WO2013150721A1 - 水素生成装置およびその運転方法、ならびに燃料電池システム - Google Patents
水素生成装置およびその運転方法、ならびに燃料電池システム Download PDFInfo
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- WO2013150721A1 WO2013150721A1 PCT/JP2013/001613 JP2013001613W WO2013150721A1 WO 2013150721 A1 WO2013150721 A1 WO 2013150721A1 JP 2013001613 W JP2013001613 W JP 2013001613W WO 2013150721 A1 WO2013150721 A1 WO 2013150721A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- 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
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- 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
- C01B3/384—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 the catalyst being continuously externally heated
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- 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
- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- 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
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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
- 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
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- 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
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1614—Controlling the temperature
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1614—Controlling the temperature
- C01B2203/1619—Measuring the temperature
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- 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 generator, an operation method thereof, and a fuel cell system, and more particularly, a hydrogen generator that generates a hydrogen-containing gas by reforming a hydrocarbon-based raw material gas with water, and the hydrogen generator and hydrogen
- the present invention relates to a fuel cell system including a fuel cell that generates power using a contained gas, and an operation method thereof.
- a fuel cell system including a hydrogen generation device that generates hydrogen necessary for power generation of a fuel cell is known.
- the steam reformer Hydrogen-rich reformed gas is generated by reforming the fuel with steam.
- the CO converter reduces the concentration of carbon monoxide by converting the carbon monoxide contained in the reformed gas with water vapor, and the CO remover selectively selects the carbon monoxide contained in the reformed gas with air. Carbon monoxide is removed by oxidation.
- the fuel cell body generates power using the reformed gas and air processed by the CO converter and the CO remover.
- the burner heats the steam reformer by burning unreacted gas (fuel) discharged from the fuel cell with air.
- the conventional fuel cell system does not take into account the change in the composition of the fuel that changes the amount of heat. Therefore, there is a problem in that the efficiency and durability of the hydrogen generator and the fuel cell system decrease with the change in the composition of the fuel. It was.
- the fuel is mainly composed of hydrocarbon gas, but the components of this hydrocarbon gas change, or mixed gas other than hydrocarbon gas such as nitrogen is included in the fuel and burned.
- the composition of may change.
- the steam carbon ratio S / C ratio
- the target value 2.5 to 3.5.
- Water vapor used for the shift reaction in the CO shifter is reduced, and the amount of carbon monoxide that can be reduced by the shift reaction is reduced.
- the hydrocarbon gas component of the fuel has changed and the number of moles of carbon atoms contained in one mole of fuel has increased, whereas the concentration of carbon monoxide in the reformed gas supplied to the CO remover has increased. If the amount of air in the CO remover does not increase accordingly, carbon monoxide remains in the reformed gas. As a result, when the reformed gas containing carbon monoxide is supplied to the combustion cell, the durability and efficiency of the fuel cell system are reduced.
- the present invention has been made to solve such problems, and a hydrogen generator capable of reducing carbon monoxide in a hydrogen-containing gas even when the composition of the raw material gas is changed, an operating method thereof, and a fuel cell.
- the purpose is to provide a system.
- a hydrogen generator includes a reformer that generates a hydrogen-containing gas by a reforming reaction of a raw material gas and water, a raw material supplier that supplies the raw material gas, and a flow rate of the raw material gas
- a raw material flow rate measuring device a first temperature detector for detecting the temperature of the reformer, and at least one combustible gas of the raw material gas and the hydrogen-containing gas is combusted with air to form the reformer.
- a combustor that heats the gas, a remover that reacts and removes carbon monoxide in the hydrogen-containing gas with a reaction gas, a reaction gas supply that supplies the reaction gas, and a controller.
- the vessel controls the supply amount of the raw material gas by the raw material supply device so that the first detected temperature detected by the first temperature detector becomes a predetermined temperature, and is measured by the raw material flow rate measuring device in the meantime. Measurement of the source gas Based on the amount, it is configured to control the supply amount of the reaction gas by the reaction gas supply device.
- the present invention provides a hydrogen generating apparatus having the configuration described above, capable of reducing carbon monoxide in a hydrogen-containing gas even when the composition of the raw material gas is changed, an operating method thereof, and a fuel cell system. There is an effect that can be.
- a hydrogen generator includes a reformer that generates a hydrogen-containing gas by a reforming reaction of a raw material gas and water, a raw material supplier that supplies the raw material gas, and a flow rate of the raw material gas.
- a raw material flow rate measuring device a first temperature detector for detecting the temperature of the reformer, and at least one combustible gas of the raw material gas and the hydrogen-containing gas is combusted with air to form the reformer.
- a combustor that heats the gas, a remover that reacts and removes carbon monoxide in the hydrogen-containing gas with a reaction gas, a reaction gas supply that supplies the reaction gas, and a controller.
- the vessel controls the supply amount of the raw material gas by the raw material supply device so that the first detected temperature detected by the first temperature detector becomes a predetermined temperature, and is measured by the raw material flow rate measuring device in the meantime. Measurement flow rate of the source gas Based on, and is configured to control the supply amount of the reaction gas by the reaction gas supply device.
- the hydrogen generator according to a second aspect of the present invention is the hydrogen generator according to the first aspect, wherein the remover includes a converter that converts the carbon monoxide with water vapor and a selective oxidizer that oxidizes the carbon monoxide with an oxidant gas.
- the reaction gas supply unit may include a water vapor supply unit that supplies the water vapor and an oxidant gas supply unit that supplies the oxidant gas.
- the hydrogen generator according to a third aspect of the present invention is the hydrogen generator according to the second aspect, wherein the controller is configured to supply the water vapor and the supply amount when the amount of the hydrogen-containing gas generated is a predetermined amount for a first predetermined time or more. It may be configured to control at least one of the supply amount of the oxidant gas based on the measured flow rate of the raw material gas.
- a hydrogen generator according to a fourth aspect of the present invention is the hydrogen generator according to the second or third aspect, further comprising a second temperature detector for detecting a temperature around the hydrogen generator, wherein the controller is configured to control the second temperature. Based on the second detection temperature detected by the detector, a reference flow rate for the source gas is set, Based on a comparison result between the measured flow rate of the source gas and the reference flow rate, at least one of the supply amount of the water vapor and the supply amount of the oxidant gas may be controlled.
- a hydrogen generator according to a fifth aspect of the present invention is the hydrogen generator according to the second or third aspect, further comprising a storage unit that stores a measured flow rate of the raw material gas during operation of the hydrogen generator, wherein the controller includes the controller
- a reference flow rate related to the raw material gas is set based on the measured flow rate of the raw material gas stored in the storage unit, and based on a comparison result between the measured flow rate of the raw material gas and the reference flow rate, the supply amount of the water vapor and It may be configured to control at least one of the supply amounts of the oxidant gas.
- a hydrogen generator according to a sixth aspect of the present invention is the hydrogen generator according to any one of the first to fifth aspects, wherein the controller is configured to correct the predetermined temperature based on an operation time of the reformer. May be.
- a fuel cell system includes the hydrogen generator according to any one of the second to sixth aspects, and a fuel cell that generates electric power using the hydrogen-containing gas.
- the fuel cell system according to an eighth aspect of the present invention is the fuel cell system according to the seventh aspect, wherein the controller is configured such that the generation amount of the hydrogen-containing gas is a first predetermined time in the start-up step before the fuel cell generates predetermined power.
- the amount is the predetermined amount
- at least one of the supply amount of the water vapor and the supply amount of the oxidant gas may be controlled based on the measured flow rate of the raw material gas.
- a fuel cell system is the seventh or eighth aspect, wherein the controller is In a power generation process in which the fuel cell is generating the predetermined power, when a second predetermined time has elapsed, at least one of the supply amount of the water vapor and the supply amount of the oxidant gas is measured for the raw material gas. It may be configured to control based on the flow rate.
