through this flow path.
スペーサ24bは、電解質膜20とエンドプレート22bとの間に配置される枠状のシール材である。カソード室18におけるカソード電極14を除く空間は、カソード液の流路を構成する。 The spacer 24b is a frame-shaped sealing material placed between the electrolyte membrane 20 and the end plate 22b. The space in the cathode chamber 18 excluding the cathode electrode 14 forms a flow path for the cathode fluid.
エンドプレート22bには、カソード室18の内外を連通する第1カソード開口30及び第2カソード開口32が設けられる。 The end plate 22b is provided with a first cathode opening 30 and a second cathode opening 32 that connect the inside and outside of the cathode chamber 18.
第1カソード開口30は、カソード室18にカソード液を供給する、所謂供給口である。第2カソード開口32は、カソード室18からカソード液を排出する、所謂排出口である。なお、第1カソード開口30が、カソード室18からカソード液を排出する、所謂排出口であってもよく、第2カソード開口32が、カソード室18にカソード液を供給する、所謂供給口であってもよい。 The first cathode opening 30 is a so-called supply port that supplies cathode fluid to the cathode chamber 18. The second cathode opening 32 is a so-called discharge port that discharges cathode fluid from the cathode chamber 18. Note that the first cathode opening 30 may be a so-called discharge port that discharges cathode fluid from the cathode chamber 18, and the second cathode opening 32 may be a so-called supply port that supplies cathode fluid to the cathode chamber 18.
第1カソード開口30が設けられる位置としては、図1~2に示されるカソード電極14に対向するエンドプレート22b面に限られず、カソード室18の下部に設けられることが好ましく、カソード室18の底面に設けられていてもよい。 The location of the first cathode opening 30 is not limited to the surface of the end plate 22b facing the cathode electrode 14 shown in Figures 1 and 2; it is preferable to provide it at the bottom of the cathode chamber 18, and it may also be provided on the bottom surface of the cathode chamber 18.
第2カソード開口32が設けられる位置としては、図1~2に示されるカソード電極14に対向するエンドプレート22b面に限られず、カソード室18の上部に設けられることが好ましく、カソード室18の天面に設けられていてもよい。 The location of the second cathode opening 32 is not limited to the surface of the end plate 22b facing the cathode electrode 14 shown in Figures 1 and 2; it is preferable to provide it at the top of the cathode chamber 18, and it may also be provided on the ceiling of the cathode chamber 18.
<<電解質膜>>
アノード室16とカソード室18とは、電解質膜20によって仕切られる。電解質膜20は、アノード電極12とカソード電極14とで挟まれる。
<<Electrolyte membrane>>
The anode chamber 16 and the cathode chamber 18 are separated by an electrolyte membrane 20. The electrolyte membrane 20 is sandwiched between the anode electrode 12 and the cathode electrode 14.
電解質膜20としては、プロトン伝導性を有する固体高分子電解質膜で構成され、アノード室16側からカソード室18側にプロトンを移動させる。固体高分子電解質膜としては、プロトンが伝導する材料であれば、特に制限はなく目的に応じて適宜選択することができ、例えば、スルホン酸基を有するフッ素系イオン交換膜などが挙げられる。 The electrolyte membrane 20 is composed of a solid polymer electrolyte membrane with proton conductivity, which transfers protons from the anode chamber 16 to the cathode chamber 18. There are no particular restrictions on the solid polymer electrolyte membrane, and it can be selected appropriately depending on the purpose, as long as it is a material that conducts protons. For example, a fluorine-based ion exchange membrane with sulfonic acid groups can be used.
アノード室16には、アノード液供給装置6によってアノード液が供給される。アノード液としては、水を含んでいれば、特に制限はなく目的に応じて適宜選択することができ、例えば、硫酸水溶液、硝酸水溶液、塩酸水溶液、純水、イオン交換水などが挙げられる。 Anode fluid is supplied to the anode chamber 16 by an anode fluid supply device 6. There are no particular restrictions on the anode fluid, and it can be selected appropriately depending on the purpose as long as it contains water. Examples include aqueous sulfuric acid solution, aqueous nitric acid solution, aqueous hydrochloric acid solution, pure water, and ion-exchanged water.
カソード室18には、カソード液供給装置8によってカソード液が供給される。カソード液としては、カソード電極14に供給するための有機ハイドライド原料(被水素化物)を含む。一例としてカソード液は、有機ハイドライド製造装置1の運転開始前は有機ハイドライドを含まず、運転開始後に電解によって生成された有機ハイドライドが混入することで、被水素化物と有機ハイドライドとの混合液となる。被水素化物及び有機ハイドライドは、20℃、1気圧で液体であることが好ましい。 Cathode chamber 18 is supplied with cathode fluid by cathode fluid supply device 8. The cathode fluid contains an organic hydride raw material (material to be hydrided) to be supplied to the cathode electrode 14. As an example, the cathode fluid does not contain any organic hydride before operation of the organic hydride production apparatus 1 begins, and after operation begins, the organic hydride produced by electrolysis is mixed in, resulting in a mixture of the material to be hydrided and the organic hydride. It is preferable that the material to be hydrided and the organic hydride are liquid at 20°C and 1 atmosphere.
被水素化物及び有機ハイドライドは、水素化反応/脱水素反応を可逆的に起こすことにより、水素を添加/脱離できる有機化合物であれば、特に制限はなく目的に応じて適宜選択することができ、アセトン-イソプロパノール系化合物、ベンゾキノン-ヒドロキノン系化合物、芳香族炭化水素系化合物などが挙げられる。これらの中でも、エネルギー輸送時の運搬性などの観点から、芳香族炭化水素系化合物が好ましい。 The substance to be hydrided and the organic hydride are not particularly limited and can be selected appropriately depending on the purpose, as long as they are organic compounds that can add/desorb hydrogen by reversibly causing hydrogenation/dehydrogenation reactions. Examples include acetone-isopropanol compounds, benzoquinone-hydroquinone compounds, and aromatic hydrocarbon compounds. Of these, aromatic hydrocarbon compounds are preferred from the perspective of transportability during energy transportation.
芳香族炭化水素系化合物は、少なくとも1つの芳香環を含む化合物であり、例えば、ベンゼン、アルキルベンゼン、ナフタレン、アルキルナフタレン、アントラセン、ジフェニルエタンなどが挙げられる。 Aromatic hydrocarbon compounds are compounds that contain at least one aromatic ring, and examples include benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, and diphenylethane.
アルキルベンゼンは、芳香環の1~4の水素原子が炭素数1~6の直鎖アルキル基又は分岐アルキル基で置換された化合物を含み、例えば、トルエン、キシレン、メシチレン、エチルベンゼン、ジエチルベンゼンなどが挙げられる。 Alkylbenzenes include compounds in which 1 to 4 hydrogen atoms on an aromatic ring are substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, and examples include toluene, xylene, mesitylene, ethylbenzene, and diethylbenzene.
アルキルナフタレンは、芳香環の1~4の水素原子が炭素数1~6の直鎖アルキル基又は分岐アルキル基で置換された化合物を含み、例えば、メチルナフタレンなどが挙げられる。 Alkylnaphthalenes include compounds in which 1 to 4 hydrogen atoms on the aromatic ring are substituted with a linear or branched alkyl group having 1 to 6 carbon atoms, such as methylnaphthalene.
これらは一種単独で使用してもよいし、二種以上を併用してもよい。 These may be used alone or in combination of two or more types.
被水素化物としては、トルエン及びベンゼンの少なくとも一方であることが好ましい。なお、ピリジン、ピリミジン、ピラジン、キノリン、イソキノリン、N-アルキルピロール、N-アルキルインドール、N-アルキルジベンゾピロールなどの含窒素複素環式芳香族化合物も、被水素化物として用いることができる。 The substance to be hydrogenated is preferably at least one of toluene and benzene. Nitrogen-containing heterocyclic aromatic compounds such as pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, N-alkylpyrrole, N-alkylindole, and N-alkyldibenzopyrrole can also be used as the substance to be hydrogenated.
有機ハイドライドとしては、上述の被水素化物が水素化されたものであり、例えば、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、ピペリジンなどが挙げられる。 Organic hydrides include the hydrogenated compounds mentioned above, such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and piperidine.
被水素化物の一例としてトルエン(TL)を用いた場合、電解槽2では以下の反応が生じる。なお、被水素化物としてトルエンを用いた場合、得られる有機ハイドライドはメチルシクロヘキサン(MCH)である。 When toluene (TL) is used as an example of the substance to be hydrogenated, the following reaction occurs in electrolytic cell 2. Note that when toluene is used as the substance to be hydrogenated, the resulting organic hydride is methylcyclohexane (MCH).
