US20140144774A1 - Device for manufacturing organic hydride - Google Patents

Device for manufacturing organic hydride Download PDF

Info

Publication number
US20140144774A1
US20140144774A1 US13/817,333 US201113817333A US2014144774A1 US 20140144774 A1 US20140144774 A1 US 20140144774A1 US 201113817333 A US201113817333 A US 201113817333A US 2014144774 A1 US2014144774 A1 US 2014144774A1
Authority
US
United States
Prior art keywords
catalyst layer
water
organic hydride
manufacturing
catalytic metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/817,333
Other languages
English (en)
Inventor
Takayuki Hirashige
Takao Ishikawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Assigned to HITACHI, LTD. reassignment HITACHI, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ISHIKAWA, TAKAO, HIRASHIGE, TAKAYUKI
Publication of US20140144774A1 publication Critical patent/US20140144774A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C25B9/10—
    • 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
    • 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 a device for electrochemically manufacturing an organic hydride.
  • Hydrogen fuel does not impose a large burden on the environment since a substance discharged when the fuel is consumed is only water and no carbon dioxide is discharged.
  • hydrogen which is a gas at a normal temperature and a normal pressure, has disadvantages about transporting, storing and supplying systems thereof.
  • hydrocarbons such as cyclohexane, methylcyclohexane and decalin as a hydrogen-storing method excellent in safety, transporting performance, and storing capacity.
  • hydrocarbons are liquid at a normal temperature and excellent in transportability.
  • toluene and methylcyclohexane are cyclic hydrocarbons having carbon atoms in the same number.
  • toluene is an unsaturated hydrocarbon in which bonds between hydrocarbon atoms are double bonds while methylcyclohexane is a saturated hydrocarbon having no double bond.
  • the present process has two steps of generating hydrogen in, for example, a water electrolysis device, and then reacting the hydrogen with toluene in a hydrogenation reaction device to generate an organic hydride.
  • the hydrogen is in a gas form from the production of hydrogen to the hydrogenation reaction, causing problems about the storage and transportation thereof.
  • a hydrogen producing device and a hydrogenation device are built up to be adjacent to each other, these problems will be solved.
  • another problem is caused about building and running costs, and total energy efficiency will be lowered.
  • the devices are made large in size, so that a place where the devices are installed is restricted.
  • an organic hydride is manufactured by arranging metal catalysts onto both sides of a hydrogen-ion-permeable solid polymer electrolyte membrane, through which hydrogen ions are selectively permeated, supplying water or water vapor to one of the sides, supplying a substance to be hydrogenated to the other side, and using hydrogen ions generated by electrolysis of the water or water vapor on the anode side to cause hydrogenation reaction with the substance to be hydrogenated on the cathode side to manufacture an organic hydride.
  • An object of the present invention is to provide a small-scale and highly-efficient device for electrochemically manufacturing an organic hydride.
  • the electrodes in the present invention are characterized in that catalyst layers have a matrix structure in which metal-catalyst supporting carbon or a metal catalyst is suitably intermingled with a proton-conductive solid polymer electrolyte, and the catalyst layers are formed on the front and back of a proton-conductive solid polymer electrolyte membrane which includes a water-blocking layer.
  • the device for manufacturing an organic hydride of the present invention includes a membrane electrode assembly including a cathode catalyst layer that reduces a substance to be hydrogenated, an anode catalyst layer that oxidizes water, and a proton-conductive solid polymer electrolyte membrane disposed between the cathode catalyst layer and the anode catalyst layer, the membrane including a water-blocking layer from passing through, a member that supplies the substance to be hydrogenated to the cathode catalyst layer, and a member that supplies water or water vapor to the anode catalyst layer.
  • the cathode catalyst layer includes a catalytic metal that reduces the substance to be hydrogenated to react into a hydride, a supporter supporting the catalytic metal, and a proton-conductive solid polymer electrolyte.
  • the anode catalyst layer includes a catalytic metal that oxidizes water to react into protons, a supporter supporting the catalytic metal, and a proton-conductive solid polymer.
  • a small-scale and highly-efficient device for electrochemically manufacturing an organic hydride can be provided.
  • FIG. 1 is a view illustrating a device for manufacturing an organic hydride or a fuel cell in accordance with an embodiment of the present invention
  • FIG. 2 is a view illustrating a membrane electrode assembly in the present invention
  • FIG. 3 is a view illustrating a membrane electrode assembly in a conventional technique
  • FIG. 4 is a view showing an embodiment of the device for manufacturing an organic hydride of the present invention.