- the fuel cell system according to a tenth aspect of the present invention is the fuel cell system according to the ninth aspect, further comprising a second temperature detector for detecting a temperature around the hydrogen generator, wherein the controller is controlled by the second temperature detector.
- a reference flow rate for the source gas is set based on the detected second detected temperature, and when the measured flow rate of the source gas changes from the reference flow rate, the generated power is set to the predetermined power, and the generated power is
- the power is the predetermined power for a predetermined time or longer, at least one of the supply amount of the water vapor and the supply amount of the oxidant gas is controlled based on a comparison result between the measured flow rate of the source gas and the reference flow rate. It may be configured.
- a fuel cell system is the fuel cell system according to the ninth aspect, further comprising a storage unit that stores a measured flow rate of the source gas during operation of the hydrogen generator, and the controller is provided in the storage unit.
- a reference flow rate related to the source gas is set based on the stored measured flow rate of the source gas, and when the measured flow rate of the source gas changes from the reference flow rate, the generated power is set to the predetermined power, and the generated power Is at the predetermined power for a second predetermined time or more, and controls at least one of the supply amount of the water vapor and the supply amount of the oxidant gas based on the comparison result between the measured flow rate of the source gas and the reference flow rate It may be configured to.
- a method for operating a hydrogen generator wherein a raw material gas and water are supplied to a reformer, and a hydrogen-containing gas is generated by a reforming reaction of the raw material gas and the water in the reformer. Then, in the combustor, at least one of the source gas and the hydrogen-containing gas is burned with air to heat the reformer, and the carbon monoxide in the hydrogen-containing oil gas is reacted with the remover.
- the amount of the raw material gas supplied to the reformer is controlled so that the reformer reaches a predetermined temperature, and the reaction gas is supplied based on the amount of the raw material gas supplied therebetween. Control the amount.
- FIG. 1 is a block diagram showing the configuration of the hydrogen generator 1.
- the hydrogen generation apparatus 1 is an apparatus that generates a hydrogen-containing gas, and includes a reformer 7 as shown in FIG.
- the reformer 7 includes a reforming catalyst (not shown), and generates a hydrogen-containing gas by reforming the raw material gas with water (hereinafter referred to as “reformed water”) under the reforming catalyst. Reactor.
- the reformer 7 is provided with a first temperature detector 10, and the first temperature detector 10 detects the temperature of the reformer 7.
- the temperature of the reformer 7 for example, the temperature of the reforming catalyst, the temperature of the raw material gas supplied to the reformer 7, or the temperature of the hydrogen-containing gas generated in the reformer 7 is detected.
- the temperature (hereinafter referred to as “first detection temperature”) is output to the controller 18.
- the reformer 7 is connected to the raw material supplier 11 by a raw material gas supply path 19 and is connected to the water supplier 13 by a water supply path 20.
- the raw material supply device 11 is a device that supplies the raw material gas to the reformer 7 through the raw material gas supply path 19 and has a function of adjusting the supply amount of the raw material gas.
- the raw material supplier 11 includes, for example, a booster and a flow rate adjustment valve connected to a cylinder filled with the raw material gas and a raw material gas supply infrastructure.
- the source gas is mainly composed of an organic compound containing hydrocarbon: C n H m composed of at least carbon and hydrogen.
- a raw material flow rate measuring device 12 is connected to the raw material gas supply path 19. Note that a desulfurizer that reduces sulfur components in the raw material gas may be connected to the raw material gas supply path 19.
- the raw material flow rate measuring device 12 measures the volume flow rate of the raw material gas supplied from the raw material supply device 11 to the reformer 7 and outputs this flow rate (hereinafter referred to as “measured flow rate”) to the controller 18.
- the water supply device 13 is a device that supplies the reformed water in a liquid or gas (steam) state to the reformer 7 through the water supply path 20, and has a function of adjusting the supply amount of the reformed water. is doing.
- the water supply device 13 is configured by, for example, a plunger pump that is connected to a water source such as tap water and that can perform a quantitative discharge.
- the upstream end of the hydrogen-containing gas supply path 122 is connected to the reformer 7, and the downstream end is connected to a hydrogen utilization device such as a fuel cell, for example. Since the hydrogen-containing gas generated in the reformer 7 contains carbon monoxide, the hydrogen-containing gas supply path 122 is connected to a remover 50 such as the transformer 8 or the selective oxidizer 9. A reaction gas supply device such as the oxidant gas supply device 14 is connected to the remover 50, and carbon monoxide in the hydrogen-containing gas is reacted with the reaction gas to be removed. However, when it is not necessary to remove carbon monoxide in the hydrogen-containing gas, the remover 50 may not be provided.
- the transformer 8 is connected to the reformer 7 by the hydrogen-containing gas supply path 122 and is not used in the reformer 8 via the hydrogen-containing gas supply path 122 from the reformer 7 and the hydrogen-containing gas and the reforming reaction. Steam is supplied.
- the transformer 8 is a remover that removes carbon monoxide by changing the carbon monoxide gas in the hydrogen-containing gas to water gas and carbon dioxide gas by a steam conversion reaction.
- the water supply unit 13 and the water supply path 20 are used for supplying water to both the reformer 7 and the transformer 8, the water supply unit 13 and the water supply path 20 for the reformer 7 are separately provided. A water supply and a water supply path for the transformer 8 may be provided.
- a branch path of the water supply path 20 may be provided, and water vapor may be directly supplied from the water supply unit 13 to the transformer 8 via this branch path.
- a water supply device different from the water supply device 13 may be provided, and steam may be supplied from the water supply device to the transformer 8.
- the selective oxidizer 9 is connected to the transformer 8 through a hydrogen-containing gas supply path 122, and a hydrogen-containing gas is supplied from the transformer 8 through the hydrogen-containing gas supply path 122.
- the selective oxidizer 9 is connected to the oxidant gas supply device 14 by the oxidant gas supply path 21, and the oxidant gas reacts with the selective oxidizer 9 from the oxidant gas supply device 14 through the oxidant gas supply path 21. Supplied as a gas.
- the selective oxidizer 9 is a remover that removes carbon monoxide by changing carbon monoxide remaining in the hydrogen-containing gas into carbon dioxide by a selective oxidation reaction using an oxidant gas.
- the oxidant gas supply device 14 is an oxidant gas supply device having a function of controlling the supply amount.
- fans such as a blower or a sirocco fan that can adjust the supply amount of the oxidant gas and have the suction opening opened to the atmosphere. Is used.
- the combustor 15 is connected to the hydrogen utilization device through the exhaust gas path 124, and the exhaust gas is supplied through the exhaust gas path 124.
- the exhaust gas includes a hydrogen-containing gas that remains without being consumed by the hydrogen utilization device and a raw material gas that remains without being reformed by the reformer 7 as a combustible gas.
- a combustion air supply unit 16 is connected to the combustor 15 through a combustion air supply path 25, and combustion air (hereinafter referred to as “combustion air”) passes from the combustion air supply unit 16 through the combustion air supply path 25.
- combustion air combustion air
- a fan such as a blower or a sirocco fan that can adjust the supply amount of the combustion air and has an intake port open to the atmosphere is used.
- the combustor 15 generates combustion heat by burning the combustible gas with the combustion air, and heats the reformer 7 existing in the vicinity.
- the raw material supply device 11, another combustible gas supply device, and the like may be connected to the combustor 15.
- the second temperature detector 17 is provided in or around the housing (not shown) of the hydrogen generator 1, detects the temperature around the hydrogen generator 1, and detects this temperature (hereinafter “second detection temperature”). Is output to the controller 18. Note that the second temperature detector 17 may indirectly detect the temperature around the hydrogen generator 1 instead of directly. In this case, the second temperature detector 17 is provided at a location where a temperature correlated with the ambient temperature of the hydrogen generator 1 can be detected, and the ambient temperature of the hydrogen generator 1 is second detected from the detected temperature based on the correlation. Calculate as temperature.
