WO2011122155A1 - Dispositif de fabrication d'hydrure organique - Google Patents

Dispositif de fabrication d'hydrure organique Download PDF

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Publication number
WO2011122155A1
WO2011122155A1 PCT/JP2011/053478 JP2011053478W WO2011122155A1 WO 2011122155 A1 WO2011122155 A1 WO 2011122155A1 JP 2011053478 W JP2011053478 W JP 2011053478W WO 2011122155 A1 WO2011122155 A1 WO 2011122155A1
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WIPO (PCT)
Prior art keywords
catalyst layer
hydride
polymer electrolyte
solid polymer
metal catalyst
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Ceased
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PCT/JP2011/053478
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English (en)
Japanese (ja)
Inventor
貴之 平重
敬郎 石川
昌俊 杉政
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Hitachi Ltd
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Hitachi Ltd
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Priority to JP2012508137A priority Critical patent/JP5705214B2/ja
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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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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

Definitions

  • the present invention relates to an organic hydride production apparatus for electrochemically producing organic hydride.
  • Hydrogen fuel has a low environmental impact because it is the only substance that is discharged when fuel is consumed and does not emit carbon dioxide.
  • hydrogen is a gas at normal temperature and pressure, transportation, storage, and supply systems are major issues.
  • organic hydride systems using hydrocarbons such as cyclohexane, methylcyclohexane, and decalin have attracted attention as hydrogen storage methods that are excellent in safety, transportability, and storage capacity. Since these hydrocarbons are liquid at room temperature, they are excellent in transportability.
  • toluene and methylcyclohexane are cyclic hydrocarbons having the same carbon number
  • toluene is an unsaturated hydrocarbon in which the bonds between hydrocarbons are double bonds
  • methylcyclohexane has double bonds. It is a saturated hydrocarbon that does not have.
  • Methylcyclohexane is obtained by hydrogenation reaction of toluene, and toluene is obtained by dehydrogenation reaction of methylcyclohexane. That is, hydrogen can be stored and supplied by utilizing the hydrogenation reaction and dehydrogenation reaction of these hydrocarbons.
  • the current process is a two-stage process in which hydrogen is generated in a water electrolysis apparatus or the like, and hydrogen and toluene are reacted in a hydrogen addition reaction apparatus to generate organic hydride.
  • Patent Document 1 a technique for producing an organic hydride in a single stage using a single apparatus has been disclosed (for example, Patent Document 1).
  • the technique disclosed in Patent Document 1 is to produce an organic hydride electrochemically.
  • metal catalysts are arranged on both sides of a hydrogen ion permeable electrolyte membrane that selectively transmits hydrogen ions, water or steam is supplied to one side, and a hydride is supplied to the other side.
  • Organic hydrides are produced by causing hydrogen addition reaction between hydrogen ions generated by electrolysis of water or water vapor on the anode side and hydrides on the cathode side.
  • the electrode reaction is considered to occur at a three-phase interface where three of metal catalyst / proton conductive solid polymer electrolyte / reactive substance (hydrogenated substance) are in contact.
  • electrons and protons must be supplied to or moved from the metal catalyst, and therefore a network connecting the metal catalyst and the solid polymer electrolyte is required. is there.
  • An object of the present invention is to provide an organic hydride manufacturing apparatus that is small and efficient in an electrochemical hydride manufacturing apparatus.
  • the present inventors have conducted intensive research, and as a result, a high-performance electrode can be obtained by forming a three-phase interface and a layer in which a solid polymer electrolyte and a metal catalyst network are formed in advance on the electrolyte membrane.
  • the catalyst layer has a structure in which a carrier carrying a metal catalyst or a metal catalyst is in a matrix appropriately mixed with a proton-conductive solid polymer electrolyte, and these layers have a high proton-conductive solid content. It is formed on the front and back surfaces of the molecular electrolyte membrane, respectively.
  • the organic hydride production apparatus of the present invention includes a membrane electrode assembly in which a cathode catalyst layer for reducing a hydride and an anode catalyst layer for oxidizing water are disposed so as to sandwich a proton conductive solid polymer electrolyte membrane.
