WO2018142615A1 - Système électrochimique et procédé de récupération de chrome pour système électrochimique - Google Patents

Système électrochimique et procédé de récupération de chrome pour système électrochimique Download PDF

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Publication number
WO2018142615A1
WO2018142615A1 PCT/JP2017/004231 JP2017004231W WO2018142615A1 WO 2018142615 A1 WO2018142615 A1 WO 2018142615A1 JP 2017004231 W JP2017004231 W JP 2017004231W WO 2018142615 A1 WO2018142615 A1 WO 2018142615A1
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Prior art keywords
gas
chromium
oxide
electrochemical cell
oxygen electrode
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PCT/JP2017/004231
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English (en)
Japanese (ja)
Inventor
健太郎 松永
亀田　常治
吉野　正人
憲和 長田
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株式会社 東芝
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Priority to JP2018565225A priority Critical patent/JP6833876B2/ja
Priority to PCT/JP2017/004231 priority patent/WO2018142615A1/fr
Publication of WO2018142615A1 publication Critical patent/WO2018142615A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • Embodiments of the present invention relate to an electrochemical system and a chromium recovery method of the electrochemical system.
  • a solid oxide type electrochemical cell uses a solid oxide having oxygen ion conductivity at a relatively high temperature (eg, 600 to 1000 ° C.) as an electrolyte, and is a fuel cell (solid electrolyte fuel cell: SOFC) or an electrolytic cell. It operates as (solid oxide electrolytic cell: SOEC).
  • SOFC solid electrolyte fuel cell: SOFC
  • the SOFC reacts a reducing agent (such as hydrogen or hydrocarbon) with an oxidizing agent (such as oxygen) through an electrolyte, and extracts the reaction energy as electricity.
  • SOEC electrolyzes high-temperature water vapor to obtain hydrogen and oxygen.
  • Chromium poisoning of the oxygen electrode Chromium is generally contained in metal constituent materials such as gas pipes and separators, and becomes an oxide at high temperatures. The chromium oxide is separated from the metal constituent material, contacts the oxygen electrode, reacts with the constituent material, and is deposited on the oxygen electrode. This deposit may inhibit the reaction at the oxygen electrode.
  • the problem to be solved by the present invention is to provide an electrochemical system and a method for recovering chromium of the electrochemical system, in which characteristic deterioration caused by chromium is reduced.
  • the electrochemical system includes at least one electrochemical cell, a supply line, a heating unit, and a chromium recovery unit.
  • the electrochemical cell has a solid oxide electrolyte layer and an oxygen electrode and a hydrogen electrode arranged on both sides thereof.
  • the supply line is made of a metal containing at least part of chromium, and supplies gas to the oxygen electrode of the at least one electrochemical cell.
  • the heating unit is disposed on the supply line and heats the gas.
  • the chromium recovery unit is disposed between the heating unit on the supply line and the electrochemical cell, and recovers chromium oxide in the gas.
  • FIG. 1 is a block diagram showing a solid oxide electrochemical system according to the first embodiment.
  • 1 is a schematic diagram illustrating a configuration of an electrochemical cell stack 10.
  • FIG. 4 is a plan view showing details of a cell unit 11 of the electrochemical cell stack 10.
  • FIG. 2 is an exploded cross-sectional view showing details of a cell unit 11 of an electrochemical cell stack 10.
  • FIG. 2 is a cross-sectional view schematically illustrating an example of a chromium recovery unit 20.
  • FIG. It is a perspective view showing typically an example of chromium recovery unit 20a.
  • It is a block diagram showing the solid oxide type electrochemical system which concerns on 2nd Embodiment.
  • FIG. 1 is a block diagram showing a solid oxide electrochemical system according to the first embodiment.
  • the solid oxide electrochemical system includes an electrochemical cell stack 10, a chromium recovery unit 20, heat exchangers 30a and 30b, and an external power source 40.
  • FIG. 2 is a schematic diagram showing the configuration of the electrochemical cell stack 10.
  • 3A and 3B are a plan view and an exploded sectional view showing details of the cell unit 11 of the electrochemical cell stack 10, respectively.
  • 3A shows a state in which a separator 16b, an insulating sheet 17, and a current collector 18b described later are excluded from the cell unit 11.
  • FIG. 1 shows a state in which a separator 16b, an insulating sheet 17, and a current collector 18b described later are excluded from the cell unit 11.
