WO2015133410A1 - Réacteur électrochimique et réacteur électrochimique composite - Google Patents

Réacteur électrochimique et réacteur électrochimique composite Download PDF

Info

Publication number
WO2015133410A1
WO2015133410A1 PCT/JP2015/055968 JP2015055968W WO2015133410A1 WO 2015133410 A1 WO2015133410 A1 WO 2015133410A1 JP 2015055968 W JP2015055968 W JP 2015055968W WO 2015133410 A1 WO2015133410 A1 WO 2015133410A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrochemical reactor
cathode electrode
anode electrode
gas
stabilized zirconia
Prior art date
Application number
PCT/JP2015/055968
Other languages
English (en)
Japanese (ja)
Inventor
平田　好洋
真奈 上野
太郎 下之薗
鮫島　宗一郎
Original Assignee
国立研究開発法人科学技術振興機構
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 国立研究開発法人科学技術振興機構 filed Critical 国立研究開発法人科学技術振興機構
Priority to JP2016506467A priority Critical patent/JPWO2015133410A1/ja
Publication of WO2015133410A1 publication Critical patent/WO2015133410A1/fr

Links

Images

Classifications

    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/0271—Perovskites
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1026—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2061—Yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20753—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y02P20/156—Methane [CH4]

Definitions

  • the present invention relates to an electrochemical reactor and a composite electrochemical reactor.
  • Patent Document 1 describes a technique aimed at artificially generating oxygen gas from carbon dioxide or carbon monoxide. Although this technique achieves the intended purpose, it is difficult to obtain oxygen gas with high efficiency.
  • JP 2013-173980 A Japanese Patent No. 5376381 JP 62-36005 A Japanese Patent Laid-Open No. Sho 62-36006 International Publication No. 2009/157454
  • Electrolytic reduction of carbon dioxide to formic acid K. S. Udupa, Gs Subraman, H. V. K. Udupa, Electrochim. Acta, vol. 16, pp. 1593-1598 (1971) Electroreduction of carbon-dioxide by metal phthalocyanines, N. Furuya, S. Koide, Electrochim. Acta, vol. 36, pp.1309-1313 (1991) Electrocatalytic formation of CH4 from CO2 on a Pt gas diffusion electrode, K. Hara, T. Sakata, J. Electrochem. Soc., Vol. 144, pp. 539-545 (1997) High-rate gas-phase CO2 reduction to ethylene and methane using gas-diffusion electrodes, R. L.
  • An object of the present invention is to provide an electrochemical reactor and a composite electrochemical reactor capable of generating oxygen gas from carbon dioxide or carbon monoxide with high efficiency.
  • the electrochemical reactor according to the present invention is provided between an anode electrode containing ruthenium and yttria stabilized zirconia, a cathode electrode containing nickel and yttria stabilized zirconia, and between the anode electrode and the cathode electrode, And an electrolyte membrane containing yttria-stabilized zirconia, allowing oxide ions to pass therethrough and preventing carbon monoxide from passing therethrough.
  • a composite electrochemical reactor includes a first electrochemical reactor that generates hydrogen and carbon monoxide from methane and carbon dioxide, and oxygen from carbon monoxide generated by the first electrochemical reactor.
  • an electrolyte membrane that is provided between the anode electrode and the cathode electrode, contains yttria-stabilized zirconia, transmits oxide ions, and blocks carbon monoxide transmission.
  • oxygen gas can be artificially generated from carbon dioxide or carbon monoxide with high efficiency by an electrochemical reaction between an anode electrode and a cathode electrode with an appropriate electrolyte membrane interposed therebetween.
  • FIG. 1 is a schematic diagram showing a configuration of an electrochemical reactor according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing a method for producing a powder for an anode electrode.
  • FIG. 3 is a view showing a method for producing a powder for a cathode electrode.
  • FIG. 4 is a diagram showing a method for producing an electrolyte membrane.
  • FIG. 5 is a diagram showing a method for integrating the powder for the anode electrode, the powder for the cathode electrode, and the electrolyte membrane.
  • FIG. 6 is a diagram showing the configuration of the electrochemical reaction system used in the experiment.
  • FIG. 7 is a graph showing the CO decomposition rate in the first experiment.
  • FIG. 1 is a schematic diagram showing a configuration of an electrochemical reactor according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing a method for producing a powder for an anode electrode.
  • FIG. 3 is a view showing a method for
  • FIG. 8 is a graph showing the results of analysis of the anode and cathode electrodes by X-ray diffraction in the first experiment.
  • FIG. 9 is a graph showing changes in the components of the outlet gas in the second experiment.
  • FIG. 10 is a graph showing changes in the components of the outlet gas in the third experiment.
  • FIG. 11 is a graph showing calculated values of the CO decomposition rate and the outlet gas ratio in the third experiment.