  • the cathode catalyst layer includes a carrier supporting the first metal catalyst, and the anode catalyst layer includes a non-carbon carrier supporting the second metal catalyst.
  • a small and efficient organic hydride manufacturing apparatus can be provided in an apparatus for electrochemically manufacturing an organic hydride.
  • FIG. 1 It is a figure which shows one Example of the organic hydride manufacturing apparatus of this invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the membrane electrode assembly (MEA) of the organic hydride manufacturing apparatus of this invention, Comprising: (a) is the top view which looked at MEA from the cathode side, (b) is the DE section in (a). Sectional drawing, (c) is an F section enlarged view in (b), and (d) is an G section enlarged view in (b).
  • FIG. 7 is a diagram showing a membrane electrode assembly of a conventional organic hydride manufacturing apparatus, where (a) is a plan view of the MEA viewed from the cathode side, (b) is a cross-sectional view taken along the line DE in (a), (c) is the F section enlarged view in (b). It is a graph which shows load voltage (V) and current density (mA / cm ⁇ 2 >) regarding one Example of the organic hydride manufacturing apparatus of this invention. It is a graph which shows the conversion rate (%) from the load voltage (V) and toluene to methylcyclohexane regarding one Example of the organic hydride manufacturing apparatus of this invention.
  • the present invention relates to an apparatus for electrochemically producing organic hydride, wherein a catalyst layer having a structure in which a proton-conducting solid polymer electrolyte and a carrier supporting a metal catalyst or a metal catalyst are mixed in a moderately mixed manner, It has the electrode structure formed in the front and back of a proton conductive solid polymer electrolyte membrane, It is characterized by the above-mentioned.
  • the water is electrolyzed in the anode by supplying a voltage between the anode and the cathode while supplying at least one of water and water vapor to the anode and supplying the hydride to the cathode.
  • a hydrogenation reaction to the hydride is caused to generate an organic hydride.
  • FIG. 1 shows an example of the organic hydride manufacturing apparatus of the present invention.
  • an anode catalyst layer 13 is joined to one surface of a solid polymer electrolyte membrane 12 and a cathode catalyst layer 14 is joined to the other surface, and an integrated membrane electrode assembly (MEA: Membrane). Electrode Assembly) is sandwiched between a gas diffusion layer 15 and a separator 11 in which a gas flow path is formed. A gasket 16 for gas sealing is inserted between the pair of separators 11.
  • MEA Membrane
  • the separator 11 has conductivity, and the material is preferably a dense graphite plate, a carbon plate formed by molding a carbon material such as graphite or carbon black with a resin, or a material having excellent corrosion resistance such as stainless steel or titanium. Further, it is also desirable to plate the surface of the separator 11 with a noble metal or to apply a surface treatment with a conductive paint having excellent corrosion resistance and heat resistance.
  • a groove serving as a reaction gas or liquid channel is formed on the surface of the separator 11 facing the anode catalyst layer 13 and the cathode catalyst layer 14. Water or water vapor is supplied to the flow channel of the anode-side separator 11. Water or water vapor flowing through the flow channel is supplied to the anode catalyst layer 13 through the gas diffusion layer 15.
  • a hydride is supplied to the cathode-side separator 11.
  • the hydride flowing through the flow channel is supplied to the cathode catalyst layer 14 through the gas diffusion layer 15.
  • a liquid hydride may be supplied as it is, or a vapor hydride using He gas or N 2 gas as a carrier may be supplied.
  • the gas diffusion layer 15 is provided to uniformly supply the reactant (gas or liquid) supplied to the flow path of the separator 11 into the surface of the catalyst layer, and has a breathable base such as carbon paper or carbon cloth. Is used. In particular, those obtained by subjecting these substrates to a water repellent treatment are preferable.
  • the gasket 16 is insulative, and any material can be used as long as it is resistant to hydrogen, hydride, and organic hydride, and the permeation thereof is small and the confidentiality is maintained.
