WO2012132409A1 - Dispositif de production d'hydrogène et son procédé de fonctionnement - Google Patents

Dispositif de production d'hydrogène et son procédé de fonctionnement Download PDF

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Publication number
WO2012132409A1
WO2012132409A1 PCT/JP2012/002117 JP2012002117W WO2012132409A1 WO 2012132409 A1 WO2012132409 A1 WO 2012132409A1 JP 2012002117 W JP2012002117 W JP 2012002117W WO 2012132409 A1 WO2012132409 A1 WO 2012132409A1
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Prior art keywords
temperature
combustion
reformer
transformer
hydrogen generator
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English (en)
Japanese (ja)
Inventor
木村　洋一
勝 福田
向井　裕二
弘樹 藤岡
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Panasonic Corp
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Panasonic Corp
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts with external heating of the catalyst
    • 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
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • 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
    • C01B2203/1614—Controlling the temperature
    • 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
    • C01B2203/1685—Control based on demand of downstream process
    • 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
    • C01B2203/1695—Adjusting the feed of the combustion
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • H01M8/04373—Temperature; Ambient temperature of 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
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • 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
    • 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

  • the present invention relates to a hydrogen generation apparatus that generates a hydrogen-containing gas from a raw material and steam by a steam reforming reaction, and an operation method thereof.
  • a hydrogen generator uses a reforming fuel (raw material) containing an organic compound composed of at least carbon and hydrogen, such as natural gas or LP gas, and water, and a steam reforming reaction in a reforming section having a reforming catalyst inside.
  • a reforming fuel raw material
  • an organic compound composed of at least carbon and hydrogen such as natural gas or LP gas, and water
  • a steam reforming reaction in a reforming section having a reforming catalyst inside.
  • a hydrogen-containing gas hereinafter referred to as a reformed gas
  • the generated reformed gas contains a high concentration of carbon monoxide.
  • the hydrogen generator reduces the carbon monoxide concentration in the reformed gas to a level that does not affect the power generation performance of the fuel cell stack by the shift shift reaction in the shift section having the shift catalyst.
  • the hydrogen generator supplies reformed gas having a sufficiently reduced carbon monoxide concentration to the fuel cell system.
  • the reforming catalyst is adjusted to a temperature suitable for the reforming reaction
  • the shift catalyst is adjusted to a temperature suitable for the shift shift reaction.
  • a hydrogen generator includes a reforming heating unit for heating a reforming unit having a reforming catalyst, and a reforming temperature detection unit for detecting the temperature of the reforming catalyst heated by the reforming heating unit.
  • the heating amount for the reforming unit by the reforming heating unit is appropriately adjusted based on the temperature of the reforming catalyst detected by the reforming temperature detection unit, and the reforming catalyst is adjusted to a temperature suitable for the reforming reaction. .
  • the present invention has been made to solve such conventional problems, and can suppress the consumption of electric power and can control the shift catalyst so as to have a temperature suitable for the reaction. And an operation method thereof.
  • a hydrogen generator includes an air supply device that supplies combustion air, a combustor that generates combustion gas by a combustion reaction between the combustion fuel and the combustion air, A reformer having a reforming catalyst that is heated using the heat of the combustion gas and generates a reformed gas from a raw material and steam by a steam reforming reaction, and a reforming temperature detection that detects the temperature of the reformer And a downstream side of the reformer, and configured to be heated by the combustion gas after heating the reformer, for reducing carbon monoxide in the reformed gas
  • a converter having a shift catalyst, a shift temperature detector for detecting the temperature of the shift converter, and controlling the combustor so that the temperature of the reformer detected by the reforming temperature detector becomes a predetermined temperature.
  • a controller for controlling the transformation temperature. When the temperature of the transformer detected by the detector falls below a predetermined threshold temperature, and controls so as to raise the temperature of the transformer to increase the flow rate of the combustion air.
  • the predetermined threshold temperature is a temperature arbitrarily set below a temperature suitable for the metamorphic shift reaction.
  • the heat of combustion gas generated in the combustor can be further transmitted to the downstream side without increasing the fuel for combustion and without increasing the power consumption to the heater.