[アノード電極での電極反応]
(数1)
3H2O→3/2O2+6H++6e-
[Electrode reaction at the anode electrode]
(Equation 1)
3H 2 O → 3/2O 2 +6H + +6e -
[カソード電極での電極反応]
(数2)
TL+6H++6e-→MCH
[Electrode reaction at the cathode electrode]
(Equation 2)
TL+6H + +6e - →MCH
アノード電極12での電極反応と、カソード電極14での電極反応とが並行して進行する。アノード電極12における水の電気分解により生じたプロトンは、電解質膜20を介してカソード電極14に供給される。また、水の電気分解により生じた電子は、エンドプレート22a、外部回路、及びエンドプレート22bを介してカソード電極14に供給される。カソード電極14に供給されたプロトン及び電子は、カソード電極14においてトルエンの水素化に用いられる。これにより、メチルシクロヘキサンが生成される。 The electrode reaction at the anode electrode 12 and the electrode reaction at the cathode electrode 14 proceed in parallel. Protons produced by the electrolysis of water at the anode electrode 12 are supplied to the cathode electrode 14 via the electrolyte membrane 20. Electrons produced by the electrolysis of water are supplied to the cathode electrode 14 via the end plate 22a, the external circuit, and the end plate 22b. The protons and electrons supplied to the cathode electrode 14 are used to hydrogenate toluene at the cathode electrode 14. As a result, methylcyclohexane is produced.
本実施形態に係る有機ハイドライド製造装置1によれば、水の電気分解と被水素化物の水素化反応とを1ステップで行うことができる。このため、水電解などで水素を製造するプロセスと、被水素化物をプラントなどのリアクタで化学水素化するプロセスと、を含む2段階プロセスで有機ハイドライドを製造する従来技術に比べて、有機ハイドライドの製造効率を高めることができる。また、化学水素化を行うリアクタや、水電解などで製造された水素を貯留するための高圧容器などが不要であるため、大幅な設備コストの低減を図ることができる。 The organic hydride manufacturing apparatus 1 according to this embodiment can perform the electrolysis of water and the hydrogenation reaction of the material to be hydrogenated in a single step. This increases the efficiency of organic hydride manufacturing compared to conventional technologies that manufacture organic hydrides using a two-stage process that includes a process for producing hydrogen using water electrolysis or the like, and a process for chemically hydrogenating the material to be hydrogenated in a reactor at a plant or the like. Furthermore, since there is no need for a reactor for chemical hydrogenation or a high-pressure vessel for storing hydrogen produced by water electrolysis or the like, significant reductions in equipment costs can be achieved.
カソード電極14では、主反応である被水素化物の水素化反応とともに、副反応として以下に示す水素ガスの発生反応が起こる場合がある。カソード電極14への被水素化物の供給量が不足するにつれて、この副反応は生じやすくなる。 At the cathode electrode 14, in addition to the main reaction of hydrogenation of the material to be hydrogenated, a side reaction of hydrogen gas generation, as shown below, may occur. As the supply of material to be hydrogenated to the cathode electrode 14 becomes insufficient, this side reaction becomes more likely to occur.
[カソード電極で生じ得る副反応]
(数3)
2H++2e-→H2
[Possible side reactions occurring at the cathode electrode]
(Equation 3)
2H + +2e - →H 2
<アノード液供給装置>
図1に示すように、アノード液供給装置6は、アノード室16にアノード液を供給する。アノード液供給装置6は、アノード液タンク36、気液分離部38、第1アノード配管40、第2アノード配管42、第3アノード配管44、第1アノードポンプ46、及び第2アノードポンプ48を有する。
<Anodic liquid supply device>
1 , the anolyte supply device 6 supplies anolyte to the anode chamber 16. The anolyte supply device 6 includes an anolyte tank 36, a gas-liquid separator 38, a first anode pipe 40, a second anode pipe 42, a third anode pipe 44, a first anode pump 46, and a second anode pump 48.
気液分離部38は、公知の気液分離槽で構成することができる。 The gas-liquid separation section 38 can be composed of a known gas-liquid separation tank.
第1アノードポンプ46及び第2アノードポンプ48は、例えば、ギアポンプやシリンダーポンプなどの公知のポンプで構成することができる。なお、アノード液供給装置6は、ポンプ以外の送液装置を用いてアノード液を流通させてもよい。 The first anode pump 46 and the second anode pump 48 can be configured with known pumps such as gear pumps or cylinder pumps. The anode fluid supply device 6 may also circulate the anode fluid using a fluid delivery device other than a pump.
アノード液タンク36には、アノード室16に供給するアノード液が貯留される。アノード液タンク36は、第1アノード配管40によってアノード室16に接続される。第1アノード配管40は、一端側がアノード液タンク36に接続され、他端側が第1アノード開口26に接続される。第1アノード配管40の途中には、第1アノードポンプ46が設けられる。 The anode fluid tank 36 stores the anode fluid to be supplied to the anode chamber 16. The anode fluid tank 36 is connected to the anode chamber 16 by a first anode pipe 40. One end of the first anode pipe 40 is connected to the anode fluid tank 36, and the other end is connected to the first anode opening 26. A first anode pump 46 is provided midway along the first anode pipe 40.
気液分離部38は、第2アノード配管42によってアノード室16に接続される。第2アノード配管42は、一端側が第2アノード開口28に接続され、他端側が気液分離部38に接続される。また、気液分離部38は、第3アノード配管44によってアノード液タンク36に接続される。第3アノード配管44の途中には、第2アノードポンプ48が設けられる。 The gas-liquid separation unit 38 is connected to the anode chamber 16 by a second anode pipe 42. One end of the second anode pipe 42 is connected to the second anode opening 28, and the other end is connected to the gas-liquid separation unit 38. The gas-liquid separation unit 38 is connected to the anode fluid tank 36 by a third anode pipe 44. A second anode pump 48 is provided midway along the third anode pipe 44.
アノード液タンク36中のアノード液は、第1アノードポンプ46の駆動により、第1アノード配管40を経由して第1アノード開口26からアノード室16に流入する。アノード液は、アップフローでアノード室16に供給され、アノード電極12での電極反応に供される。アノード室16内のアノード液は、第2アノード配管42を経由して気液分離部38に流入する。アノード電極12では電極反応によって酸素ガスが発生する。このため、アノード室16から排出されるアノード液には、酸素ガスが混入している。気液分離部38は、アノード液中の酸素ガスをアノード液から分離して系外に排出する。酸素ガスが分離されたアノード液は、第2アノードポンプ48の駆動により、第3アノード配管44を経由してアノード液タンク36に戻される。 By driving the first anode pump 46, the anode fluid in the anode fluid tank 36 flows through the first anode piping 40 and into the anode chamber 16 from the first anode opening 26. The anode fluid is supplied to the anode chamber 16 by upflow and is used for the electrode reaction at the anode electrode 12. The anode fluid in the anode chamber 16 flows into the gas-liquid separation unit 38 via the second anode piping 42. Oxygen gas is generated by the electrode reaction at the anode electrode 12. As a result, oxygen gas is mixed into the anode fluid discharged from the anode chamber 16. The gas-liquid separation unit 38 separates the oxygen gas in the anode fluid from the anode fluid and discharges it outside the system. By driving the second anode pump 48, the anode fluid from which the oxygen gas has been separated is returned to the anode fluid tank 36 via the third anode piping 44.
<カソード液供給装置>
図1に示すように、カソード液供給装置8は、カソード室18にカソード液を供給する。
カソード液供給装置8は、カソード液タンク50、気液分離部52、油水分離部54、ガスタンク56、第1カソード配管58~第6カソード配管72、第1カソードポンプ74~第4カソードポンプ80、及び第1開閉弁84~第4開閉弁94を有する。
<Catholyte Supply Device>
As shown in FIG. 1, the catholyte supply device 8 supplies catholyte to the cathode chamber 18 .
The cathode fluid supply device 8 includes a cathode fluid tank 50, a gas-liquid separation unit 52, an oil-water separation unit 54, a gas tank 56, a first cathode pipe 58 to a sixth cathode pipe 72, a first cathode pump 74 to a fourth cathode pump 80, and a first on-off valve 84 to a fourth on-off valve 94.
気液分離部52は、公知の気液分離槽で構成することができる。 The gas-liquid separation section 52 can be composed of a known gas-liquid separation tank.
油水分離部54は、公知の油水分離槽で構成することができる。 The oil-water separation section 54 can be constructed from a known oil-water separation tank.
