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WO2005078160A1 - Procédé de production d'hydrogène et appareil associé - Google Patents

Procédé de production d'hydrogène et appareil associé Download PDF

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Publication number
WO2005078160A1
WO2005078160A1 PCT/JP2005/002420 JP2005002420W WO2005078160A1 WO 2005078160 A1 WO2005078160 A1 WO 2005078160A1 JP 2005002420 W JP2005002420 W JP 2005002420W WO 2005078160 A1 WO2005078160 A1 WO 2005078160A1
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WIPO (PCT)
Prior art keywords
anode side
gas
electrolytic cell
anode
electrolysis
Prior art date
Application number
PCT/JP2005/002420
Other languages
English (en)
Japanese (ja)
Inventor
Tohru Kato
Ken Nozaki
Hiroshi Yokota
Chi Matsumura
Hiroyuki Yamada
Original Assignee
Ebara Corporation
National Institute Of Advanced Industrial Science And Technology
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
Priority claimed from JP2004042040A external-priority patent/JP4512788B2/ja
Priority claimed from JP2004042041A external-priority patent/JP4500907B2/ja
Application filed by Ebara Corporation, National Institute Of Advanced Industrial Science And Technology filed Critical Ebara Corporation
Priority to DE112005000495T priority Critical patent/DE112005000495T5/de
Priority to US10/589,815 priority patent/US20070163889A1/en
Publication of WO2005078160A1 publication Critical patent/WO2005078160A1/fr

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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
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a method and an apparatus for producing hydrogen by high-temperature steam electrolysis, and more particularly to an electrolysis apparatus in which an electrolytic cell is partitioned into an anode side and a force sword side by a solid oxide electrolyte membrane.
  • the present invention relates to an electrolysis apparatus suitable for use in an electrolysis method in which electrolysis is reduced by supplying steam to a power source side and supplying a reducing gas to an anode side to perform electrolysis.
  • Water electrolysis methods for the purpose of hydrogen production include alkaline water electrolysis, solid polymer water electrolysis, and high-temperature steam electrolysis.
  • the electrolysis voltage is 1. Since 8V or more is required, the electrical efficiency is less than 80% and the amount of electricity required for hydrogen production is large.
  • using a solid oxide electrolyte as a diaphragm the electrolytic cell is divided into an anode side and a power source side, and high-temperature water vapor is supplied to the power source side, so that the water vapor is electrolyzed at a high temperature of about 800 ° C.
  • heat energy can be used to decompose water due to the high temperature, and electrode overvoltage and resistance overvoltage can be suppressed low, so that an electrical efficiency of 90% or more can be expected. It can be reduced to 5V or less, and the amount of power required for hydrogen production can be reduced. Furthermore, recently, by supplying natural gas to the anode side of the electrolytic cell, oxygen ions which move to the anode side in the solid oxide electrolyte membrane are reacted on the anode side to reduce the chemical potential. An electrolysis method that can greatly reduce power consumption by using it for water decomposition has been proposed (US Pat. No. 6,051,125).
  • the electrolytic cell used for ordinary high-temperature steam electrolysis has the same material and structure as the cell of a solid oxide fuel cell (SOFC), and is used as an electrode on the power source side on which steam is introduced to generate hydrogen.
  • SOFC solid oxide fuel cell
  • Ni cermet suitable for a reducing atmosphere is used, while conductive electrodes such as lanthanum cobaltite and lanthanum manganate are used as electrodes on the anode side where oxygen is generated.
  • Figure 1 shows the concept of a normal high-temperature steam electrolyzer. In the device shown in Fig.
  • the electrolyzer (electrolyzer) is divided into a power source side and an anode side by a solid oxide electrolyte membrane, and high-temperature steam is supplied to the power source side to supply power source electrodes and By supplying power to the anode electrode, electrolysis of water vapor is performed on the power source side to obtain high-purity hydrogen.
  • Oxygen ions o 2 — generated by the electrolysis of water vapor move to the anode side through the solid oxide electrolyte diaphragm.
  • the present invention provides a reducing gas supplied to the anode side of an electrolytic cell, which is divided into an anode side and a cathode side by the above-described membrane of the solid oxide electrolyte, and is supplied to the power source side.
  • An object of the present invention is to find a configuration of an electrolytic cell suitable for a method for producing hydrogen by electrolysis of water vapor by supplying water vapor and supplying power to an anode electrode and a power source electrode.