  • any material can be used as long as it is resistant to hydrogen, hydride, and organic hydride, and the permeation thereof is small and the confidentiality is maintained.
  • the organic hydride apparatus of this embodiment is an apparatus for electrochemically producing organic hydride by the above reaction.
  • FIG. 2 shows an electrode portion of the organic hydride manufacturing apparatus of the present embodiment.
  • 2A is a plan view of the MEA 20 as viewed from the cathode side, in which the cathode catalyst layer 22 is formed on the surface of the solid polymer electrolyte membrane 21 and the anode catalyst layer 23 (see FIG. 2B) is formed on the back surface.
  • FIG. 4B is a cross-sectional view taken along the line DE in FIG. 4A
  • FIG. 4C is an enlarged view of the F part in FIG. 2B
  • the cathode and the anode are formed as dense catalyst layers above and below the solid polymer electrolyte membrane 21, respectively.
  • a reduction reaction of the hydride occurs in the cathode catalyst layer 22 .
  • a proton-conducting solid polymer electrolyte 26 may include a carrier 25 carrying a metal catalyst 24. The carriers 25 are bonded to each other by a solid polymer electrolyte 26.
  • the metal catalyst 24 in the cathode catalyst layer 22 has a network structure connected to each other through the carrier 25, and forms an electron path necessary for the reaction of the formula (2).
  • the solid polymer electrolyte 26 in the catalyst layer also has a connected network structure, and forms a passage for protons necessary for the reaction of the formula (2).
  • the electrode reaction is carried out at the three-phase interface where the metal catalyst 24 on the carrier 25 contacts the electrolyte and the reactant.
  • the electrode of this embodiment since the passage of protons is formed by the solid polymer electrolyte 26, a three-phase interface is also formed in the metal catalyst 24 that is not in direct contact with the solid polymer electrolyte membrane 21. Therefore, it has a structure in which many metal catalysts 24 can contribute to the electrode reaction.
  • an oxidation reaction of water occurs.
  • a metal catalyst 24 (corresponding to the second metal catalyst in the claims) 24 that oxidizes water to generate protons, and a proton And a conductive solid polymer electrolyte 26.
  • the metal catalyst 24 in the anode catalyst layer 23 has a network structure connected to each other, and forms a path for electrons necessary for the reaction of the formula (1).
  • the solid polymer electrolyte 26 in the catalyst layer also has a connected network structure, and forms a passage for protons necessary for the reaction of the formula (1).
  • the electrode reaction is performed at the three-phase interface where the metal catalyst 24 contacts the electrolyte and the reactant.
  • the electrode of this embodiment since the passage of protons is formed by the solid polymer electrolyte 26, a three-phase interface is also formed in the metal catalyst 24 that is not in direct contact with the solid polymer electrolyte membrane 21. Therefore, it has a structure in which many metal catalysts 24 can contribute to the electrode reaction.
  • the anode catalyst layer 23 of the organic hydride manufacturing apparatus of the present embodiment is characterized by including only the metal catalyst 24.
  • the reactions of the formulas (1) and (2) occur when a voltage of 1.2 V or more is applied between the anode and the cathode.
  • carbon is used as the carrier in the anode catalyst layer 23, the carbon may burn or the like due to an oxidation reaction when a voltage of 1.2 V or higher is applied. Therefore, the anode catalyst layer 23 of the organic hydride manufacturing apparatus of this embodiment is characterized in that no carbon is contained. Since the anode catalyst layer 23 does not need to contain carbon, the anode catalyst layer 23 may include a metal catalyst 24 and a non-carbon support (not shown in FIG. 2D) carrying the metal catalyst 24. Needless to say.
  • FIG. 3 shows a membrane electrode assembly (MEA) of a conventional organic hydride manufacturing apparatus.
  • 3A is a plan view of the MEA 30 as viewed from the cathode side, in which the cathode catalyst layer 32 is formed on the surface of the solid polymer electrolyte membrane 31 and the anode catalyst layer 33 (see FIG. 3B) is formed on the back surface.