第1カソードポンプ74~第4カソードポンプ80は、例えば、ギアポンプやシリンダーポンプなどの公知のポンプで構成することができる。なお、カソード液供給装置8は、ポンプ以外の送液装置を用いてカソード液を流通させてもよい。 The first cathode pump 74 to the fourth cathode pump 80 can be configured with known pumps such as gear pumps or cylinder pumps. The cathode fluid supply device 8 may also circulate the cathode fluid using a fluid delivery device other than a pump.
第1開閉弁84~第4開閉弁94は、例えば、電磁弁やエアー駆動弁などの公知の弁で構成することができる。 The first on-off valve 84 to the fourth on-off valve 94 can be constructed using known valves such as solenoid valves or air-operated valves.
カソード液タンク50には、カソード室18に供給されるカソード液が貯留される。カソード液タンク50は、第1カソード配管58によってカソード室18に接続される。第1カソード配管58は、一端側がカソード液タンク50に接続され、他端側が第1カソード開口30に接続される。第1カソード配管58の途中には、第1カソードポンプ74及び第1開閉弁84が設けられる。第1カソードポンプ74は、第1開閉弁84よりもカソード室18側に配置される。 The cathode fluid tank 50 stores the cathode fluid to be supplied to the cathode chamber 18. The cathode fluid tank 50 is connected to the cathode chamber 18 by a first cathode piping 58. One end of the first cathode piping 58 is connected to the cathode fluid tank 50, and the other end is connected to the first cathode opening 30. A first cathode pump 74 and a first on-off valve 84 are provided midway along the first cathode piping 58. The first cathode pump 74 is positioned closer to the cathode chamber 18 than the first on-off valve 84.
気液分離部52は、第2カソード配管60によってカソード室18に接続される。第2カソード配管60は、一端側が第2カソード開口32に接続され、他端側が気液分離部52に接続される。第2カソード配管60の途中には、第2開閉弁86が設けられる。 The gas-liquid separation unit 52 is connected to the cathode chamber 18 by a second cathode piping 60. One end of the second cathode piping 60 is connected to the second cathode opening 32, and the other end is connected to the gas-liquid separation unit 52. A second on-off valve 86 is provided midway along the second cathode piping 60.
油水分離部54は、第3カソード配管62によって気液分離部52に接続される。第3カソード配管62の途中には、第2カソードポンプ76及び第3開閉弁88が設けられる。第2カソードポンプ76は、第3開閉弁88よりも気液分離部52側に配置される。また、油水分離部54は、第4カソード配管64によってカソード液タンク50に接続される。第4カソード配管64の途中には、第3カソードポンプ78が設けられる。さらに、油水分離部54には、第5カソード配管66が接続される。第5カソード配管66は、一端側が油水分離部54に接続され、他端側が例えば排水槽(図示せず)に接続される。第5カソード配管66の途中には、第4カソードポンプ80及び水量センサ96が設けられる。水量センサ96は、第5カソード配管66内を流れる水の流量を検知する。水量センサ96は、公知の流量計で構成することができる。 The oil-water separation section 54 is connected to the gas-liquid separation section 52 by a third cathode piping 62. A second cathode pump 76 and a third on-off valve 88 are provided in the middle of the third cathode piping 62. The second cathode pump 76 is positioned closer to the gas-liquid separation section 52 than the third on-off valve 88. The oil-water separation section 54 is also connected to the cathode liquid tank 50 by a fourth cathode piping 64. A third cathode pump 78 is provided in the middle of the fourth cathode piping 64. A fifth cathode piping 66 is also connected to the oil-water separation section 54. One end of the fifth cathode piping 66 is connected to the oil-water separation section 54, and the other end is connected to, for example, a drainage tank (not shown). A fourth cathode pump 80 and a water volume sensor 96 are provided in the middle of the fifth cathode piping 66. The water volume sensor 96 detects the flow rate of water flowing through the fifth cathode pipe 66. The water volume sensor 96 can be configured as a known flow meter.
ガスタンク56は、第6カソード配管72によってカソード室18に接続される。第6カソード配管72は、一端側がガスタンク56に接続され、他端側が第2カソード配管60を介して第2カソード開口32に接続される。第6カソード配管72の途中には、第4開閉弁94が設けられる。本実施形態において、第6カソード配管72の他端側は、第2カソード配管60における第2開閉弁86よりもカソード室18側の領域に接続されることで、第2カソード配管60を介して第2カソード開口32に接続されているが、この構成に限定されず、第6カソード配管72は直に第2カソード開口32に接続されてもよい。 The gas tank 56 is connected to the cathode chamber 18 by a sixth cathode pipe 72. One end of the sixth cathode pipe 72 is connected to the gas tank 56, and the other end is connected to the second cathode opening 32 via the second cathode pipe 60. A fourth on-off valve 94 is provided midway along the sixth cathode pipe 72. In this embodiment, the other end of the sixth cathode pipe 72 is connected to a region of the second cathode pipe 60 closer to the cathode chamber 18 than the second on-off valve 86, and is thereby connected to the second cathode opening 32 via the second cathode pipe 60. However, this configuration is not limited, and the sixth cathode pipe 72 may be connected directly to the second cathode opening 32.
図1に示すように、カソード液供給装置8は、カソード液タンク50、第1カソード配管58、カソード室18、第2カソード配管60、気液分離部52、第3カソード配管62、油水分離部54、及び第4カソード配管64によって、カソード液の第1経路を形成することができる。
第1経路では、カソード室18内にカソード液のアップフローが形成される。本開示におけるカソード液の「アップフロー」とは、下方にある第1カソード開口30からカソード室18にカソード液を流入させ、上方にある第2カソード開口32からカソード液を排出させることをいう。なお、上方にある第2カソード開口32からカソード室18にカソード液を流入させ、下方にある第1カソード開口30からカソード液を排出させる「ダウンフロー」であってもよい。
As shown in FIG. 1 , the cathode fluid supply device 8 can form a first path of the cathode fluid by using a cathode fluid tank 50, a first cathode pipe 58, a cathode chamber 18, a second cathode pipe 60, a gas-liquid separation unit 52, a third cathode pipe 62, an oil-water separation unit 54, and a fourth cathode pipe 64.
In the first path, an upflow of the cathode fluid is formed in the cathode chamber 18. In this disclosure, the "upflow" of the cathode fluid refers to the flow of the cathode fluid into the cathode chamber 18 from the first cathode opening 30 located below and the discharge of the cathode fluid from the second cathode opening 32 located above. Note that a "downflow" may also be used, in which the cathode fluid flows into the cathode chamber 18 from the second cathode opening 32 located above and the discharge of the cathode fluid from the first cathode opening 30 located below.
具体的には、カソード液タンク50中のカソード液は、第1カソードポンプ74の駆動により、第1カソード配管58を経由して第1カソード開口30からカソード室18に流入する。第1開閉弁84は開状態をとり、カソード液タンク50から第1カソード開口30へのカソード液の流通が許容される。カソード液は、アップフローでカソード室18に供給される。 Specifically, when the first cathode pump 74 is driven, the cathode fluid in the cathode fluid tank 50 flows through the first cathode piping 58 and into the cathode chamber 18 from the first cathode opening 30. The first on-off valve 84 is open, allowing the cathode fluid to flow from the cathode fluid tank 50 to the first cathode opening 30. The cathode fluid is supplied to the cathode chamber 18 by upflow.
カソード室18内のカソード液は、第2カソード配管60を経由して気液分離部52に流入する。第2開閉弁86は開状態をとり、第2カソード開口32から気液分離部52へのカソード液の流通が許容される。第4開閉弁94は閉状態をとり、第2カソード開口32からガスタンク56へのカソード液の流通が遮断される。上述のとおり、カソード電極14では副反応によって水素ガスが発生する。このため、カソード室18から排出されるカソード液には、水素ガスが混入している。気液分離部52は、カソード液中の水素ガスをカソード液から分離して系外に排出する。 The cathode fluid in the cathode chamber 18 flows into the gas-liquid separation unit 52 via the second cathode piping 60. The second on-off valve 86 is open, allowing the flow of cathode fluid from the second cathode opening 32 to the gas-liquid separation unit 52. The fourth on-off valve 94 is closed, blocking the flow of cathode fluid from the second cathode opening 32 to the gas tank 56. As mentioned above, hydrogen gas is generated by a side reaction at the cathode electrode 14. As a result, hydrogen gas is mixed into the cathode fluid discharged from the cathode chamber 18. The gas-liquid separation unit 52 separates the hydrogen gas in the cathode fluid from the cathode fluid and discharges it outside the system.