- the controller 18 is connected to the components of the hydrogen generator 1 through signal lines, and controls them by transmitting and receiving signals to and from the components. For example, the controller 18 is based on the measured values from the first temperature detector 10, the raw material flow meter 12 and the second temperature detector 17, the raw material supplier 11, the water supplier 13, and the oxidant gas supplier 14. And the supply amount from each of the combustion air supply device 16 is controlled.
- the controller 18 may be configured by a microcontroller, or may be configured by an MPU, a PLC (Programmable Logic Controller), a logic circuit, or the like.
- the controller 18 also includes a storage unit 18a.
- the storage unit 18a includes an average composition of saturated hydrocarbon gas contained in the source gas and the number of moles of carbon atoms contained in the source gas having an average composition of 1 mol. Etc. are stored. Note that the storage unit 18 a may not be included in the controller 18 as long as the controller 18 is accessible.
- the operation of the hydrogen generator 1 having the above configuration is mainly performed based on control by the controller 18.
- the source gas is mainly composed of saturated hydrocarbon gas: C n H 2n + 2 will be described, but the same applies to other hydrocarbon gases.
- the raw material gas is supplied to the combustor 15 by the raw material supplier 11 through the reformer 7, and the combustion air is supplied by the combustion air supplier 16.
- the raw material gas is burned with combustion air, and the reformer 7 is heated by this combustion heat.
- the raw material gas and the reforming water are supplied to the reformer 7 that has reached a high temperature.
- the raw material is subjected to a reforming reaction mainly represented by C n H 2n + 2 + 2nH 2 O ⁇ (3n + 1) H 2 + nCO 2 and C n H 2n + 2 + nH 2 O ⁇ (2n + 1) H 2 + nCO.
- a hydrogen-containing gas is generated from the gas and the reformed water.
- the rate at which the raw material gas undergoes the reforming reaction mainly depends on the temperature of the reformer 7.
- the temperature of the reformer 7 is set to a predetermined temperature: 700 ° C. so that the ratio of the raw material gas undergoing the reforming reaction is 85 to 95%. Yes.
- the hydrogen-containing gas generated in the reformer 7 includes, for example, about 10% carbon monoxide.
- the hydrogen-containing gas is supplied to the transformer 8.
- the steam that was not used for the reforming reaction in the reformer 7 is also supplied to the shifter 8, and the shifter 8 generates hydrogen by a shift reaction mainly represented by CO + H 2 O ⁇ H 2 + CO 2. Carbon monoxide contained in the contained gas is removed.
- the hydrogen-containing gas contains a small amount of carbon monoxide
- the hydrogen-containing gas is supplied to the selective oxidizer 9.
- An oxidant gas is also supplied to the selective oxidizer 9 by the oxidant gas supply device 14.
- hydrogen is contained by an oxidation reaction mainly represented by CO + (1/2) O 2 ⁇ CO 2.
- the concentration of carbon monoxide in the gas is reduced to 10 ppm or less.
- the hydrogen-containing gas from which the carbon monoxide has been removed is supplied to a hydrogen utilization device such as a fuel cell, and the remaining exhaust gas is supplied to the combustor 15.
- This exhaust gas contains, as combustible gas, a hydrogen-containing gas that remains without being consumed by the hydrogen utilization device and a raw material gas that has not been utilized for the reforming reaction.
- combustion air is supplied to the combustor 15 by the combustion air supply device 16, and H 2 + (1/2) O 2 ⁇ H 2 O and C n H 2n + 2 + ⁇ (3n + 1) / 2 ⁇ O 2 ⁇ nCO 2 + (n + 1) mainly represented by the combustion reaction with H 2 O occurs.
- the temperature of the reformer 7 is maintained at a predetermined temperature by this combustion heat.
- the temperature of the reformer 7 depends on the amount of combustible gas, that is, the volume flow rate of the raw material gas supplied from the raw material supplier 11, the temperature of the reformer 7 becomes a predetermined temperature. As described above, the volume flow rate of the raw material gas supplied by the raw material supplier 11 is feedback-controlled.
- each supply amount of the reforming water, the oxidant gas, and the combustion air depends on the supply amount and the composition of the raw material gas.
- the supply amount of source gas is calculated
- the composition of the raw material gas may change due to a change in the ratio of the hydrocarbon gas in the raw material gas and the components of the hydrocarbon gas. For this reason, as will be described later, a change in the composition of the source gas is detected, and each supply amount is controlled in an operation mode corresponding to the changed composition.
- the operation mode include a normal mode when the composition of the source gas is not changed, and a decrease mode and an increase mode when the composition of the source gas is changed. In this normal mode, a value in which the ratio of the hydrocarbon gas in the raw material gas and the carbon number of the raw material gas: n are set in advance is used.
- the supply amount (volume flow rate) of the reforming water by the water supplier 13 is the first ratio: S / C, which is the molar ratio between the reforming water supplied to the reformer 7 and the carbon in the raw material gas. It is controlled by the controller 18 so that Since the molar ratio is equal to the volume ratio if the pressure and temperature are constant, the first ratio can be expressed as Vw / (n ⁇ Vf) from the volumetric flow rate of reforming water: Vw and the volumetric flow rate of raw material gas: Vf. .
- the volume flow rate Vf of the raw material gas is measured by the raw material flow rate measuring device 12, and the ratio of the hydrocarbon gas in the raw material gas and the carbon number n of the hydrocarbon gas are preset in the storage unit 18a.
- the target value depends on the amount of water used in the reforming reaction in the reformer 7, the shift reaction in the shift converter 8, the characteristics of the hydrogen generator 1, and the specifications required by the hydrogen utilization device. For example, it is preset to 3.0.
- the water supply device 13 is controlled so as to be supplied. For example, when methane is set as the source gas, the number of carbon atoms: n is 1, so that 3 mol of reformed water is supplied for 1 mol of methane. When propane is set as the raw material gas, the number of carbon atoms: n is 3, so that 9 mol of reforming water is supplied to 1 mol of propane.
- the reforming water is supplied to the reformer 7 so that the first ratio becomes the target value. For this reason, a situation that occurs when the first ratio is smaller than the target value, that is, excess raw material gas is thermally decomposed due to lack of water vapor, and a carbon component is deposited, and this carbon component adheres to the reforming catalyst. Thus, it is possible to prevent a situation where the durability of the hydrogen generator 1 is lowered. On the other hand, it is possible to reduce the situation that occurs when the first ratio is greater than the target value, that is, the situation where the amount of heat for converting the reformed water into steam increases and the efficiency of the hydrogen generator 1 decreases. it can. In addition, it is possible to prevent a situation in which the reforming catalyst gets wet and deteriorates due to excess steam that is not used in the reforming reaction, and the durability of the hydrogen generator 1 is lowered.
- the supply amount (volume flow rate) of combustion air by the combustion air supply device 16 is controlled by the controller 18 so that the second ratio (air ratio): A / Ao becomes a target value.
- the second ratio is the ratio of the supply amount of combustion air actually supplied to the combustor 15: A and the minimum amount of air (theoretical air amount): Ao required to completely burn the combustible gas. is there.
- the target value of the second ratio is set in advance to 1.5 in the normal mode, for example.
- Combustion reactions in the combustor 15 are mainly H 2 + (1/2) O 2 ⁇ H 2 O and C n H 2n + 2 + ⁇ (3n + 1) / 2 ⁇ O 2 ⁇ nCO 2 + (n + 1) H 2 O. Since it is expressed, the theoretical air amount: Ao depends on the amount of combustible gas and the carbon number of the raw material gas: n. The carbon number: n of this source gas is preset in the storage unit 18a as described above. Further, the amount of combustible gas is the total amount of the amount of hydrogen supplied to the combustor 15 and the amount of hydrocarbon gas in the raw material gas remaining without being used in the reformer 7. This amount of hydrogen is an amount obtained by subtracting the amount of hydrogen consumed in the hydrogen utilization device from the amount of hydrogen produced in the reformer 7.