  • FIG. 5 is a view showing an embodiment of the device for manufacturing an organic hydride of the present invention.
  • FIG. 6 is a view showing an example of the device for manufacturing an organic hydride according to a conventional technique.
  • FIG. 7 is a view showing an example of the device for manufacturing an organic hydride according to a conventional technique.
  • a device for electrochemically manufacturing an organic hydride of the present invention has an electrode structure that a catalyst layer, the layer having a matrix structure in which a proton-conductive solid polymer electrolyte and a metal-catalyst supporting carbon or metal catalyst are suitably intermingled with each other, is formed on the front and back of a proton-conductive solid polymer electrolyte membrane, the membrane including a water-blocking layer.
  • a catalyst layer the layer having a matrix structure in which a proton-conductive solid polymer electrolyte and a metal-catalyst supporting carbon or metal catalyst are suitably intermingled with each other, is formed on the front and back of a proton-conductive solid polymer electrolyte membrane, the membrane including a water-blocking layer.
  • a substance to be hydrogenated is supplied to the cathode.
  • a voltage is applied to between the anode and the cathode to cause the electrolysis reaction of water in the anode and hydrogenation reaction of the substance to
  • FIG. 1 illustrates a device for manufacturing an organic hydride in accordance with an embodiment of the present invention.
  • the device for manufacturing an organic hydride of the present embodiment includes a membrane electrode assembly (MEA), a pair of gas diffusion layers 15 and a pair of separators 11 which are disposed to sandwich the membrane electrode assembly.
  • the membrane electrode assembly (MEA) includes a solid polymer electrolyte membrane 12 having a water-blocking layer, an anode catalyst layer 13 on one surface of the sol id polymer electrolyte membrane 12 , and a cathode catalyst layer 14 on the other surface of the membrane 12 , the anode catalyst layer 13 , the membrane 12 and the cathode catalyst layer 14 being joined and integrated.
  • Each of the separators 11 includes a gas channel.
  • a gasket 16 for gas seal is inserted into between the pair of separators 11 .
  • Each of the separators 11 has electroconductivity, and the material thereof is desirably a dense graphite plate, a carbon plate obtained by shaping a carbon material such as graphite or carbon black by aid of a resin, or a metal material excellent in corrosion resistance, such as stainless steel or titanium. It is also desired to plate surfaces of the separators 11 with a noble metal, or apply a conductive paint excellent in corrosion resistance and heat resistance to the surfaces to subject the separators 11 to the surface-treatment. A groove which is a channel for a reactive gas or liquid is formed on each of the surfaces of the separators 11 that face the anode catalyst layer 13 and the cathode catalyst layer 14 , respectively.
  • the method for supplying the substance to be hydrogenated includes a method of supplying the substance to be hydrogenated which is a liquid substance as it is or supplying the substance to be hydrogenated which is a vapor-form substance using He gas or N 2 gas as a carrier.
  • Each of the gas diffusion layers 15 is provided for supplying uniformly a reactive substance (gas or a liquid), which has been supplied to the channel of the separator 11 , over the plane of the catalyst layer.
  • a substrate having permeability to gases is used for the gas diffusion layers 15 , such as carbon paper or carbon cloth. Particularly, a water-repellent substrate is preferable.
  • the gasket 16 has an electrically-insulating property, resistant particularly against hydrogen or the substance to be hydrogenated, and the organic hydride, and made of a material which passes through small amount of these components and has airtightness. Examples of such materials include butyl rubber, Viton rubber, and EPDM rubber.
  • the water-blocking layer is formed on the solid polymer electrolyte membrane, so that the water in the anode does not pass to the cathode.
  • the organic hydride can be manufactured with a high efficiency.
  • FIG. 2 illustrates an electrode part of the device for manufacturing an organic hydride of the present embodiment.
  • FIG. 2 shows a plan view of the MEA viewed from the cathode side, a cross sectional view taken from line D-E in the plan view, and an enlarged view.
  • the MEA includes a solid polymer electrolyte membrane 21 on which a water-blocking layer 27 is formed, a cathode catalyst layer 22 and an anode catalyst layer 23 which are formed on the front and back of the solid polymer electrolyte membrane 21 .
  • the cathode and the anode are formed on the upper and lower sides of the solid polymer electrolyte membrane 21 , respectively, as dense catalyst layers, the water-bloc layer 27 formed on the membrane 21 .
  • a catalytic metal 24 is supported on a catalyst supporter 25 .
  • the catalyst supporters 25 are bonded to each other by a solid polymer electrolyte 26 .
  • the catalytic metal 24 has a network structure in which its portions are connected to each other through the catalyst supporter 25 , and forms a passing way for electrons necessary for the reaction (2).