水素ガスが分離されたカソード液は、第2カソードポンプ76の駆動により、第3カソード配管62を経由して油水分離部54に流入する。第3開閉弁88は開状態をとり、気液分離部52から油水分離部54へのカソード液の流通が許容される。 The cathode fluid from which hydrogen gas has been separated flows into the oil-water separation section 54 via the third cathode piping 62 by driving the second cathode pump 76. The third on-off valve 88 is in an open state, allowing the cathode fluid to flow from the gas-liquid separation section 52 to the oil-water separation section 54.
カソード電極14には、アノード電極12からプロトンとともに水が移動してくる場合があり、それに伴い、カソード室18から排出されるカソード液には、水が混入していることがある。
油水分離部54は、カソード液中の水をカソード液から分離する。分離された水は、第4カソードポンプ80の駆動により、第5カソード配管66を経由して排水槽に排出される。油水分離部54でカソード液から分離される水の量、換言するとカソード室18から排出される水の量は、水量センサ96によって検知される。水が分離されたカソード液は、第3カソードポンプ78の駆動により、第4カソード配管64を経由してカソード液タンク50に戻される。
Water may migrate from the anode electrode 12 to the cathode electrode 14 together with protons, and as a result, the catholyte discharged from the cathode chamber 18 may contain water.
The oil-water separation unit 54 separates the water in the cathode fluid from the cathode fluid. The separated water is discharged to the drain tank via the fifth cathode piping 66 by driving the fourth cathode pump 80. The amount of water separated from the cathode fluid by the oil-water separation unit 54, in other words, the amount of water discharged from the cathode chamber 18, is detected by a water volume sensor 96. The cathode fluid from which the water has been separated is returned to the cathode fluid tank 50 via the fourth cathode piping 64 by driving the third cathode pump 78.
図1には1つの電解槽2のみが図示されているが、有機ハイドライド製造装置1は、複数の電解槽2を有してもよい。この場合、各電解槽2は、例えば、アノード室16及びカソード室18の並びが同じになるように向きが揃えられ、隣り合う電解槽2の間に通電板を挟んで積層される。これにより、各電解槽2は電気的に直列接続される。通電板は、例えば、金属などの導電性材料で構成される。なお、各電解槽2は、並列接続されてもよいし、直列接続と並列接続とが組み合わされてもよい。 Although only one electrolytic cell 2 is shown in Figure 1, the organic hydride manufacturing apparatus 1 may have multiple electrolytic cells 2. In this case, each electrolytic cell 2 is aligned, for example, so that the anode chambers 16 and cathode chambers 18 are aligned in the same direction, and adjacent electrolytic cells 2 are stacked with a current-carrying plate sandwiched between them. This electrically connects each electrolytic cell 2 in series. The current-carrying plate is made of a conductive material such as metal. The electrolytic cells 2 may be connected in parallel, or a combination of series and parallel connections may be used.
<電源>
電源4は、電解槽2に電力を供給する直流電源である。電源4から電解槽2に電力が供給されると、電解槽2のアノード電極12とカソード電極14との間に所定の電解電圧が印加され、電解電流が流れる。
電源4は、電力供給装置34から電力供給を受けて、電解槽2に電力を供給する。
<Power source>
The power supply 4 is a DC power supply that supplies power to the electrolytic cell 2. When power is supplied from the power supply 4 to the electrolytic cell 2, a predetermined electrolysis voltage is applied between the anode electrode 12 and the cathode electrode 14 of the electrolytic cell 2, causing an electrolysis current to flow.
The power supply 4 receives power from a power supply device 34 and supplies power to the electrolytic cell 2 .
電力供給装置34は、有機ハイドライド製造装置1の電源4に電力を直流で供給する電力供給装置であり、第1電力供給装置341及び第2電力供給装置342の少なくとも一方を有する。また、第1電力供給装置341の出力電圧を所定の電圧に変換する電力変換部を有していてもよい。 The power supply device 34 is a power supply device that supplies DC power to the power supply 4 of the organic hydride manufacturing apparatus 1, and includes at least one of a first power supply device 341 and a second power supply device 342. It may also include a power conversion unit that converts the output voltage of the first power supply device 341 to a predetermined voltage.
第1電力供給装置341は、例えば、再生可能エネルギー由来の電力を発電する発電装置とすることができる。具体例としては、風力発電装置、太陽光発電装置、水力発電装置、地熱発電装置、波力発電装置、温度差発電装置、バイオマス発電装置などが挙げられる。 The first power supply device 341 can be, for example, a power generation device that generates electricity from renewable energy sources. Specific examples include wind power generation devices, solar power generation devices, hydroelectric power generation devices, geothermal power generation devices, wave power generation devices, temperature difference power generation devices, and biomass power generation devices.
電力変換部は、第1電力供給装置341の出力電圧を所定の電圧に変換する。電力変換部としては、例えば、DC/DCコンバータなどが用いられる。電力変換部は、第1電力供給装置341から電力が交流で入力される場合、トランスにより電圧変換し、ブリッジ形ダイオードにより整流し、平滑電解コンデンサにより平滑化し、出力端子から電解槽2に電力を供給する。なお、電力変換部は、第2電力供給装置342の出力電圧を所定の電圧に変換してもよい。 The power conversion unit converts the output voltage of the first power supply device 341 to a predetermined voltage. For example, a DC/DC converter is used as the power conversion unit. When AC power is input from the first power supply device 341, the power conversion unit converts the voltage using a transformer, rectifies it using a bridge-type diode, smooths it using a smoothing electrolytic capacitor, and supplies the power to the electrolytic cell 2 from the output terminal. The power conversion unit may also convert the output voltage of the second power supply device 342 to a predetermined voltage.
第2電力供給装置342は、例えば、蓄電池、天然ガス及び石炭などの化石燃料を燃焼させる火力発電所とすることができる。第2電力供給装置342の電力は、第1電力供給装置341から供給される電力が不十分であるときに副電力として使用してよい。これにより、有機ハイドライド製造装置1は、第1電力供給装置341の他に、第2電力供給装置342の電力が電解槽2に供給されることで、運転を安定して行うことができる。また、第2電力供給装置342が蓄電池で構成される場合、第2電力供給装置342は第1電力供給装置341からの電力供給を受けて充電されることで、電力供給装置34から発生するCO2排出量を抑制できる。第2電力供給装置342は、第1電力供給装置341とは独立して電源4に電力を供給してよい。第2電力供給装置342は、制御装置10による制御に基づいて電源部22に電力を供給してよい。 The second power supply device 342 may be, for example, a storage battery or a thermal power plant that burns fossil fuels such as natural gas and coal. The power of the second power supply device 342 may be used as a secondary power when the power supplied from the first power supply device 341 is insufficient. Thus, the organic hydride manufacturing apparatus 1 can stably operate by supplying power from the second power supply device 342 to the electrolytic cell 2 in addition to the power from the first power supply device 341. Furthermore, if the second power supply device 342 is configured as a storage battery, the second power supply device 342 can be charged by receiving power from the first power supply device 341, thereby reducing CO2 emissions from the power supply device 34. The second power supply device 342 may supply power to the power source 4 independently of the first power supply device 341. The second power supply device 342 may supply power to the power source unit 22 under control of the control device 10.
なお、電力供給装置34は、蓄電池を備え、第1電力供給装置341及び第2電力供給装置342の少なくとも一方で発電して生じた電力を蓄電し、蓄電池から電力を必要に応じて有機ハイドライド製造装置1に供給してもよい。 The power supply device 34 may also be equipped with a storage battery, store the power generated by at least one of the first power supply device 341 and the second power supply device 342, and supply power from the storage battery to the organic hydride manufacturing apparatus 1 as needed.
<制御装置>
制御装置10は、電源4から電解槽2への電力の供給を制御する。アノード電極12及びカソード電極14の電位は、制御装置10によって制御される。制御装置10は、ハードウェア構成としてはコンピュータのCPUやメモリをはじめとする素子や回路で実現され、ソフトウェア構成としてはコンピュータプログラムなどによって実現されるが、図1では、それらの連携によって実現される機能ブロックとして描いている。この機能ブロックがハードウェア及びソフトウェアの組合せによって、いろいろなかたちで実現できることは、当業者には当然に理解されるところである。
<Control device>
The control device 10 controls the supply of power from the power source 4 to the electrolytic cell 2. The potentials of the anode electrode 12 and the cathode electrode 14 are controlled by the control device 10. The control device 10 is realized as a hardware configuration by elements and circuits such as a computer CPU and memory, and as a software configuration by a computer program, etc., but in Figure 1 it is depicted as a functional block realized by the cooperation of these. It will naturally be understood by those skilled in the art that these functional blocks can be realized in various ways by combining hardware and software.