  • FIG. 4B is a cross-sectional view taken along the line DE in FIG. 4A
  • FIG. 4C is an enlarged view of the F part in FIG.
  • the MEA 30 directly forms a catalyst carrier 35 such as carbon carrying a metal catalyst 34 on the surface of the solid polymer electrolyte membrane 31, and FIG.
  • a catalyst carrier 35 such as carbon carrying a metal catalyst 34
  • the solid polymer electrolyte 26 is not included like the MEA 20 used in the present invention illustrated in FIG. Therefore, the metal catalyst 34 not in direct contact with the solid polymer electrolyte membrane 31 has a structure that cannot contribute to the electrode reaction. That is, as shown in FIG. 3C, in the MEA 30 of the conventional organic hydride manufacturing apparatus, the catalyst that contributes to the electrode reaction is only the metal catalyst 34 that is in direct contact with the solid polymer electrolyte membrane 31. Therefore, the number of three-phase interfaces is small, the number of catalysts contributing to the reaction is limited, and the formation of a catalyst network structure is also small. As a result, it is difficult to obtain high energy efficiency, and the production efficiency of organic hydride is deteriorated.
  • MEA 20 used in the present invention can be manufactured by the following method. First, a carrier 25 supporting a metal catalyst 24 such as platinum, a solid polymer electrolyte 26, and a cathode catalyst paste in which a solvent for dissolving the solid polymer electrolyte 26 is added and mixed sufficiently; a metal catalyst 24; a solid polymer electrolyte; Then, a solvent for dissolving the solid polymer electrolyte 26 is added to prepare a fully mixed anode catalyst paste. Each of these pastes is sprayed onto a release film such as a polyfluoroethylene (PTFE) film by a spray drying method, etc., dried at 80 ° C.
  • PTFE polyfluoroethylene
  • the cathode catalyst layer 22 and the anode catalyst layer 23 are formed. To do. Next, by using the cathode catalyst layer 22 and the anode catalyst layer 23, the solid polymer electrolyte membrane 21 is sandwiched from both sides so as to be centered and bonded by a hot press method, and the release film (PTFE) is peeled off, The MEA 20 used in the present invention can be manufactured.
  • a solvent used in preparing the cathode catalyst paste and the anode catalyst paste a solution (221 solution) in which 1-propanol, 2-propanol and water are mixed at a mass ratio of 2: 2: 1 is preferably mentioned. Can do.
  • the anode catalyst paste may include a non-carbon support carrying the metal catalyst 24 instead of the metal catalyst 24.
  • the carrier 25 supporting the metal catalyst 24 such as platinum, the solid polymer electrolyte 26, and a solvent for dissolving the solid polymer electrolyte 26 are sufficiently added.
  • the mixed cathode catalyst paste, the metal catalyst 24, the solid polymer electrolyte 26, and the anode catalyst paste sufficiently mixed by adding a solvent for dissolving the solid polymer electrolyte 26 are directly solid polymer electrolyte membranes by a spray drying method or the like. It can also be produced by spraying on 21.
  • the anode catalyst paste may contain the non-carbon support
  • Examples of the organic polymer constituting the solid polymer electrolyte membrane 21 include perfluorocarbon sulfonic acid, polystyrene, polyether ketone, polyether ether ketone, polysulfone, polyether sulfone, other engineering plastic materials, sulfonic acid groups, A proton donor such as a phosphonic acid group or a carboxyl group that is immobilized by doping or chemically bonding can be used. In addition, it is also desirable to improve the material stability by forming a crosslinked structure or partially fluorinating the material.
  • a polymer material exhibiting proton conductivity is used for the solid polymer electrolyte 26 contained in the catalyst layer.
  • sulfonated or alkylenesulfonated typified by perfluorocarbon-based sulfonic acid resin or polyperfluorostyrene-based sulfonic acid resin.
  • Fluorinated polymers and polystyrenes include polysulfones, polyether sulfones, polyether ether sulfones, polyether ether ketones, and materials obtained by introducing a proton donor such as a sulfonic acid group into a hydrocarbon polymer.