- the reforming reaction in the reformer 7 is mainly expressed as C n H 2n + 2 + 2nH 2 O ⁇ (3n + 1) H 2 + nCO 2 and C n H 2n + 2 + nH 2 O ⁇ (2n + 1) H 2 + nCO.
- the amount of hydrogen produced is determined by the amount of raw material gas supplied, the proportion of hydrocarbon gas in the raw material gas, the number of carbon in the raw material gas: n, and the proportion of the raw material gas undergoing a reforming reaction. Further, the amount of the raw material gas remaining without being used in the reformer 7 is determined by the supply amount of the raw material gas and the ratio of the raw material gas undergoing the reforming reaction.
- the supply amount of the raw material gas is a raw material gas flow rate measured by the raw material flow rate measuring device 12, and the ratio of the hydrocarbon gas in the raw material gas and the number of carbons of the raw material gas: n are set in advance in the reformer 7.
- the ratio of the raw material gas subjected to the reforming reaction is controlled to be 85 to 95%, for example.
- the amount of hydrogen produced in the reformer 7 and the amount of the raw material gas remaining unused in the reformer 7 are obtained from the measured flow rate of the raw material gas.
- the amount of hydrogen consumed by the hydrogen utilization device is obtained from the amount of hydrogen consumed by the hydrogen consumption calculator 4 (FIG. 3) of the fuel cell system 100 described later. Therefore, the amount of combustible gas in the combustor is determined based on the measured flow rate of the source gas and the amount of hydrogen consumed.
- the device 16 is controlled.
- the oxidation reaction in the selective oxidizer 9 is mainly represented by CO + (1/2) O 2 ⁇ CO 2 . Therefore, the supply amount (volume flow rate) of the oxidant gas by the oxidant gas supply unit 14 is determined based on the amount of carbon monoxide in the hydrogen-containing gas, and the oxidant gas supply unit 14 It is controlled by the controller 18 so that the oxidant gas is supplied.
- This carbon monoxide is produced by a reaction in the reformer 7 mainly represented as C n H 2n + 2 + nH 2 O ⁇ (2n + 2) H 2 + nCO.
- the volume flow rate of carbon monoxide depends on the volume flow rate of the source gas: Vf, the ratio of the hydrocarbon gas in the source gas and the number of carbons: n, and the ratio of the hydrocarbon gas in the source gas and the number of carbons: n is set in advance.
- the target value of the supply amount (volume flow rate) of the oxidant gas from the oxidant gas supply device 14 has a correlation with the volume flow rate of the raw material gas, and this correlation is stored in the storage unit 18a.
- the controller 18 obtains the target value of the supply amount of the oxidant gas from the measured flow rate of the raw material gas and the number of carbons by the raw material flow rate measuring device 12 based on this correlation.
- the oxidant gas supply unit 14 is controlled so that the supply amount by the oxidant gas supply unit 14 becomes the target value.
- the operation mode is the normal mode so that the supply amounts of the reforming water, the oxidant gas, and the combustion air become the amounts suitable for the composition of the raw material gas after the change. Can be switched to decrease mode or increase mode.
- the water supplier 13, the oxidant gas supplier 14, and the combustion air supplier 16 are controlled.
- the composition of the source gas is determined by the components constituting the source gas and the ratio of the amount.
- the hydrocarbon gas: CnHm, the number of carbons: n, and the ratio of the hydrocarbon gas in the raw material gas, which are the main components constituting the basic raw material gas, are preset in the storage unit 18a.
- the ratio of the hydrocarbon gas in the raw material gas and the composition of the hydrocarbon gas change to change the composition of the raw material gas, the amount of heat per unit volume of the raw material gas changes according to the change in composition.
- the raw material gas when the raw material gas is mainly composed of a chain-type saturated hydrocarbon gas such as methane, ethane, or propane, the amount of heat per unit volume of the raw material gas decreases as the carbon number: n decreases. To do. Further, if the raw material gas does not generate an exothermic reaction in the combustor 15 or contains a mixed gas whose calorific value is smaller than that of the hydrocarbon, and the proportion of the hydrocarbon gas in the raw material gas decreases, the unit volume of the raw material gas The amount of heat per unit decreases.
- a chain-type saturated hydrocarbon gas such as methane, ethane, or propane
- the amount of heat per unit volume of the raw material gas is changed, if the amount of the raw material gas supplied is the same as that before the composition change of the raw material gas, the amount of heat of the combustible gas in the combustor 15 is reduced.
- the amount of heat supplied to the reformer 7 decreases.
- the temperature of the reformer 7 is “amount of heat supplied from the combustor 15 to the reformer 7”, “amount of heat used for the reforming reaction in the reformer 7”, “transformer 8 downstream from the reformer 7. And “amount of heat released from the reformer 7 to the outside”. For this reason, if the “amount of heat supplied from the combustor 15 to the reformer 7” decreases, the first detected temperature, which is the temperature of the reformer 7, decreases.
- the supply amount of the source gas is feedback-controlled so that the first detection temperature becomes a predetermined temperature. For this reason, the supply amount of the source gas is increased in order to maintain the first detection temperature at a predetermined temperature and compensate for the decrease in “the amount of heat supplied from the combustor 15 to the reformer 7”. Therefore, the controller 18 can detect such a change in the composition of the source gas that accompanies a change in the calorific value of the source gas based on the measured flow rate of the source gas by the source flow rate measuring device 12.
- the controller 18 determines the raw material based on the temperature around the hydrogen generator 1, that is, the second temperature detected by the second temperature detector 17.
- a reference flow rate for determining whether or not the gas composition has changed is set.
- the reference flow rate for the raw material gas is the temperature of the reformer 7 when the surroundings of the hydrogen generator 1 are at the second detected temperature in a state where the composition change accompanying the change in the calorific value of the raw material gas has not occurred.
- the volume flow rate of the source gas necessary for the detected temperature to become a predetermined temperature In this way, it is possible to detect that the composition of the source gas has changed because the measured flow rate of the source gas does not match the reference flow rate based on the second detection temperature.
- the reference flow rate can be determined as a predetermined range of flow rate defined by the upper limit value and the lower limit value. Further, as can be seen from the definition, the reference flow rate becomes larger as the surrounding second detected temperature is lower.
- the operation mode is set to the normal mode, assuming that the composition change of the raw material gas has not occurred.
- each supply amount is based on the composition of the raw material gas (the ratio of the hydrocarbon gas in the raw material gas and the number of carbon atoms of the hydrocarbon gas) preset in the storage unit 18a.
- the water supplier 13, the oxidant gas supplier 14 and the combustion air supplier 16 are controlled.
- the composition of the source gas is estimated based on the difference between the measured flow rate and the reference flow rate, assuming that the composition change in which the calorific value of the source gas is reduced, and the operation mode is Set to decrease mode.
- the composition change in which the calorific value of the raw material gas is increased and the composition of the raw material gas is estimated based on the difference between the measured flow rate and the reference flow rate, Set to increase mode.
- the water supply device 13, the oxidant gas supply device 14, and the combustion air supply device 16 are controlled so that the supply amounts are based on the estimated composition.
- FIG. 2 is a flowchart showing an example of an operation method of the hydrogen generator 1.
- the controller 18 acquires the second detection temperature from the second temperature detector 17, and sets the first flow rate and the second flow rate from the second detection temperature based on the raw material flow rate data (step S1). ).
- the raw material flow rate data is data in which the second detected temperature is associated with the first flow rate and the second flow rate, and is stored in the storage unit 18a.
- the first flow rate and the second flow rate are flow values included in the reference flow rate, and are, for example, an upper limit value and a lower limit value of the reference flow rate.
- the raw material flow rate data is set so that the first flow rate and the second flow rate become higher.
- the first flow rate and the second flow rate may not be the upper limit value and the lower limit value of the reference flow rate, but may be a value obtained by adding the predetermined flow rate to the reference flow rate and a value obtained by subtracting the predetermined flow rate from the reference flow rate.