  • one embodiment of the present invention provides an electrolytic cell separated into an anode side and a power source side by a membrane of a solid oxide electrolyte, and a reducing gas flowing through an electrolytic cell.
  • This is a hydrogen production apparatus using a high-temperature steam electrolysis method equipped with a pipeline for supplying water to the cathode side and a pipeline for supplying water vapor to the power source of the electrolytic cell.
  • the material of the anode electrode and the power source electrode is 400-1000 °
  • an apparatus characterized by using a cermet made of ceramic and metal which is stable in a reducing atmosphere at a temperature of C.
  • a reducing gas is supplied to the anode side of the electrolysis apparatus.
  • the reducing gas reacts with oxygen passing through the solid oxide electrolyte membrane to the anode side of the electrolytic cell in the steam electrolytic cell according to the present invention to lower the oxygen concentration on the anode side.
  • natural gas and hydrocarbon gas such as methane.
  • FIG. 1 is a view showing the concept of a normal high-temperature steam electrolysis apparatus.
  • FIG. 2 is a view showing the concept of a high-temperature steam electrolysis apparatus according to the present invention.
  • FIG. 3 is a view showing an interconnector structure according to the present invention.
  • FIG. 4 is a view showing the concept of a high-temperature steam electrolysis apparatus used in the second embodiment of the present invention.
  • FIG. 5 is a flowchart showing the concept of an example of a hydrogen production method that works on the second aspect of the present invention.
  • FIG. 6 is a view showing the concept of a hydrogen production apparatus used in Example 1.
  • FIG. 7 is a view showing a structure of a hydrogen production experimental apparatus used in Example 2 of the present invention.
  • FIG. 8 is a graph showing the results of Example 2 of the present invention.
  • FIG. 2 shows the concept of one embodiment of a hydrogen production apparatus that is active in the present invention.
  • a reducing atmosphere is provided on the power source side of the electrolysis apparatus (electrolyzer) by the generated hydrogen and on the anode side by the supply of reducing gas. Therefore, since both the anode electrode and the force electrode are exposed to the reducing gas, these materials also have stable ceramic and metallic power in a reducing atmosphere at a temperature of 400 to 1000 ° C. It is characterized by using cermet.
  • the introduced steam is electrolyzed to generate hydrogen, so that the gas composition in the electrolytic cell changes from the entrance side to the exit side.
  • the outlet has the lowest hydrogen concentration, and the outlet has the highest hydrogen concentration.
  • metals such as Ni undergo steam oxidation at high temperatures.
  • it is effective to mix a reducing gas, but on the cathode side of the electrolytic cell of the present invention, since the purpose is to produce high-purity hydrogen, reduction is necessary. It is appropriate to mix hydrogen as a neutral gas.
  • H / HO is 0.01 or more.
  • the concentration is 0.04 or more, steam concentration does not occur, so that the concentration becomes the necessary minimum hydrogen partial pressure.
  • the electrolysis voltage changes depending on the oxygen partial pressure on the anode side and the power source side of the electrolytic cell, and P (cathode)
  • the molar ratio of reducing gas to acidic gas near the outlet on the anode side of the electrolytic cell reducing gas Z Since acidic gas is 0.4 or less, it is necessary to reduce the electrolytic voltage.
  • the H / HO at the inlet on the power source side of the electrolytic cell should be 0.4 or less, preferably 0.2 or less.
  • Hydrogen to be mixed is preferably circulated to a part of the hydrogen generated by steam electrolysis, since the system is simplified.
  • the concentration of the reducing gas is highest at the entrance and decreases toward the exit.
  • the oxygen partial pressure is lowest at the inlet and highest at the outlet.
  • the hydrogen concentration increases toward the outlet, and the oxygen partial pressure decreases toward the outlet.
  • the molar ratio of water to reducing gas is 0.4 or less, and preferably 0.2 or less.
  • anode electrode and the force sword electrode have gas diffusivity, have electron conduction, and have activity as an electrode catalyst.
  • the anode electrode and the force source electrode are mainly composed of a metal material which does not form a compound.
  • Metals having electron conductivity and catalytic activity without forming oxides under such conditions include Ni, Fe, Co, Cu, Pt, Ag, Pd, Ru, and mixtures and alloys thereof.
  • the electrode material is generally used as a cermet mixed with a ceramic powder in order to suppress sintering at a high temperature.