  • the above-mentioned composite electrolyte of organic polymer and metal oxide hydrate can also be used.
  • the solid polymer electrolyte 26 can also be obtained by dissolving a part of the solid polymer electrolyte membrane 21 using a solvent that can dissolve the solid polymer electrolyte membrane 21.
  • a catalyst material having a hydrogen addition action can be used as the metal catalyst 24 used in the present invention.
  • metals such as Ni, Pd, Pt, Rh, Ir, Re, Ru, Mo, W, V, Os, Cr, Co, and Fe, and alloy catalysts thereof can be used.
  • the hydrogenation catalyst is preferably finely divided in order to reduce the cost by reducing the metal catalyst 24 and increase the reaction surface area. Further, in order to prevent a decrease in specific surface area due to aggregation of fine particles, it may be supported on a carrier described later.
  • the method for producing the catalyst is not particularly limited, such as a coprecipitation method, a thermal decomposition method, and an electroless plating method.
  • carbon materials such as activated carbon, carbon nanotubes, and graphite, and alumina silicate such as silica, alumina, and zeolite can be used.
  • a non-carbon support (not shown) is used as the support that is contained in the anode catalyst layer 23 and can support the metal catalyst 24.
  • alumina silicate such as silica, alumina and zeolite can be used.
  • the anode catalyst layer 23 may use only the metal catalyst 24 without using a non-carbon carrier.
  • Hydrogen can be stored by adding hydrogen to the double bond between these carbon atoms.
  • Nafion (registered trademark) manufactured by DuPont was used as the electrolyte membrane.
  • the cathode catalyst layer was formed by directly applying a catalyst paste to Nafion using a spray coater.
  • the cathode catalyst layer was applied to Nafion in the following order.
  • ⁇ Nafion was placed on the hot plate of the substrate and fixed by suction.
  • the temperature of the hot plate was 50 ° C.
  • a mask was applied from above, and the cathode catalyst paste was applied with a spray coater (manufactured by Nordson).
  • the application conditions were a liquid pressure of 0.01 MPa, a swirl pressure of 0.15 MPa, an atomization pressure of 0.15 MPa, a gun / substrate distance of 60 mm, and a substrate temperature of 50 ° C.
  • the amount of the metal catalyst in the cathode catalyst layer was 0.4 mg ⁇ cm ⁇ 2 in terms of the amount of Pt per unit area.
  • an anode catalyst layer was formed on the back surface.
  • the anode catalyst layer was formed by a transfer method.
  • an anode catalyst paste was prepared.
  • an anode catalyst paste a mixture of platinum black HiSPEC1000 (manufactured by Johnson Matthey), 5% by mass Nafion solution and 221 solution at a mass ratio of 1: 1.11: 2.22 was used. It was apply
  • An anode catalyst layer coated on a Teflon (registered trademark) sheet was formed on the surface of Nafion by thermal transfer using a hot press (SA-401-M manufactured by Tester Sangyo Co., Ltd.).
  • the hot press pressure was 3.65 MPa (37.2 kgf ⁇ cm ⁇ 2 )
  • the hot press temperature was 120 ° C.
  • the hot press time was 2 minutes.
  • the amount of the metal catalyst in the anode catalyst layer was 4.8 mg ⁇ cm ⁇ 2 in terms of the amount of Pt per unit area.
  • the fabricated MEA was incorporated into the organic hydride manufacturing apparatus shown in FIG.
  • the cell resistance was 200 m ⁇ .
  • FIG. 4 shows the current value with respect to the load voltage.
  • a load of 1.6 V or higher was applied, current flowed and the reaction proceeded.
  • the voltage was increased to 2.2 V, the current increased and the reaction proceeded.
  • the cathode exhaust gas was analyzed by gas chromatography, toluene and methylcyclohexane were detected.
  • FIG. 5 shows the conversion rate (%) from toluene to methylcyclohexane calculated from the peak intensity of gas chromatography. The higher the voltage, the higher the conversion rate, and the maximum value under this condition was 60% when a load of 2.2 V was applied.