制御装置10には、電解槽2に設けられる検知部98から、電解槽2の電圧を示す信号、アノード電極12の電位を示す信号、及びカソード電極14の電位を示す信号の少なくとも1つが入力される。検知部98は、各電極の電位や電解槽2の電圧を公知の方法で検出することができる。検知部98は、例えば公知の電圧計を有する。 The control device 10 receives at least one of a signal indicating the voltage of the electrolytic cell 2, a signal indicating the potential of the anode electrode 12, and a signal indicating the potential of the cathode electrode 14 from a detection unit 98 provided in the electrolytic cell 2. The detection unit 98 can detect the potential of each electrode and the voltage of the electrolytic cell 2 using a known method. The detection unit 98 includes, for example, a known voltmeter.
検知部98がアノード電極12の電位又はカソード電極14の電位を検知する場合、参照極が電解質膜20に設けられる。参照極は、参照電極電位に保持される。例えば、参照極は、可逆水素電極(RHE:Reversible Hydrogen Electrode)である。そして、検知部98の一方の端子が参照極に、他方の端子が検知対象となる電極に接続されて、参照極に対する電極の電位が検知される。また、検知部98が電解槽2の電圧を検知する場合、検知部98の一方の端子がアノード電極12に、他方の端子がカソード電極14に接続されて、両電極の電位差、つまり電圧が検知される。検知部98は、検知結果を示す信号を制御装置10に送信する。 When the detection unit 98 detects the potential of the anode electrode 12 or the cathode electrode 14, a reference electrode is provided on the electrolyte membrane 20. The reference electrode is maintained at a reference electrode potential. For example, the reference electrode is a reversible hydrogen electrode (RHE). One terminal of the detection unit 98 is connected to the reference electrode, and the other terminal is connected to the electrode to be detected, thereby detecting the electrode potential relative to the reference electrode. When the detection unit 98 detects the voltage of the electrolytic cell 2, one terminal of the detection unit 98 is connected to the anode electrode 12, and the other terminal is connected to the cathode electrode 14, thereby detecting the potential difference between the two electrodes, i.e., the voltage. The detection unit 98 sends a signal indicating the detection result to the control device 10.
検知部98は、アノード電極12とカソード電極14との間を流れる電流を検出する電流検出部を含む。電流検出部は、例えば、公知の電流計で構成される。電流検出部で検出された電流値は、制御装置10に入力される。 The detection unit 98 includes a current detection unit that detects the current flowing between the anode electrode 12 and the cathode electrode 14. The current detection unit is configured, for example, with a known ammeter. The current value detected by the current detection unit is input to the control device 10.
制御装置10は、電解槽2の電流-電圧特性(I-V特性)の情報を予め保持していてもよい。制御装置10がI-V特性の情報を保持する場合、この情報は任意に更新可能であってもよい。電解槽2のI-V特性は、各電極の触媒組成、拡散層や基材の種類、電解質膜20の種類、電解槽2が有するアノード液及びカソード液の流路構造、各部の寸法などに応じて定まる特性であり、予め測定し把握しておくことができる。この場合、制御装置10は、電力供給装置34から供給される電力量を示す信号を受信することで、電源4から電解槽2に供給可能な電力量を把握し、I-V特性から電解槽2に印加すべき電圧値を算出すること、つまり、電解槽2に流れる電流値を制御することができる。 The control device 10 may previously store information on the current-voltage characteristics (IV characteristics) of the electrolytic cell 2. If the control device 10 stores information on the IV characteristics, this information may be updateable as needed. The IV characteristics of the electrolytic cell 2 are determined by factors such as the catalyst composition of each electrode, the type of diffusion layer and substrate, the type of electrolyte membrane 20, the flow path structure of the anolyte and catholyte in the electrolytic cell 2, and the dimensions of each part, and can be measured and determined in advance. In this case, the control device 10 receives a signal indicating the amount of power supplied from the power supply device 34, thereby determining the amount of power that can be supplied to the electrolytic cell 2 from the power source 4, and can calculate the voltage value to be applied to the electrolytic cell 2 from the IV characteristics, i.e., control the value of the current flowing through the electrolytic cell 2.
制御装置10は、アノード液供給装置6及びカソード液供給装置8を制御する。具体的には、制御装置10は、第1アノードポンプ46、第2アノードポンプ48、及び第1カソードポンプ74~第4カソードポンプ80の駆動を制御する。また、制御装置10は、第1開閉弁84~第4開閉弁94の開閉を制御する。また、制御装置10は、水量センサ29及び水量センサ96から検知結果を示す信号を受信する。 The control device 10 controls the anode fluid supply device 6 and the cathode fluid supply device 8. Specifically, the control device 10 controls the operation of the first anode pump 46, the second anode pump 48, and the first cathode pump 74 to the fourth cathode pump 80. The control device 10 also controls the opening and closing of the first on-off valve 84 to the fourth on-off valve 94. The control device 10 also receives signals indicating the detection results from the water volume sensor 29 and the water volume sensor 96.
上述のとおり、カソード電極14では主反応として被水素化物の水素化反応が起こるとともに、副反応として水素発生反応が起こる場合がある。副反応の発生は、有機ハイドライド製造装置1のファラデー効率の低下につながる。また、プロトンが水を伴ってアノード電極12側からカソード電極14側に移動して、カソード室18に水が溜まっていく場合がある。水は、被水素化物の流れを阻害するため、カソード室18に多量の水が溜まると、カソード電極14の反応場への被水素化物の供給量が低下し、副反応が進行しやすくなる。また、副反応で発生する水素ガスも、被水素化物の流れを阻害するため、副反応で生じた水素ガスによって副反応がさらに起こりやすくなる。したがって、カソード室18内に滞留する水素ガス及び水をカソード室18から排出することが好ましい。 As mentioned above, at the cathode electrode 14, the hydrogenation reaction of the material to be hydrogenated occurs as the main reaction, and a hydrogen generation reaction may occur as a side reaction. The occurrence of side reactions leads to a decrease in the faradaic efficiency of the organic hydride production apparatus 1. In addition, protons, accompanied by water, may move from the anode electrode 12 side to the cathode electrode 14 side, causing water to accumulate in the cathode chamber 18. Because water inhibits the flow of the material to be hydrogenated, if a large amount of water accumulates in the cathode chamber 18, the amount of material to be hydrogenated supplied to the reaction site of the cathode electrode 14 decreases, making it easier for side reactions to proceed. Furthermore, hydrogen gas generated in side reactions also inhibits the flow of the material to be hydrogenated, making side reactions even more likely to occur. Therefore, it is preferable to discharge the hydrogen gas and water remaining in the cathode chamber 18 from the cathode chamber 18.
(有機ハイドライド製造システム)
本実施形態の実施形態に係る有機ハイドライド製造装置を備える有機ハイドライド製造システムについて、図1を用いて説明する。図1に示すように、本実施形態の有機ハイドライド製造システム3は、有機ハイドライド製造装置1と、電力供給装置34とを備える。なお、有機ハイドライド製造システム3において、上述の(有機ハイドライド製造装置)と重複する構成の説明を省略する。
(Organic hydride production system)
An organic hydride manufacturing system including an organic hydride manufacturing apparatus according to an embodiment of the present invention will be described with reference to Fig. 1. As shown in Fig. 1, an organic hydride manufacturing system 3 according to the present embodiment includes an organic hydride manufacturing apparatus 1 and a power supply device 34. Note that a description of the components of the organic hydride manufacturing system 3 that overlap with those of the above-described (organic hydride manufacturing apparatus) will be omitted.
有機ハイドライド製造システム3は、有機ハイドライド製造装置1と、電力供給装置34として、再生可能エネルギー由来の電力を有機ハイドライド製造装置1の電源に供給する第1電力供給装置、及び化石燃料由来の電力を有機ハイドライド製造装置1の電源に供給する第2電力供給装置の少なくとも一方を備える。 The organic hydride production system 3 includes an organic hydride production apparatus 1 and, as a power supply device 34, at least one of a first power supply device that supplies electricity derived from renewable energy to the power supply of the organic hydride production apparatus 1, and a second power supply device that supplies electricity derived from fossil fuels to the power supply of the organic hydride production apparatus 1.
例えば、有機ハイドライド製造システム3は、上記の有機ハイドライド製造装置1と、第1電力供給装置341とを備える。これにより、有機ハイドライド製造システム3は、有機ハイドライド製造装置1において、第1電力供給装置341から供給される再生可能エネルギー由来の電力を用いて有機ハイドライドを生成することで、有機ハイドライドを効率的に生成できる。 For example, the organic hydride production system 3 includes the organic hydride production apparatus 1 described above and a first power supply device 341. As a result, the organic hydride production system 3 can efficiently produce organic hydride by producing organic hydride in the organic hydride production apparatus 1 using electricity derived from renewable energy supplied from the first power supply device 341.
