WO2016067589A1 - 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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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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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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- 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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- 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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- 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
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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
- C01B2203/08—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
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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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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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
- C01B2203/1241—Natural gas or methane
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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
- C01B2203/1258—Pre-treatment of the feed
- C01B2203/1264—Catalytic pre-treatment of the feed
- C01B2203/127—Catalytic desulfurisation
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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
- C01B2203/1642—Controlling the product
- C01B2203/1647—Controlling the amount of the product
- C01B2203/1652—Measuring the amount of product
- C01B2203/1657—Measuring the amount of product the product being hydrogen
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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
- C01B2203/169—Controlling the feed
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention includes a hydrogen generation apparatus that reforms a raw material gas containing hydrocarbons to generate hydrogen, an operation method thereof, and a fuel cell that generates power using the hydrogen-containing gas obtained by the hydrogen generation apparatus.
- the present invention relates to a fuel cell system.
- a fuel cell capable of high-efficiency power generation even with a small device is a power generation device with a distributed energy source.
- Hydrogen gas used as fuel for fuel cell power generation has not been developed as a general infrastructure. For this reason, when a fuel cell is used as a distributed device, for example, city gas or a raw material gas containing hydrocarbons obtained from an existing fossil raw material infrastructure such as LPG is subjected to a steam reforming reaction to generate a hydrogen-containing gas.
- a configuration in which a hydrogen generator to be used is provided is also provided.
- the composition of the gas used as the raw material may change due to the infrastructure configuration.
- the composition may vary depending on the gas supply company or region, and the composition may vary over time.
- the amount of hydrogen produced by the hydrogen generator decreases. Further, when the hydrogen generator and the fuel cell are combined, the amount of hydrogen is insufficient and power generation cannot be maintained. In addition, when unreacted off-gas is returned to the reformer and burned to generate heat necessary for the reforming reaction, the amount of heat decreases due to lack of hydrogen, so the temperature of the reformer decreases and the reaction is maintained. become unable.
- the raw material supply amount is controlled and the raw material supply amount is adjusted so that the temperature detected by the reforming temperature detector becomes a predetermined target temperature.
- a configuration has been proposed in which the power generation amount of the fuel cell is reduced when the temperature detected by the reforming temperature detector is lower than the target temperature by a first temperature or more (see, for example, Patent Document 2).
- the reformer when trying to estimate the raw material gas composition from the temperature change of the reformer, the reformer is composed of a catalyst and a structure and has a large heat capacity. Therefore, it takes time until the temperature of the reformer changes. Cost. Therefore, there is still room for improvement in order to detect earlier that the composition of the raw material gas has changed, such as when control does not catch up when the composition change instantaneously exceeds that expected.
- the present invention provides a hydrogen generation apparatus capable of maintaining a proper amount of generated hydrogen and capable of stable operation, an operation method thereof, and a fuel cell system.
- the hydrogen generator of the present invention includes a reforming unit that reforms a raw material to generate a hydrogen-containing gas, a raw material feeder that supplies the raw material to the reforming unit, and a hydrogen generation amount that detects the generation amount of the hydrogen-containing gas And a detector. Then, when the production amount of the hydrogen-containing gas decreases, the control parameter corresponding to the relative low calorific gas is set and the raw material feeder is operated. A controller configured to set a control parameter corresponding to a high heat quantity gas and operate the raw material supplier.
- the fuel cell system of the present invention includes the above-described hydrogen generator and a fuel cell that generates power using a hydrogen-containing gas supplied from the hydrogen generator.
- the operation method of the hydrogen generator of the present invention includes a reformer that reforms a raw material to generate a hydrogen-containing gas, and a raw material supplier that supplies the raw material to the reformer. This is the driving method. And when the production amount of the hydrogen-containing gas decreases, when the production parameter of the hydrogen-containing gas increases, the step of setting the control parameter corresponding to the relative low calorific gas and operating the raw material feeder, And setting a control parameter corresponding to the relative high calorific gas to operate the raw material supplier.