  • a material having conductivity of electrons and oxygen ions is used, the number of reaction sites increases when an electrode is used, and the area where oxygen ions can be diffused increases, which is effective in reducing the reaction overvoltage.
  • a steam electrolyzer when a plurality of electrolysis cells are connected in series to form a multistage, an interconnector for connecting an anode electrode and a force sword electrode is required.
  • the gas contacts both the gas on the anode side and the gas on the power source side of the electrolytic cell, and also serves to separate (gas seal) these gases.
  • one side has a reducing atmosphere and the other has an oxidizing atmosphere, so that it is difficult to select a material suitable for these, and it is also difficult to manufacture the cell.
  • a metal can be used as an interconnector material, which is easy to mold and join, and A highly reliable electrolytic device that can withstand stress can be manufactured.
  • the interconnector material include Ni, Ni-based alloys, Fe-based alloys, Co-based alloys, Cu-based alloys, and Ag-based alloys.
  • FIG. 3 shows a concept of an interconnector structure according to the present invention.
  • the electrolytic cell 5 is divided into an outer anode side 12 and an inner power source side 11 by a cylindrical solid oxide electrolyte membrane 3, and an anode electrode 4 is provided outside the solid oxide electrolyte and an inner electrode side is provided inside.
  • Force sword electrode 2 is arranged.
  • the upper and lower two cylindrical electrodes ⁇ the solid oxidant electrolyte composite are joined via the insulator 21, and the anode and the power source are connected by the interconnector 22. They are connected in series.
  • High-temperature steam is supplied to the power source side 11 of the electrolytic cell, and reducing gas (indicated as CH) is supplied to the anode side 12, and power is supplied to both electrodes.
  • reducing gas indicated as CH
  • the above-mentioned metal material can be used as the interconnector material because both the anode side and the force source side of the electrolytic cell are in a reducing atmosphere.
  • a second aspect of the present invention is to provide a technique for preventing the above-described problem of electrode blocking due to generated carbon by a simple method without increasing the cost.
  • the present inventors have conducted intensive studies to find a means for solving the above-mentioned problems, and as a result, have found that natural gas (hydrocarbon-containing gas) supplied to the anode side of the electrolysis tank has water vapor or carbon dioxide. As a result, carbon produced by the decomposition of the hydrocarbon-containing gas on the anode side immediately reacts with water vapor and carbon dioxide to form CO or CO.
  • natural gas hydrogen-containing gas supplied to the anode side of the electrolysis tank has water vapor or carbon dioxide.
  • the present inventors described that water vapor was applied to the power source side of a high-temperature steam electrolyzer in which the electrolytic cell was partitioned into an anode side and a power source side using a solid oxide electrolyte as a diaphragm as described above.
  • the exhaust gas discharged from the anode side of the electrolysis device Focusing on the fact that water and carbon dioxide generated by the reaction between hydrocarbons and the like in the supplied gas and oxygen passing through the solid oxidant electrolyte membrane are included, the anode-side exhaust gas is It has been found that water vapor and Z or carbon dioxide can be easily mixed by mixing with a hydrocarbon-containing gas supplied to the anode side of the electrolysis apparatus.
  • a steam is supplied to a power source side of a high-temperature steam electrolysis apparatus in which an electrolytic cell is partitioned into an anode side and a power source side using a solid oxide electrolyte as a diaphragm,
  • a method for producing hydrogen by high-temperature steam electrolysis for reducing the electrolysis voltage is characterized in that exhaust gas discharged from the anode side of the electrolysis apparatus is mixed with hydrocarbon-containing gas supplied to the anode side of the electrolysis apparatus.
  • the present invention relates to a method for producing hydrogen.
  • the second aspect of the present invention also relates to an apparatus for performing a brute force method. Therefore, in still another embodiment of the present invention, an electrolytic cell partitioned into an anode side and a cathode side by a membrane of a solid oxide electrolyte, and a hydrocarbon-containing gas supplied to the anode side of the electrolytic cell. And a conduit for supplying water vapor to the force sword of the electrolytic cell. Further, the exhaust gas discharged from the anode side of the electrolytic cell is provided with a hydrocarbon-containing gas supplied to the anode side of the electrolytic cell.
  • the present invention relates to an apparatus for producing hydrogen, which is provided with a conduit for mixing hydrogen therein.