  • the solid oxide electrochemical system performs power generation or electrolysis using the hydrogen electrode gas G10 and the oxygen electrode gas G20, and discharges the hydrogen electrode waste gas G11 and the oxygen electrode waste gas G21.
  • the cell unit 11 has a through hole H through which these gases pass. Further, a hydrogen electrode gas supply line and an oxygen electrode gas supply line (pipe) are used to supply the hydrogen electrode gas G10 and the oxygen electrode gas G20 to the electrochemical cell stack 10, respectively.
  • a reducing gas such as hydrogen or hydrocarbon
  • an oxidizing gas such as oxygen
  • the hydrogen electrode waste gas G11 contains unreacted reducing gas and water vapor generated by the power generation reaction.
  • the oxygen electrode waste gas G21 contains an unreacted oxidizing gas.
  • the hydrogen electrode waste gas G11 includes unreacted water vapor and hydrogen gas generated by electrolysis.
  • the oxygen electrode waste gas G21 contains oxygen gas generated by electrolysis.
  • the electrochemical cell stack 10 normally operates at a high temperature of about 600 to 1000 ° C., as will be described later, the hydrogen electrode gas G10 and the oxygen electrode gas G20 are heated by a heating mechanism (heat exchangers 30a, 30b, etc.). Then, it is supplied to the electrochemical cell stack 10. Therefore, members such as a supply line (piping) and a heating mechanism for the high-temperature hydrogen electrode gas G10 and the oxygen electrode gas G20 are made of a metal material (metal containing chromium, for example, stainless steel) having excellent oxidation resistance at high temperatures. It is customary to form. A chromium oxide layer having a certain thickness is formed on the surface of the member, and further oxidation (corrosion) is prevented. In addition, the heating mechanism of the hydrogen electrode gas G10 is not shown for easy understanding.
  • the electrochemical cell stack 10 includes a cell unit 11, bus bars 12a and 12b, and end plates 13a and 13b. A plurality of cell units 11 are stacked, and bus bars 12a and 12b and end plates 13a and 13b are arranged above and below them.
  • the cell unit 11 includes a solid oxide electrochemical cell (single cell) 15, separators 16a and 16b, an insulating sheet 17, and current collectors 18a and 18b, and performs power generation and electrolysis.
  • the bus bars 12a and 12b are conductive terminals for extracting electric power from the plurality of solid oxide electrochemical cells 15 during power generation and supplying current during electrolysis. End plates 13 a and 13 b fix bus bars 12 a and 12 b above and below a plurality of solid oxide electrochemical cells 15. As a result, electrical connection and gas sealing in the entire electrochemical cell stack 10 are ensured.
  • the solid oxide electrochemical cell 15 is a unit cell that functions as an SOFC or SOEC, and a plurality of the solid oxide electrochemical cells 15 are used in order to increase the output.
  • the solid oxide electrochemical cell 15 includes a hydrogen electrode 151, an electrolyte layer 152, and an oxygen electrode 153.
  • An oxygen electrode 153 and a hydrogen electrode 151 are disposed on both sides of the solid oxide electrolyte layer 152. Electricity is generated by supplying a reducing gas and an oxidizing gas to the hydrogen electrode 151 and the oxygen electrode 153 of the solid oxide electrochemical cell 15, respectively. Alternatively, water vapor is supplied to the hydrogen electrode 151 for electrolysis.
  • the hydrogen electrode 151 includes particles of a hydrogen electrode catalytic metal and oxygen ion conductive oxide particles.
  • a hydrogen electrode catalyst metal metal oxides, such as metals, such as nickel, silver, or platinum, nickel oxide, or cobalt oxide, are mentioned, for example.
  • the oxygen ion conductive oxide is a ceramic, for example, a ceria-based oxide such as samaria-stabilized ceria (SDC) or gadolinia-stabilized ceria (GDC), or a zirconia-based oxide such as yttria-stabilized zirconia (YSZ). Can be mentioned.
  • a solid oxide of the electrolyte layer 152 described later may be used.
  • the electrolyte layer 152 is a solid oxide layer having electronic insulation and oxygen ion conductivity.
  • the solid oxide include stabilized zirconia, perovskite oxide, and ceria (CeO 2 ) -based electrolyte solid solution.
  • Stabilized zirconia is zirconia in which a stabilizer is dissolved in zirconia.
  • the stabilizer for example, Y 2 O 3, Sc 2 O 3, Yb 2 O 3, Gd 2 O 3, Nd 2 O 3, CaO, MgO or the like can be mentioned.