  • the solid polymer electrolyte 26 in the catalyst layer also has a network structure in which its portions are connected to each other, and forms a passing way for protons necessary for the reaction (2).
  • the electrode reaction is conducted on three-phase interfaces in which the metal catalyst 24 on the catalyst supporter 25 , the electrolyte and the reactive substance contact each other.
  • the solid polymer electrolyte membrane 26 forms the passing way for protons, so that the three-phase interfaces are formed also in the metal catalyst 24 , which does not directly contact the solid polymer electrolyte membrane 21 . Accordingly, the electrode has a structure in which a large volume of the metal catalyst can contribute to the electrode reaction.
  • the water-blocking layer 27 is formed on the solid polymer electrolyte membrane, so that the water in the anode can be prevented from passing to the cathode.
  • an organic hydride can be manufactured with a high efficiency.
  • FIG. 3 illustrates a structure of electrodes in a conventional technique.
  • a catalyst supporter 35 supporting a metal catalyst 34 is directly formed on each surface of a solid polymer electrolyte membrane 31 .
  • a portion of the metal catalyst 34 which contributes to the electrode reaction is present only in its region directly contacting the electrolyte membrane.
  • the metal catalyst 34 has small quantity of three-phase interface, so that the catalyst quantity contributing to the reaction is limited. Moreover, it is considered that the formation of the network structure of the catalyst is small in quantity, leading to high resistance.
  • FIG. 3 the electrode structure in a conventional technique has been illustrated.
  • the electrodes illustrated in FIG. 3 have a structure in which the catalyst supporter 35 supporting the catalytic metal 34 is mixed with a solid polymer electrolyte 36 on each surface of the solid polymer electrolyte membrane 31 .
  • passed water 37 is present in the cathode catalyst layer, the passed water 37 being water which has passed through the solid polymer electrolyte membrane 31 from the anode.
  • Water and a substance to be hydrogenated, such as toluene are insoluble into each other, not miscible with each other.
  • the water hinders the supply of toluene into the catalyst.
  • the catalytic metal 38 to which no substance to be hydrogenated, such as toluene is supplied, it considered that hydrogen is generated according to a formula (3) illustrated below, without hydrogenation reaction.
  • the electrodes in a conventional technique include the catalyst causing no reaction of hydrogenation onto the substance to be hydrogenated, so that the manufacture of any organic hydride is restricted. As a result, it is considered that energy efficiency is low in a conventional technique.
  • the MEA of the present invention can be produced by the following method. First, a cathode catalyst paste and an anode catalyst paste are produced.
  • the cathode catalyst paste is obtained by sufficiently mixing a supporter supporting a catalytic metal, a solid polymer electrolyte, and a solvent in which the solid polymer electrolyte is soluble.
  • the anode catalyst paste is obtained by sufficiently mixing a catalytic metal, a solid polymer electrolyte, and a solvent in which the solid polymer electrolyte is soluble. These pastes are each sprayed onto a peelable film, such as a polyfluoroethylene (PTFE) film, by a spray drying method, for example. The resultants are dried at 80° C.
  • PTFE polyfluoroethylene
  • the MEA of the invention can be produced.
  • a spray-dry method is used to spray a cathode catalyst paste and an anode catalyst paste directly onto a solid polymer electrolyte membrane including a water-blocking layer.
  • the cathode catalyst paste is obtained by sufficiently mixing a supporter supporting a catalytic metal, a solid polymer electrolyte, and a solvent in which the solid polymer electrolyte is soluble.
  • the anode catalyst paste is obtained by sufficiently mixing a catalytic metal and a solid polymer electrolyte, and a solvent in which the solid polymer electrolyte is soluble.
  • the organic polymer included in the solid polymer electrolyte membrane can be perfluorocarbon sulfonic acid, or a polymer yielded by incorporating a dopant of a proton donor, such as a sulfonate, phosphonate or carboxylate group, or bonding/fixing the donor chemically into polystyrene, polyetherketone, polyetheretherketone, polysulfone, polyethersulfone or some other engineering plastic. It is desired to make the material into a crosslinked structure, or fluoridate the material partially to make the material high in stability.
  • a composite electrolyte membrane may be used which is composed of an organic polymer and, e.g., a metal oxide hydrate.
  • the layer that blocks water from passing through is a layer which can pass through hydrogen ions and blocks water.
  • the layer includes inorganic substance such as palladium and any palladium alloy, for example.
  • metals which form the alloy with palladium include transition metals such as Rh, Cu, Co, Ir, and Ag.
  • transition metals such as Rh, Cu, Co, Ir, and Ag.
  • various metals are conceivable, examples thereof including alkaline earth metals such as Mg and Ca, and rare earth metals such as La and Nd.
  • a hydrogen storage alloy may be used.