有機ハイドライド製造システム3は、第1電力供給装置341で生じる再生可能エネルギー由来の電力を用いて有機ハイドライドを製造できるため、水素の製造に伴う化石燃料の消費の削減及びCO2排出量を削減できる。 The organic hydride production system 3 can produce organic hydride using electricity derived from renewable energy generated by the first power supply device 341, thereby reducing the consumption of fossil fuels and CO 2 emissions associated with hydrogen production.
有機ハイドライド製造システム3は、第1電力供給装置341から有機ハイドライド製造装置1の電解槽2に供給される電力が不十分の場合には、第2電力供給装置342で生成される電力を電解槽2に供給することで、有機ハイドライド製造装置1の運転を安定して行うことができる。これにより、有機ハイドライド製造システム3は、有機ハイドライド製造装置1において、有機ハイドライドを安定的に生成できる。 When the power supplied from the first power supply device 341 to the electrolytic cell 2 of the organic hydride production apparatus 1 is insufficient, the organic hydride production system 3 supplies the electrolytic cell 2 with power generated by the second power supply device 342, thereby enabling stable operation of the organic hydride production apparatus 1. This allows the organic hydride production system 3 to stably produce organic hydride in the organic hydride production apparatus 1.
有機ハイドライド製造システム3では、電力供給装置34が、第1電力供給装置341由来の電力、即ち、第1電力供給装置341で生成される電力を有機ハイドライド製造装置1の電解槽2に供給する場合には、有機ハイドライド製造装置1は運転し、第1電力供給装置341由来の電力が電解槽2に供給されない場合には、有機ハイドライド製造装置1は運転を停止してよい。 In the organic hydride production system 3, when the power supply device 34 supplies power from the first power supply device 341, i.e., power generated by the first power supply device 341, to the electrolytic cell 2 of the organic hydride production device 1, the organic hydride production device 1 operates, and when power from the first power supply device 341 is not supplied to the electrolytic cell 2, the organic hydride production device 1 may stop operating.
なお、「運転」とは、有機ハイドライド製造装置1の主目的である有機ハイドライドを生成しているときをいう。そのため、有機ハイドライド製造装置1が運転停止中であっても、第2電力供給装置342から有機ハイドライド製造装置1に電力の供給などが行われてもよい。 Note that "operation" refers to the time when the organic hydride production apparatus 1 is producing organic hydride, which is its main purpose. Therefore, even when the organic hydride production apparatus 1 is not operating, power may be supplied to the organic hydride production apparatus 1 from the second power supply device 342.
以上のように、有機ハイドライド製造システム3は、再生可能エネルギーなどのエネルギーを、水素ガスを経由せずに、被水素化物を用いて、エネルギー由来の水素を輸送、貯蔵などするためのエネルギーキャリアとして、直接、有機ハイドライドを効率良く生成できる。このため、有機ハイドライド製造システム3は、第1電力供給装置341及び第2電力供給装置342で生じた電力の輸送及び貯蔵などに使用されるエネルギーキャリアを製造する装置として有効に用いることができる。特に、有機ハイドライド製造システム3を用いれば、有機ハイドライドを介して再生可能エネルギーを輸送及び貯蔵することで、再生可能エネルギーを無駄なく効率良く利用できる。よって、有機ハイドライド製造システム3は、再生可能エネルギーを輸送及び貯蔵するエネルギーキャリアの製造に好適に用いることができる。 As described above, the organic hydride production system 3 can efficiently produce organic hydrides directly from renewable energy and other energy sources using the material to be hydrided, without passing through hydrogen gas, as an energy carrier for transporting and storing energy-derived hydrogen. Therefore, the organic hydride production system 3 can be effectively used as a device for producing energy carriers used for transporting and storing electricity generated by the first power supply device 341 and the second power supply device 342. In particular, the organic hydride production system 3 can be used to transport and store renewable energy via organic hydrides, allowing for efficient use of renewable energy without waste. Therefore, the organic hydride production system 3 can be suitably used for producing energy carriers for transporting and storing renewable energy.
以上、本発明の実施形態について詳細に説明した。前述した実施形態は、本発明を実施するにあたっての具体例を示したものにすぎない。実施形態の内容は、本発明の技術的範囲を限定するものではなく、請求の範囲に規定された発明の思想を逸脱しない範囲において、構成要素の変更、追加、削除などの多くの設計変更が可能である。設計変更が加えられた新たな実施形態は、組み合わされる実施形態及び変形それぞれの効果をあわせもつ。前述の実施形態では、このような設計変更が可能な内容に関して、「本実施形態の」、「本実施形態では」などの表記を付して強調しているが、そのような表記のない内容でも設計変更が許容される。以上の構成要素の任意の組み合わせも、本発明の態様として有効である。 The above describes in detail the embodiments of the present invention. The above-described embodiments merely illustrate specific examples of how the present invention may be put into practice. The content of the embodiments does not limit the technical scope of the present invention, and many design modifications, such as changing, adding, or deleting components, are possible within the scope of the inventive concept defined in the claims. A new embodiment with design modifications will combine the effects of the combined embodiments and modifications. In the above-described embodiments, content for which such design modifications are possible is emphasized by using notations such as "in this embodiment" or "in this embodiment," but design modifications are also permitted even in content without such notation. Any combination of the above-described components is also valid as an aspect of the present invention.
以下に本実施形態を、実施例を挙げて具体的に説明するが、本実施形態は実施例に何ら限定されるものではない。 The present embodiment will be specifically explained below using examples, but the present embodiment is not limited to these examples.
(実施例1)
<カソード-電解質膜複合体の作製>
電解質膜としてのN117(ケマーズ製、厚さ180μm)の片面に対して、カソード触媒層をスプレー塗布し、カソード-電解質膜複合体を得た。具体的には、PtRu/C触媒TEC61E54(田中貴金属工業株式会社製、触媒金属54重量%、Pt:Ru比(モル比)1:2)粉末に、アイオノマーNafion(登録商標)分散液DE2020(ケマーズ製)を添加した。このとき、アイオノマーNafion(登録商標)分散液DE2020(ケマーズ製)と、触媒中のカーボン重量との重量比が、乾燥後の重量で1:2となるように添加した。その後、必要に応じて、溶媒(1-プロパノールと水の混合液)を添加してインクを調製した。
得られたインクを、N117上にスプレー塗布した。このとき、触媒中のPtとRuとの合計重量が、カソード-電解質膜複合体における電極面積当たり1.0mg/cm2となるように塗布した。次いで、80℃にて、インク中の溶媒成分を乾燥させてカソード触媒層を得た。
カソード触媒層の表面に、電極面に合わせて切り抜いたカソード拡散層SIGRACET(登録商標)39BC(SGL Carbon社製)を貼合した。このとき、カソード触媒層の表面温度を測定するため、シースT熱電対(林電工株式会社製、D-ST6T-10-300)をカソード触媒層とカソード拡散層との間に挿入した。上記熱電対は、カソード室の入口付近、中央部、出口付近の3ヵ所に設置した。また、N117の中央部には、ピンホールを模した直径0.2mmの貫通孔を開けた。
Example 1
<Preparation of cathode-electrolyte membrane composite>
A cathode catalyst layer was spray-coated onto one side of an N117 (manufactured by Chemours, thickness 180 μm) electrolyte membrane to obtain a cathode-electrolyte membrane composite. Specifically, ionomer Nafion® dispersion DE2020 (manufactured by Chemours) was added to PtRu/C catalyst TEC61E54 (manufactured by Tanaka Kikinzoku Kogyo K.K., catalytic metal 54 wt %, Pt:Ru ratio (molar ratio) 1:2) powder. The weight ratio of ionomer Nafion® dispersion DE2020 (manufactured by Chemours) to the carbon weight in the catalyst was added so that the weight ratio after drying was 1:2. Thereafter, a solvent (a mixture of 1-propanol and water) was added as necessary to prepare an ink.
The resulting ink was sprayed onto N117 so that the total weight of Pt and Ru in the catalyst was 1.0 mg/ cm2 per electrode area of the cathode-electrolyte membrane composite. The solvent component in the ink was then dried at 80°C to obtain a cathode catalyst layer.
A cathode diffusion layer SIGRACET® 39BC (manufactured by SGL Carbon) cut to fit the electrode surface was laminated to the surface of the cathode catalyst layer. To measure the surface temperature of the cathode catalyst layer, a sheathed T thermocouple (manufactured by Hayashi Denko Co., Ltd., D-ST6T-10-300) was inserted between the cathode catalyst layer and the cathode diffusion layer. The thermocouples were installed at three locations: near the entrance, center, and exit of the cathode chamber. A 0.2 mm diameter through-hole simulating a pinhole was drilled in the center of the N117.