- FIG. 1 is a diagram showing a schematic configuration of a hydrogen generator according to the first embodiment of the present invention.
- FIG. 2 is a diagram illustrating a change example of the amount of generated hydrogen when the gas composition is switched in the first embodiment of the present invention.
- FIG. 3 is a diagram for explaining an image of changing a control parameter when an external factor is within a predetermined range in the first embodiment of the present invention.
- FIG. 4 is a diagram showing a generation amount correction image of the hydrogen-containing gas in the first embodiment of the present invention.
- FIG. 5 is a diagram illustrating an example of setting control parameters according to the first embodiment of the present invention.
- FIG. 6 is a diagram showing a relationship example between the combustion air ratio and the carbon monoxide emission concentration in the first embodiment of the present invention.
- FIG. 1 is a diagram showing a schematic configuration of a hydrogen generator according to the first embodiment of the present invention.
- FIG. 2 is a diagram illustrating a change example of the amount of generated hydrogen when the gas composition is switched in the
- FIG. 7 is a diagram illustrating a setting example of three or more control parameters in Modification 1 of the hydrogen generator according to the first embodiment of the present invention.
- FIG. 8 is a diagram showing a schematic configuration of the hydrogen generator in the second embodiment of the present invention.
- FIG. 9 shows the flow rate of the selectively oxidized air and the output of the selectively oxidized air supply device when the gas type is switched (in this case, from the high calorific gas to the low calorific gas) in the modification of the second embodiment of the present invention. It is a figure which shows the comparison of the change of this, and the change of the temperature of a modification
- FIG. 10 is a diagram showing a schematic configuration of the hydrogen generator in the third embodiment of the present invention.
- FIG. 10 is a diagram showing a schematic configuration of the hydrogen generator in the third embodiment of the present invention.
- FIG. 11 is a diagram showing a schematic configuration of a fuel cell system according to the fifth embodiment of the present invention.
- FIG. 12 is a diagram showing a hydrogen-containing gas generation amount correction image corresponding to a change in the output of the fuel cell in the fifth embodiment of the present invention.
- FIG. 13 is a diagram showing a schematic configuration of a fuel cell system according to Modification 1 of the fifth embodiment of the present invention.
- FIG. 14 is a diagram showing a schematic configuration of a fuel cell system according to Modification 2 of the fifth embodiment of the present invention.
- FIG. 15 shows a fuel cell according to the second modification of the fifth embodiment when a gas of 100% methane is supplied and a gas of 20% nitrogen / 80% methane is supplied. It is a figure which shows the change of an off-gas flow rate when a power generation output, ie, an electric current value, and the amount of hydrogen consumption are the same.
- This change in pressure loss may be directly measured by, for example, a pressure gauge, or may be indirectly measured based on, for example, a change in flow rate based on a change in pressure loss in the path.
- a change in composition can be detected by detecting a decrease in the amount of hydrogen-containing gas produced and the amount of fuel cell off-gas.
- a change in the composition of the raw material gas that is, an increase in the calorific value is detected by detecting an increase in the production amount of the hydrogen-containing gas and an increase in the production amount of the fuel cell off gas. Can be detected.
- FIG. 1 is a diagram showing a schematic configuration of a hydrogen generator 50 according to the first embodiment of the present invention.
- the hydrogen generator 50 in the present embodiment includes a reforming unit 1 that reforms a raw material gas containing hydrocarbons to generate a hydrogen-containing gas, a raw material supplier 2 that supplies the raw material to the reforming unit 1, hydrogen A hydrogen-containing gas flow meter 3a as a hydrogen generation amount detection unit for detecting the generation amount of the containing gas and a controller 4 are provided.