  • the hydrogen storage alloy include Ti—Fe based metals, V based metals, Mg based alloys, and Ca based alloys.
  • AB 2 type metals each of which contains, as a base, a transition metal such as Ti, Mn, Zr or Ni; and LaNi 5 , ReNi 5 , and other AB 5 type metals, each of which contains, as a base, an alloy containing a rare earth metal, Nb or Zr, and 5 atoms of a transition metal having a catalytic effect (such as Ni, Co or Al) per atom of the rare earth metal, Nb or Zr.
  • the organic polymer small in the proton donor quantity is desirably an organic polymer having an amount of ion exchange of 0.75 meq/g or less per dry weight.
  • the water-blocking layer may be formed on the surface of the solid polymer electrolyte membrane or the inside of the solid polymer electrolyte membrane.
  • a layer that blocks water from passing through is formed to restrict the amount of water passing through. The water moves following the movement of protons. Then, the amount of the water passing through is varied in accordance with the value of the flowing current.
  • the membrane electrode assembly including the water-blocking layer in the invention desirably has an amount of water passing through of 30 ⁇ g/cm 2 ⁇ sec or less when the current density value is 60 mA/cm 2 .
  • a water-blocking layer described above is used to satisfy this requirement.
  • a polymer material exhibiting proton conductivity is used.
  • examples thereof include sulfonated or alkylenesulfonated fluorine-contained polymers and polystyrenes, typical examples thereof including perfluorocarbon based sulfonic acid resins, and polyperfluorostyrene based sulfonic acid resins.
  • Other examples thereof include polysulfones, polyethersulfones, polyetherethersulfones, polyetheretherketones, and materials in which a proton donor such as a sulfonate group is introduced in a hydrocarbon based polymer.
  • the catalytic metal used in the invention can be a catalytic material having a hydrogenating effect.
  • the material may be, for example, a metal such as Ni, Pd, Pt, Rh, Ir, Re, Ru, Mo, W, V, Os, Cr, Co or Fe, or a catalyst of an alloy of any of these metals.
  • the hydrogenating catalyst is preferably made into fine particles to decrease costs by a reduction in the catalytic metal and increase the reaction surface area.
  • the catalyst may be supported on a supporter.
  • the method for producing the catalyst may be a co-precipitation method, a thermal decomposition method or an electroless plating method, and is not particularly limited.
  • the material of the supporter for the cathode catalyst may be, for example, a carbon material such as activated carbon, carbon nanotube or graphite, silica, alumina, or an alumina silicate such as zeolite.
  • a carbon material such as activated carbon, carbon nanotube or graphite, silica, alumina, or an alumina silicate such as zeolite.
  • the carbon may be unfavorably oxidized.
  • the material of the supporter for the anode catalyst may be a non-carbon material such as silica, alumina, or an alumina silicate such as zeolite.
  • the catalytic metal may be used without using any supporting material.
  • the substance to be hydrogenated may be anyone of benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, anthracene, biphenyl and phenanthroline, and alkyl-substituted compounds thereof, or a mixture of two or more of these compounds.
  • the compounds can store the hydrogen.
  • a membrane As a solid polymer electrolyte membrane, a membrane was used which was obtained by physically bonding a palladium membrane having a thickness of 25 ⁇ m onto a surface of a Nafion (manufactured by Du Pont). The palladium membrane was bonded to the surface on the anode side.
  • a spray coater was used to apply a catalyst slurry directly onto the solid polymer electrolyte membrane to form a cathode catalyst layer.
  • the cathode catalyst layer was formed by the application onto the solid polymer electrolyte membrane.
  • the Nafion onto which the palladium membrane was bonded was put on a hot plate of a substrate, and then sucked to be fixed thereon.
  • the temperature of the hot plate was set to 50° C.
  • Conditions for the application were as follows. The solution pressure was set to 0.01 MPa. The swirl pressure was set to 0.15 MPa.
  • the spraying pressure was set to 0.15 MPa.
  • the distance from the gun to the substrate was set to 60 mm.
  • the temperature of the substrate was set to 50° C.
  • the amount of the cathode catalyst was set to 0.4 mgPt ⁇ cm ⁇ 2 .
  • the cathode catalyst layer was formed on the surface of the Nafion on which the palladium membrane was bonded.
  • An anode catalytic slayer was formed on the back surface of the Nafion.
  • the anode catalyst layer was formed by a transferring method.
  • an anode catalyst slurry was prepared.
  • the used anode catalyst slurry was obtained by mixing a platinum black HiSPEC1000 (manufactured by Johnson Matthey PLC), a 5% by weight Nafion solution, and a 221 solution with each other at a ratio by weight of 1:1.11:2.22.
  • An applicator was used to apply this slurry onto a sheet made of Teflon (registered trademark).
  • the anode catalyst layer applied on the sheet of Teflon (registered trademark) was formed on the surface of the Nafion on which the palladium membrane was bonded by thermal transfer using a hot press (SA-401-M manufactured by Tester Sangyo Co., Ltd.).