<アノードの作製>
アノード基板としてのエキスパンドメッシュ(短目方向中心間距離:3.5mm、長目方向中心間距離:6.0mm、板厚:1.0mm、刻み幅:1.1mm、開口率:42%)の表面に乾式ブラスト処理を行った後、20%硫酸水溶液中で洗浄した。その後、アノード基板表面を、アークイオンプレーティング装置と純チタン材のターゲットJIS1種チタン円板とを用いて、基板温度:150℃、真空度:1.0×10-2Torr、コーティング厚さ2μmにて被覆した。
得られたアノード基板に対して、四塩化イリジウム水溶液を塗布し、電気炉にて550℃の熱処理を施す操作を複数回繰返すことによりアノードを得た。このとき、酸化イリジウムによるアノード電極触媒層を、電極面積当たりのIr金属量換算で12g/m2となるよう形成したものをアノードとした。
<Preparation of anode>
The surface of an expanded mesh anode substrate (short mesh center distance: 3.5 mm, long mesh center distance: 6.0 mm, plate thickness: 1.0 mm, pitch width: 1.1 mm, opening ratio: 42%) was dry blasted and then washed in a 20% aqueous sulfuric acid solution. The anode substrate surface was then coated using an arc ion plating device and a pure titanium target JIS Class 1 titanium disk at a substrate temperature of 150°C, a vacuum of 1.0 × 10-2 Torr, and a coating thickness of 2 μm.
An aqueous solution of iridium tetrachloride was applied to the obtained anode substrate, and the substrate was subjected to a heat treatment at 550°C in an electric furnace. This process was repeated several times to obtain an anode. The anode had an iridium oxide anode electrode catalyst layer formed thereon in an amount of 12 g/ m2 in terms of the amount of Ir metal per electrode area.
<集電体の作製>
集電体として、厚さ0.3mmのTi板を加工して形成した、10mmピッチの平バネを並べた形状を有する弾性体を用いた。なお、当該弾性体の、アノードと接触する部分には、微量の白金層を形成した。
<Preparation of current collector>
The current collector was an elastic body made of flat springs arranged at a 10 mm pitch, which was made by processing a 0.3 mm thick Ti plate. A small amount of platinum layer was formed on the part of the elastic body that came into contact with the anode.
<電解槽の作製>
カソード-電解質膜複合体、アノードスペーサ(EPDMゴムシート)、アノード、集電体、及びエンドプレート(金メッキSUS板、厚さ1.0mm)をこの順に積層し、各層が押圧されて密着した電解槽を作製した。このとき、アノードスペーサの厚さ、即ち、電解質膜とアノードとの間のギャップは、0.05mmであった。
<Preparation of electrolytic cell>
An electrolytic cell was fabricated by laminating a cathode-electrolyte membrane composite, an anode spacer (EPDM rubber sheet), an anode, a current collector, and an end plate (gold-plated SUS plate, 1.0 mm thick) in this order, and pressing the layers together to form an intimate contact. The thickness of the anode spacer, i.e., the gap between the electrolyte membrane and the anode, was 0.05 mm.
<有機ハイドライド製造装置の作製>
得られた電解槽におけるカソード室に、カソード液としてトルエンを0.8mL/min/cm2の流量で流通させた。同様に、得られた電解槽におけるアノード室にアノード液として1mol/L希硫酸水溶液を0.8mL/min/cm2の流量で流通させた。このとき、アノード室内のアノード液の液面高さが、カソード電極の上端面の高さよりも高くなるように調整した。その後、電解電流が0.4A/cm2になるように制御して電解運転を実施した。
<Construction of organic hydride production apparatus>
Toluene was passed through the cathode chamber of the obtained electrolytic cell as the cathode fluid at a flow rate of 0.8 mL/min/ cm2 . Similarly, a 1 mol/L dilute sulfuric acid aqueous solution was passed through the anode chamber of the obtained electrolytic cell as the anode fluid at a flow rate of 0.8 mL/min/ cm2 . At this time, the liquid level of the anode fluid in the anode chamber was adjusted to be higher than the height of the upper end surface of the cathode electrode. Thereafter, electrolysis operation was performed while controlling the electrolysis current to 0.4 A/ cm2 .
上記の有機ハイドライド製造装置の電解運転を実施しているときのカソード触媒層表面の温度プロファイルの結果を図3に示す。 Figure 3 shows the temperature profile on the surface of the cathode catalyst layer during electrolysis operation of the organic hydride production equipment described above.
実施例1は、アノード室のアノード液の液面高さが、カソード電極の上端面の高さよりも高くなる構造であり、カソード電極がアノード液によって常に濡れた状態が維持されたため、セル温度の上昇が抑制された。 In Example 1, the liquid level of the anode fluid in the anode chamber was higher than the height of the upper surface of the cathode electrode, and the cathode electrode was kept constantly wet with the anode fluid, thereby suppressing an increase in cell temperature.
(比較例1)
比較例1は、アノード室内のアノード液の液面高さが、カソード電極の上端面の高さよりも低くなるように液量を調整したこと以外は、実施例1と同様に有機ハイドライド製造装置を作製し、温度プロファイルを測定した。その結果を図4に示す。
(Comparative Example 1)
In Comparative Example 1, an organic hydride manufacturing apparatus was fabricated in the same manner as in Example 1, except that the amount of the anolyte in the anode chamber was adjusted so that the liquid level was lower than the height of the upper end surface of the cathode electrode, and the temperature profile was measured. The results are shown in Figure 4.
比較例1は、アノード室内のアノード液の液面高さが、カソード電極の上端面の高さよりも低くなる構造であるため、カソード電極の一部は乾燥状態であった。電解質膜に生じたピンホールからリークされた酸素ガスと、カソード電極に付着していたトルエン及びカソード室に充填された水素ガスとの燃焼反応が生じた。 In Comparative Example 1, the liquid level of the anode fluid in the anode chamber was lower than the height of the upper surface of the cathode electrode, so part of the cathode electrode was dry. A combustion reaction occurred between oxygen gas leaking through a pinhole in the electrolyte membrane, toluene adhering to the cathode electrode, and hydrogen gas filled in the cathode chamber.
本実施の形態は、以下に記載する項目によって特定されてもよい。
[項目1]
電解質膜(20)と、
前記電解質膜(20)の一方側に配され、アノード液及びアノード電極(12)を収容するアノード室(16)と、
前記電解質膜(20)の他方側に配され、カソード電極(14)を収容するカソード室(18)と、
を有する電解槽(2)を備え、
前記アノード室(16)内の前記アノード液の液面高さは、前記カソード電極(14)の上端面の高さ以上である、有機ハイドライド製造装置(1)。
[項目2]
前記アノード室(16)は、前記アノード室(16)の上部に気体滞留部(17)を有する、項目1に記載の有機ハイドライド製造装置(1)。
[項目3]
前記気体滞留部(17)は、前記カソード電極(14)の上端面の高さよりも高い位置に設けられる、項目2に記載の有機ハイドライド製造装置(1)。
[項目4]
前記アノード室(16)は、前記アノード室(16)から排出される前記アノード液を検知する検知部(29)を有する、項目1又は項目2に記載の有機ハイドライド製造装置(1)。
[項目5]
前記検知部(29)が流量計である、項目4に記載の有機ハイドライド製造装置(1)。
[項目6]
前記検知部(29)によって検知される前記アノード液の液量が所定量未満である場合、前記有機ハイドライド製造装置(1)の稼働を停止するように制御する、項目4に記載の有機ハイドライド製造装置(1)。
[項目7]
前記アノード室(16)は、前記カソード電極(14)の上端面の高さよりも高い位置に設けられる第2アノード開口(28)を有する、項目1又は項目2に記載の有機ハイドライド製造装置(1)。
[項目8]
有機ハイドライド製造装置(1)と、電力供給装置(34)と、を備え、
前記有機ハイドライド製造装置(1)は、電解質膜(20)と、前記電解質膜(20)の一方側に配され、アノード液及びアノード電極(12)を収容するアノード室(16)と、前記電解質膜(20)の他方側に配され、カソード電極(14)を収容するカソード室(18)と、を有する電解槽(2)を有し、
前記アノード室(16)内の前記アノード液の液面高さは、前記カソード電極(14)の上端面の高さ以上である有機ハイドライド製造システム(3)。
[項目9]
前記電力供給装置(34)は、再生可能エネルギー由来の電力を前記有機ハイドライド製造装置の電源に供給する第1電力供給装置(341)、及び化石燃料由来の電力を前記有機ハイドライド製造装置の前記電源に供給する第2電力供給装置(342)の少なくとも一方を備える、項目8に記載の有機ハイドライド製造システム(3)。
[項目10]
前記第1電力供給装置(341)、及び第2電力供給装置(342)を備える、項目9に記載の有機ハイドライド製造システム(3)。
[項目11]
電解質膜(20)と、前記電解質膜(20)の一方側に配され、アノード液及びアノード電極(12)を収容するアノード室(16)と、前記電解質膜(20)の他方側に配され、カソード電極(14)を収容するカソード室(18)と、を有する電解槽(2)を備える有機ハイドライド製造装置(1)を用いて、有機ハイドライドを製造する有機ハイドライド製造方法であって、
前記アノード室(16)内の前記アノード液の液面高さを、前記カソード電極(14)の上端面の高さ以上に調整する、有機ハイドライド製造方法。
This embodiment may be specified by the following items.