  • FIG. 12 is a graph showing the standard Gibbs free energy change ( ⁇ G 0 ) in the reaction in which C is oxidized.
  • FIG. 13 is a graph showing the relationship between precipitated C and the amount of gas used in the experiment.
  • FIG. 1 is a schematic diagram showing a configuration of an electrochemical reactor according to an embodiment of the present invention.
  • the composite electrochemical reactor 1 includes an electrochemical reactor 10, a separation membrane 30, a partition plate 31, and an electrochemical reactor 20, as shown in FIG.
  • an electrolyte membrane 13 of gadolinium-doped ceria (GDC) is sandwiched between the anode electrode 11 and the cathode electrode 12.
  • the anode electrode 11 is made of, for example, a porous body made of a mixture of Ru and GDC.
  • the cathode electrode 12 is made of, for example, a porous body made of a mixture of Ni and GDC.
  • the electrolyte membrane 13 is made of, for example, a GDC porous body.
  • the composition of GDC is not particularly limited, but is represented by, for example, Ce 0.8 Gd 0.2 O 1.9 . In this way, the electrochemical reactor 10 is configured.
  • Separation membrane 30 permeates hydrogen and prevents carbon monoxide permeation.
  • the separation membrane 30 include a polymonochloroparaxylene membrane (UCC), an amorphous nylon film (Allied Chemical and Dye Co.), an amorphous film (Du Pont) of a copolymer of an aromatic tetrabasic acid and an aromatic amine, or the like is used as a polymer non-porous film. Hydrogen molecules having a small size pass through the separation membrane 30 by molecular diffusion, but carbon monoxide does not permeate the separation membrane 30 because of its large size.
  • the separation membrane 30 When the composite electrochemical reactor 1 is used in a relatively high temperature environment, for example, an amorphous silica film is used as the separation membrane 30. In a relatively high temperature environment, hydrogen molecules can diffuse through the gaps in the silica structure, so the hydrogen molecules pass through the separation membrane 30, but carbon monoxide is large in size, so it diffuses through the gaps in the silica structure. Without passing through the separation membrane 30.
  • the partition plate 31 prevents the permeation of hydrogen. As the partition plate 31, a plate that prevents the permeation of gas is used.
  • an electrolyte membrane 23 of yttria-stabilized zirconia (YSZ) is sandwiched between the anode electrode 21 and the cathode electrode 22.
  • the anode electrode 21 is made of, for example, a porous body made of a mixture of Ru and YSZ.
  • the cathode electrode 22 is made of, for example, a porous body made of a mixture of Ni and YSZ.
  • the electrolyte membrane 23 is made of, for example, YSZ.
  • the electrolyte membrane 23 is preferably dense. That is, even if the electrolyte membrane 23 has closed pores, it is preferable that there are no open pores or communication holes.
  • the composition of YSZ is not particularly limited, for example, the proportion of Y 2 O 3 is 8 mol%, the proportion of ZrO 2 is 92 mol%, and represented by Y 0.15 Zr 0.85 O 1.93 .
  • the thickness of the electrolyte membrane 23 is, for example, about 40 ⁇ m. The thickness here is a dimension in a direction connecting the anode electrode 21 and the cathode electrode 22. In this way, the electrochemical reactor 20 is configured.
  • the electrochemical reactors 10 and 20 are used by being put in the tube 2 so that the anode electrode 11 and the cathode electrode 22 face each other with the separation membrane 30 interposed therebetween.
  • a voltage of about 1 V to 5 V is applied between the anode electrode 11 and the cathode electrode 12
  • about 1 V to 8 V is applied between the anode electrode 21 and the cathode electrode 22.
  • the temperature of the electrochemical reactor 10 is about 700 ° C. to 800 ° C.
  • the temperature of the electrochemical reactor 20 is about 800 ° C.
  • Oxide ions (O 2 ⁇ ) generated by this reduction reaction pass through the electrolyte membrane 13 together with carbon monoxide (CO) and methane (CH 4 ) and reach the anode electrode 11.
  • CO carbon monoxide
  • CH 4 methane
  • an oxidation reaction of methane represented by the formula (12) occurs at the anode electrode 11.
  • the electrochemical reactor 10 generates hydrogen and carbon monoxide from carbon dioxide and methane.
  • carbon monoxide cannot pass through the separation membrane 30 but is supplied to the cathode electrode 22 of the electrochemical reactor 20 through the bypass portion 32.
  • Oxide ions (O 2 ⁇ ) generated by this reduction reaction pass through the electrolyte membrane 23 and reach the anode electrode 21.
  • Oxide ions (O 2 ⁇ ) pass through the electrolyte membrane 23 and reach the anode electrode 21.
  • the oxide ions (O 2 ⁇ ) reach the anode electrode 21, reactions shown in the formulas (24) and (25) occur in the anode electrode 21.
  • the reaction ratio of the formula (24) is x (0 ⁇ x ⁇ 1)