  • the hot press pressure was set to 37.2 kgf ⁇ cm ⁇ 2 , the hot press temperature to 120° C., and the hot press time to 2 minutes.
  • the amount of the anode catalyst was set to 4.8 mgPt ⁇ cm ⁇ 2 .
  • the produced MEA was integrated into the device for manufacturing an organic hydride illustrated in FIG. 1 .
  • the cell resistance thereof was 200 m ⁇ .
  • Toluene was supplied as a substance to be hydrogenated to the cathode at each of flow rates of 0.03 mL/min and 0.1 mL/min. Pure water was supplied to the anode at a flow rate of 5 mL/min. In these states, a voltage of 2.2 V was applied to between the anode and the cathode. The temperature of the cell was set to each of 25, 40, 60 and 80° C.
  • FIG. 4 shows the current values relative to the temperatures of the cell. As the cell temperature was made higher, the current densities became larger. The reason of this is considered that as the temperature became higher, the reaction activity of the electrode catalysts for the reaction became higher. In the case of supplying toluene in the amounts of 0.03 mL/min and 0.1 mL/min, the result was that the current flowed at substantially the same level.
  • the cathode solution was collected and analyzed by gas chromatography to find a generation of methylcyclohexane, which is an organic hydride. This suggests that the hydrogenation reaction of toluene yielded methylcyclohexane with the electrodes in the invention.
  • the solution collected from the cathode contained no water. It is believed that the palladium membrane formed on the surface of the Nafion was able to prevent the water from passing through from the anode.
  • FIG. 5 shows the conversion ratios from toluene to methylcyclohexane in the hydrogenation reaction.
  • the conversion ratios were calculated from peak areas of the gas chromatograph according to the following equation:
  • Methylcyclohexane was detected at each of the cell temperatures of 25, 40, 60 and 80° C., and the conversion ratios became larger as the cell temperature became higher.
  • the conversion ratios were higher at the supply amount of toluene of 0.03 mL/min than at that of 0.1 mL/min. The reason of this is considered that as the supply rate of toluene was smaller, a chance for toluene to contact the electrode catalysts was increased.
  • the condition that the cell temperature was 80° C. and the toluene flow rate was 0.03 mL/min gave the highest conversion ratio of 68% among the conditions in this embodiment.
  • an MEA was produced using a Nafion. Other producing conditions were same as described above.
  • the produced MEA was integrated into the device for manufacturing an organic hydride illustrated in FIG. 1 .
  • the cell resistance thereof was measured to be 250 m ⁇ .
  • FIG. 6 shows the current values relative to the temperatures of the cell. As the temperature of the cell was made higher, larger currents flowed. However, at each of the temperatures, the current densities were lower than in embodiment 1.
  • the cathode solution was collected and analyzed by gas chromatography to find a generation of methylcyclohexane, which is an organic hydride.
  • the waste solution collected from the cathode was separated into two phases.
  • the upper phase was presumed to be toluene and methylcyclohexane, and the lower phase was presumed to be water. As the temperature was higher, the proportion of the water in the lower phase was larger. It is considered that the water came to the cathode from the anode passing through the electrolyte membrane.
  • FIG. 7 shows the conversion ratios from toluene to methylcyclohexane.
  • the conversion ratios were smaller than in embodiment 1. The reason of this is considered that the passed water was present in the cathode catalyst layer and the water hindered the supply of toluene to the catalyst. As a result, it is presumed that hydrogen was generated on the catalyst to which no toluene was supplied, so that methylcyclohexane was not generated to lower the conversion ratios.
  • a Nafion was used as an electrolyte membrane, and an S-PES (sulfonated polyethersulfone) having thickness of 10 ⁇ m was bonded onto the surface of the National.
  • S-PES is an organic polymer obtained by introducing sulfonate groups into polyethersulfone.
  • the used S-PES had an amount of ion exchange of 0.6 meq/g per dry weight.
  • Other conditions for producing the MEA were same as in embodiment 1.
  • the produced MEA was integrated into the device for manufacturing an organic hydride illustrated in FIG. 1 .
  • the cell resistance thereof was measured to be 350 m ⁇ .
  • a test of the hydrogenation reaction to toluene was conducted. At a cell temperature of each of 25, 40, 60 and 80° C., a voltage of 2.2 V was applied to between the anode and the cathode.
  • the cathode solution was collected and analyzed by gas chromatography to find a generation of methylcyclohexane, which is an organic hydride.
  • the waste solution collected from the cathode was separated into two phases, although the solution contained smaller amount of water than in comparative example 1. The reason of this is considered that the S-PES did not completely prevent the water from passing through.
  • higher conversion ratios were obtained in this case since the amount of the passed water was reduced. The highest conversion ratio was 58% when the cell temperature was 80° C. and the toluene flow rate was 0.03 mL/min.