- the controller 4 in the present embodiment sets a control parameter corresponding to the relative low calorific gas, and when the production amount of the hydrogen-containing gas increases, The control parameter corresponding to the relative high calorific gas is set, and the components of the hydrogen generator 50 including at least the raw material supplier 2 are operated.
- a steam reforming reaction for reforming hydrocarbons and steam is used, and a Ru-based catalyst is used as the reforming catalyst charged in the reforming unit 1. Yes.
- water may be supplied to the reforming unit 1 by the water supplier 5.
- the steam reforming reaction is exemplified as the reforming reaction, but the same effect can be obtained by, for example, an autothermal reaction or a partial oxidation reforming reaction.
- the reforming unit 1 may be structured to be heated by heat transfer from the combustor 6, and the outside of the reforming unit 1 may be covered with a heat insulating material.
- the raw material gas or the hydrogen-containing gas may be combusted.
- the combustion air may be configured to be supplied to the combustor 6 by the combustion air supply device 7.
- a hydrogen-containing gas flow meter 3a for hydrogen-containing gas is installed in the hydrogen-containing gas path as a hydrogen generation amount detection unit.
- the hydrogen-containing gas flow meter 3a is designed on the assumption of a predetermined composition of the hydrogen-containing gas, and can output a flow rate signal and detect the amount of hydrogen-containing gas produced from the output signal.
- the operation of the hydrogen generator 50 in the first embodiment of the present invention will be described.
- the following operations are performed by the controller 4 controlling each device of the hydrogen generator 50.
- a control parameter corresponding to 100% methane gas is used as the raw material gas.
- the controller 4 of the hydrogen generator controls the raw material supplier 2 to supply the raw material gas to the reforming unit 1.
- a booster pump that boosts the raw material gas is used as the raw material supply device 2
- a flow meter for the raw material gas is used as the raw material flow rate detector 8. Then, the controller 4 is configured to control the raw material supplier 2 so that the raw material gas flow rate becomes a predetermined flow rate.
- the raw material gas may be supplied in a state where the sulfur component in the raw material gas is desulfurized by passing through a desulfurizer.
- the flow rate of the raw material gas is preferably set in consideration of the composition of the raw material gas based on the flow rate of the hydrogen-containing gas or hydrogen gas to be generated, and is set here to 3.0 NL / min.
- the controller 4 controls the water supplier 5 to supply the reforming unit 1 with steam necessary for the steam reforming reaction (hereinafter referred to as reformed water).
- the flow rate of the reforming water is adjusted so that the S / C indicating the ratio of water to the number of carbons in the raw material gas supplied to the reforming unit 1 is 2.9. Supply quality water.
- the ratio of the number of carbon atoms in 1 mol of the source gas is 1.0, and the supply amount of water is 2.9 ⁇ .
- 1.0 ⁇ 18 ⁇ 3.0 ⁇ 22.4 7.0 cc / min.
- the raw material gas and the reformed water supplied to the reforming unit 1 are reformed into a hydrogen-containing gas by a steam reforming reaction in the presence of the reforming catalyst in the reforming unit 1.
- the controller 4 controls the combustion air supply unit 7 to supply combustion air necessary for burning the raw material gas or the hydrogen-containing gas supplied to the combustor 6.
- the controller 4 controls the flow rate of the combustion air so that the air ratio representing the supply air flow rate with respect to the theoretical combustion air flow rate when the composition of the raw material gas is 100% methane is 1.7.
- the controller 4 is configured to appropriately set at least one of the control parameters of the water supply device 5 and the combustion air supply device 7.
- the controller 3 sets the control parameter corresponding to the relative low calorific gas and operates the water supply device 5 to generate the hydrogen-containing gas.
- the water supply device 5 may be operated by setting the control parameter ⁇ ⁇ corresponding to the relative high calorific gas.
- the controller 4 sets the control parameter corresponding to the relative low heat quantity gas and operates the combustion air supply unit 7 to produce the production amount of the hydrogen-containing gas.