- the controller 18 acquires the measured flow rate of the raw material gas from the raw material flow rate measuring device 12, and determines whether or not this measured flow rate is equal to or higher than the first flow rate (step S2).
- the first detected temperature is lowered from a predetermined temperature due to the composition change of the raw material gas in which the calorific value of the raw material gas is reduced. Gas supply is increasing. Therefore, the controller 18 performs control in the “decrease mode”, which is a control method when the composition of the source gas is changed so that the amount of heat of the source gas decreases.
- step S3 it is determined whether or not the increase flag in the storage unit 18a is ON (S3). If the increase flag is ON (step S3: YES), it is set to “increase mode” which is a control method at the time of composition change of the source gas in which the amount of heat of the source gas increases. Therefore, the controller 18 releases the increase mode and turns off the increase flag (step S4).
- step S3 when the increase flag is not ON (step S3: NO) and when the increase flag is turned OFF (step S4), the increase mode is not set. Therefore, the controller 18 sets the decrease mode, and sets the decrease flag in the storage unit 18a to ON (step S5).
- the reduction flag is set to ON by setting the reduction mode.
- the controller 18 controls the supply amounts of the water supplier 13, the oxidant gas supplier 14 and the combustion air supplier 16 in the decrease mode.
- the composition change of the raw material gas occurs such that the ratio of the hydrocarbon gas in the raw material gas or the carbon number of the hydrocarbon gas is reduced.
- the controller 18 estimates the composition of the raw material gas based on the difference between the measured flow rate of the raw material gas and the first flow rate, and sets the target values for the first ratio, the second ratio, and the oxidant gas amount. Then, the value is changed to a small value suitable for the estimated composition of the source gas.
- the controller 18 controls each of the feeders 13, 14, and 16 in the same manner as in the normal mode, the supply amounts of the reforming water, the combustion air, and the oxidant gas become amounts suitable for the composition of the raw material gas. Therefore, it is possible to prevent problems caused by excessive supply amounts.
- step S2 if the measured flow rate of the raw material gas is less than the first flow rate in the process of step S2 (step S2: NO), the supply amount of the raw material gas increases with the composition change of the raw material gas in which the heat amount of the raw material gas decreases.
- the control method is not in the decrease mode. Therefore, the controller 18 first determines whether or not the decrease flag is ON in the storage unit 18a (S6). If the decrease flag is ON (step S6: YES), the controller 18 cancels the shifted decrease mode and turns the decrease flag OFF (step S7).
- step S6 When the decrease flag is not ON (step S6: NO) and when the decrease flag is turned OFF (step S7), the decrease mode is not set. Therefore, in order to determine whether the composition change of the raw material gas in which the calorific value of the raw material gas is changed or the composition change in which the calorific value of the raw material gas is increased, the controller 18 It is determined whether or not the measured gas flow rate is less than the second flow rate (step S8).
- step S8 YES
- the controller 18 sets the increase mode and turns on the increase flag in the storage unit 18a (step S9).
- the controller 18 controls each supply amount of the water supplier 13, the oxidant gas supplier 14 and the combustion air supplier 16 in the increase mode. Specifically, the controller 18 estimates the composition of the raw material gas based on the difference (comparison result) between the measured flow rate of the raw material gas and the second flow rate, and the first ratio, the second ratio, and the oxidant gas amount. Each target value is changed to a large value suitable for the estimated raw material gas composition. And if the controller 18 controls each supply device 13,14,16 similarly to control in normal mode, each supply amount of reforming water, combustion air, and oxidant gas will be the quantity suitable for the composition change of source gas Thus, it is possible to prevent problems due to a shortage of each supply amount.
- step S8 if the measured flow rate of the source gas is not less than the second flow rate (step S8: NO), there is no composition change in which the amount of heat of the source gas changes. Therefore, since the control method is the normal mode, not the increase mode or the decrease mode, if the increase flag is ON (S10: YES), the controller 18 cancels the increase mode that has been transferred, and sets the increase flag. Set to OFF (step S11).
- the controller 18 controls each of the feeders 13, 14, and 16 in the normal mode, an amount of reforming water, combustion air, and oxidant gas suitable for the composition of the raw material gas is supplied.
- FIG. 3 is a block diagram showing the configuration of the combustion battery system 100.
- the fuel cell system 100 includes a hydrogen generator 1 that generates a hydrogen-containing gas, and a fuel cell 2 that generates power using the hydrogen-containing gas and a power generating oxidant gas.
- the fuel cell 2 includes an anode (not shown) and a cathode (not shown).
- the hydrogen generator 1 is connected to the anode via a fuel gas supply path 22, and the cathode is connected to an oxidant gas supply path 23 for power generation.
- An oxidant gas supply device 3 for power generation is connected.
- the fuel cell 2 generates power by causing a power generation reaction between hydrogen in the fuel gas and oxygen in the power generation oxidant gas supplied to the cathode. Heat and water are generated along with this power generation.
- a conventional configuration such as hot water recovery means is used.
- the hydrogen generator 1 supplies the hydrogen-containing gas as a fuel gas to the anode of the fuel cell 2 via the fuel gas supply path 22. At this time, the fuel gas contains a certain amount of water vapor used for the reforming reaction, but water vapor may be further added.
- the hydrogen generator 1 is equipped with the converter 8 and the selective oxidizer 9 as a removal device.
- the transformer 8 and the selective oxidizer 9 may not be provided in the hydrogen generator 1.
- controller 18 may not be disposed in the hydrogen generator 1, and may be disposed separately from the hydrogen generator 1, for example.
- a controller that controls the operation of components other than the hydrogen generator 1 in the fuel cell system 100 may be provided.
- the power generation oxidant gas supply unit 3 is a device that supplies power generation oxidant gas to the cathode of the fuel cell 2 via the power generation oxidant gas supply path 23, and supplies the power generation oxidant gas supply amount. It has a function to adjust. For example, when air is used as the power generation oxidant gas, the power generation oxidant gas supply unit 3 uses a fan such as a blower or a sirocco fan whose inlet is open to the atmosphere. A humidifier may be connected to the power generation oxidizing gas supply path 23. In this case, the oxidant gas for power generation is humidified with a certain amount of water vapor.
- the consumed hydrogen amount calculator 4 is composed of a computing unit such as a microcontroller, and the amount of hydrogen consumed in the power generation reaction based on the power generated by the power generation reaction of the fuel cell 2 (hereinafter referred to as “consumed hydrogen amount”). And the hydrogen consumption is output to the controller 18.
- the water condenser 5 is connected to the anode of the fuel cell 2 through an exhaust fuel gas path 24 and is connected to the cathode of the fuel cell 2 through an exhaust oxidant gas path 26. Exhaust fuel gas and exhaust oxidant gas are discharged from the fuel cell 2 to the water condenser 5 via the exhaust fuel gas path 24 and the exhaust oxidant gas path 26. Since the exhaust fuel gas and the exhaust oxidant gas contain water vapor, the water condenser 5 condenses water by cooling the exhaust fuel gas and the exhaust oxidant gas. As the water condenser 5, for example, a heat exchanger is used. Note that water may be aggregated from either the exhaust fuel gas or the exhaust oxidant gas.
- the water recovery unit 6 is connected to the water condenser 5 through a condensed water path 27, and the water condensed in the water condenser 5 is supplied through the condensed water path 27 to recover this water.
- the water recovery unit 6 may include a purifier or a filter that removes mixed gas such as conductive ions.
- the water recovery unit 6 is connected to the water supply unit 13 through the water supply path 20 and supplies the water collected as a water supply source to the water supply unit 13 through the water supply path 20.
- the combustor 15 is connected to the water condenser 5 through an exhaust fuel gas path 24, and the exhaust fuel gas from which water has been removed in the water condenser 5 is supplied.
- the exhausted fuel gas includes hydrogen gas that has not been consumed in the power generation reaction in the fuel cell 2 and raw material gas that has not been used in the reforming reaction in the reformer 7 as combustible gas.
- the combustor 15 burns these combustible gases and heats the reformer 7 with this combustion heat.
- the consumed hydrogen amount calculator 4 calculates the consumed hydrogen amount in the power generation reaction based on the generated power of the fuel cell 2 and outputs it to the controller 18.
- the controller 18 determines the temperature of the reformer 7 so as to generate more hydrogen than the consumed hydrogen amount. If the production amount of the hydrogen-containing gas in the reformer 7 at this time is a predetermined amount, the temperature of the reformer 7, that is, the first detected temperature by the first temperature detector 10 is the predetermined temperature. Then, the controller 18 controls the raw material supplier 11 so that the first detected temperature becomes a predetermined temperature.
- the raw material gas is supplied to the reformer 7 by the raw material supplier 11, and the reformed water is supplied to the reformer 7 by the water supplier 13.
- the raw material gas undergoes a reforming reaction with the reforming water, and a predetermined amount of hydrogen-containing gas is generated.
- This hydrogen-containing gas is supplied to the transformer 8, and carbon monoxide is transformed by the steam in the transformer 8 and reduced.
- the hydrogen-containing gas is supplied to the selective oxidizer 9, and carbon monoxide is oxidized and removed by the oxidant gas supplied from the oxidant gas supply unit 14 in the selective oxidizer 9.
- the hydrogen-containing gas from which carbon monoxide has been removed is supplied from the hydrogen generator 1 to the fuel cell 2, and the oxidant gas for power generation is supplied to the fuel cell 2 by the oxidant gas supply unit 3 for power generation. Then, the hydrogen in the hydrogen-containing gas and the oxygen in the power generating oxidant gas undergo a power generation reaction in the fuel cell 2 to generate power with a predetermined power. This power is supplied to a power load (not shown).
- the exhaust oxidant gas discharged from the fuel cell 2 is discharged out of the system.
- the discharged fuel gas is supplied to the combustor 15, and the combustible gas in the discharged fuel gas is burned with the combustion air, and the reformer 7 is heated by this combustion heat.
- the controller 18 controls the reforming water, combustion air, and oxidant gas when the amount of hydrogen-containing gas generated is a predetermined amount for a first predetermined time or more.
- Each supply amount is controlled based on the measured flow rate of the source gas.
- the control of each supply amount of the water supplier 13, the combustion air supplier 16, and the oxidant gas supplier 14 is the same as that in the first embodiment.
- the predetermined electric power is electric power generated by the fuel cell 2 using a predetermined amount of hydrogen-containing gas and a power generation oxidant gas necessary for the power generation reaction.
- the amount of hydrogen-containing gas produced is a predetermined amount for the first predetermined time or longer, the temperature of the reformer 7 and the like and each supply amount are stable. This is based on a change in the temperature around the generator 1 and a change in the composition of the raw material gas accompanied by a change in the amount of heat. Therefore, by comparing the first flow rate and the second flow rate based on the second detected temperature with the measured flow rate of the raw material gas, the composition change accompanying the change in the calorific value of the raw material gas is accurately detected, and the change is made according to this composition change.
- Each supply amount of quality water, combustion air, and oxidant gas can be controlled accurately.
- the controller 18 controls the amount of the oxidant gas supplied to the selective oxidizer 9 in the remover 50 based on the measured flow rate of the raw material gas measured by the raw material flow rate measuring device 12.
- the controller 18 may control the supply amount of water vapor supplied to the transformer 8 based on the measured flow rate of the raw material gas.
- a water vapor supply device is provided as a reaction gas supply device, and the water vapor supply device supplies water vapor to the transformer 8 as a reaction gas.
- This water vapor supply device may be the water supply device 13 or may be provided separately from the water supply device 13.
- the water supply device 13 has a water vapor supply route for supplying water vapor to the transformer 8 separately from the water supply route 20 for supplying reformed water to the reformer 7. May be connected.
- the first flow rate and the second flow rate are used as the reference flow rates for the determination regarding the composition change of the source gas based on the second detected temperature, but the present invention is not limited to this.
- the present invention is not limited to this.
- the supply amount of the raw material gas necessary for maintaining the temperature of the reformer 7 does not change, or the change is so small that it can be ignored.
- the supply amount of the raw material gas necessary for setting the first detection temperature to a predetermined temperature is set as the reference flow rate.
- the first flow rate and the second flow rate based on the second detected temperature are used as the reference flow rate for determining the composition change of the raw material gas, but in addition to or instead of this, the storage unit A reference flow rate based on the measured flow rate of the source gas stored in 18a can be used.
- the controller 18 stores the measured flow rate of the source gas during operation in the storage unit 18a, and sets the reference flow rate based on the measured flow rate of the source gas stored in the storage unit 18a. Good.
- the second temperature detector 17 that detects the temperature around the hydrogen generator 1 may not be provided.
- the controller 18 stores the measured flow rate of the source gas in the storage unit 18a. deep. Then, when the operation of the hydrogen generator 1 is started, the controller 18 can read the measured flow rate of the source gas at the previous operation from the storage unit 18a and use this as the reference flow rate. In this case, a flow rate obtained by adding a predetermined flow rate to the measured flow rate during the previous operation may be set as the first flow rate, and a flow rate obtained by subtracting the predetermined flow rate from the measured flow rate during the previous operation may be set as the second flow rate.
- the controller 18 can read the measured flow rate of the raw material gas from the storage unit 18a at the same time (time zone) as when the hydrogen generator 1 is operated, and use this as the reference flow rate.
- the flow rate obtained by adding the predetermined flow rate to the stored measurement flow rate at the same time can be set as the first flow rate
- the flow rate obtained by subtracting the predetermined flow rate from the measurement flow rate at the same time can be set as the second flow rate.
- the controller 18 can read the measured flow rate measured last time from the storage unit 18a and use this as the reference flow rate.
- a flow rate obtained by adding a predetermined flow rate to the measurement flow rate at the previous measurement can be set as the first flow rate
- a flow rate obtained by subtracting the predetermined flow rate from the measurement flow rate at the previous measurement can be set as the second flow rate.
- the controller 18 may correct the predetermined temperature based on the operation time of the reformer 7. In this case, as the reforming catalyst or the like deteriorates according to the operation time, the amount of hydrogen-containing gas generated in the reformer 7 decreases. In order to compensate for the decrease in the generation amount, the controller 18 stores the operation time of the reformer 7 in the storage unit 18a, and sets the predetermined temperature higher every time the operation time elapses. Since the first flow rate and the second flow rate are set based on the predetermined temperature, the first flow rate and the second flow rate are also corrected based on the operation time of the reformer 7.
- the temperature of the reformer 7 rises in response to a decrease in the characteristics of the reformer 7 as the operation time of the reformer 7 increases, so that the amount of hydrogen-containing gas produced in the hydrogen generator 1 is constant. Can be maintained. Further, the first flow rate and the second flow rate are also corrected based on the operation time of the reformer 7, so that the composition change accompanying the change in the calorific value of the raw material gas can be accurately detected, and the reforming water is changed according to the composition change. In addition, each supply amount of combustion air and oxidant gas can be accurately controlled.
- the controller 18 can also control these supply amounts. In this case, the state in which the predetermined amount of the hydrogen-containing gas is generated continues for the first predetermined time, so that the temperature of each component and each supply amount are stable. For this reason, the measured flow rate of the raw material gas varies according to the temperature change around the hydrogen generator 1 and the compositional change of the raw material gas accompanied by a change in the amount of heat.
- each of the reforming water, the combustion air, and the oxidant gas is changed based on the change in the measured flow rate of the raw material gas.
- the supply amount can be accurately controlled.
- the controller 18 supplies each of reformed water, combustion air, and oxidant gas.
- the amount may be controlled based on the measured flow rate of the source gas. In this case, each supply amount is controlled when the second predetermined time or more has elapsed.
- the controller 18 sets the generated power to a predetermined power when the measured flow rate of the raw material gas is larger than the first flow rate or smaller than the second flow rate, and the second predetermined time or more is exceeded. When the time has passed, each supply amount of reforming water or the like may be controlled.
- the generation amount of the hydrogen-containing gas may change. For this reason, once the amount of the hydrogen-containing gas becomes a predetermined amount and the generated power becomes the predetermined power, and this predetermined power continues for the second predetermined time or longer, the temperature of the reformer 7 and the supply of each The amount is stable. Therefore, the measured flow rate of the raw material gas varies according to the temperature change around the hydrogen generator 1 and the composition change of the raw material gas accompanied by a change in the amount of heat.
- the composition change accompanying the change in the calorific value of the raw material gas is accurately detected, and the change is made according to this composition change.
- Each supply amount of quality water, combustion air, and oxidant gas can be controlled accurately.
- the theoretical air amount: Ao depends on the amount of combustible gas and the carbon number of the raw material gas: n, so the number of carbons corresponding to the composition of the raw material gas: n and the combustible gas
- the supply amount of combustion air may be controlled by changing the volume flow rate.
- the hydrogen generator of the present invention, its operating method, and the fuel cell system are a hydrogen generator capable of reducing carbon monoxide in the hydrogen-containing gas even when the composition of the raw material gas is changed, its operating method, and the fuel cell system. Useful as such.
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Abstract
Description
前記原料ガスの計測流量と前記基準流量との比較結果に基づいて、前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を制御するように構成されていてもよい。
前記燃料電池が前記所定電力を発電している発電行程において、第2所定時間が経過している場合に、前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を前記原料ガスの計測流量に基づいて制御するように構成されていてもよい。
(水素生成装置の構成)
図1は、水素生成装置1の構成を示すブロック図である。水素生成装置1は、水素含有ガスを生成する装置であって、図1に示すように、改質器7を含む。改質器7は、改質触媒(図示せず)を含み、改質触媒下において原料ガスを水(以下、「改質水」と言う。)で改質反応させることにより水素含有ガスを生成する反応器である。改質器7には第1温度検知器10が設けられ、第1温度検知器10は改質器7の温度を検知する。この改質器7の温度として、たとえば、改質触媒の温度、改質器7に供給される原料ガスの温度、または、改質器7で生成される水素含有ガスの温度が検知され、この温度(以下、「第1検知温度」と言う。)が制御器18に出力される。また、改質器7は、原料ガス供給経路19により原料供給器11と接続され、水供給経路20により水供給器13と接続されている。
上記構成の水素生成装置1における動作は制御器18による制御に基づいて主に行われる。ここでは、原料ガスは主に飽和炭化水素ガス:CnH2n+2で構成されている場合について説明するが、他の炭化水素ガスでも同様である。
上記のように、水素生成装置1の動作中、改質器7および変成器8での反応には、水供給器13から供給される改質水が使用される。以下、このような改質水の供給量の制御態様について説明する。
上記のように、水素生成装置1の動作中、燃焼器15には燃焼空気供給器16から燃焼空気が供給される。以下、この燃焼空気の供給量の制御態様について説明する。
上記のように、水素生成装置1の動作中、選択酸化器9には酸化剤ガス供給器14から酸化剤ガスが供給される。以下、この酸化剤ガスの供給量の制御態様について説明する。
上記のように、原料ガスの組成が変化した際、変化後の原料ガスの組成に適した量に改質水、酸化剤ガスおよび燃焼空気の各供給量がなるように、運転モードが通常モードから減少モードや増加モードに切り替えられる。この運転モードに従って、水供給器13、酸化剤ガス供給器14および燃焼空気供給器16が制御される。
図3は、燃焼電池システム100の構成を示すブロック図である。燃料電池システム100は、図3に示すように、水素含有ガスを生成する水素生成装置1、および、水素含有ガスおよび発電用酸化剤ガスを用いて発電する燃料電池2を備える。
消費水素量算出器4は、燃料電池2の発電電力に基づいて発電反応における消費水素量を算出して、制御器18に出力する。制御器18は、消費水素量以上の水素を生成するように改質器7の温度を定める。このときの改質器7における水素含有ガスの生成量が所定量であれば、改質器7の温度、つまり、第1温度検知器10による第1検知温度が所定温度である。そして、制御器18は、第1検知温度が所定温度になるように原料供給器11を制御する。
制御器18は、燃料電池2が所定電力を発電する前の起動工程において、水素含有ガスの生成量が第1所定時間以上所定量である場合に、改質水、燃焼空気および酸化剤ガスの各供給量を原料ガスの計測流量に基づいて制御する。この水供給器13、燃焼空気供給器16および酸化剤ガス供給器14の各供給量の制御は、実施の形態1と同様である。ここで、所定電力は、所定量の水素含有ガスと、この発電反応に必要な量の発電用酸化剤ガスとを用いて燃料電池2により生成される電力である。
上記全実施の形態では、除去器50のうち、選択酸化器9へ供給される酸化剤ガスの量を原料流量計測器12による原料ガスの計測流量に基づいて制御器18は制御した。この酸化剤ガスの供給量に代えてまたは酸化剤ガスの供給量と共に、変成器8へ供給される水蒸気の供給量を原料ガスの計測流量に基づいて制御器18は制御してもよい。この場合、水蒸気供給器が反応ガス供給器として設けられ、水蒸気供給器は水蒸気を反応ガスとして変成器8に供給する。この水蒸気供給器は、水供給器13であってもよいし、水供給器13とは別に設けられてもよい。水供給器13が水蒸気供給器として用いられる場合、水供給器13には、改質器7に改質水を供給する水供給経路20とは別に、変成器8に水蒸気を供給する水蒸気供給経路が接続されていてもよい。
上記全実施の形態では、第2検知温度に基づいて第1流量および第2流量を、原料ガスの組成変化に関する判定のための基準流量に用いたが、これに限定されない。この場合、水素生成装置1の周囲の温度変動が小さい場合や、断熱により改質器7から外部への放熱量が抑制されている場合、水素生成装置1の周囲の温度が変動しても、改質器7の温度を維持するために必要な原料ガスの供給量は変化しない、または、その変化が無視できるほど小さい。このような第2検知温度の変化による原料ガスの供給量に対する影響が小さい場合、たとえば、第1検知温度を所定温度にするために必要な原料ガスの供給量を基準流量とする。
上記全実施の形態では、第2検知温度に基づいた第1流量および第2流量を、原料ガスの組成変化を判定のための基準流量に用いたが、これと共にまたはこれに代えて、記憶部18aに記憶されている原料ガスの計測流量に基づいた基準流量を用いることができる。この場合、制御器18は、運転時における原料ガスの計測流量を記憶部18aに記憶すると共に、この記憶部18aに記憶されている前記原料ガスの計測流量に基づいて基準流量を設定してもよい。なお、この場合、水素生成装置1の周囲の温度を検知する第2温度検知器17が設けられなくてもよい。