[Item 1]
an electrolyte membrane (20);
an anode chamber (16) disposed on one side of the electrolyte membrane (20) and containing an anolyte and an anode electrode (12);
a cathode chamber (18) disposed on the other side of the electrolyte membrane (20) and accommodating a cathode electrode (14);
an electrolytic cell (2) having
The organic hydride manufacturing apparatus (1) has a liquid level of the anolyte in the anode chamber (16) that is equal to or higher than the height of the upper end surface of the cathode electrode (14).
[Item 2]
2. The organic hydride manufacturing apparatus (1) according to item 1, wherein the anode chamber (16) has a gas retention section (17) in an upper portion of the anode chamber (16).
[Item 3]
3. The organic hydride manufacturing apparatus (1) according to item 2, wherein the gas retention section (17) is provided at a position higher than the height of an upper end surface of the cathode electrode (14).
[Item 4]
3. The organic hydride manufacturing apparatus (1) according to item 1 or 2, wherein the anode chamber (16) has a detection unit (29) that detects the anolyte discharged from the anode chamber (16).
[Item 5]
5. The organic hydride manufacturing apparatus (1) according to item 4, wherein the detection unit (29) is a flow meter.
[Item 6]
5. The organic hydride manufacturing apparatus (1) according to item 4, wherein, when the amount of the anolyte detected by the detection unit (29) is less than a predetermined amount, control is performed to stop operation of the organic hydride manufacturing apparatus (1).
[Item 7]
3. The organic hydride manufacturing apparatus (1) according to claim 1, wherein the anode chamber (16) has a second anode opening (28) provided at a position higher than the height of the upper end surface of the cathode electrode (14).
[Item 8]
The apparatus comprises an organic hydride manufacturing apparatus (1) and a power supply device (34),
The organic hydride manufacturing apparatus (1) includes an electrolytic cell (2) having an electrolyte membrane (20), an anode chamber (16) disposed on one side of the electrolyte membrane (20) and containing an anolyte and an anode electrode (12), and a cathode chamber (18) disposed on the other side of the electrolyte membrane (20) and containing a cathode electrode (14);
The organic hydride production system (3) has a liquid level of the anolyte in the anode chamber (16) that is equal to or higher than the height of the upper end surface of the cathode electrode (14).
[Item 9]
Item 9. The organic hydride production system (3) according to Item 8, wherein the power supply device (34) comprises at least one of a first power supply device (341) that supplies electricity derived from renewable energy to a power source of the organic hydride production apparatus, and a second power supply device (342) that supplies electricity derived from fossil fuels to the power source of the organic hydride production apparatus.
[Item 10]
10. The organic hydride manufacturing system (3) according to item 9, comprising the first power supply device (341) and the second power supply device (342).
[Item 11]
A method for producing an organic hydride using an organic hydride producing apparatus (1) including an electrolytic cell (2) having an electrolyte membrane (20), an anode chamber (16) disposed on one side of the electrolyte membrane (20) and accommodating an anolyte and an anode electrode (12), and a cathode chamber (18) disposed on the other side of the electrolyte membrane (20) and accommodating a cathode electrode (14), comprising:
The method for producing an organic hydride includes adjusting the liquid level of the anolyte in the anode chamber (16) to be equal to or higher than the height of the upper end surface of the cathode electrode (14).
本出願は、2024年4月26日に日本国特許庁に出願した特願2024-072860号に基づいて優先権を主張し、前記出願に記載された全ての内容を援用する。 This application claims priority based on Patent Application No. 2024-072860, filed with the Japan Patent Office on April 26, 2024, and incorporates the entire contents of said application by reference.
1 有機ハイドライド製造装置
2 電解槽
3 有機ハイドライド製造システム
4 電源
8 カソード液供給装置
10 制御装置
12 アノード電極
14 カソード電極
16 アノード室
18 カソード室
20 電解質膜
REFERENCE SIGNS LIST 1 Organic hydride production apparatus 2 Electrolytic cell 3 Organic hydride production system 4 Power supply 8 Catholyte supply device 10 Control device 12 Anode electrode 14 Cathode electrode 16 Anode chamber 18 Cathode chamber 20 Electrolyte membrane
Claims (11)
前記電解質膜の一方側に配され、アノード液及びアノード電極を収容するアノード室と、
前記電解質膜の他方側に配され、カソード電極を収容するカソード室と、
を有する電解槽を備え、
前記アノード室内の前記アノード液の液面高さは、前記カソード電極の上端面の高さ以上である、有機ハイドライド製造装置。 an electrolyte membrane;
an anode chamber disposed on one side of the electrolyte membrane and containing an anode solution and an anode electrode;
a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode;
an electrolytic cell having
The organic hydride manufacturing apparatus, wherein the liquid level of the anolyte in the anode chamber is equal to or higher than the height of the upper end surface of the cathode electrode.
前記有機ハイドライド製造装置は、電解質膜と、前記電解質膜の一方側に配され、アノード液及びアノード電極を収容するアノード室と、前記電解質膜の他方側に配され、カソード電極を収容するカソード室と、を有する電解槽を有し、
前記アノード室内の前記アノード液の液面高さは、前記カソード電極の上端面の高さ以上である、有機ハイドライド製造システム。 An organic hydride manufacturing apparatus and a power supply apparatus,
the organic hydride manufacturing apparatus includes an electrolytic cell having an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anolyte and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode;
The organic hydride manufacturing system, wherein the liquid level of the anolyte in the anode chamber is equal to or higher than the height of the upper end surface of the cathode electrode.
前記アノード室内の前記アノード液の液面高さは、前記カソード電極の上端面の高さ以上に調整する、有機ハイドライド製造方法。 A method for producing an organic hydride using an organic hydride producing apparatus including an electrolytic cell having an electrolyte membrane, an anode chamber disposed on one side of the electrolyte membrane and accommodating an anolyte and an anode electrode, and a cathode chamber disposed on the other side of the electrolyte membrane and accommodating a cathode electrode, the method comprising:
The method for producing an organic hydride, wherein the liquid level of the anolyte in the anode chamber is adjusted to be equal to or higher than the height of the upper end surface of the cathode electrode.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2024-072860 | 2024-04-26 | ||
| JP2024072860 | 2024-04-26 |
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| Publication Number | Publication Date |
|---|---|
| WO2025225345A1 true WO2025225345A1 (en) | 2025-10-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2025/013827 Pending WO2025225345A1 (en) | 2024-04-26 | 2025-04-04 | Organic hydride production device, organic hydride production system, and organic hydride production method |
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| Country | Link |
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| WO (1) | WO2025225345A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021188085A (en) * | 2020-05-28 | 2021-12-13 | Eneos株式会社 | Organic hydride production apparatus and production method of membrane electrode assembly |
| WO2022092257A1 (en) * | 2020-10-30 | 2022-05-05 | Eneos株式会社 | Cathode catalyst layer, organic hydride production device, and method for preparing cathode catalyst ink |
| WO2022118933A1 (en) * | 2020-12-04 | 2022-06-09 | Eneos株式会社 | Organic hydride production system, control device for organic hydride production system, and control method for organic hydride production system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021188085A (en) * | 2020-05-28 | 2021-12-13 | Eneos株式会社 | Organic hydride production apparatus and production method of membrane electrode assembly |
| WO2022092257A1 (en) * | 2020-10-30 | 2022-05-05 | Eneos株式会社 | Cathode catalyst layer, organic hydride production device, and method for preparing cathode catalyst ink |
| WO2022118933A1 (en) * | 2020-12-04 | 2022-06-09 | Eneos株式会社 | Organic hydride production system, control device for organic hydride production system, and control method for organic hydride production system |
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