Landscapes

  • 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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
US13/817,333 2010-09-30 2011-08-18 Device for manufacturing organic hydride Abandoned US20140144774A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010220254A JP2012072477A (ja) 2010-09-30 2010-09-30 有機ハイドライド製造装置
JP2010-220254 2010-09-30
PCT/JP2011/068660 WO2012043086A1 (ja) 2010-09-30 2011-08-18 有機ハイドライド製造装置

Publications (1)

Publication Number Publication Date
US20140144774A1 true US20140144774A1 (en) 2014-05-29

Family

ID=45892561

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/817,333 Abandoned US20140144774A1 (en) 2010-09-30 2011-08-18 Device for manufacturing organic hydride

Country Status (4)

Country Link
US (1) US20140144774A1 (enrdf_load_stackoverflow)
JP (1) JP2012072477A (enrdf_load_stackoverflow)
CN (1) CN103069051A (enrdf_load_stackoverflow)
WO (1) WO2012043086A1 (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130087451A1 (en) * 2011-10-06 2013-04-11 Hitachi, Ltd. Membrane Electrode Assembly and Organic Hydride Manufacturing Device
US10202698B2 (en) 2014-03-28 2019-02-12 Yokohama National University Device for manufacturing organic hydride
US10563313B2 (en) * 2013-08-23 2020-02-18 Commissariat A L'energie Atomique Et Aux Energies Alternatives Active layer/membrane arrangement for a hydrogen production device and assembly comprising said arrangement suitable for a porous current collector and method for producing the arrangement
US10815575B2 (en) 2013-03-29 2020-10-27 Eneos Corporation Electrochemical reduction device and method for manufacturing hydride of aromatic compound
US10889903B2 (en) 2014-11-10 2021-01-12 National University Corporation Yokohama National University Oxygen-generating anode
US11035045B2 (en) * 2014-11-21 2021-06-15 National University Corporation Yokohama National University Apparatus for producing organic hydride and method for producing organic hydride using same
US11236428B2 (en) * 2014-09-25 2022-02-01 National University Corporation Yokohama National University Electrolytic cell for production of organic chemical hydrides
US11519082B2 (en) 2016-11-15 2022-12-06 National University Corporation Yokohama National University Organic hydride production apparatus and method for producing organic hydride
WO2023146457A3 (en) * 2022-01-25 2024-06-06 Ghorbani Shiraz Hamid A method and device for electrochemical hydrogenation of liquid organic hydrogen carriers