  • the perovskite oxide include LaSrGaMg oxide, LaSrGaMgCo oxide, and LaSrGaMgCoFe oxide.
  • ceria-based electrolyte solid solution a solid solution in which Sm 2 O 3 , Gd 2 O 3 , Y 2 O 3 , La 2 O 3 , or the like is dissolved in a material containing CeO 2 can be given.
  • the electrolyte layer 152 has electronic insulation and oxygen ion conductivity within a temperature range of 600 to 1000 ° C., for example. Within this temperature range, oxygen ions can pass through the electrolyte layer 152.
  • the oxygen electrode 153 is made of a material that can efficiently dissociate oxygen and has electron conductivity.
  • the material include lanthanum, strontium, manganese (LaSrMn) -based perovskite oxide (LSM), LaSrCo oxide (LSC), LaSrCoFe oxide (LSCF), LaSrFe oxide (LSF), LaSrMnCo oxide (LSMCoCo oxide).
  • LaSrMnCr oxide LaCoMn oxide (LCM), LaSrCu oxide (LSC), LaSrFeNi oxide (LSFN), LaNiFe oxide (LNF), LaBaCo oxide (LBC), LaNiCo oxide (LNC) LaSrAlFe oxide (LSAF), LaSrCoNiCu oxide (LSCNC), LaSrFeNiCu oxide (LSFNC), LaNi oxide (LN), GdSrCo oxide (GSC), GdSrMn oxide (GSM) PrCaMn oxide (PCaM), PrSrMn oxide (PSM), PrBaCo oxide (PBC), SmSrCo oxide (SSC), NdSmCo oxide (NSC), BiSrCaCu oxide (BSCC), BaLaFeCo oxide (BLFC), BaSrFeCo An oxide (BSFC), a YSrFeCo oxide (YLFC), a YCuCoFe oxide (YCCF), or
  • the oxygen electrode 153 may be a mixture of these oxides.
  • it may be formed of LSM-YSZ, LSCF-SDC, LSCF-GDC, LSCF-YDC, LSCF-LDC, LSCF-CDC, LSM-ScSZ, LSM-SDC, LSM-GDC, or the like.
  • components such as Pt, Ru, Au, Ag, and Pd may be added to the oxygen electrode 153, for example.
  • the separators 16a and 16b are for blocking the solid oxide electrochemical cell 15 from the outside, and are made of a metal having conductivity and heat resistance (for example, stainless steel).
  • the separator 16 a has a recess 161, a groove 162, and a through hole H.
  • the solid oxide electrochemical cell 15 is accommodated in the recess 161.
  • a plurality of grooves 162 are arranged in the recess 161, and the hydrogen electrode gas G10 flows in the vertical direction of FIG. 3A.
  • the separator 16 b has a groove 163.
  • a plurality of grooves 163 are arranged, and the oxygen electrode gas G20 flows in the left-right direction in FIG. 3A.
  • the hydrogen electrode gas G10 and the hydrogen electrode exhaust gas G11 flow into and out of the groove 162 from the pair of upper and lower through holes H in FIG. 3A.
  • the hydrogen electrode gas G ⁇ b> 10 is supplied from one of these through holes H to the hydrogen electrode 151 through the groove 162.
  • the reacted hydrogen electrode gas (hydrogen electrode exhaust gas) G11 passes through the groove 162 and is discharged from the other through hole H.
  • the oxygen electrode gas G20 and the oxygen electrode exhaust gas G21 flow into and out of the groove 163 from the pair of left and right through holes H in FIG. 3A.
  • the oxygen electrode gas G ⁇ b> 20 is supplied from one of these through holes H to the oxygen electrode 153 through the groove 163.
  • the reacted oxygen electrode gas (oxygen electrode exhaust gas) G21 is discharged from the other through hole H through the groove 163.
  • the insulating sheet 17 electrically insulates between the separators 16a and 16b.
  • Current collectors 18a and 18b electrically connect hydrogen electrode 151 and oxygen electrode 153 to corresponding separators 16a and 16b, respectively.
  • members such as a gas supply line (piping) and a heating mechanism are formed of a metal containing chromium, and are protected from corrosion at high temperatures by the chromium oxide layer.
  • this oxide may leave the member and move by the oxygen electrode gas G20. That is, a part of the chromium oxide is sublimated (in a gaseous state) or broken into a fine powder and scattered (in a solid state).
  • the chromium oxide released from the member reaches the oxygen electrode 153, reacts and precipitates, and inhibits the reaction at the oxygen electrode 153.
  • FIG. 4 is a cross-sectional view schematically illustrating an example of the chromium recovery unit 20.
  • the chromium recovery unit 20 is disposed between the heat exchanger 30a (heating unit) and the electrochemical cell stack 10, and recovers and fixes the chromium oxide in the oxygen electrode gas G20.
  • the chromium recovery unit 20 includes an outer shell 21, a gas supply port 22, a gas discharge port 23, a partition wall 24, an insulating layer 25, an absorption layer 26, and an electrode 27.
  • the outer shell 21 and the partition wall 24 can be made of a material having conductivity and heat resistance (for example, metal).
  • the outer shell 21 blocks the inside from the outside.
  • the gas supply port 22 and the gas discharge port 23 are gas outlets for supplying and discharging the oxygen electrode gas G ⁇ b> 20 into the outer shell 21.
  • the partition wall 24 divides the inside of the outer shell 21 into a plurality of sections to increase the surface area in the outer shell 21 (the area of the absorption layer 26).
  • the partition wall 24 corresponds to a member having a predetermined surface.
  • the partition wall 24 has a flow path 241 (for example, a through hole) for connecting adjacent partitions.
  • an insulating layer 25, an absorption layer 26, and an electrode 27 are formed on the surface of the partition wall 24, on the surface of the partition wall 24, an insulating layer 25, an absorption layer 26, and an electrode 27 are formed. Note that the insulating layer 25, the absorption layer 26, and the electrode 27 can also be formed inside the outer shell 21.
  • the insulating layer 25 electrically insulates between the absorption layer 26 and the partition wall 24 (and the outer shell 21). As described later, the absorption of chromium can be promoted by keeping the absorption layer 26 at a negative potential.
  • the absorption layer 26 is a layer of the substance M that reacts with the chromium oxide in the oxidizing electrode gas G10 to generate the oxide C1. Chromium in the oxidizing gas reacts with the substance M in the absorption layer 26 to generate a stable oxide C1, thereby adsorbing and fixing chromium.
  • the vapor pressure P1 of the oxide C1 is equal to or lower than the vapor pressure P2 of the compound C2 formed by the reaction of the chromium oxide in the oxidizing electrode gas G10 with the oxygen electrode 153 (P1 ⁇ P2). If the vapor pressure is such a relationship, the chromium oxide in the gas G10 is accumulated in the absorption layer 26. If such a relationship is broken, the chromium oxide in the gas G10 is not accumulated in the absorption layer 26 finally, but is accumulated in the oxygen electrode 153 of the electrochemical cell stack 10.
  • the magnitude relationship between the vapor pressures may be the result of comparing the vapor pressure at the same temperature with the generated oxide C1 and the compound C2 being different, or the generated oxide C1 and the compound C2 being the same, You may achieve by making the temperature of the absorption layer 26 lower than the oxygen electrode 153.
  • the following materials (1) and (2) can be used.
  • Metal or metal oxide containing manganese As the substance M, for example, manganese alone, manganese chromium steel, ferromanganese manganese iron ferrite, or the like can be used.
  • Oxide Material Used for Oxygen Electrode 153 Substance M includes, for example, LSM, LSC, LSCF, LSF, LSMCo, LSMCr, LCM, LSC, LSFN, LNF, LBC, LNC, LSAF, LSCNC, LSFNC, LN , GSC, GSM, PCaM, PSM, PBC, SSC, NSC, BSCC, BLFC, BSFC, YLFC, YCCF, or YBC can be used.
  • materials containing Mn, LSM, LSMCo, LSMCr, LCM, GSM, PCaM, and PSM are preferable, and LSM is particularly preferable. Chromium precipitation can be accelerated
  • the constituent materials of the oxygen electrode 153 and the absorption layer 26 may be the same or different.
  • a temperature difference for example, 50 to 100 ° C.
  • the necessity of applying a temperature difference (for example, 50 to 100 ° C.) to the chromium recovery unit 20 (oxygen electrode 153) and the electrochemical cell stack 10 (absorption layer 26) increases.
  • a certain temperature difference for example, 50 to 100 ° C.
  • the absorption layer 26 may be made porous to increase the probability of contact with chromium oxide (vapor or fine powder) in the oxygen electrode gas G20.
  • the porous absorption layer 26 can be formed by applying or molding an oxide material powder.
  • the electrode 27 is a conductor disposed on the absorption layer 26, and applies a negative potential from the external power supply 40 to the absorption layer 26. By making the absorption layer 26 have a negative potential, absorption of chromium can be promoted.
  • the electrode 27 has air permeability (for example, a mesh shape or a porous shape) in order to bring the absorbing layer 26 into contact with the oxidizing gas.
  • FIG. 5 is a perspective view schematically showing another example of the chromium recovery unit 20a.
  • the chromium recovery unit 20 a includes a base 28, an insulating layer 25, an absorption layer 26, and an electrode 27.
  • the base 28 is made of a material having conductivity and heat resistance (for example, a metal such as stainless steel) and has a plurality of through holes 29.
  • An insulating layer 25, an absorption layer 26, and an electrode 27 are stacked in the through hole 29.
  • the gas G20 meanders and flows, whereas in the chromium recovery unit 20a, the gas G20 flows linearly.
  • the chromium in the gas G20 is absorbed by the absorption layer 26 and discharged to the outside. Since the chromium absorption mechanism in the chromium recovery unit 20a is the same as that of the chromium recovery unit 20, detailed description thereof is omitted.
  • the heat exchanger 30a heats the gas G20 using the high-temperature exhaust gas G21 discharged from the electrochemical cell stack 10 and supplies the gas G20 to the chromium recovery unit 20, and is disposed on the supply line to heat the gas. Corresponds to the heating part.
  • the temperature of the heated gas G20 is set to be somewhat lower than the temperature in the electrochemical cell stack 10.
  • the temperature of the absorption layer 26 is lowered to some extent (for example, by making it lower than the operating temperature of the oxygen electrode 153, it becomes possible to effectively recover chromium.
  • the temperature is too high, the chromium that has reacted once detaches and the absorption of chromium does not proceed.
  • the average temperature of the absorption layer 26 (on the surface of the partition wall 24 and on the inner surface of the through hole 29) may be lower than the temperature of the oxygen electrode 153 (the operating temperature of the solid oxide electrochemical cell 15). That is, the temperature of a part of the absorption layer 26 is allowed to be equal to or higher than the temperature of the oxygen electrode 153.
  • the heat exchanger 30 b heats the gas G ⁇ b> 20 exhausted from the chromium recovery unit 20 and supplies it to the electrochemical cell stack 10.
  • the heat exchanger 30b is disposed between the chromium recovery unit 20 and the electrochemical cell 10 on the gas G20 supply line, and functions as a second heating unit that heats the gas G20.
  • the heat exchanger 30b it becomes easier to provide an appropriate temperature difference between the chromium recovery unit 20 and the electrochemical cell stack 10. In addition, when this temperature difference does not matter so much, the heat exchanger 30b may be omitted.
  • the heat exchangers 30a and 30b are heating the gas G20 using the exhaust gas G21.
  • the gas G20 may be heated using the gas G11 instead of the exhaust gas G21 or together with the exhaust gas G21.
  • one or both of the heat exchangers 30a and 30b may be replaced with a heater to heat the gas G20 with electricity.
  • the external power supply 40 applies a voltage between the electrode 27 and the partition wall 24 (and the outer shell 21) of the chromium recovery unit 20, and makes the absorption layer 26 have a negative potential.
  • the absorption of chromium by the absorption layer 26 can be promoted.
  • the chromium recovery unit 20 absorbs chromium oxide gas or fine powder generated from the piping of the oxygen electrode gas G20 and the surface of the heat exchanger 30a. As a result, deterioration of the characteristics of the electrochemical cell stack 10 can be suppressed and operation can be efficiently performed over a long period.
  • FIG. 6 is a block diagram showing a solid oxide electrochemical system according to the second embodiment.
  • the same components as those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.
  • the solid oxide electrochemical system according to the second embodiment includes an electrochemical cell stack 10, a chromium recovery unit 20a, a heat exchanger 30a, a heater 50, and a controller 60.
  • the chromium recovery unit 20 a has a configuration corresponding to the electrochemical cell stack 10. That is, the chromium recovery unit 20a includes a cell unit 11, bus bars 12a and 12b, and end plates 13a and 13b.
  • the cell unit 11 includes a solid oxide electrochemical cell (single cell) 15a, separators 16a and 16b, an insulating sheet 17, and current collectors 18a and 18b.
  • the solid oxide electrochemical cell 15a includes a hydrogen electrode 151a, an electrolyte layer 152a, and an oxygen electrode 153a.
  • Chromium in the oxygen electrode gas G20 is adsorbed and fixed to the oxygen electrode 153a of the chromium recovery unit 20a.
  • the oxygen electrode 153a is an oxide material used for the oxygen electrode 153, such as LSM, LSC, LSCF, LSF, LSMCo, LSMCr, LCM, LSC, LSFN, LNF, LBC, LNC, LSAF, LSCNC, LSFNC, LN, GSC GSM, PCaM, PSM, PBC, SSC, NSC, BSCC, BLFC, BSFC, YLFC, YCCF, or YBC can be used.
  • materials containing Mn, LSM, LSMCo, LSMCr, LCM, GSM, PCaM, and PSM are preferable, and LSM is particularly preferable.
  • LSM is particularly preferable.
  • a used solid oxide electrochemical cell stack may be used for the chromium recovery unit 20a. That is, a solid oxide electrochemical cell stack having a reduced SOFC or SOEC property (due to factors other than chromium poisoning) can be used as the chromium recovery unit 20a.
  • the electrochemical cell stack used as the chromium recovery unit 20a is preferably operated as a fuel cell. Adsorption of chromium in the gas G20 to the oxygen electrode 153a can be promoted by the voltage accompanying the power generation. For this reason, reducing gas (gas G10) is supplied to the hydrogen electrode 151a of the chromium recovery unit 20a. As a result, combined with the supply of the oxidizing gas (gas G20) to the oxygen electrode 153a, the chromium recovery unit 20a generates power.
  • Controller 50 controls overvoltage in power generation reaction of chromium recovery unit 20a. That is, the electric power generated in the chromium recovery unit 20a is appropriately supplied to other places or consumed. By appropriately consuming the electric power generated in the chromium recovery unit 20a, the reaction in the chromium recovery unit 20a (oxygen electrode 153a) and hence the absorption of chromium can be promoted. When the electric power generated in the chromium recovery unit 20a is accumulated in the chromium recovery unit 20a, the fuel cell reaction in the chromium recovery unit 20a is hindered.
  • the heat exchanger 30a heats the gas G20 using the high-temperature exhaust gas G21 discharged from the electrochemical cell stack 10 and supplies it to the chromium recovery unit 20.
  • the chromium recovery unit 20 oxygen electrode 153a
  • the electrochemical cell stack 10 oxygen electrode 153
  • the heater 60 heats the gas G20 discharged from the chromium recovery unit 20a and supplies it to the electrochemical cell stack 10. By using the heater 60, it becomes easier to make an appropriate temperature difference between the chromium recovery unit 20a and the electrochemical cell stack 10. In addition, when this temperature difference does not matter so much, the heater 60 may be omitted. In the present embodiment, the electric power generated by the chromium recovery unit 20a is used for heating the gas G20 by the heater 60, and the system can be efficiently operated.
  • the chromium recovery unit 20a absorbs chromium oxide gas or fine powder generated from the piping of the oxygen electrode gas G20 and the surface of the heat exchanger 30a. As a result, deterioration of the characteristics of the electrochemical cell stack 10 can be suppressed and operation can be efficiently performed over a long period.

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Abstract

Un système électrochimique selon un mode de réalisation comprend au moins une cellule électrochimique, une ligne d'alimentation, une partie de chauffage et une unité de récupération de chrome. La cellule électrochimique a une couche d'électrolyte d'un oxyde solide, et une électrode à oxygène ainsi qu'une électrode à hydrogène qui sont respectivement disposées sur les deux côtés de la couche d'électrolyte. La ligne d'alimentation a au moins une partie composée d'un métal qui comprend du chrome, et fournit un gaz à l'électrode à oxygène de la ou des cellules électrochimiques. La partie chauffante est disposée sur la ligne d'alimentation et chauffe le gaz. L'unité de récupération de chrome est disposée entre la partie de chauffage sur la ligne d'alimentation et la cellule électrochimique, et récupère les oxydes de chrome à partir du gaz.
PCT/JP2017/004231 2017-02-06 2017-02-06 Système électrochimique et procédé de récupération de chrome pour système électrochimique WO2018142615A1 (fr)

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JP2018565225A JP6833876B2 (ja) 2017-02-06 2017-02-06 電気化学システムおよび電気化学システムのクロム回収方法
PCT/JP2017/004231 WO2018142615A1 (fr) 2017-02-06 2017-02-06 Système électrochimique et procédé de récupération de chrome pour système électrochimique

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