- a control parameter corresponding to the relative high calorific gas may be set to operate the combustion air supply device 7.
- the composition of the raw material gas is switched from 100% methane to 20% nitrogen / 80% methane, for example.
- methane gas containing 20% nitrogen is a relatively low calorific gas.
- the temperature of the reforming section 1 does not change abruptly due to its heat capacity, so that the hydrocarbon conversion rate can be regarded as equivalent before and after the gas type switching. That is, if the flow rate and the conversion rate of the raw material gas are equal, the amount of generated hydrogen decreases.
- FIG. 2 is a diagram showing an example of a change in the amount of generated hydrogen when the gas composition is switched in the first embodiment of the present invention.
- the gas of 20% nitrogen / 80% methane which is a relatively low calorific gas, contains more inert gas than the gas of 100% methane, which is a relatively high calorific gas.
- the inert gas is included in the raw material, the flow rate of the raw material gas that does not contribute to hydrogen generation increases with respect to the flow rate of the raw material gas, so that a change in the production amount of the hydrogen-containing gas can be detected more significantly.
- the hydrogen-containing gas flow meter 3a is used as the hydrogen production amount detection unit.
- a method for determining whether or not the production amount has decreased for example, within a predetermined time, Consider the behavior when the amount of hydrogen-containing gas produced decreases by a predetermined value, when it decreases to a predetermined flow rate threshold, or when the amount of change and gas composition change under normal operating conditions Thus, it is preferable to appropriately select a method that can detect a change in composition more reliably.
- the production amount of the hydrogen-containing gas has increased by a predetermined value within a predetermined time or when the production amount has increased to a predetermined flow rate threshold value. It can be determined that the generation amount has increased. These may be compared by taking an average value for each predetermined time. Here, it was determined that the production amount increased when the average value of the production amount of the hydrogen-containing gas for 10 seconds changed by 5% or more compared to the average value of one minute ago.
- the amount of hydrogen-containing gas produced can vary not only with the composition of the source gas, but also with various external factors such as the ambient temperature, the pressure of the source gas, or changes with the passage of operating time. . Therefore, the setting may be changed if the parameter contributing to the production amount of the hydrogen-containing gas is within a predetermined range. Alternatively, the setting may be changed if the change amount per predetermined time of the parameter contributing to the generation amount of the hydrogen-containing gas is within a predetermined range.
- FIG. 3 is a diagram for explaining an image of changing a control parameter when an external factor is within a predetermined range in the first embodiment of the present invention.
- the environmental temperature is cited as a parameter that contributes to the amount of hydrogen-containing gas produced.
- the generation amount of the hydrogen-containing gas detected by the hydrogen generation amount detection unit decreases and reaches the threshold value.
- the controller 4 operates by setting control parameters corresponding to the relative low calorific gas.
- the controller 4 operates by setting control parameters corresponding to the relative high calorific gas.
- FIG. 4 is a diagram showing an image of correcting the generation amount of the hydrogen-containing gas in the first embodiment of the present invention.
- the above-mentioned external factors may continue to change. For example, when the environmental temperature continues to rise under a predetermined condition, the amount of generated hydrogen may increase due to an increase in the conversion rate in the reforming unit 1. Therefore, after correcting the amount of generated hydrogen that has changed due to this external factor, it may be determined whether the amount of hydrogen-containing gas generated detected by the hydrogen generation amount detector has changed. The same effect can be obtained even if the threshold value for changing the control parameter is corrected.
- the controller 4 operates by setting control parameters corresponding to the relative low calorific gas when the production amount of the hydrogen-containing gas decreases, and when the production amount of the hydrogen-containing gas increases, the controller 4 Set the control parameters corresponding to the high calorific gas and operate.
- control parameters for example, control parameters caused by the raw material gas composition such as the raw material gas supply amount, the water supply amount (or S / C), and the combustion air flow rate (or combustion air ratio) may be set.