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014156126A1 (ja) * 2013-03-29 2014-10-02 Ｊｘ日鉱日石エネルギー株式会社 電気化学還元装置および芳香族化合物の水素化体の製造方法
WO2015029366A1 (ja) * 2013-08-30 2015-03-05 Ｊｘ日鉱日石エネルギー株式会社 電気化学還元装置
KR101773969B1 (ko) 2016-11-11 2017-09-04 한국과학기술연구원 환원반응을 향상시키는 전기화학 반응 셀
JP7115728B2 (ja) * 2017-02-03 2022-08-09 国立大学法人 東京大学 膜電極接合体
JP6882676B2 (ja) * 2017-06-29 2021-06-02 富士通株式会社 二酸化炭素還元膜、及びその製造方法、並びに二酸化炭素還元装置
CN107913653B (zh) * 2017-12-26 2023-08-15 大连理工大学盘锦产业技术研究院 一种电化学加氢装置及方法
JP7540645B2 (ja) * 2020-05-28 2024-08-27 Ｅｎｅｏｓ株式会社 有機ハイドライド製造装置および膜電極接合体の製造方法
WO2022118695A1 (ja) * 2020-12-03 2022-06-09 Ｅｎｅｏｓ株式会社 有機ハイドライド製造装置、水除去装置および水除去方法
CN113135614A (zh) * 2021-03-10 2021-07-20 中国工程物理研究院材料研究所 一种基于质子交换膜的有机污染物阳极氧化处理装置
WO2025069620A1 (ja) * 2023-09-25 2025-04-03 旭化成株式会社 電解システム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6238530B1 (en) * 1999-02-15 2001-05-29 Permelec Electrode Ltd. Cathode for electrolysis and electrolytic cell using the same
JP2003045449A (ja) * 2001-08-01 2003-02-14 Masaru Ichikawa 化学発電／有機ハイドライド製造装置および化学発電／有機ハイドライド製造方法
US6949178B2 (en) * 2002-07-09 2005-09-27 Lynntech, Inc. Electrochemical method for preparing peroxy acids
US20060199062A1 (en) * 2004-09-09 2006-09-07 Asahi Kasei Chemicals Corporation Solid polymer electrolyte membrane and production method of the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5789488A (en) * 1980-11-25 1982-06-03 Tokuyama Soda Co Ltd Electrolysis of organic compound
JPH0645908B2 (ja) * 1988-02-29 1994-06-15 株式会社日本触媒 １―アミノアントラキノン類の製造法
JP3561108B2 (ja) * 1997-01-07 2004-09-02 ペルメレック電極株式会社 水素化方法及び電解槽
JP2006049110A (ja) * 2004-08-05 2006-02-16 Hitachi Ltd 燃料電池用触媒、それを用いた膜電極接合体、その製造方法及び燃料電池
JP2009007647A (ja) * 2007-06-29 2009-01-15 Hitachi Ltd 有機ハイドライド製造装置、及び、それを用いた分散電源と自動車

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6238530B1 (en) * 1999-02-15 2001-05-29 Permelec Electrode Ltd. Cathode for electrolysis and electrolytic cell using the same
JP2003045449A (ja) * 2001-08-01 2003-02-14 Masaru Ichikawa 化学発電／有機ハイドライド製造装置および化学発電／有機ハイドライド製造方法
US6949178B2 (en) * 2002-07-09 2005-09-27 Lynntech, Inc. Electrochemical method for preparing peroxy acids
US20060199062A1 (en) * 2004-09-09 2006-09-07 Asahi Kasei Chemicals Corporation Solid polymer electrolyte membrane and production method of the same