  • the temperature of the transformer disposed downstream of the reformer can be increased.
  • the hydrogen generator of the present invention when the temperature of the transformer is controlled to a temperature suitable for the shift shift reaction, consumption of electric power and fuel for combustion is suppressed, and energy efficiency is reduced. It becomes possible to suppress.
  • FIG. 1 is a block diagram showing an overview of a fuel cell system including a hydrogen generator according to Embodiment 1 of the present invention.
  • FIG. 2 is a flowchart showing operation control of the hydrogen generator according to Embodiment 1 of the present invention.
  • FIG. 3 is a flowchart showing operation control of the hydrogen generator according to Embodiment 2 of the present invention.
  • a hydrogen generation apparatus includes an air supply device that supplies combustion air, a combustor that generates combustion gas by a combustion reaction between combustion fuel and combustion air, and heat of the combustion gas , A reformer having a reforming catalyst that generates a reformed gas from a raw material and steam by a steam reforming reaction, a reforming temperature detector that detects the temperature of the reformer, and a reformer And a converter having a conversion catalyst for reducing carbon monoxide in the reformed gas, which is configured to be heated by the combustion gas after heating the reformer, and the converter And a controller that controls the combustor so that the temperature of the reformer detected by the reforming temperature detector becomes a predetermined temperature. When the temperature of the transformer detected by the detector falls below a predetermined threshold temperature, Increase of flow rate is to illustrate aspects of controlling so as to raise the temperature of the transformer.
  • the controller when the temperature of the transformer detected by the transformation temperature detector is lower than a predetermined threshold temperature, the controller reduces the flow rate of the combustion air with respect to the flow rate of the combustion fuel.
  • the ratio may be increased to control the combustion gas flow rate to be increased.
  • FIG. 1 is a block diagram showing an outline of a fuel cell system provided with a hydrogen generator according to Embodiment 1 of the present invention.
  • the fuel cell system includes a fuel cell 1 and a hydrogen generator 2 that generates a reformed gas containing hydrogen gas necessary for the fuel cell 1.
  • the fuel cell 1 is typically a solid polymer fuel cell, and is configured by laminating a plurality of cells 3 including an anode, a cathode, and a polymer electrolyte membrane disposed between the anode and the cathode. ing.
  • the fuel cell 1 generates power using a reformed gas containing hydrogen supplied to the anode and an oxidant gas (for example, air) containing oxygen supplied to the cathode.
  • the fuel cell 1 includes an anode channel 4 for supplying reformed gas to the anode, a cathode channel 5 for supplying oxidant gas to the cathode, and heat generated by the electrochemical reaction of hydrogen and oxygen.
  • a cooling flow path (not shown) for supplying a cooling medium (for example, water) to take away is provided.
  • the hydrogen generator 2 includes a reformer 6, a transformer 7, a selective oxidizer 8, an evaporator 9, a combustor 10, and an air supply device 14 for combustion.
  • the evaporator 9 is supplied with reforming fuel (raw material) containing hydrocarbon and reforming water.
  • the evaporator 9 generates steam from the supplied reformed water, mixes the generated steam and reforming fuel, and supplies them to the reformer 6.
  • the reformer 6 generates reformed gas containing hydrogen by a steam reforming reaction using the reforming fuel and water.
  • the reformer 6 and the evaporator 9 are integrated.
  • a combustor 10 is disposed on the central axis of the reformer 6 and the evaporator 9.
  • the combustor 10 includes a burner 11 that forms a flame, an ignition electrode 12, and a combustion state detector 13.
  • An air supply 14 and an air flow rate detector 15 are connected to the combustor 10.
  • the air supplier 14 supplies combustion air (combustion air) to the combustor 10.
  • combustion air combustion air
  • an air pump or a fan can be used as the air supplier 14.
  • the air flow rate detector 15 measures the flow rate of the combustion air.
  • the combustor 10 may be configured to be incorporated in the hydrogen generator 2 or may be configured as a separate component from the hydrogen generator 2.
  • the concentration of the raw material (combustion gas) and carbon monoxide that have passed until the hydrogen generator 2 rises to a predetermined temperature is reduced to a concentration that can be supplied to the fuel cell.
  • Unreformed reformed gas (combustion gas) or unreacted reformed gas (off gas: combustion gas) discharged from the anode of the fuel cell 1 is supplied.
  • the combustor 10 burns these combustion gases to generate heat supplied to the reformer 6, for example.
  • the hydrogen generator 2 has a plurality of concentric quadruple pipe shapes, and is composed of a combustion cylinder 16, a first cylinder 17, a second cylinder 18, and a third cylinder 19 in order from the inside.
  • the combustion cylinder 16 is configured such that combustion gas is discharged from the burner 11.
  • a combustion gas flow path 20 is formed by the annular space between the combustion cylinder 16 and the first cylinder 17.
  • a reforming fuel supply unit 21 that supplies reforming fuel and a reforming water supply unit 22 that supplies reforming water are connected to the outer peripheral surface of the second cylinder 18 on the upstream side of the evaporator 9. Yes.
  • the reforming fuel supply unit 21 for example, a booster pump or a gas control valve, and as the reforming water supply unit 22, for example, a water pump can be used.
  • a transformer 7 and a selective oxidizer 8 are provided in the annular space between the second cylinder 18 and the third cylinder 19, a transformer 7 and a selective oxidizer 8 are provided.
  • a selective oxidized air supply unit 23 is connected to the outer peripheral surface of the third cylinder 19 to supply air necessary for the carbon monoxide selective oxidation reaction of the reformed gas to the selective oxidizer 8. Further, a reformed gas flow path 24 that leads out the reformed gas from the hydrogen generator 2 and supplies the reformed gas to the fuel cell 1 is connected to the outer peripheral surface of the third cylinder 19.
  • a reforming temperature detector 25, a transformation temperature detector 26, and a selective oxidation temperature detector 27 are arranged on the outer peripheral surface of the third cylinder 19, respectively.
  • the reforming temperature detector 25, the shift temperature detector 26, and the selective oxidation temperature detector 27 detect the temperatures of the reformer 6, the shift converter 7, and the selective oxidizer 8, respectively.
  • a thermocouple or a thermistor can be used as the reforming temperature detector 25, the transformation temperature detector 26, and the selective oxidation temperature detector 27, for example, a thermocouple or a thermistor can be used.
  • the reformed gas channel 24 is provided with a reformed gas on / off valve 28, and the supply of the reformed gas to the anode channel 4 of the fuel cell 1 can be controlled by opening / closing the reformed gas on / off valve 28.
  • the anode flow path 4 and the combustor 10 are connected via an anode off gas flow path 29.
  • An anode off gas opening / closing valve 30 is disposed in the anode off gas flow path 29.
  • reformed gas passage 24 upstream of the reformed gas on-off valve 28 and the anode off-gas passage 29 downstream of the anode off-gas on-off valve 30 are connected by a reformed gas bypass passage 31.
  • the reformed gas bypass passage 31 is provided with a bypass on-off valve 32, which can control the gas flow.
  • the reformed gas derived from the reformer 6 is introduced into the fuel cell 1 to generate hydrogen that has not been used for the electrochemical reaction in the fuel cell 1 after power generation.
  • the anode offgas containing can be introduced into the combustor 10.
  • the reforming fuel and reformed gas that have circulated through the reformer 6 can be introduced into the combustor 10 without being introduced into the fuel cell 1.
  • the burner 11 of the combustor 10 includes a fuel separator having a plurality of fuel ejection holes and an air ejection member having a plurality of air ejection holes.
  • an ignition electrode 12 and a combustion state detector 13 for detecting the ignition or extinguishing of the flame of the burner 11 are arranged.
  • a flame rod that detects an ion current in a flame to determine the presence or absence of a flame or a thermocouple that detects a flame temperature and determines the presence or absence of a flame can be used.
  • the hydrogen generator 2 is discharged from the fuel cell 1 supplied from the reforming fuel and reformed gas or the anode off-gas channel 29 that has passed through the reformer 6 supplied from the reformed gas bypass channel 31.
  • the anode off-gas and the combustion air supplied from the air supplier 14 can be burned by the burner 11.
  • the hydrogen generator 2 can heat the reformer 6 and the evaporator 9 by discharging the high-temperature combustion gas generated by the combustion reaction to the combustion cylinder 16 and circulating the combustion gas passage 20.
  • the controller 33 controls the fuel cell 1 and the hydrogen generator 2, and at least the air supplier 14, the reforming fuel supplier 21, the reforming water supplier 22, the reforming temperature detector 25, and the transformation temperature detection.
  • the controller 26 controls the selective oxidation temperature detector 27, the reformed gas on-off valve 28, the anode off-gas on-off valve 30, the bypass on-off valve 32, the ignition electrode 12, and the combustion state detector 13.
  • the controller 33 may be in any form as long as it is a device that controls each device constituting the fuel cell system (hydrogen generator 2).
  • the controller 33 includes an arithmetic processing unit exemplified by a microprocessor, a CPU, and the like, and a storage unit configured by a memory that stores a program for executing each control operation.
  • the controller 33 is related to a fuel cell system in which the arithmetic processing section reads out a predetermined control program stored in the storage section and executes the predetermined control program, thereby processing these pieces of information and including these controls. Perform various controls.
  • the controller 33 is not limited to a single controller, but may be a controller group in which a plurality of controllers cooperate to execute control of the fuel cell system. Absent.
  • the controller 33 may be configured by a micro control, or may be configured by an MPU, a PLC (Programmable Logic Controller), a logic circuit, or the like.
  • FIG. 2 is a flowchart showing the operation control of the hydrogen generator according to Embodiment 1 of the present invention. The following operation is performed by the controller 33 executing a predetermined program.
  • the reformed gas on-off valve 28 is closed, the anode off-gas on-off valve 30 is closed, and the bypass on-off valve 32 is opened.
  • the supplied reforming fuel flows through the evaporator 9 and the reformer 6, then passes through the reformed gas channel 24, passes through the reformed gas bypass channel 31, the bypass opening / closing valve 32, and the anode offgas channel 29. Then, the gas is led out to the combustor 10, jetted from the fuel jet hole of the fuel separator, mixed with the combustion air jetted from the air jet hole of the air jet member, and ignited by the burner 11 to start combustion.
  • the combustion state detector 13 detects the ignition of the flame of the combustor 10
  • the operation of the ignition electrode 12 is stopped, and thereafter the reforming temperature detector 25, the modification temperature detector 26, and the selective oxidation temperature detector 27 are modified.
  • Combustion is continued while detecting the temperature of the mass device 6, the transformer 7, and the selective oxidizer 8, the high-temperature combustion gas is discharged into the combustion cylinder 16, and the combustion gas passage 20 is circulated to thereby reformer 6. And the evaporator 9 is heated.
  • the reforming temperature detector 25, the modification temperature detector 26, and the selective oxidation temperature detector 27 are supplied with a predetermined amount of reforming water by the combustion gas at a temperature equal to or higher than the temperature at which the water evaporates, dew condensation occurs.
  • the reforming water supply unit 22 starts to supply reforming water to the evaporator 9 via the reforming water supply unit.
  • the reformed gas on-off valve 28 is opened, the anode off-gas on-off valve 30 is opened, the bypass on-off valve 32 is closed, and the reformed gas with reduced carbon monoxide is supplied from the reformed gas flow path 24 to the fuel cell 1.
  • the reformed gas with reduced carbon monoxide is supplied from the reformed gas flow path 24 to the fuel cell 1.
  • the fuel cell 1 power generation is performed using the reformed gas supplied to the anode channel 4 and the air that is the oxidant gas supplied to the cathode channel 5.
  • an anode off-gas containing hydrogen that has not been used for the electrochemical reaction in the fuel cell 1 is led out to the combustor 10 from the anode off-gas flow path 29 of the fuel cell 1 and burned by the burner 11, thereby generating a hydrogen generator. While maintaining the temperature of 2 at an appropriate value, the reformed gas is supplied to the fuel cell 1 for operation, and power generation is continued.
  • the controller 33 supplies the reforming fuel and the reforming water necessary for generating the amount of hydrogen consumed for power generation in the fuel cell system to the reforming fuel supplier 21 and the reforming water supplier 22.
  • the temperatures of the reformer 6, the shift converter 7, the selective oxidizer 8, etc. are constantly detected by the reforming temperature detector 25, the shift temperature detector 26, and the selective oxidation temperature detector 27.
  • a predetermined amount of combustion air is supplied from the air supply unit 14 so that the temperature of each unit such as the unit 6, the transformer 7 and the selective oxidizer 8 becomes a temperature suitable for each catalyst.
  • the amount of combustion air corresponding to the required reforming fuel and reforming water is supplied from the air supplier 14.
  • the controller 33 controls the reforming fuel supply device 21 and the like so that the reformer 6 reaches a predetermined temperature based on the temperature detected by the reforming temperature detector 25, thereby converting the reformer.
  • the temperature of the vessel 7 is maintained at a predetermined temperature.
  • the temperature of the shift catalyst may decrease. is there.
  • the activity of the shift catalyst becomes low, and the concentration of carbon monoxide contained in the reformed gas cannot be sufficiently reduced by the shift shift reaction in the shift converter 7 and does not affect the power generation performance of the fuel cell 1. May not be able to be reduced.
  • the controller 33 when the temperature of the transformer detected by the transformation temperature detector 26 is lower than a predetermined threshold temperature, the controller 33 reduces the combustion air.
  • the air supplier 14 is controlled so that the flow rate increases.
  • the controller 33 measures the flow rate of combustion air (hereinafter referred to as the first flow rate) according to the amount of reforming fuel and the amount of reforming water with the air flow rate detector 15, and the temperature of the transformer 7 is predetermined.
  • T4 threshold temperature
  • the controller 33 controls the air supplier 14 so that the ratio of the flow rate of combustion air to the flow rate of combustion fuel increases. At this time, the controller 33 may control the air supply device 14 so that the air-fuel ratio becomes 1.7 or more and 1.9 or less.
  • the air-fuel ratio is a ratio between air and combustible gas determined based on the reaction of combustion, and is a numerical value at which the ratio at which the combustible gas completely burns with oxygen in the air without excess or deficiency is 1.
  • an air-fuel ratio of 1.7 means that an amount of air that is 1.7 times the amount of air required when the combustible gas completely burns is supplied.
  • the predetermined threshold temperature (T4) can be arbitrarily set according to the type or amount of the shift catalyst disposed in the shift converter 7, and is obtained in advance by experiments or the like.
  • the predetermined threshold temperature may be 220 to 250 ° C., for example.
  • the heat of the combustion gas generated in the combustor can be further transmitted to the downstream side, so that the temperature of the transformer 7 disposed downstream from the reforming section can be further increased. it can.
  • the temperature of the transformer 7 is raised with a simple configuration so that the temperature of the transformer 7 becomes a temperature suitable for the shift shift reaction. Can do. Therefore, the concentration of carbon monoxide contained in the reformed gas can be sufficiently reduced by the shift shift reaction in the transformer 7, and can be sufficiently reduced to a level that does not affect the power generation performance of the fuel cell stack.
  • the temperature of the shift catalyst is suitable for the catalytic activity by increasing the flow rate of the combustion air by the air supply device 14 without heating the heater. Therefore, the energy efficiency can be prevented from decreasing.
  • the combustion fuel when the temperature of the shift catalyst is increased, the combustion fuel is not increased (that is, the combustion amount is not increased), so that the consumption of the combustion fuel is also suppressed. It is possible to suppress the decrease in energy efficiency.
  • the flow rate of the combustion air is measured by the air flow rate detector 15.
  • the present invention is not limited to this, and the flow rate of the combustion air is estimated from the operation amount of the air supply device 14. May be used.
  • Embodiment 2 The hydrogen generator according to Embodiment 2 of the present invention exemplifies a mode in which the controller performs control so as to increase the predetermined threshold temperature when the cumulative operation time of the hydrogen generator has elapsed for a predetermined time.
  • FIG. 3 is a flowchart showing the operation control of the hydrogen generator according to Embodiment 2 of the present invention.
  • the operation of the hydrogen generator 2 according to Embodiment 2 of the present invention is basically the same as that of the hydrogen generator according to Embodiment 1, but the operation of the hydrogen generator is cumulative.
  • control is performed to increase the predetermined threshold temperature when the predetermined time elapses.
  • the controller 33 sets the predetermined threshold temperature to a temperature higher than the threshold temperature before the predetermined time elapses, and sets the set temperature.
  • a predetermined threshold temperature is set.
  • the concentration of carbon monoxide in the reformed gas supplied from the reformer 6 is sufficiently reduced by the shift shift reaction, and the power generation performance of the fuel cell stack is not affected. It is necessary to reduce it enough to the level.
  • the present inventors have found that the catalytic activity of the shift catalyst tends to gradually decrease due to the progress of sintering, in which the catalyst particles become larger. Guess. If the activity of the shift catalyst is reduced, the concentration of carbon monoxide in the reformed gas supplied from the reformer 6 may not be sufficiently reduced.
  • the temperature of the transformer 7 it is preferable to control the temperature of the transformer 7 to be higher in order to further promote the transformation reaction.
  • the operation of the shift catalyst is controlled at a relatively high temperature from the initial state (for example, when the operation of the hydrogen generator 2 starts), the energy efficiency of the hydrogen generator decreases.
  • the controller 33 causes the flow rate of the combustion air when the temperature of the shift generator 7 decreases when the accumulated operation time of the hydrogen generator 2 elapses for a predetermined time.
  • a predetermined threshold temperature (T4) for increasing the temperature of the transformer 7 is controlled to be higher.
  • the controller 33 sets the threshold temperature (T4) to 240 ° C. at the initial stage of the cumulative operation time of the hydrogen generator 2.
  • the temperature (T4) is raised to 250 ° C. (240 ° C. + 10 ° C.), and the cumulative operation time counter is cleared to zero. That is, the controller 33 sets the threshold temperature (T4) from the initial 240 ° C. to a temperature (250 ° C.) higher than the threshold temperature before the predetermined time elapses, sets the cumulative operation time to 0, and sets the hydrogen generator 2 operation is controlled.
  • the controller 33 is configured to increase the predetermined threshold temperature T4 by 10 ° C. every time 10,000 hours elapse in the cumulative operation time counter.
  • the predetermined time can be arbitrarily set based on the durability performance of the shift catalyst that is obtained in advance through experiments or the like. For this reason, in the hydrogen generator 2 according to the second embodiment, 10,000 hours are set as the predetermined time, but for example, the predetermined time may be set to 15000 hours.
  • the configuration that “controls the predetermined threshold temperature to be increased when the cumulative operation time has elapsed for a predetermined time” is a configuration that controls to increase the predetermined threshold temperature after the cumulative operation time has elapsed for the predetermined time.
  • the configuration may be such that when the accumulated operation time has elapsed for a predetermined time, control is performed to increase the predetermined threshold temperature after the next activation.
  • the case where “the cumulative operation time elapses for a predetermined time” may be a case where at least one of the number of times of starting and the number of times of stopping becomes a predetermined number of times or more.
  • the hydrogen generator 2 according to the second embodiment configured as described above has the same effects as the hydrogen generator 2 according to the first embodiment. Further, in the hydrogen generator 2 according to the second embodiment, even if the catalytic activity in the transformer 7 decreases as the cumulative operation time increases, a predetermined temperature is set so as to keep the temperature of the transformer 7 higher. By setting the threshold temperature higher, the concentration of carbon monoxide in the reformed gas can be sufficiently reduced.
  • the combustion air supplied from the air supplier 14 is simply not heated by the heater or increased in combustion fuel (increase in combustion amount).
  • the temperature of the transformer 7 can be set to a predetermined threshold temperature set higher. For this reason, compared with the conventional hydrogen generator, the fall of energy efficiency can be suppressed more.
  • the transformer 7 is configured to be heated by the combustion gas after the reformer 6 is heated.
  • the present invention is not limited to this, and at least the reformer 6 is heated. What is necessary is just to be comprised so that it may be heated with the combustion gas after doing.
  • the transformer 7 may be configured to be heated by the combustion gas before heating the reformer 6 and the combustion gas after heating the reformer 6.
  • you may be comprised so that it may be heated with the combustion gas and heater after heating a reformer.