  • a hydrocarbon-containing gas is supplied to the anode side of the electrolysis apparatus.
  • the hydrocarbon-containing gas means a gas containing a hydrocarbon such as natural gas or methane.
  • the expression “reducing gas” used in the present specification means that in the steam electrolytic cell according to the present invention, oxygen reacts with oxygen passing through the solid oxide electrolyte membrane to the anode side of the electrolytic cell, and It means a gas that can lower the oxygen concentration.
  • the high-temperature steam electrolyzer 113 is divided into an anode side 115 and a force sword side 116 by a membrane 114 of a solid oxide electrolyte.
  • high-temperature steam 119 is supplied to the power source side 116 of the electrolytic cell, and the hydrocarbon-containing gas 110 is supplied to the anode side 115 of the electrolytic cell, and the electric power 117 is converted to direct current by the AC-DC converter 18 and the electricity is supplied to the electrolytic cell.
  • the high temperature steam 119 supplied to the power source side 116 is decomposed into hydrogen and oxygen by the electrolytic action.
  • the produced hydrogen 120 is recovered as high-purity hydrogen.
  • the generated oxygen 121 becomes oxygen ions and selectively passes through the solid oxide electrolyte diaphragm 114 and moves to the anode side 115.
  • oxygen ions 121 are consumed in reaction with the hydrocarbon-containing gas and contribute to the formation of a concentration gradient of oxygen ions. Voltage and power consumption is greatly reduced.
  • the second embodiment of the present invention is directed to a hydrocarbon-containing solution supplied to the anode side of a high-temperature steam electrolyzer.
  • An exhaust gas discharged from the anode side of the electrolytic cell is mixed with the gas.
  • a hydrocarbon-containing gas is supplied to the anode side of the high-temperature steam electrolysis tank described above, and high-temperature steam is supplied to the cathode side of the electrolysis tank to supply power.
  • high-temperature exhaust gas is generated from the anode side of the electrolytic cell, and high-temperature hydrogen-containing gas (including hydrogen and water vapor) is generated from the power source side.
  • the high-temperature exhaust gas discharged from the anode side of the electrolytic cell is mixed with the hydrocarbon-containing gas supplied to the electrolytic cell anode side.
  • the method according to the second aspect of the present invention comprises mixing the exhaust gas discharged from the anode side of the electrolytic cell with the hydrocarbon-containing gas supplied to the anode side of the electrolytic cell. Is supplied to the anode side of the electrolytic cell. As a result, water vapor and carbon dioxide contained in the mixed exhaust gas immediately react with carbon generated by thermal decomposition of hydrocarbons such as methane on the anode side of the electrolytic cell, and CO or CO
  • the total amount of water vapor or carbon dioxide added is determined by the amount of carbon (carbon equivalent If the amount is equimolar to (number), the carbon in the hydrocarbon-containing gas is all converted to CO, so that carbon precipitation hardly occurs.
  • the total amount of water vapor or carbon dioxide mixed into the hydrocarbon-containing gas depends on the amount of hydrocarbons supplied to the anode side of the electrolytic cell. It is preferably at least equimolar to the amount of carbon (moles of carbon atoms) in the gas.
  • the off-gas component contains water generated by methane oxidation and carbon dioxide in a ratio of 2: 1 and contains unburned reducing gas components (hydrocarbons such as methane). Therefore, according to the method of the present invention, instead of adding water vapor from the outside, if the offgas discharged from the anode side of the electrolytic cell is added to the supplied hydrocarbon-containing gas, the high-temperature offgas can be used as it is.
  • the steam contained in the off-gas and the carbon dioxide both have the effect of suppressing the precipitation of carbon, and also have the effect of depolarizing together with the unburned reducing gas component catalyst, thus making energy more effective. Can be used for
  • the mixed gas of methane, water vapor, and carbon dioxide easily reacts with the catalyst at the temperature (about 650 ° C to 1000 ° C) used in the high-temperature steam electrolysis that is effective in the present invention. CO and hydrogen, or CO and hydrogen. If this reaction is actively used, methane will touch the electrode
  • the mixed gas of the hydrocarbon-containing gas and the exhaust gas on the anode side supplied to the anode side of the electrolysis apparatus is subjected to a hydrogen reaction by a thermal reaction before coming into contact with the anode of the electrolysis apparatus. And converting the gas into a mixed gas containing carbon monoxide as a main component, and then bringing the mixed gas into contact with the anode.