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130087451A1 (en) * 2011-10-06 2013-04-11 Hitachi, Ltd. Membrane Electrode Assembly and Organic Hydride Manufacturing Device
US10815575B2 (en) 2013-03-29 2020-10-27 Eneos Corporation Electrochemical reduction device and method for manufacturing hydride of aromatic compound
US10563313B2 (en) * 2013-08-23 2020-02-18 Commissariat A L'energie Atomique Et Aux Energies Alternatives Active layer/membrane arrangement for a hydrogen production device and assembly comprising said arrangement suitable for a porous current collector and method for producing the arrangement
US10202698B2 (en) 2014-03-28 2019-02-12 Yokohama National University Device for manufacturing organic hydride
US11236428B2 (en) * 2014-09-25 2022-02-01 National University Corporation Yokohama National University Electrolytic cell for production of organic chemical hydrides
US10889903B2 (en) 2014-11-10 2021-01-12 National University Corporation Yokohama National University Oxygen-generating anode
US11035045B2 (en) * 2014-11-21 2021-06-15 National University Corporation Yokohama National University Apparatus for producing organic hydride and method for producing organic hydride using same
US11519082B2 (en) 2016-11-15 2022-12-06 National University Corporation Yokohama National University Organic hydride production apparatus and method for producing organic hydride
WO2023146457A3 (en) * 2022-01-25 2024-06-06 Ghorbani Shiraz Hamid A method and device for electrochemical hydrogenation of liquid organic hydrogen carriers

Also Published As

Publication number Publication date
CN103069051A (zh) 2013-04-24
WO2012043086A1 (ja) 2012-04-05
JP2012072477A (ja) 2012-04-12

Similar Documents

Publication Publication Date Title
US20140144774A1 (en) Device for manufacturing organic hydride
JP5705214B2 (ja) 有機ハイドライド製造装置
KR101417354B1 (ko) 막 전극 접합체 및 유기 하이드라이드 제조 장치
JP6501141B2 (ja) 有機ハイドライド製造装置およびこれを用いた有機ハイドライドの製造方法
US20060099482A1 (en) Fuel cell electrode
CA2910242C (en) Catalyst, and electrode catalyst layer, membrane electrode assembly and fuel cell using the catalyst
WO2018216356A1 (ja) 有機ハイドライド製造装置
KR101640731B1 (ko) 연료 전지 시스템
TWI222236B (en) Liquid fuel supplying type fuel cell
JP6998797B2 (ja) 有機ハイドライド製造装置、有機ハイドライドの製造方法およびエネルギー輸送方法
CA2321391C (en) Fuel-cell electrode and method of manufacturing the fuel-cell electrode
WO2014192089A1 (ja) 有機ハイドライド製造装置
CN100377396C (zh) 燃料电池的电极及其制备方法以及包含它的膜电极组件和燃料电池系统
JP2018060716A (ja) 膜電極接合体
KR20190125885A (ko) 전기화학적 탈수소화 반응기 및 이것을 이용한 수소의 제조방법
JP7540645B2 (ja) 有機ハイドライド製造装置および膜電極接合体の製造方法
WO2022091360A1 (ja) 有機ハイドライド製造装置
WO2022091361A1 (ja) 有機ハイドライド製造装置およびカソード触媒層の形成方法
KR20170004747A (ko) 막 전극 접합체, 이를 포함하는 연료 전지 및 연료 전지를 포함하는 전지 모듈
WO2024219065A1 (ja) 有機ハイドライド製造装置および有機ハイドライド製造方法
WO2024048340A1 (ja) 有機ハイドライド製造装置および有機ハイドライド製造方法
JP2024055578A (ja) 電極、膜電極接合体、電気化学セル、スタック、電解装置
AU2023323068A1 (en) Apparatus for producing organic hydride
JP2023079558A (ja) 固体高分子型燃料電池

Legal Events

Date Code Title Description
AS Assignment

Owner name: HITACHI, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HIRASHIGE, TAKAYUKI;ISHIKAWA, TAKAO;SIGNING DATES FROM 20130306 TO 20130311;REEL/FRAME:030309/0216

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION