WO2009096221A1 - 間接内部改質型固体酸化物形燃料電池とその停止方法 - Google Patents
間接内部改質型固体酸化物形燃料電池とその停止方法 Download PDFInfo
- Publication number
- WO2009096221A1 WO2009096221A1 PCT/JP2009/050351 JP2009050351W WO2009096221A1 WO 2009096221 A1 WO2009096221 A1 WO 2009096221A1 JP 2009050351 W JP2009050351 W JP 2009050351W WO 2009096221 A1 WO2009096221 A1 WO 2009096221A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reformer
- anode
- reforming
- hydrocarbon
- solid oxide
- Prior art date
Links
Images
Classifications
-
- 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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/386—Catalytic partial combustion
-
- 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
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
-
- 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
- H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
- H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
- H01M8/04303—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during shut-down
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
- H01M8/04328—Temperature; Ambient temperature of anode reactants at the inlet or inside the fuel cell
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04388—Pressure; Ambient pressure; Flow of anode reactants at the inlet or inside the fuel cell
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04425—Pressure; Ambient pressure; Flow at auxiliary devices, e.g. reformers, compressors, burners
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04746—Pressure; Flow
- H01M8/04776—Pressure; Flow at auxiliary devices, e.g. reformer, compressor, burner
-
- 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
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04955—Shut-off or shut-down of fuel cells
-
- 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1609—Shutting down the process
-
- 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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an indirect internal reforming solid oxide fuel cell having a reformer in the vicinity of the fuel cell.
- Solid oxide electrolyte fuel cell Solid Oxide Fuel Cell
- SOFC Solid Oxide Fuel Cell
- SOFC is usually operated at a high temperature of 550-1000 ° C.
- SR steam reforming
- POX partial oxidation reforming
- ATR autothermal reforming
- Patent Document 2 If the method described in Patent Document 2 is used, it is considered that the anode can be held in a reducing atmosphere when the fuel cell is stopped, and oxidation deterioration of the anode can be prevented.
- An object of the present invention is to provide a method for stopping an indirect internal reforming SOFC capable of reliably reforming a hydrocarbon-based fuel and preventing oxidative deterioration of the anode by the reformed gas.
- Another object of the present invention is to provide an indirect internal reforming SOFC suitable for carrying out such a stopping method.
- a reformer having a reforming catalyst layer for reforming hydrocarbon fuel to produce reformed gas, A solid oxide fuel cell that generates electric power using the reformed gas; and A combustion region for burning anode off-gas discharged from the solid oxide fuel cell;
- a method for stopping an indirect internal reforming solid oxide fuel cell comprising: a reformer, a solid oxide fuel cell, and a housing that houses a combustion region; The following conditions i to iv, i) The anode temperature of the solid oxide fuel cell is steady, ii) the anode temperature is below the oxidative degradation point; iii) In the reformer, the hydrocarbon-based fuel is reformed, and a reformed gas having a composition suitable for supplying to the anode is generated, iv) The amount of the reformed gas generated is equal to or higher than the minimum flow rate necessary to prevent oxidative deterioration of the anode when the anode temperature of the solid oxide fuel cell is at or above the oxidative
- FE represents the flow rate of the hydrocarbon-based fuel supplied to the reformer in a state where all of the above are satisfied
- the flow rate of the hydrocarbon fuel supplied to the reformer at the start of the stop method is expressed as FS
- a) the step of changing the flow rate of the hydrocarbon-based fuel supplied to the reformer from FS to FE; and b) the supply of the hydrocarbon-based fuel to the reformer is stopped when the anode temperature falls below the oxidation deterioration point.
- the present invention is particularly effective when the hydrocarbon fuel includes a hydrocarbon fuel having 2 or more carbon atoms.
- the concentration of the compound having 2 or more carbon atoms in the reformed gas is preferably 50 ppb or less on a mass basis.
- a reformer having a reforming catalyst layer for reforming hydrocarbon fuel to produce reformed gas; A solid oxide fuel cell that generates electric power using the reformed gas; and A combustion region for burning anode off-gas discharged from the solid oxide fuel cell;
- An indirect internal reforming solid oxide fuel cell having the reformer, a solid oxide fuel cell, and a housing containing a combustion region, The following conditions i to iv, i) The anode temperature of the solid oxide fuel cell is steady, ii) the anode temperature is below the oxidative degradation point; iii) In the reformer, the hydrocarbon-based fuel is reformed, and a reformed gas having a composition suitable for supplying to the anode is generated, iv) The amount of the reformed gas generated is equal to or higher than the minimum flow rate necessary to prevent oxidative deterioration of the anode when the anode temperature of the solid oxide fuel cell is at or above the oxidative deterioration point.
- FE represents the flow rate of the hydrocarbon-based fuel supplied to the reformer in a state where all of the above are satisfied
- flow rate of the hydrocarbon fuel supplied to the reformer at the start of the stop method is expressed as FS
- Means for changing the flow rate of the hydrocarbon fuel supplied to the reformer from FS to FE and II) When the anode temperature falls below the oxidative deterioration point, supply the hydrocarbon fuel to the reformer.
- An indirect internal reforming solid oxide fuel cell having means for stopping is provided.
- a method for stopping an indirect internal reforming SOFC that can reliably reform a hydrocarbon-based fuel and prevent oxidative deterioration of the anode by the reformed gas.
- the present invention also provides an indirect internal reforming SOFC suitable for carrying out such a stopping method.
- FIG. 1 schematically shows an embodiment of an indirect internal reforming SOFC that can implement the present invention.
- the indirect internal reforming SOFC has a reformer 3 that reforms a hydrocarbon fuel to produce a reformed gas (hydrogen-containing gas).
- the reformer has a reforming catalyst layer 4.
- the indirect internal reforming SOFC has an SOFC 6 that generates electric power using the reformed gas, and also has a combustion region 5 in which anode off-gas discharged from the SOFC (particularly its anode) is combusted.
- the indirect internal reforming SOFC has a reformer, a solid oxide fuel cell, and a housing 8 that houses a combustion region.
- Indirect internal reforming SOFC refers to the housing (module container) 8 and the equipment contained therein.
- an igniter 7 that is an ignition means for igniting the anode off-gas is provided, and the reformer includes an electric heater 9.
- Each supply gas is preheated as necessary and then supplied to the reformer or SOFC.
- the indirect internal reforming SOFC is connected with a water vaporizer 1 equipped with an electric heater 2, and a pipe for supplying hydrocarbon fuel to the reformer is connected in the middle of the connecting pipe.
- the water vaporizer 1 generates water vapor by heating with the electric heater 2. Water vapor can be superheated appropriately in the water vaporizer or downstream thereof and then supplied to the reforming catalyst layer.
- air is also supplied to the reforming catalyst layer.
- air can be supplied to the reforming catalyst layer after preheating with a water vaporizer. Water vapor can be obtained from the water vaporizer, and a mixed gas of air and water vapor can be obtained.
- Hydrocarbon fuel is mixed with hydrocarbon fuel and supplied to the reformer 3, particularly the reforming catalyst layer 4.
- hydrocarbon-based fuel can be appropriately vaporized and then supplied to the reforming catalyst layer.
- the reformed gas obtained from the reformer is supplied to the SOFC 6, particularly the anode thereof. Although not shown, air is appropriately preheated and supplied to the SOFC cathode.
- the combustible component in the anode off gas (gas discharged from the anode) is burned by oxygen in the cathode off gas (gas discharged from the cathode) at the SOFC outlet.
- ignition can be performed using the igniter 7.
- the outlets of both the anode and the cathode are opened in the module container 8.
- the combustion gas is appropriately discharged from the module container.
- Reformer and SOFC are accommodated in one module container and modularized.
- the reformer is disposed at a position where heat can be received from the SOFC. For example, if the reformer is disposed at a position where it receives heat radiation from the SOFC, the reformer is heated by heat radiation from the SOFC during power generation.
- the reformer is preferably disposed at a position where radiation heat can be directly transferred from the SOFC to the outer surface of the reformer. Therefore, it is preferable that a shielding object is not substantially disposed between the reformer and the SOFC, that is, a gap is provided between the reformer and the SOFC. Further, it is preferable to shorten the distance between the reformer and the SOFC as much as possible.
- the reformer 3 is heated by the combustion heat of the anode off gas generated in the combustion region 5. Further, when the SOFC is at a higher temperature than the reformer, the reformer is also heated by radiant heat from the SOFC.
- the reformer may be heated by heat generated by reforming. If the reforming is partial oxidation reforming or autothermal reforming (autothermal reforming) and the heat generation by the partial oxidation reforming reaction is greater than the endothermic reaction by the steam reforming reaction, Fever accompanies.
- a state in which all of the following conditions i to iv are satisfied is referred to as a reforming stoppable state.
- the anode temperature of the SOFC is steady.
- the anode temperature is lower than the oxidation deterioration point.
- a reformed gas having a composition suitable for supply to the anode is generated in the reformer.
- the amount of the reformed gas generated is equal to or higher than the minimum flow rate necessary to prevent oxidative degradation of the anode when the SOFC anode temperature is at or above the oxidation degradation point.
- the anode temperature means the temperature of the anode electrode.
- it can be the temperature of a stack component such as a separator in the vicinity of the anode.
- As the anode temperature measurement position it is preferable to adopt a location where the temperature is relatively high, more preferably a location where the temperature is highest, from the viewpoint of safety control.
- the position where the temperature rises can be known through preliminary experiments and simulations.
- the oxidation deterioration point is a temperature at which the anode is oxidized and deteriorated.
- the electrical conductivity of the anode material is measured by the direct current four-terminal method by changing the temperature in a reducing or oxidizing gas atmosphere, and in an oxidizing gas atmosphere.
- the minimum temperature at which the electrical conductivity at is lower than the value in the reducing gas atmosphere can be set as the oxidation deterioration point.
- the condition iii means that the hydrocarbon-based fuel is reformed in the reformer and a reformed gas having a composition suitable for supplying to the anode is obtained.
- the hydrocarbon-based fuel contains a hydrocarbon-based fuel having 2 or more carbon atoms
- the reformed gas is reducible, and the C2 + component (compound having 2 or more carbon atoms) in the reformed gas flows due to carbon deposition.
- the concentration of the C2 + component at this time is preferably 50 ppb or less as a mass fraction in the reformed gas.
- the minimum necessary reformed gas flow rate for preventing oxidative deterioration of the anode is the smallest flow rate among the flow rates at which the anode electrode is not oxidized and deteriorated due to diffusion of the cathode off gas from the anode outlet to the inside of the anode.
- This reformed gas flow rate can be known in advance by performing experiments and simulations by changing the reformed gas flow rate while maintaining the anode temperature at or above the oxidation deterioration point.
- the anodic oxidation degradation can be judged by, for example, measuring the electrical conductivity of the anode electrode in an experiment and comparing it with an anode electrode that has not undergone oxidation degradation.
- the gas composition partial pressure of the anode can be calculated by simulation using an equation including an advection diffusion term, and can be determined by comparison with the equilibrium partial pressure in the oxidation reaction of the anode electrode.
- the equilibrium partial pressure of oxygen in the anode electrode oxidation reaction represented by the following formula is 1.2 ⁇ 10 ⁇ 14 atm (1.2 ⁇ 10 ⁇ 9 Pa), and this value If the calculated value of the oxygen partial pressure of the anode is smaller, it can be determined that the anode electrode is not oxidized and deteriorated.
- the reformed gas flow rate (the amount of reformed gas generated by the reformer) supplied to the SOFC to prevent oxidative deterioration of the anode can be combusted when the reformed gas passes through the SOFC and is discharged from the anode.
- the flow rate is preferably as follows. When the smallest flow rate among the combustible reformed gas flow rates is larger than the above-mentioned minimum required reformed gas flow rate, the smallest flow rate among the combustible reformed gas flow rates is referred to as “required minimum flow rate” in the condition iv. Thus, the reformed gas flow rate can be obtained. Whether combustion is possible can be determined by, for example, sampling the gas in the combustion gas discharge line by experiment and performing composition analysis, or calculating by simulation.
- the flow rate of hydrocarbon fuel supplied to the reformer (particularly the reforming catalyst layer) in a state where the reforming can be stopped is represented by FE.
- FE can be obtained in advance by experiments or simulations.
- the flow rate of the fluid supplied to the indirect internal reforming SOFC such as the flow rate of the fluid such as water or air supplied to the heat exchanger; the reformer, the evaporator of water or liquid fuel, the SOFC, the fluid supply piping
- the electric input / output to the indirect internal reforming SOFC such as the electric heater output for heating etc., the electric input extracted from the thermoelectric conversion module, etc., is changed, that is, the operating conditions of the indirect internal reforming SOFC are changed.
- the FE may be any value as long as the conditions i to iv are satisfied, but it is preferable to use the smallest FE from the viewpoint of thermal efficiency.
- the operating condition of the indirect internal reforming SOFC including the FE is determined in advance as the operating condition in a state where the reforming can be stopped.
- the flow rate of the hydrocarbon-based fuel that has been supplied to the reformer at the start of the stop method is denoted as FS.
- the stopping method of the present invention includes the following steps a and b.
- the flow rate of the fluid supplied to the indirect internal reforming SOFC such as the flow rate of fuel and air supplied to the burner, the flow rate of fluid such as water and air supplied to the heat exchanger, the evaporator and the evaporator of water and liquid fuel
- Predetermined reforming stops the input / output of electricity to the indirect internal reforming SOFC, such as the electric heater output for heating the cell stack, fluid supply piping, etc., and the electric input extracted from the thermoelectric conversion module, etc.
- Use operating conditions in the possible state That is, the operation condition of the indirect internal reforming SOFC in a predetermined reforming stoppable state is set.
- step a When the indirect internal reforming SOFC is stopped, that is, when the stopping method is started, step a can be performed immediately.
- the supply amount of the hydrocarbon fuel to the reformer may be kept as FE.
- step a when the anode temperature falls below the oxidative degradation point, reducing gas is no longer necessary, so the supply of hydrocarbon fuel to the reformer can be stopped. From the viewpoint of thermal efficiency, it is preferable to stop the supply of the hydrocarbon-based fuel to the reformer within as short a time as possible when the anode temperature falls below the oxidation deterioration point.
- the anode temperature can be appropriately monitored (continuously measured) using a temperature sensor such as a thermocouple.
- the monitoring of the anode temperature is preferably started immediately after the stop method is started. If these temperatures are monitored before the stop method is started, the temperature may be continuously monitored even when the stop method is performed.
- the reformer may perform any type of reforming among steam reforming, partial oxidation reforming, and autothermal reforming.
- ⁇ Different types of reforming may be performed before and after starting the stopping method.
- steam reforming can be performed before the stop method is started, and autothermal reforming can be performed after the stop method is started, or vice versa.
- steam reforming can be performed before the stop method is started, and partial oxidation reforming can be performed after the stop method is started, or vice versa.
- a reforming catalyst layer capable of promoting a steam reforming reaction is used, and after performing step a until performing step b, that is, when reforming a hydrocarbon-based fuel having a flow rate FE. It is preferable to perform steam reforming. This is because steam reforming involves a large endotherm, so that the temperature of the reformer can be lowered more quickly.
- steam is supplied to the reforming catalyst layer.
- a partial oxidation reforming reaction that is, when performing partial oxidation reforming or autothermal reforming
- an oxygen-containing gas is supplied to the reforming catalyst layer.
- the oxygen-containing gas a gas containing oxygen can be used as appropriate, but air is preferable because it is easily available.
- the present invention is particularly effective when the hydrocarbon fuel has 2 or more carbon atoms. This is because such fuel is particularly required to be reformed.
- This indirect internal reforming SOFC is a reformer 3 that reforms hydrocarbon fuel to produce reformed gas (this reformer has a reforming catalyst layer 4); power generation using the reformed gas A combustion zone 5 for burning anode off-gas discharged from the SOFC; and a housing 8 for housing the reformer, the solid oxide fuel cell, and the combustion zone.
- This indirect internal reforming SOFC further includes the following means I and II.
- Means I can include control means that can input and store the flow rate FE.
- control means a control means known in the field of process control or fuel cell system control such as the computer 10 can be used.
- the means I can include a flow rate adjusting valve 11a for the hydrocarbon fuel and a flow meter 12a for adjusting the flow rate of the hydrocarbon fuel.
- the pump for hydrocarbon fuels which can change a flow volume according to an input signal can be included.
- Means II is a temperature sensor such as a thermocouple 13 for detecting the anode temperature; a valve capable of stopping the supply of hydrocarbon fuel to the reformer (the flow control valve 11a may be used, but a separate stop valve) And a pump capable of stopping the supply of hydrocarbon fuel by an input signal; and a control means such as the computer 10 can be included.
- the control means used here can input and store the oxidation deterioration point.
- the control means can also receive the anode temperature from the temperature sensor, compare the anode temperature with the oxidation degradation point, and determine that the anode temperature is below the oxidation degradation point, An instruction to close the flow rate adjusting valve 11a (or a stop valve or the like) to stop the supply of hydrocarbon fuel to the reformer and an instruction to stop the operation of the pump can be issued.
- the indirect internal reforming SOFC can include, for example, a flow control valve 11b for water and a flow meter 12b in order to supply steam to the reforming catalyst layer as necessary.
- the pump for water which can change a flow volume according to an input signal can be provided.
- the indirect internal reforming SOFC can be provided with, for example, a flow control valve 11c for air and a flow meter 12c in order to supply the oxygen-containing gas to the reforming catalyst layer as necessary.
- the blower for air which can change a flow volume according to an input signal can be provided.
- hydrocarbon fuel As the hydrocarbon-based fuel, as a reformed gas raw material, a compound known from the field of SOFC, containing carbon and hydrogen (may contain other elements such as oxygen) or a mixture thereof, or a mixture thereof may be used as appropriate. And compounds having carbon and hydrogen in the molecule such as hydrocarbons and alcohols can be used.
- hydrocarbon fuels such as methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, gasoline, naphtha, kerosene, light oil, etc., alcohols such as methanol and ethanol, ethers such as dimethyl ether, etc. is there.
- kerosene and LPG are preferred because they are readily available. Moreover, since it can be stored independently, it is useful in areas where city gas lines are not widespread. Furthermore, SOFC power generators using kerosene or LPG are useful as emergency power supplies. In particular, kerosene is preferable because it is easy to handle.
- the reformer produces a reformed gas containing hydrogen from a hydrocarbon fuel.
- any of steam reforming, partial oxidation reforming, and autothermal reforming accompanied by a partial oxidation reaction in the steam reforming reaction may be performed.
- the reformer is appropriately equipped with a steam reforming catalyst having steam reforming ability, a partial oxidation reforming catalyst having partial oxidation reforming ability, and a self-thermal reforming catalyst having both partial oxidation reforming ability and steam reforming ability. Can be used.
- a structure known as a reformer can be appropriately adopted.
- a structure having a region for accommodating the reforming catalyst in a sealable container and having an inlet for fluid necessary for reforming and an outlet for reforming gas can be appropriately adopted.
- the material of the reformer can be appropriately selected and adopted from materials known as reformers in consideration of resistance in the use environment.
- the shape of the reformer can be an appropriate shape such as a rectangular parallelepiped or a circular tube.
- the reformed gas obtained from the reformer is supplied to the anode of the SOFC.
- an oxygen-containing gas such as air is supplied to the cathode of the SOFC.
- the SOFC generates heat with power generation, and the heat is transmitted from the SOFC to the reformer by radiant heat transfer or the like.
- the SOFC exhaust heat is used to heat the reformer. Gas exchange and the like are appropriately performed using piping or the like.
- SOFC a known SOFC can be selected and adopted as appropriate.
- oxygen ion conductive ceramics or proton ion conductive ceramics are generally used as an electrolyte.
- the SOFC may be a single cell, but in practice, a stack in which a plurality of single cells are arranged (in the case of a cylindrical type, sometimes referred to as a bundle, but the stack in this specification includes a bundle) is preferable. Used. In this case, one or more stacks may be used.
- the shape of the SOFC is not limited to the cubic stack, and an appropriate shape can be adopted.
- oxidation deterioration of the anode may occur at about 400 ° C.
- an appropriate container capable of accommodating the SOFC, the reformer, and the combustion region can be used.
- the material for example, an appropriate material having resistance to the environment to be used, such as stainless steel, can be used.
- the container is appropriately provided with a connection port for gas exchange and the like.
- the module container has airtightness so that the inside of the module container and the outside (atmosphere) do not communicate with each other.
- the combustion region is a region where the anode off gas discharged from the anode of the SOFC can be combusted.
- the anode outlet can be opened in the housing, and the space near the anode outlet can be used as a combustion region.
- This combustion can be performed using, for example, a cathode off gas as the oxygen-containing gas.
- the cathode outlet can be opened in the housing.
- An ignition means such as an igniter can be appropriately used to burn the combustion fuel or anode off gas.
- Any of the steam reforming catalyst, partial oxidation reforming catalyst, and autothermal reforming catalyst used in the reformer can be a known catalyst.
- the partial oxidation reforming catalyst include platinum-based catalysts
- examples of the steam reforming catalyst include ruthenium-based and nickel-based catalysts
- examples of the autothermal reforming catalyst include rhodium-based catalysts.
- reforming catalysts that can promote combustion include platinum-based and rhodium-based catalysts.
- the temperature at which the partial oxidation reforming reaction can proceed is, for example, 200 ° C. or more, and the temperature at which the steam reforming reaction can proceed is, for example, 400 ° C. or more.
- steam reforming steam is added to reforming raw materials such as kerosene.
- the reaction temperature of the steam reforming can be performed, for example, in the range of 400 ° C. to 1000 ° C., preferably 500 ° C. to 850 ° C., more preferably 550 ° C. to 800 ° C.
- the amount of steam introduced into the reaction system is defined as the ratio of the number of moles of water molecules to the number of moles of carbon atoms contained in the hydrocarbon fuel (steam / carbon ratio), and this value is preferably 1 to 10, more preferably It is 1.5-7, more preferably 2-5.
- the space velocity (LHSV) at this time is A / B when the flow rate in the liquid state of the hydrocarbon fuel is A (L / h) and the catalyst layer volume is B (L).
- This value is preferably set in the range of 0.05 to 20 h ⁇ 1 , more preferably 0.1 to 10 h ⁇ 1 , still more preferably 0.2 to 5 h ⁇ 1 .
- an oxygen-containing gas is added to the reforming raw material in addition to steam.
- the oxygen-containing gas may be pure oxygen, but air is preferred because of its availability.
- An oxygen-containing gas can be added so that the endothermic reaction accompanying the steam reforming reaction is balanced, and a heat generation amount capable of maintaining the temperature of the reforming catalyst layer and SOFC or raising the temperature thereof can be obtained.
- the addition amount of the oxygen-containing gas is preferably 0.005 to 1, more preferably 0.01 to 0.00 as the ratio of the number of moles of oxygen molecules to the number of moles of carbon atoms contained in the hydrocarbon fuel (oxygen / carbon ratio). 75, more preferably 0.02 to 0.6.
- the reaction temperature of the autothermal reforming reaction is set, for example, in the range of 400 ° C. to 1000 ° C., preferably 450 ° C. to 850 ° C., more preferably 500 ° C. to 800 ° C.
- the space velocity (LHSV) at this time is preferably 0.05 to 20 h ⁇ 1 , more preferably 0.1 to 10 h ⁇ 1 , further preferably 0.2 to 5 h ⁇ 1. Is selected within the range.
- the amount of steam introduced into the reaction system is preferably 1 to 10, more preferably 1.5 to 7, and still more preferably 2 to 5 as a steam / carbon ratio.
- an oxygen-containing gas is added to the reforming material.
- the oxygen-containing gas may be pure oxygen, but air is preferred because of its availability.
- the amount added is appropriately determined in terms of heat loss and the like.
- the amount is preferably 0.1 to 3, more preferably 0.2 to 0.7, as the ratio of the number of moles of oxygen molecules to the number of moles of carbon atoms contained in the hydrocarbon fuel (oxygen / carbon ratio).
- the reaction temperature of the partial oxidation reaction can be set, for example, in the range of 450 ° C. to 1000 ° C., preferably 500 ° C. to 850 ° C., more preferably 550 ° C. to 800 ° C.
- the space velocity (LHSV) at this time is preferably selected in the range of 0.1 to 30 h ⁇ 1 .
- steam can be introduced, and the amount thereof is preferably 0.1 to 5, more preferably 0.1 to 3, more preferably 1 to 3 as the steam / carbon ratio. 2.
- Known components of the indirect internal reforming SOFC can be appropriately provided as necessary.
- Specific examples include a vaporizer for vaporizing liquid, a pump for pressurizing various fluids, a pressure increasing means such as a compressor and a blower, a valve for adjusting the flow rate of the fluid, or for blocking / switching the flow of the fluid.
- the present invention can be applied to an indirect internal reforming SOFC used for, for example, a stationary or moving power generator or a cogeneration system.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
該改質ガスを用いて発電を行う固体酸化物形燃料電池と、
該固体酸化物燃料電池から排出されるアノードオフガスを燃焼させる燃焼領域と、
該改質器、固体酸化物形燃料電池および燃焼領域を収容する筐体と、を有する間接内部改質型固体酸化物形燃料電池の停止方法であって、
次の条件iからiv、
i)該固体酸化物燃料電池のアノード温度が定常であり、
ii)該アノード温度が酸化劣化点未満であり、
iii)改質器において、炭化水素系燃料が改質され、アノードに供給するのに適した組成の改質ガスが生成しており、
iv)前記改質ガスの生成量が、該固体酸化物燃料電池のアノード温度が酸化劣化点以上の温度にある場合においてアノードの酸化劣化を防止するために必要最小限な流量以上である、
が全て満たされる状態において改質器に供給される炭化水素系燃料の流量をFEと表し、
該停止方法開始時点で改質器に供給していた炭化水素系燃料の流量をFSと表したとき、
a)改質器に供給する炭化水素系燃料の流量をFSからFEにする工程、および
b)アノード温度が酸化劣化点を下回ったら、該改質器への炭化水素系燃料の供給を停止する工程
を有する間接内部改質型固体酸化物形燃料電池の停止方法が提供される。
炭化水素系燃料を改質して改質ガスを製造する、改質触媒層を有する改質器と、
該改質ガスを用いて発電を行う固体酸化物形燃料電池と、
該固体酸化物燃料電池から排出されるアノードオフガスを燃焼させる燃焼領域と、
該改質器、固体酸化物形燃料電池および燃焼領域を収容する筐体と、を有する間接内部改質型固体酸化物形燃料電池であって、
次の条件iからiv、
i)該固体酸化物燃料電池のアノード温度が定常であり、
ii)該アノード温度が酸化劣化点未満であり、
iii)改質器において、炭化水素系燃料が改質され、アノードに供給するのに適した組成の改質ガスが生成しており、
iv)前記改質ガスの生成量が、該固体酸化物燃料電池のアノード温度が酸化劣化点以上の温度にある場合においてアノードの酸化劣化を防止するために必要最小限な流量以上である、
が全て満たされる状態において改質器に供給される炭化水素系燃料の流量をFEと表し、
該停止方法開始時点で改質器に供給していた炭化水素系燃料の流量をFSと表したとき、
I)改質器に供給する炭化水素系燃料の流量をFSからFEにするための手段、および
II)アノード温度が酸化劣化点を下回ったら、該改質器への炭化水素系燃料の供給を停止するための手段
を有する間接内部改質型固体酸化物形燃料電池が提供される。
2 水気化器に付設された電気ヒータ
3 改質器
4 改質触媒層
5 燃焼領域
6 SOFC
7 イグナイター
8 筐体(モジュール容器)
9 改質器に付設された電気ヒータ
10 コンピュータ
11 流量調節バルブ
12 流量計
13 熱電対
図1に、本発明を実施することのできる間接内部改質型SOFCの一形態を模式的に示す。
本明細書において、次の条件i~ivの全てが満たされている状態を改質停止可能状態と呼ぶ。
i)SOFCのアノード温度が定常である。
ii)前記アノード温度が酸化劣化点未満である。
iii)改質器においてアノードに供給するのに適した組成の改質ガスが生成している。
iv)この改質ガスの生成量が、SOFCのアノード温度が酸化劣化点以上の温度にある場合においてアノードの酸化劣化を防止するために必要最小限な流量以上である。
アノード温度は、アノード電極の温度を意味するが、アノード電極の温度を物理的に直接測定することが困難な場合には、アノード近傍のセパレータなどのスタック構成部材の温度とすることができる。アノード温度の測定位置は、安全制御の観点から相対的に温度が高くなる箇所、より好ましくは最も温度が高くなる箇所を採用することが好ましい。温度が高くなる位置は、予備実験やシミュレーションにより知ることができる。
条件iiiは、改質器において炭化水素系燃料が改質されており、アノードに供給するのに適した組成の改質ガスが得られている状態であることを意味している。例えば、炭化水素系燃料が炭素数2以上の炭化水素系燃料を含む場合、改質ガスが還元性であるとともに、改質ガス中のC2+成分(炭素数2以上の化合物)が炭素析出による流路閉塞やアノード劣化に対して問題にならない濃度以下である状態であることを意味している。このときのC2+成分の濃度は、改質ガス中の質量分率として50ppb以下が好ましい。
アノードの酸化劣化を防止するために必要最小限の改質ガス流量は、カソードオフガスのアノード出口からアノード内部への拡散によりアノード電極が酸化劣化しない流量のうち最も小さい流量である。この改質ガス流量は、アノード温度を酸化劣化点以上に保持した状態で、改質ガス流量を変えて実験やシミュレーションを行い、予め知っておくことができる。アノード酸化劣化は、例えば、実験でアノード電極の電気伝導度を測定し、酸化劣化していないアノード電極との比較により判断することができる。あるいは、移流拡散項を含む方程式を用いたシミュレーションによりアノードのガス組成分圧を計算し、アノード電極の酸化反応における平衡分圧との比較により判断することができる。例えば、アノード電極材料がNiの場合、次式で表されるアノード電極酸化反応における酸素の平衡分圧は1.2×10-14atm(1.2×10-9Pa)であり、この値よりアノードの酸素分圧の計算値が小さければ、アノード電極が酸化劣化しないと判断することができる。
停止方法開始時点で改質器に供給していた炭化水素系燃料の流量をFSと表す。
上記方法を行うために好適に用いることのできる間接内部改質型SOFCの一形態について、図3を用いて説明する。
I)改質器に供給する炭化水素系燃料の流量を、FS(停止方法開始時点で改質器に供給していた炭化水素系燃料の流量)からFE(改質停止可能状態において改質器に供給される炭化水素系燃料の流量)にするための手段。
II)アノード温度が酸化劣化点を下回ったら、改質器への炭化水素系燃料の供給を停止するための手段。
炭化水素系燃料としては、改質ガスの原料としてSOFCの分野で公知の、分子中に炭素と水素を含む(酸素など他の元素を含んでもよい)化合物もしくはその混合物から適宜選んで用いることができ、炭化水素類、アルコール類など分子中に炭素と水素を有する化合物を用いることができる。例えばメタン、エタン、プロパン、ブタン、天然ガス、LPG(液化石油ガス)、都市ガス、ガソリン、ナフサ、灯油、軽油等の炭化水素燃料、また、メタノール、エタノール等のアルコール、ジメチルエーテル等のエーテル等である。
改質器は、炭化水素系燃料から水素を含む改質ガスを製造する。
改質器から得られる改質ガスが、SOFCのアノードに供給される。一方、SOFCのカソードには空気などの酸素含有ガスが供給される。発電時には、発電に伴いSOFCが発熱し、その熱がSOFCから改質器へと、輻射伝熱などにより伝わる。こうしてSOFC排熱が改質器を加熱するために利用される。ガスの取り合い等は適宜配管等を用いて行う。
筐体(モジュール容器)としては、SOFC、改質器および燃焼領域を収容可能な適宜の容器を用いることができる。その材料としては、例えばステンレス鋼など、使用する環境に耐性を有する適宜の材料を用いることができる。容器には、ガスの取り合い等のために、適宜接続口が設けられる。
燃焼領域は、SOFCのアノードから排出されるアノードオフガスを燃焼可能な領域である。例えば、アノード出口を筐体内に開放し、アノード出口近傍の空間を燃焼領域とすることができる。酸素含有ガスとして例えばカソードオフガスを用いてこの燃焼を行なうことができる。このために、カソード出口を筐体内に開放することができる。
改質器で用いる水蒸気改質触媒、部分酸化改質触媒、自己熱改質触媒のいずれも、それぞれ公知の触媒を用いることができる。部分酸化改質触媒の例としては白金系触媒、水蒸気改質触媒の例としてはルテニウム系およびニッケル系、自己熱改質触媒の例としてはロジウム系触媒を挙げることができる。燃焼を促進可能な改質触媒の例としては白金系およびロジウム系触媒を挙げることができる。
以下、水蒸気改質、自己熱改質、部分酸化改質のそれぞれにつき、改質器における定格運転時および停止運転時の条件について説明する。
間接内部改質型SOFCの公知の構成要素は、必要に応じて適宜設けることができる。具体例を挙げれば、液体を気化させる気化器、各種流体を加圧するためのポンプ、圧縮機、ブロワなどの昇圧手段、流体の流量を調節するため、あるいは流体の流れを遮断/切り替えるためのバルブ等の流量調節手段や流路遮断/切り替え手段、熱交換・熱回収を行うための熱交換器、気体を凝縮する凝縮器、スチームなどで各種機器を外熱する加熱/保温手段、炭化水素系燃料(改質原料)や燃焼用燃料の貯蔵手段、計装用の空気や電気系統、制御用の信号系統、制御装置、出力用や動力用の電気系統、燃料中の硫黄分濃度を低減する脱硫器などである。
Claims (4)
- 炭化水素系燃料を改質して改質ガスを製造する、改質触媒層を有する改質器と、
該改質ガスを用いて発電を行う固体酸化物形燃料電池と、
該固体酸化物燃料電池から排出されるアノードオフガスを燃焼させる燃焼領域と、
該改質器、固体酸化物形燃料電池および燃焼領域を収容する筐体と、を有する間接内部改質型固体酸化物形燃料電池の停止方法であって、
次の条件iからiv、
i)該固体酸化物燃料電池のアノード温度が定常であり、
ii)該アノード温度が酸化劣化点未満であり、
iii)改質器において、炭化水素系燃料が改質され、アノードに供給するのに適した組成の改質ガスが生成しており、
iv)前記改質ガスの生成量が、該固体酸化物燃料電池のアノード温度が酸化劣化点以上の温度にある場合においてアノードの酸化劣化を防止するために必要最小限な流量以上である、
が全て満たされる状態において改質器に供給される炭化水素系燃料の流量をFEと表し、
該停止方法開始時点で改質器に供給していた炭化水素系燃料の流量をFSと表したとき、
a)改質器に供給する炭化水素系燃料の流量をFSからFEにする工程、および
b)アノード温度が酸化劣化点を下回ったら、該改質器への炭化水素系燃料の供給を停止する工程
を有する間接内部改質型固体酸化物形燃料電池の停止方法。 - 前記炭化水素系燃料が、炭素数が2以上の炭化水素系燃料を含む請求項1記載の方法。
- 前記改質ガス中の、炭素数2以上の化合物の濃度が、質量基準で50ppb以下である請求項2記載の方法。
- 炭化水素系燃料を改質して改質ガスを製造する、改質触媒層を有する改質器と、
該改質ガスを用いて発電を行う固体酸化物形燃料電池と、
該固体酸化物燃料電池から排出されるアノードオフガスを燃焼させる燃焼領域と、
該改質器、固体酸化物形燃料電池および燃焼領域を収容する筐体と、を有する間接内部改質型固体酸化物形燃料電池であって、
次の条件iからiv、
i)該固体酸化物燃料電池のアノード温度が定常であり、
ii)該アノード温度が酸化劣化点未満であり、
iii)改質器において、炭化水素系燃料が改質され、アノードに供給するのに適した組成の改質ガスが生成しており、
iv)前記改質ガスの生成量が、該固体酸化物燃料電池のアノード温度が酸化劣化点以上の温度にある場合においてアノードの酸化劣化を防止するために必要最小限な流量以上である、
が全て満たされる状態において改質器に供給される炭化水素系燃料の流量をFEと表し、
該停止方法開始時点で改質器に供給していた炭化水素系燃料の流量をFSと表したとき、
I)改質器に供給する炭化水素系燃料の流量をFSからFEにするための手段、および
II)アノード温度が酸化劣化点を下回ったら、該改質器への炭化水素系燃料の供給を停止するための手段
を有する間接内部改質型固体酸化物形燃料電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/864,963 US8927166B2 (en) | 2008-01-28 | 2009-01-14 | Indirect internal reforming solid oxide fuel cell and method for shutting down the same |
CA2713273A CA2713273A1 (en) | 2008-01-28 | 2009-01-14 | Indirect internal reforming solid oxide fuel cell and method for shutting down the same |
EP09705122.1A EP2246926B1 (en) | 2008-01-28 | 2009-01-14 | Indirect internally reforming solid oxide fuel cell and a method of stopping same |
CN200980102817.7A CN101953010B (zh) | 2008-01-28 | 2009-01-14 | 间接内部转化型固体氧化物型燃料电池及其停止方法 |
US14/282,337 US9040206B2 (en) | 2008-01-28 | 2014-05-20 | Indirect internal reforming solid oxide fuel cell and method for shutting down the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008016346A JP2009176660A (ja) | 2008-01-28 | 2008-01-28 | 間接内部改質型固体酸化物形燃料電池の停止方法 |
JP2008-016346 | 2008-01-28 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/864,963 A-371-Of-International US8927166B2 (en) | 2008-01-28 | 2009-01-14 | Indirect internal reforming solid oxide fuel cell and method for shutting down the same |
US14/282,337 Division US9040206B2 (en) | 2008-01-28 | 2014-05-20 | Indirect internal reforming solid oxide fuel cell and method for shutting down the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009096221A1 true WO2009096221A1 (ja) | 2009-08-06 |
Family
ID=40912574
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/050351 WO2009096221A1 (ja) | 2008-01-28 | 2009-01-14 | 間接内部改質型固体酸化物形燃料電池とその停止方法 |
Country Status (8)
Country | Link |
---|---|
US (2) | US8927166B2 (ja) |
EP (1) | EP2246926B1 (ja) |
JP (1) | JP2009176660A (ja) |
KR (1) | KR20100120171A (ja) |
CN (1) | CN101953010B (ja) |
CA (1) | CA2713273A1 (ja) |
TW (1) | TWI449251B (ja) |
WO (1) | WO2009096221A1 (ja) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2758153A1 (en) * | 2009-04-08 | 2010-10-14 | Susumu Hatada | Shutdown method for shutting down indirect internal reforming solid oxide fuel cell |
JP2011054377A (ja) * | 2009-09-01 | 2011-03-17 | Toto Ltd | 燃料電池システム |
JP5469440B2 (ja) * | 2009-11-24 | 2014-04-16 | Jx日鉱日石エネルギー株式会社 | 間接内部改質型固体酸化物形燃料電池の停止方法 |
US8245671B2 (en) * | 2010-04-08 | 2012-08-21 | Ford Global Technologies, Llc | Operating an engine with reformate |
JP6070923B2 (ja) * | 2011-09-07 | 2017-02-01 | Toto株式会社 | 固体酸化物型燃料電池 |
US20140308596A1 (en) * | 2011-11-09 | 2014-10-16 | Jx Nippon Oil & Energy Corporation | Method and device for stopping solid-oxide fuel cell system |
JP6477892B2 (ja) | 2015-09-04 | 2019-03-13 | 日産自動車株式会社 | 燃料電池システム及び燃料電池制御方法 |
EP3396762B1 (en) | 2015-12-25 | 2020-02-26 | Nissan Motor Co., Ltd. | Fuel cell system and method for controlling same |
CN108091907B (zh) | 2016-11-22 | 2020-09-25 | 通用电气公司 | 燃料电池系统及其停机方法 |
AT520156B1 (de) * | 2017-07-03 | 2020-11-15 | Avl List Gmbh | Verfahren zum Kühlen eines Brennstoffzellenstapels mit teilweise reformiertem Brennstoff |
CN113574709B (zh) * | 2019-07-19 | 2024-03-08 | 松下知识产权经营株式会社 | 燃料电池系统和燃料电池系统的控制方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11162492A (ja) * | 1997-12-02 | 1999-06-18 | Tokyo Gas Co Ltd | 固体電解質燃料電池の起動停止方法 |
JP2004319420A (ja) | 2003-02-25 | 2004-11-11 | Kyocera Corp | 燃料電池及びその運転方法 |
JP2005293951A (ja) * | 2004-03-31 | 2005-10-20 | Sumitomo Precision Prod Co Ltd | 燃料電池及びその運転方法 |
JP2005340075A (ja) * | 2004-05-28 | 2005-12-08 | Kyocera Corp | 燃料電池の稼動停止方法 |
JP2006294508A (ja) | 2005-04-13 | 2006-10-26 | Mitsubishi Materials Corp | 燃料電池発電装置および運転停止方法 |
JP2007128717A (ja) * | 2005-11-02 | 2007-05-24 | Mitsubishi Materials Corp | 燃料電池の運転方法 |
JP2007273311A (ja) * | 2006-03-31 | 2007-10-18 | Central Res Inst Of Electric Power Ind | 固体酸化物形燃料電池の運転方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0613095A (ja) * | 1992-06-29 | 1994-01-21 | Sanyo Electric Co Ltd | 内部改質溶融炭酸塩型燃料電池の昇温及び降温方法 |
US6562496B2 (en) * | 2000-05-01 | 2003-05-13 | Delphi Technologies, Inc. | Integrated solid oxide fuel cell mechanization and method of using for transportation industry applications |
JP4967185B2 (ja) * | 2000-10-24 | 2012-07-04 | トヨタ自動車株式会社 | 改質器内の析出炭素の除去 |
US6680136B2 (en) | 2001-01-25 | 2004-01-20 | Delphi Technologies, Inc. | Gas containment/control valve for a solid oxide fuel cell |
JP4056770B2 (ja) | 2002-02-05 | 2008-03-05 | 東京瓦斯株式会社 | 固体酸化物形燃料電池システム |
EP2287954A3 (en) | 2005-02-22 | 2011-03-02 | Mitsubishi Materials Corporation | Solid oxide type fuel cell and operating method thereof |
KR100804703B1 (ko) * | 2006-11-01 | 2008-02-18 | 삼성에스디아이 주식회사 | 전기 출력량 측정장치 및 이를 포함하는 연료 전지용 스택 |
-
2008
- 2008-01-28 JP JP2008016346A patent/JP2009176660A/ja active Pending
-
2009
- 2009-01-14 WO PCT/JP2009/050351 patent/WO2009096221A1/ja active Application Filing
- 2009-01-14 KR KR1020107018960A patent/KR20100120171A/ko active IP Right Grant
- 2009-01-14 EP EP09705122.1A patent/EP2246926B1/en not_active Not-in-force
- 2009-01-14 CN CN200980102817.7A patent/CN101953010B/zh not_active Expired - Fee Related
- 2009-01-14 US US12/864,963 patent/US8927166B2/en not_active Expired - Fee Related
- 2009-01-14 CA CA2713273A patent/CA2713273A1/en not_active Abandoned
- 2009-01-20 TW TW098102026A patent/TWI449251B/zh not_active IP Right Cessation
-
2014
- 2014-05-20 US US14/282,337 patent/US9040206B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11162492A (ja) * | 1997-12-02 | 1999-06-18 | Tokyo Gas Co Ltd | 固体電解質燃料電池の起動停止方法 |
JP2004319420A (ja) | 2003-02-25 | 2004-11-11 | Kyocera Corp | 燃料電池及びその運転方法 |
JP2005293951A (ja) * | 2004-03-31 | 2005-10-20 | Sumitomo Precision Prod Co Ltd | 燃料電池及びその運転方法 |
JP2005340075A (ja) * | 2004-05-28 | 2005-12-08 | Kyocera Corp | 燃料電池の稼動停止方法 |
JP2006294508A (ja) | 2005-04-13 | 2006-10-26 | Mitsubishi Materials Corp | 燃料電池発電装置および運転停止方法 |
JP2007128717A (ja) * | 2005-11-02 | 2007-05-24 | Mitsubishi Materials Corp | 燃料電池の運転方法 |
JP2007273311A (ja) * | 2006-03-31 | 2007-10-18 | Central Res Inst Of Electric Power Ind | 固体酸化物形燃料電池の運転方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2246926A4 * |
Also Published As
Publication number | Publication date |
---|---|
US8927166B2 (en) | 2015-01-06 |
CA2713273A1 (en) | 2009-08-06 |
EP2246926A1 (en) | 2010-11-03 |
TWI449251B (zh) | 2014-08-11 |
KR20100120171A (ko) | 2010-11-12 |
EP2246926B1 (en) | 2014-07-23 |
US20140255809A1 (en) | 2014-09-11 |
TW200941813A (en) | 2009-10-01 |
US20110189566A1 (en) | 2011-08-04 |
CN101953010B (zh) | 2014-05-07 |
US9040206B2 (en) | 2015-05-26 |
EP2246926A4 (en) | 2013-01-02 |
CN101953010A (zh) | 2011-01-19 |
JP2009176660A (ja) | 2009-08-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5164441B2 (ja) | 燃料電池システムの起動方法 | |
WO2009096221A1 (ja) | 間接内部改質型固体酸化物形燃料電池とその停止方法 | |
WO2009131010A1 (ja) | 間接内部改質型固体酸化物形燃料電池システムの運転方法 | |
JP5078696B2 (ja) | 燃料電池システムの負荷追従運転方法 | |
JP2009295380A (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5325666B2 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5078698B2 (ja) | 燃料電池システムの負荷追従運転方法 | |
JP2010044909A (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5078697B2 (ja) | 燃料電池システムの負荷追従運転方法 | |
WO2010117033A1 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5469440B2 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5461834B2 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5325641B2 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5325662B2 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5281996B2 (ja) | 燃料電池システムの負荷追従運転方法 | |
JP5325661B2 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5325660B2 (ja) | 間接内部改質型固体酸化物形燃料電池の停止方法 | |
JP5281998B2 (ja) | 燃料電池システムの負荷追従運転方法 | |
JP5281991B2 (ja) | 燃料電池システムの負荷追従運転方法 | |
JP5281997B2 (ja) | 燃料電池システムの負荷追従運転方法 | |
JP2011014386A (ja) | 燃料電池システムの負荷追従運転方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980102817.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09705122 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2713273 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009705122 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20107018960 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12864963 Country of ref document: US |