  • the produced MEA was incorporated into the organic hydride production apparatus shown in FIG.
  • the cell resistance was 950 m ⁇ .
  • the reason why the cell resistance is larger than in Example 1 is that a network between the catalysts is not formed.
  • FIG. 6 shows the current value with respect to the load voltage. The current value was smaller than that in Example 1. This may be because the resistance is large or the formation of the three-phase interface is small.
  • FIG. 7 shows the conversion (%) from toluene to methylcyclohexane. The maximum value under this condition was 12% when a load of 2.2 V was applied.
  • Example 2 A cathode catalyst layer was formed under the same conditions and in the same manner as in Example 1.
  • a platinum-supported carbon catalyst was used for the anode catalyst layer as well as the cathode catalyst layer.
  • the production conditions for the anode catalyst paste were the same as the production conditions for the cathode catalyst paste of Example 1.
  • the produced MEA was incorporated into the organic hydride production apparatus of FIG. 1 and a hydrogen addition reaction test on toluene was performed under the same conditions as in Example 1.
  • the cell resistance was 180 m ⁇ .
  • a voltage was applied between the anode and the cathode, the drainage from the anode became black and cloudy at 1.8 V or more. This is presumably because the carbon used as the support for the anode catalyst layer was oxidized. It was found that the reaction of the formula (1) does not occur in the anode of Comparative Example 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention concerne un dispositif compact et efficace pour la fabrication d'un hydrure organique. Le dispositif de fabrication d'un hydrure organique comprend : un ensemble d'électrodes de membrane disposé de telle manière qu'une couche (14) de catalyseur cathodique qui désoxyde la matière à hydrogéner et une couche (13) catalyseur anodique qui oxyde l'eau enferment entre elles un film d'électrolyte polymère solide conducteur de protons ; un composant qui fournit la matière à hydrogéner à la couche (14) catalyseur cathodique ; et un composant qui fournit de l'eau ou de la vapeur d'eau à la couche (13) catalyseur anodique. La couche (14) catalyseur cathodique comprend un premier catalyseur métallique qui désoxyde la matière à hydrogéner et produit un hydrure et un film d'électrolyte polymère solide conducteur de protons. La couche (13) catalyseur anodique comprend un second catalyseur métallique qui oxyde l'eau et produit des protons et un film d'électrolyte polymère solide conducteur de protons.
PCT/JP2011/053478 2010-03-31 2011-02-18 Dispositif de fabrication d'hydrure organique Ceased WO2011122155A1 (fr)

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WO2013111585A1 (fr) * 2012-01-24 2013-08-01 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique et procédé de production d'un composé aromatique hétérocyclique contenant de l'hydrure d'azote ou un composé d'hydrocarbure aromatique
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WO2013145782A1 (fr) * 2012-03-29 2013-10-03 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique, et procédé de production de produit hydrogéné de composé hydrocarbure aromatique ou de composé aromatique hétérocyclique contenant de l'azote
WO2013187066A1 (fr) * 2012-06-12 2013-12-19 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique et procédé de génération de produit hydrogéné de composé hydrocarboné aromatique ou de composé aromatique hétérocyclique azoté
WO2014156125A1 (fr) * 2013-03-29 2014-10-02 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique et procédé de production d'un produit hydrogéné d'un composé aromatique
WO2014156126A1 (fr) * 2013-03-29 2014-10-02 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique et procédé de production d'un produit hydrogéné de composé aromatique
WO2014192089A1 (fr) * 2013-05-29 2014-12-04 株式会社日立製作所 Dispositif pour produire un hydrure organique
WO2015015769A1 (fr) * 2013-07-30 2015-02-05 Ｊｘ日鉱日石エネルギー株式会社 Appareil de réduction électrochimique et procédé de préparation d'un composé aromatique hydrogéné
WO2015029361A1 (fr) * 2013-08-30 2015-03-05 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique et procédé de production d'un composé aromatique hydrogéné
WO2015029367A1 (fr) * 2013-08-30 2015-03-05 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique
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