  • the reaction ratio of the formula (25) is (1 ⁇ x). Therefore, when the reaction ratio x is taken into account, the reactions of the equations (24) and (25) are expressed by the equations (24 ′) and (25 ′). In the anode electrode 21, the reaction shown in the equation (26) occurs from the sum of the equations (24 ′) and (25 ′).
  • oxygen gas can be produced using the electrochemical reactor 20.
  • hydrogen and oxygen can be produced from methane and carbon dioxide.
  • hydrogen can be used as fuel for fuel cells.
  • biogas As methane, those contained in natural gas and biogas can be used. This embodiment is particularly suitable for the use of biogas. This is because biogas often contains 50 volume% to 70 volume% methane and 30 volume% to 50 volume% carbon dioxide. That is, the biogas contains not only methane supplied to the cathode electrode 22 but also carbon dioxide.
  • the electrochemical reactor 20 can also be used separately from the electrochemical reactor 10.
  • carbon dioxide is supplied toward the cathode electrode 22 of the electrochemical reactor 20, the reactions shown in the equations (31) and (32) occur at the cathode electrode 22.
  • the cathode electrode 22 undergoes a carbon dioxide reduction reaction represented by the equation (33). CO 2 + 2e ⁇ ⁇ CO + O 2 ⁇ (33)
  • the cathode electrode 22 undergoes a carbon dioxide reduction reaction represented by the equation (36). CO 2 + 4e ⁇ ⁇ C + 2O 2 ⁇ (36)
  • the reaction rate of the formula (33) is y (0 ⁇ y ⁇ 1)
  • the reaction rate of the formula (36) is (1-y). Therefore, when the reaction ratio y is taken into account, the reactions of the equations (33) and (36) are represented by the equations (33 ′) and (36 ′). In the anode electrode 21, the reaction shown in the equation (37) occurs from the sum of the equations (33 ′) and (36 ′).
  • Oxide ions (O 2 ⁇ ) generated by this reduction reaction pass through the electrolyte membrane 23 and reach the anode electrode 21.
  • the reaction shown in the equation (38) occurs at the anode electrode 21.
  • oxygen gas can be produced using the electrochemical reactor 20.
  • FIG. 2 is a diagram showing a method for producing a powder for the anode electrode 21
  • FIG. 3 is a diagram showing a method for producing a powder for the cathode electrode 22.
  • a suspension (suspension) dispersed with double-distilled water is prepared so that the solid content of the mixture is 30% by volume, and the pH of the suspension is adjusted to, for example, 10 using a 13M NH 4 OH solution. adjust.
  • the suspension is freeze-dried and calcined at 800 ° C. for 1 hour and calcined at 1000 ° C. for 2 hours in air. In this way, RuO 2 —YSZ powder is obtained as the powder for the anode electrode 21.
  • FIG. 4 is a view showing a method for producing the electrolyte membrane 23.
  • a suspension (suspension) is produced by dispersing YSZ powder in a mixed solution of toluene and isopropanol so that the solid content is 20% by volume.
  • the volume ratio of toluene and isopropanol in the mixed solution is, for example, 1: 2.
  • 9% by mass of polyethylene glycol (plasticizer) and 5% by mass of polyvinyl butyral (binder) are added to the suspension. Thereafter, the suspension is stirred for 24 hours.
  • a YSZ film is formed by the doctor blade method using the suspension after stirring.
  • the front blade is 80 ⁇ m
  • the rear blade is 150 ⁇ m
  • the feed rate is 50 mm / min
  • the drying time is one week.
  • FIG. 5 is a diagram showing a method for integrating the powder for the anode electrode 21, the powder for the cathode electrode 22, and the electrolyte membrane 23.
  • the electrolyte membrane 23 and the NiO—YSZ powder for the cathode electrode 22 are laminated together, and a pellet-like laminate is produced by uniaxial pressing at 50 MPa for 1 minute and isotropic pressing at 100 MPa for 1 minute. To do.
  • the laminate is co-sintered in air at 1400 ° C. for 4 hours to produce a co-sintered body.
  • a suspension was prepared by dispersing RuO 2 -YSZ powder for the anode electrode 21 in a 90 volume% ethanol-10 volume% polyethylene glycol mixed solution so that the solid content was 15 volume%. Screen printing is performed on the surface of the electrolyte film 23 of the co-sintered body. Subsequently, baking is performed at 900 ° C. for 1 hour.
  • the electrochemical reactor 20 provided with the anode electrode 21, the cathode electrode 22, and the electrolyte membrane 23 can be manufactured.
  • the electrochemical reactor 20 was produced by the same method as in the above embodiment. Then, the electrochemical reactor 20 was inserted into the alumina holders 121 and 122 through the glass seal 123. A glass ring 124 was interposed between the alumina holders 121 and 122. A magnetic tube 127 was connected to the lower end of the alumina holder 121 via a glass seal 125, and a magnetic tube 129 was connected to the upper end of the alumina holder 122 via a glass seal 126. An opening through which gas flows is provided at the lower end of the alumina holder 121, and an opening through which gas flows is provided at the upper end of the alumina holder 122.