  • the transformer in addition to the configuration in which when the temperature of the transformer falls below a predetermined threshold temperature, the flow rate of the combustion air is increased to raise the temperature of the transformer 7, the transformer may be heated with a heater. Even in this case, compared with the case where the transformer 7 is heated only by the heater, the heating amount by the heater can be suppressed, and the power consumption can be suppressed.
  • the hydrogen generator 2 is provided with the selective oxidizer 8, but is not limited thereto, and the hydrogen generator 2 is not provided with the selective oxidizer 8. May be.
  • the hydrogen generator 2 is constituted by a multi-cylinder (multi-cylinder) type hydrogen generator, but the invention is not limited to this, and each reactor (flat module) such as a reformer is arranged in parallel. You may comprise with the type of hydrogen generator arranged in close contact with.
  • the hydrogen generator and the operation method thereof according to the present invention can suppress a decrease in energy efficiency, and can be used for, for example, a stationary fuel cell system.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Fuel Cell (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Health & Medical Sciences (AREA)

Abstract

Le dispositif de production d'hydrogène selon l'invention est équipé comme suit : une alimentation en air (14); une chambre de combustion (10); un reformeur (6); un détecteur de température de reformeur (25) qui détecte la température du reformeur (6); un transformateur (7) qui se trouve en aval du reformeur (6) et est conçu pour être chauffé à l'aide du gaz de combustion généré par le chauffage du reformeur (6); un détecteur de température de transformateur (26) qui détecte la température du transformateur (7); et un contrôleur (33) qui gère la chambre de combustion (10) de façon que la température du reformeur (6) détectée par le détecteur de température de reformeur (25) devienne une température prédéfinie. Le contrôleur (33) commande l'alimentation en air (14) de façon à augmenter le débit de l'air pour la combustion quand la température du transformateur (7) détectée par le détecteur de température de transformateur (26) descend au-dessous d'une température de seuil prédéfinie.
PCT/JP2012/002117 2011-03-30 2012-03-27 Dispositif de production d'hydrogène et son procédé de fonctionnement Ceased WO2012132409A1 (fr)

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JP2011-075056 2011-03-30
JP2011075056 2011-03-30
JP2011274163A JP2014111509A (ja) 2011-03-30 2011-12-15 水素生成装置及びその運転方法
JP2011-274163 2011-12-15

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WO2012132409A1 true WO2012132409A1 (fr) 2012-10-04

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CN108168919B (zh) * 2016-12-07 2023-10-20 中国科学院大连化学物理研究所 一种多通道重整器测试系统
EP3886223B1 (fr) * 2018-11-22 2022-08-24 Nissan Motor Co., Ltd. Système de combustion et procédé permettant de commander un système de combustion
JP7839072B2 (ja) * 2022-10-07 2026-04-01 カナデビア株式会社 生成装置及び生成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003217636A (ja) * 2002-01-23 2003-07-31 Matsushita Electric Ind Co Ltd 変成触媒体劣化判定装置、及び水素生成装置
JP2006169068A (ja) * 2004-12-17 2006-06-29 Matsushita Electric Ind Co Ltd 水素生成装置及びそれを用いた燃料電池システム
JP2008201638A (ja) * 2007-02-22 2008-09-04 Matsushita Electric Ind Co Ltd 水素生成装置とその運転方法及びそれを備える燃料電池システム
JP2010257915A (ja) * 2009-04-28 2010-11-11 Eneos Celltech Co Ltd 燃料電池用改質装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003217636A (ja) * 2002-01-23 2003-07-31 Matsushita Electric Ind Co Ltd 変成触媒体劣化判定装置、及び水素生成装置
JP2006169068A (ja) * 2004-12-17 2006-06-29 Matsushita Electric Ind Co Ltd 水素生成装置及びそれを用いた燃料電池システム
JP2008201638A (ja) * 2007-02-22 2008-09-04 Matsushita Electric Ind Co Ltd 水素生成装置とその運転方法及びそれを備える燃料電池システム
JP2010257915A (ja) * 2009-04-28 2010-11-11 Eneos Celltech Co Ltd 燃料電池用改質装置

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