上記全実施の形態において、制御器18は、改質器7の運転時間に基づいて所定温度を補正してもよい。この場合、改質触媒などが運転時間に応じて劣化するに伴い、改質器7における水素含有ガスの生成量が低下する。この生成量の低下を補うため、制御器18は、改質器7の運転時間が記憶部18aに記憶し、運転時間が所定時間を経過する毎に所定温度を高く設定する。この所定温度に基づいて第1流量および第2流量が設定されるため、改質器7の運転時間に基づいて第1流量および第2流量も補正される。
上記全実施の形態において、原料ガスの熱量が変化する組成変化が生じた場合、この組成変化に応じて改質水、燃焼空気および酸化剤ガスの全ての供給量が制御されたが、改質水、燃焼空気および酸化剤ガスの少なくともいずれか1つの供給量が制御されてもよい。
上記実施の形態1において、水素含有ガスの生成量が第1所定時間以上所定量である場合に、制御器18は、これらの各供給量を制御することもできる。この場合、所定量の水素含有ガスが生成されている状態が第1所定時間継続することにより、各構成部の温度や各供給量が安定している。このため、原料ガスの計測流量は、水素生成装置1の周囲の温度変化と、熱量変化を伴う原料ガスの組成変化とに応じて変動する。よって、第2検知温度に基づく第1流量および第2流量と原料ガスの計測流量とを比較することにより、原料ガスの計測流量の変化に基づいて改質水、燃焼空気および酸化剤ガスの各供給量を精度よく制御することができる。
上記実施の形態2において、起動工程に代えてまたは起動工程と共に、燃料電池2が所定電力を発電している発電行程において、制御器18は、改質水、燃焼空気および酸化剤ガスの各供給量を原料ガスの計測流量に基づいて制御してもよい。この場合、第2所定時間以上が経過している場合に、各供給量が制御される。これにより、発電行程においても、原料ガスの組成変化が生じても原料ガスの組成に適した量の改質水などが供給されるため、一酸化炭素が除去され、かつ、発電に必要な量の水素含有ガスが燃料電池2に供給される。よって、燃料電池2の発電効率および耐久性を維持することができる。
上記実施の形態2において、制御器18は、原料ガスの計測流量が第1流量より大きく、または、第2流量より小さくなった変化した場合、発電電力を所定電力にし、第2所定時間以上が経過している場合に、改質水などの各供給量を制御してもよい。
上記全実施の形態において、原料ガスの熱量が変化する組成変化が生じた場合、この組成変化に応じて第1比率、第2比率および酸化剤ガスの全ての目標値が変更されることにより、改質水、燃焼空気および酸化剤ガスの各供給量が制御された。各供給量の制御方法はこれに限らない。たとえば、第1比率が、Vw/(n・Vf)と表される場合、原料ガスの組成に対応した炭素数:nや原料ガスの体積流量:Vf(原料ガス中の炭化水素ガスの割合)を変更することにより、改質水の供給量が制御されてもよい。また、第2比率:A/Aoについて、理論空気量:Aoが可燃性ガスの量および原料ガスの炭素数:nに依存するため、原料ガスの組成に対応した炭素数:nや可燃性ガスの体積流量を変更することにより、燃焼空気の供給量が制御されてもよい。
2 燃料電池
7 改質器
9 選択酸化器
10 第1温度検知器
11 原料供給器
12 原料流量計測器
13 水供給器
14 酸化剤ガス供給器
15 燃焼器
16 燃焼空気供給器
17 第2温度検知器
18 制御器
18a 記憶部
50 除去器
100 燃料電池システム
Claims (12)
- 原料ガスおよび水の改質反応により水素含有ガスを生成する改質器と、
前記原料ガスを供給する原料供給器と、
前記原料ガスの流量を計測する原料流量計測器と、
前記改質器の温度を検知する第1温度検知器と、
前記原料ガスおよび前記水素含有ガスのうちの少なくとも一方の可燃性ガスを空気で燃焼させて前記改質器を加熱する燃焼器と、
前記水素含有ガス中の一酸化炭素を反応ガスで反応させて除去する除去器と、
前記反応ガスを供給する反応ガス供給器と、
制御器と、を備え、
前記制御器は、
前記第1温度検知器により検知された第1検知温度が所定温度になるように前記原料供給器による前記原料ガスの供給量を制御し、その間に前記原料流量計測器により計測された前記原料ガスの計測流量に基づいて、前記反応ガス供給器による前記反応ガスの供給量を制御するように構成されている、水素生成装置。 - 前記除去器は、前記一酸化炭素を水蒸気で変成する変成器と、前記一酸化炭素を酸化剤ガスで酸化する選択酸化器と、を含み、
前記反応ガス供給器は、前記水蒸気を供給する水蒸気供給器と、前記酸化剤ガスを供給する酸化剤ガス供給器と、を含む、請求項1に記載の水素生成装置。 - 前記制御器は、
前記水素含有ガスの生成量が第1所定時間以上所定量である場合に、
前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を前記原料ガスの計測流量に基づいて制御するように構成されている、請求項2に記載の水素生成装置。 - 前記水素生成装置の周囲の温度を検知する第2温度検知器をさらに備え、
前記制御器は、
前記第2温度検知器により検知された第2検知温度に基づいて前記原料ガスに関する基準流量を設定し、
前記原料ガスの計測流量と前記基準流量との比較結果に基づいて、前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を制御するように構成されている、請求項2または3に記載の水素生成装置。 - 前記水素生成装置の運転時における前記原料ガスの計測流量を記憶する記憶部をさらに備え、
前記制御器は、
前記記憶部に記憶されている前記原料ガスの計測流量に基づいて前記原料ガスに関する基準流量を設定し、
前記原料ガスの計測流量と前記基準流量との比較結果に基づいて、前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を制御するように構成されている、請求項2または3に記載の水素生成装置。 - 前記制御器は、前記改質器の運転時間に基づいて前記所定温度を補正するように構成されている、請求項1~5のいずれか一項に記載の水素生成装置。
- 請求項2~6のいずれか一項に記載の水素生成装置と、
前記水素含有ガスを用いて発電する燃料電池と、を備える燃料電池システム。 - 前記制御器は、
前記燃料電池が所定電力を発電する前の起動工程において、前記水素含有ガスの生成量が第1所定時間以上所定量である場合に、
前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を前記原料ガスの計測流量に基づいて制御するように構成されている、請求項7に記載の燃料電池システム。 - 前記制御器は、
前記燃料電池が前記所定電力を発電している発電行程において、第2所定時間が経過している場合に、
前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を前記原料ガスの計測流量に基づいて制御するように構成されている、請求項7または8に記載の燃料電池システム。 - 前記水素生成装置の周囲の温度を検知する第2温度検知器をさらに備え、
前記制御器は、
前記第2温度検知器により検知された第2検知温度に基づいて前記原料ガスに関する基準流量を設定し、
前記原料ガスの計測流量が基準流量から変化した場合に、前記発電電力を前記所定電力にし、
前記発電電力が第2所定時間以上前記所定電力である場合に、前記原料ガスの計測流量と前記基準流量との比較結果に基づいて、前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を制御するように構成されている、請求項9に記載の燃料電池システム。 - 前記水素生成装置の運転時における前記原料ガスの計測流量を記憶する記憶部をさらに備え、
前記制御器は、
前記記憶部に記憶されている前記原料ガスの計測流量に基づいて前記原料ガスに関する基準流量を設定し、
前記原料ガスの計測流量が基準流量から変化した場合に、前記発電電力を前記所定電力にし、
前記発電電力が第2所定時間以上前記所定電力である場合に、前記原料ガスの計測流量と前記基準流量との比較結果に基づいて、前記水蒸気の供給量および前記酸化剤ガスの供給量の少なくとも一方を制御するように構成されている、請求項9に記載の燃料電池システム。 - 原料ガスおよび水を改質器へ供給し、
前記改質器にて、前記原料ガスおよび前記水の改質反応により水素含有ガスを生成し、
燃焼器にて、前記原料ガスおよび前記水素含有ガスのうち少なくとも一方を空気で燃焼させて前記改質器を加熱し、
除去器にて、前記水素含油ガス中の一酸化炭素を反応ガスで反応させて除去し、
前記改質器が所定温度になるように前記改質器への前記原料ガスの供給量を制御し、その間の前記原料ガスの供給量に基づき、前記反応ガスの供給量を制御する、水素生成装置の運転方法。
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JP5906423B2 (ja) | 2016-04-20 |
EP2835342B1 (en) | 2021-09-08 |
EP2835342A4 (en) | 2015-05-06 |
EP2835344B1 (en) | 2017-05-03 |
JPWO2013150721A1 (ja) | 2015-12-17 |
EP2835344A1 (en) | 2015-02-11 |
JPWO2013150722A1 (ja) | 2015-12-17 |
WO2013150722A1 (ja) | 2013-10-10 |
JP5906424B2 (ja) | 2016-04-20 |
EP2835344A4 (en) | 2015-05-06 |
EP2835342A1 (en) | 2015-02-11 |
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