  • the platinum wire 133 connected to the DC power source 131 and the platinum wire 134 connected to the ammeter 132 were connected to the anode electrode 21 and the cathode electrode 22 through these openings.
  • platinum mesh 136 and platinum paste were used to connect the platinum wires 133 and 134 to the anode electrode 21, and platinum mesh 135 and platinum paste were used to connect the platinum wires 133 and 134 to the cathode electrode 22.
  • a magnetic tube 128 that bisects the space inside the magnetic tube 127 is provided, and a magnetic tube 130 that bisects the space inside the magnetic tube 129 is provided.
  • the alumina holders 121 and 122 and the magnetic tubes 127 to 130 include HB (component: 40.6% by mass SiO 2 , 56.2% by mass Al 2 O 3 , 0.2% by mass TiO 2 , manufactured by Nikkato Co., Ltd. 0.5 wt% Fe 2 O 3, 0.2 wt% CaO, 0.1 wt% MgO, 0.5 wt% Na 2 O, with 1.7 wt% K 2 O).
  • the electrochemical reactor 20 the alumina holders 121 and 122, and the magnetic tubes 127 to 130 were kept at 870 ° C. for 15 minutes.
  • the vertical axis in FIG. 7 indicates the CO decomposition rate.
  • the CO decomposition rate was determined from the amount of O 2 gas generated at the anode electrode 21 derived from the CO decomposition reaction (2CO ⁇ 2C + O 2 ).
  • the CO decomposition rate when the applied voltage was 1.0 V was 9% to 15%.
  • the applied voltage was increased to 2.0 V or more the decomposition rate increased rapidly and reached 67% to 100% over a long period of time, although there was variation.
  • the current flowing through the electrochemical reactor 20 showed a detection limit value of 1.1 A regardless of the applied voltage, but in reality, it is considered that the current increases as the applied voltage increases.
  • FIG. 8A shows the analysis result of the surface of the cathode electrode 22
  • FIG. 8B shows the analysis result of the surface of the anode electrode 21.
  • the presence of YSZ, Ni and Pt was confirmed in the cathode electrode 22.
  • the anode electrode 21, YSZ, Ru, presence of RuO 2 and Pt was confirmed. It can be seen that Ru was oxidized to RuO 2 by a part of the transported O 2 ⁇ ions.
  • FIG. 9A shows the ratio of gas on the cathode electrode 22 side
  • FIG. 9B shows the ratio of gas on the anode electrode 21 side.
  • the cathode electrode 22 side the ratio of CO 2 was about 92% to 94%. That is, the ratio of CO 2 decreased by about 6% to 8%, and the ratio of CO gas increased by about 6% to 8%. This tendency did not depend on the applied voltage.
  • the O 2 gas ratio on the anode electrode 21 side was 2% to 9%.
  • reaction of CO 2 at the cathode electrode 22 will be considered.
  • Reactions considered to occur at the cathode electrode 22 include reactions of the formulas (41) and (42).
  • FIG. 10A shows the ratio of gas on the cathode electrode 22 side
  • FIG. 10B shows the ratio of gas on the anode electrode 21 side.
  • the composition of the outlet gas on the cathode electrode 22 side was close to the composition of the supply gas.
  • the proportion of CO gas was 50%
  • the concentration of CO gas in the outlet gas on the cathode electrode 22 side increased and the concentration of CO 2 gas decreased.
  • the current flowing through the electrochemical reactor 20 showed a detection limit value of 1.1 A regardless of the applied voltage, but in reality, it is considered that the current increases as the applied voltage increases.
  • reaction of CO and CO 2 at the cathode electrode 22 will be considered.
  • Reactions considered to occur at the cathode electrode 22 include reactions of the formulas (47) to (50).
  • CO 2 ⁇ CO + 1 / 2O 2 (47)
  • CO 2 + C ⁇ 2CO (49)
  • FIG. 11 shows calculated values of (a) CO decomposition rate (v) and (b) cathode side outlet gas ratio.
  • the calculated values according to equations (51) and (52) explain the experimental results.
  • the v value was 0%.
  • the calculated CO 2 content was about 7% lower than the measured value.
  • FIG. 12 shows the standard Gibbs free energy value for the reaction of equation (49).
  • the standard Gibbs free energy is negative at the experimental temperature (800 ° C.), which confirms that the reaction of equation (49) proceeds thermodynamically.
  • FIG. 13 is a graph showing the relationship between precipitated C and the amount of gas used in the experiment.
  • the amount of deposited carbon confirmed by the analysis result of the electron beam probe analyzer by the total amount of CO or CO 2 used in the experiment, the amount of deposited carbon with respect to 1 ml of the supply gas can be derived. From the results shown in FIG. 13, it can be said that the carbon deposition amount of CO decomposition is 21.6 times higher than the carbon deposition amount of CO 2 decomposition. Further, the amount of carbon deposited in the CO and CO 2 mixed gas decomposition is almost the same as that of CO 2 alone. This is because C precipitated from CO reacts with CO 2 and changes to CO.
  • the present invention can be used, for example, in industries related to electrochemical reactors.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