  • the structure is such that the mixed gas of methane, water vapor and carbon dioxide supplied to the electrolytic cell passes through the catalyst layer before hitting the electrode, the methane will not directly hit the electrode.
  • the purpose of pollution prevention can be sufficiently achieved.
  • a mixed gas of steam and the exhaust gas on the anode side of the electrolysis tank is used for the electrolysis apparatus.
  • a catalyst layer is placed in the pipeline that supplies the anode side, and the mixed gas of the hydrocarbon-containing gas and the exhaust gas on the anode side mainly converts hydrogen and carbon monoxide by a thermal reaction before coming into contact with the anode of the electrolyzer. It is more preferable to be configured to be converted to a mixed gas as a component.
  • the generation of hydrogen by the reaction between methane and water is a slightly endothermic reaction, and the high-temperature steam electrolyzer used in the present invention maintains a high temperature of 650-1000 ° C. Energy may be insufficient at an overvoltage of about 0.5V.
  • overvoltage is reduced by adopting a thin YSZ (yttrium-stabilized zirconia) film as a solid oxide electrolyte diaphragm, energy injection is required to maintain the temperature required for the steam electrolysis reaction. . It is not advisable to supplement this with electric energy, so it is preferable to use the combustion energy of methane.
  • the simplest and most efficient method is to add partial oxygen to methane and supply it to the electrolyzer to cause a partial oxidation reaction of methane, and use the heat of this reaction. Since the amount of oxygen required for this reaction is not very large, there is little danger from oxygen contamination. Also, the use of air instead of oxygen does not increase the increase in waste heat due to nitrogen. Furthermore, the water vapor and CO generated by this reaction are more preferable because they are used to prevent carbon deposition on the electrode.
  • still another embodiment of the present invention relates to the above-described method for producing hydrogen, wherein oxygen or air is mixed with the exhaust gas on the anode side of the electrolysis apparatus, and the obtained mixed gas is mixed on the anode side of the electrolysis apparatus.
  • the present invention further relates to a method characterized by mixing with a hydrocarbon-containing gas supplied to a gas, and converting the mixture into a mixed gas containing hydrogen and carbon monoxide as main components by heat of partial oxidation reaction of the hydrocarbon-containing gas.
  • a cylindrical scandium-stabilized zirconia (SSZ) having a closed end was used as a solid oxide electrolyte diaphragm 3, and on both sides thereof, an anode 2 and a force sword 4 were provided with a Ni-zirconia cermet electrode.
  • An exhaust pipe 6 for discharging a mixed gas of hydrogen and water vapor is installed on the power source side 11, and a reducing gas (shown as CH) is introduced on the anode side 12 of the electrolytic cell.
  • a gas inlet 7 for the gas inlet was formed.
  • Methane is supplied from the gas inlet 7 to the anode side 12 of the electrolysis apparatus, and steam is supplied from the power source side inlet 8, and power is supplied to the anode 2 and power source 4 from the DC power supply 13 at 700 ° C.
  • high-temperature steam electrolysis was performed. It was confirmed that hydrogen was generated from the outlet 9 of the generated gas exhaust pipe 6.
  • the high-temperature steam electrolyzer 1 shown in FIG. 7 has electrodes (anode 2 and force source 4) attached to both sides of a cylindrical solid oxide electrolyte membrane 3 having one end closed, and an electrolytic cell 5 Is divided into an anode side 12 and a force sword side 11.
  • An exhaust pipe 6 for discharging a mixed gas of generated hydrogen and water vapor is provided on the power source side 11.
  • a gas inlet 7 for introducing a hydrocarbon-containing gas is formed on the anode side 12 of the electrolytic cell.
  • This structure is almost the same as that of the solid oxide fuel cell (SOFC) cell, and its manufacturing method is almost the same as that of the SOFC cell.
  • SOFC solid oxide fuel cell
  • a thin film of YSZ (yttrium-stabilized zirconia) (thickness: 100 ⁇ m) is used as the solid oxide electrolyte diaphragm 3, and nickel cermet electrodes 2 and 4 are formed on both sides of the YSZ film 3. Attach, the outer electrode 2 was the anode and the inner electrode 4 was the force source.
  • the electrolysis test was performed by disposing the electrolysis tank 5 in an electric furnace, applying a DC voltage 13 to both electrodes while maintaining the temperature at 1,000 ° C.