Réacteur électrochimique (20) comprenant : une anode (21) qui contient du ruthénium et de la zircone stabilisée à l'yttrium; une cathode (22) qui contient du nickel et de la zircone stabilisée à l'yttrium; et une membrane électrolytique (23) qui est disposée entre l'anode (21) et la cathode (22), contient de la zircone stabilisée à l'yttrium, assure le transfert des ions d'oxydes et empêche celui du monoxyde de carbone.
PCT/JP2015/055968 2014-03-03 2015-02-27 Réacteur électrochimique et réacteur électrochimique composite WO2015133410A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016506467A JPWO2015133410A1 (ja) 2014-03-03 2015-02-27 電気化学反応器及び複合電気化学反応器

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-040719 2014-03-03
JP2014040719 2014-03-03

Publications (1)

Publication Number Publication Date
WO2015133410A1 true WO2015133410A1 (fr) 2015-09-11

Family

ID=54055216

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/055968 WO2015133410A1 (fr) 2014-03-03 2015-02-27 Réacteur électrochimique et réacteur électrochimique composite

Country Status (2)

Country Link
JP (1) JPWO2015133410A1 (fr)
WO (1) WO2015133410A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112770837A (zh) * 2018-10-01 2021-05-07 国立研究开发法人产业技术综合研究所 电化学催化剂、集成体、电化学反应器、烃生成系统以及烃的生成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007261917A (ja) * 2006-03-29 2007-10-11 Chugoku Electric Power Co Inc:The 水素製造装置
JP2011036149A (ja) * 2009-08-07 2011-02-24 Daicel Chemical Industries Ltd 微生物による酢酸の製造方法
JP2013173980A (ja) * 2012-02-24 2013-09-05 Kagoshima Univ 電気化学反応器並びにそれを使用した二酸化炭素又は一酸化炭素からの炭素及び酸素ガスの製造方法
WO2013180081A1 (fr) * 2012-05-28 2013-12-05 国立大学法人 鹿児島大学 Réacteur électrochimique et procédé de production de gaz combustible