  • only steam was supplied to the power source side 11 of the electrolytic cell at normal pressure, and a mixture of simulated exhaust gas having a gas volume ratio twice that of methane was supplied to the anode side 12.
  • a mixture of steam, carbon dioxide, and methane at a ratio of 4: 2: 1 was supplied.
  • the actual anode side exhaust gas contains hydrogen and CO generated by the reaction of methane instead of methane as unburned gas.
  • methane was substituted.
  • the mixing ratio of methane was determined assuming a fuel utilization rate of about 85%. The reason why the outside of the electrolytic cell is set to the anode side is to make it easier to observe the state of carbon deposited on the anode.
  • the open circuit electrolysis voltage that is, the voltage at which a current starts to flow when the voltage is increased is about 0.9 V, which is practical steam electrolysis.
  • an electrolysis voltage of 2 V was required.
  • the open-circuit voltage does not become a definite value, and the electrolytic current starts to flow at a very small voltage, and when the voltage is increased, the current value becomes almost linear.
  • the electrolysis voltage was 1.3 V at lAZcm 2 which is a practical current value.
  • the effect of preventing electrode contamination by mixing steam and carbon dioxide into the hydrocarbon-containing gas supplied to the anode side of the electrolytic cell is to reduce the current value by keeping the electrolytic voltage 1.3V for a long time. It was checked by observation.
  • the change in electrolysis current value between the case where only methane is supplied to the anode side 12 of the electrolytic cell and the case where simulated anode exhaust gas with a volume ratio twice that of methane is mixed and supplied to the anode side 12 of the electrolytic cell are as follows: As shown in the graph of Fig. 8, the current value continued to decrease when only methane was supplied, whereas the current value remained almost constant when the simulated anode side exhaust gas was mixed with methane and supplied. Met.
  • the ratio of water vapor and carbon dioxide mixed into methane supplied to the anode side 12 of the electrolytic cell was changed, and the amount of water vapor mixed was twice that of methane. Even if the volume ratio is less than or equal to the volume ratio, the electrode was not immediately clogged.However, when the ratio of methane to the sum of water vapor and the carbon dioxide in the exhaust gas was an equimolar ratio, the ratio was low. The onset of occlusion was observed in a relatively short time. In the tests so far, when the sum of the water vapor added to methane and the carbon dioxide was twice the molar ratio of methane, no carbon deposition was observed.
  • Mixing of the anode side exhaust gas containing carbon dioxide is considered to be the most preferable amount for preventing the electrode from being clogged. Mixing a larger amount of exhaust gas is preferable in terms of clogging of the electrodes, but it is not preferable because the concentration of methane supplied to the anode side of the electrolytic cell decreases, so that a large electrolytic current value cannot be obtained.
  • the anode side force is adjusted so that the sum of water vapor and carbon dioxide is equal to or greater than the molar number of carbon atoms in the hydrocarbon-containing gas supplied to the anode side of the electrolysis apparatus. 2.
  • the anode-side force is set such that the sum of water vapor and carbon dioxide becomes about twice the molar number of carbon atoms in the hydrocarbon-containing gas supplied to the anode side of the electrolysis apparatus. 2. The method for producing hydrogen according to item 1, wherein the exhaust gas is mixed.
  • the mixed gas of the hydrocarbon-containing gas and the exhaust gas on the anode side to be supplied to the anode side of the electrolytic device is mixed with hydrogen and carbon monoxide as main components by a thermal reaction before contacting the anode of the electrolytic device. 4.
  • Oxygen or air is mixed with the exhaust gas on the anode side of the electrolyzer, and the obtained mixed gas is mixed with the hydrocarbon-containing gas supplied to the anode side of the electrolyzer to partially oxidize the hydrocarbon-containing gas. 5.
  • An electrolytic cell separated into an anode side and a force source side by a membrane of a solid oxide electrolyte, a pipeline for supplying a hydrocarbon-containing gas to the anode side of the electrolytic cell, A conduit for supplying the power source, and a conduit for mixing exhaust gas discharged from the anode side of the electrolytic cell into a hydrocarbon-containing gas supplied to the anode side of the electrolytic cell.
  • Hydrogen production equipment Hydrogen production equipment.
  • a catalyst layer is arranged in a conduit for supplying a mixed gas of water vapor and the exhaust gas on the anode side of the electrolytic cell to the anode side of the electrolytic cell, and the mixed gas of the hydrocarbon-containing gas and the exhaust gas on the anode side is subjected to electrolysis.
  • a high-temperature steam electrolysis method for producing hydrogen comprising An apparatus characterized in that a cermet which has a stable ceramic and metallic force in a reducing atmosphere at a temperature of 400 to 1000 ° C is used as a material for a cathode electrode and a force electrode.
  • cermet used as an electrode material a temperature of 400 to 1000 ° C. and a molar ratio of hydrogen to water vapor in the atmosphere: H / H 0, or a mole of water to a reducing gas
  • a reducing gas is supplied to the anode side of an electrolytic cell separated into an anode side and a force sword side by a membrane of a solid oxide electrolyte, and steam is supplied to the force sword side.
  • a method for producing hydrogen by electrolysis of steam by supplying electric power to an electrode and a force sword electrode, wherein hydrogen is mixed into steam supplied to a force sword side of an electrolytic cell.
  • Hydrogen is added to steam supplied to the power source side of the electrolytic cell, Ratio: H / HO is mixed in an amount of 0.4 or less and 0.01 or more,
  • the present invention relates to a method and an apparatus for producing hydrogen by high-temperature steam electrolysis, and in particular, an electrolytic cell is divided into an anode side and a force source side by a solid oxide electrolyte membrane.
  • a hydrocarbon-containing gas is supplied to the anode side of an electrolyzer in which an electrolytic cell is divided into an anode side and a power source side by a solid oxide electrolyte membrane.
  • the method of producing hydrogen by supplying high-temperature steam to the power source side and performing steam electrolysis to prevent clogging of electrodes due to solid carbon precipitated by the thermal decomposition of hydrocarbons
  • hydrogen can be efficiently produced by effectively utilizing the heat of the anode-side exhaust gas after the reaction and the unburned gas components contained therein.

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

: Cellule électrolytique de structure adaptée à un processus de production d'hydrogène par l'électrolyse de vapeur dans laquelle une cellule électrolytique partagée en un côté anode et un côté cathode grâce à un diaphragme d'électrolyte oxyde rigide; un gaz réducteur est alimenté dans le côté anode et de la vapeur dans le côté cathode avec un courant électrique appliqué aux électrodes de l'anode et de la cathode. Dans un aspect, il est prévu un appareil de production d'hydrogène par la technique de l'électrolyse de vapeur à haute température, comprenant une cellule électrolytique partagée en un côté anode et un côté cathode grâce à un diaphragme d'électrolyte oxyde rigide, une conduite d'alimentation d'un gaz réducteur vers côté anode de la cellule électrolytique et une conduite d'alimentation vapeur vers le côté cathode de la cellule électrolytique, caractérisée par le fait qu'un cermet métallique stable en réduisant l'atmosphère est utilisé comme matériau pour les électrodes de l'anode et de la cathode. Dans un autre aspect, il est prévu un processus de production d'hydrogène par l'électrolyse de vapeur à haute température, comprenant l'utilisation d'un appareil d'électrolyse de vapeur à haute température ayant une cellule électrolytique partagée en un côté anode et un côté cathode grâce à un diaphragme d'électrolyte oxyde rigide, avec une alimentation de vapeur vers le côté cathode et une alimentation de gaz à teneur d'hydrocarbure vers le côté anode, de façon que la réaction avec les ions oxygène qui en résulte diminue le voltage d'électrolyse, caractérisé par le fait qu'un gaz résiduaire évacué depuis le côté anode de l'appareil d'électrolyse soit mélangé dans le gaz à teneur d'hydrocarbure alimenté dans le côté anode de l'appareil d'électrolyse.
PCT/JP2005/002420 2004-02-18 2005-02-17 Procédé de production d'hydrogène et appareil associé WO2005078160A1 (fr)

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DE112005000495T DE112005000495T5 (de) 2004-02-18 2005-02-17 Verfahren und Vorrichtung zur Erzeugung von Wasserstoff
US10/589,815 US20070163889A1 (en) 2004-02-18 2005-02-17 Method and apparatus for producing hydrogen

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JP2004042040A JP4512788B2 (ja) 2004-02-18 2004-02-18 高温水蒸気電解装置
JP2004-042040 2004-02-18
JP2004-042041 2004-02-18
JP2004042041A JP4500907B2 (ja) 2004-02-18 2004-02-18 水素の製造方法

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