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007261917A (ja) * 2006-03-29 2007-10-11 Chugoku Electric Power Co Inc:The 水素製造装置
JP2011036149A (ja) * 2009-08-07 2011-02-24 Daicel Chemical Industries Ltd 微生物による酢酸の製造方法
JP2013173980A (ja) * 2012-02-24 2013-09-05 Kagoshima Univ 電気化学反応器並びにそれを使用した二酸化炭素又は一酸化炭素からの炭素及び酸素ガスの製造方法
WO2013180081A1 (fr) * 2012-05-28 2013-12-05 国立大学法人 鹿児島大学 Réacteur électrochimique et procédé de production de gaz combustible

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112770837A (zh) * 2018-10-01 2021-05-07 国立研究开发法人产业技术综合研究所 电化学催化剂、集成体、电化学反应器、烃生成系统以及烃的生成方法
CN112770837B (zh) * 2018-10-01 2024-03-26 国立研究开发法人产业技术综合研究所 电化学催化剂、集成体、电化学反应器、烃生成系统以及烃的生成方法

Also Published As

Publication number Publication date
JPWO2015133410A1 (ja) 2017-04-06

Similar Documents

Publication Publication Date Title
Kim-Lohsoontorn et al. Electrochemical performance of solid oxide electrolysis cell electrodes under high-temperature coelectrolysis of steam and carbon dioxide
Lei et al. The co-electrolysis of CO 2–H 2 O to methane via a novel micro-tubular electrochemical reactor
JP6728226B2 (ja) 二酸化炭素および硫化水素を共処理する方法
Kleiminger et al. Syngas (CO-H2) production using high temperature micro-tubular solid oxide electrolysers
EP2857554A1 (fr) Réacteur électrochimique et procédé de production de gaz combustible
US20070163889A1 (en) Method and apparatus for producing hydrogen
Bausa et al. Direct CO2 conversion to syngas in a BaCe0. 2Zr0. 7Y0. 1O3-δ-based proton-conducting electrolysis cell
JP2008533678A (ja) 混合アニオン／プロトン伝導を有する高温型燃料電池
WO2018029994A1 (fr) Dispositif de traitement d'hydrogène
CN112770837B (zh) 电化学催化剂、集成体、电化学反应器、烃生成系统以及烃的生成方法
JP4977621B2 (ja) 電気化学セル及び電気化学セルの製造方法
Velraj et al. A novel solid oxide electrolytic cell with reduced endothermic load for CO2 electrolysis using (La0. 80Sr0. 20) 0.95 MnO3-δ cathode
Lee et al. Symmetrical solid oxide electrolyzer cells (SOECs) with La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF)-Gadolinium doped ceria (GDC) composite electrodes
WO2021085426A1 (fr) Appareil de production de monoxyde de carbone
WO2015133410A1 (fr) Réacteur électrochimique et réacteur électrochimique composite
JP5848985B2 (ja) 電気化学反応器
JP2008260971A (ja) 水蒸気電解装置及び水蒸気電解方法
Zhang et al. CO2 electroreduction enhanced by transitional layer at cathode/electrolyte interface
JP4512788B2 (ja) 高温水蒸気電解装置
Hirata et al. Reforming of biogas using electrochemical cell
Ando et al. Electrochemical reforming of CH4–CO2 mixed gas using porous yttria-stabilized zirconia cell
JP2007270256A (ja) 水素製造装置、水素製造方法および燃料電池発電装置
JP2013014820A (ja) 燃料ガス改質用電解セル、及び電解セルを利用した改質ガスの生成方法
Papazisi et al. High temperature co-electrolysis of CO2 and water on doped lanthanum chromites
JP6480330B2 (ja) 電気化学反応器並びにそれを使用した一酸化炭素及び水蒸気からの水素及び二酸化炭素の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15758883

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016506467

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15758883

Country of ref document: EP

Kind code of ref document: A1