- FIG. 5 is a diagram showing a setting example of control parameters in the first embodiment of the present invention.
- the raw material composition of the control parameter corresponding to the relative high calorific gas is 100% methane
- the raw material composition of the control parameter corresponding to the relative low calorific gas is 20% nitrogen / 80% methane.
- Material gas supply volume is directly linked to the amount of hydrogen produced.
- the lower the amount of heat of the supplied raw material gas the lower the proportion of hydrogen in the raw material gas, and the smaller the amount of hydrogen gas that can be generated.
- the amount of source gas supply increases as the amount of heat of the source gas supplied decreases. More specifically, when the production amount of the hydrogen-containing gas detected by the hydrogen production amount detection unit is decreased, the operation is performed by relatively increasing the raw material gas flow rate, and the production amount of the hydrogen-containing gas is increased. In addition, it is preferable to operate by relatively reducing the raw material gas flow rate.
- the number of moles of carbon in one mole of the raw material gas is 1.0.
- the number of moles of carbon in one mole of the raw material gas is 0.8. That is, in the case of an equivalent raw material gas flow rate and an equivalent water supply amount, the value of S / C is 1.25 times.
- the amount of water supplied is reduced as the amount of heat of the supplied raw material gas is lower.
- it may be set in consideration of the composition and flow rate of the source gas so as to keep S / C constant.
- FIG. 6 is a diagram showing an example of the relationship between the combustion air ratio and the carbon monoxide emission concentration in the first embodiment of the present invention.
- the flow rate of combustible gas is larger than that in the case of 20% nitrogen / 80% methane, which is a relatively low calorific gas. If the raw material supply amount and the supplied combustion air amount are the same when the composition changes, the ratio of the combustion air, which is the supply air flow rate, to the combustion air flow rate required for complete combustion becomes relatively large, and carbon monoxide. Proper combustion cannot be maintained due to the occurrence of fuel.
- the combustion air ratio in order to keep the combustion air ratio at a predetermined value, it is preferable to set so that the lower the amount of heat of the supplied raw material gas, the lower the combustion air flow rate.
- it may be set in consideration of the composition and flow rate of the raw material gas so as to keep the combustion air ratio constant.
- control parameters resulting from the raw material gas composition in order to operate the hydrogen generator efficiently and stably.
- a control parameter including at least one of these parameters may be set, and by changing these control parameters in combination, a more stable operation is possible and a more remarkable effect is obtained.
- the raw material gas has three types of control parameters with different amounts of heat.
- the composition of the relatively high calorific raw material gas is 20% propane / 80% methane, 100% methane as the intermediate calorific gas, 20% nitrogen / 80% methane as the relatively low calorific gas. % Is set.
- FIG. 7 is a diagram illustrating a setting example of three or more control parameters in the first modification of the hydrogen generator 50 according to the first embodiment of the present invention.
- a control parameter corresponding to a gas of 100% methane which is a relatively intermediate calorific gas is used, and it is assumed that a gas of 100% methane is actually supplied.
- the controller 4 sets control parameters corresponding to the relative low calorific gas. Then drive.
- the composition of the source gas is switched from 100% methane to 20% nitrogen / 80% methane, for example.
- methane gas containing 20% nitrogen is a relatively low calorific gas.
- the composition of the raw material gas is switched from 100% methane to, for example, 20% propane / 80% methane.
- methane gas containing 20% propane is a relatively high calorific gas. Since propane has a large number of hydrogen atoms in one molecule, the amount of produced hydrogen increases when the raw material flow rate is the same and the conversion is the same.
- the hydrogen-containing gas flowmeter 3a is used and detected in the same manner as in the first embodiment.
- the controller 4 controls the control parameter corresponding to the relative low calorific gas (
- 20% nitrogen / 80% methane is set and the production amount of the hydrogen-containing gas increases
- the control parameter corresponding to the relative high calorific gas here 20% propane / 80% methane.
- control parameter to be selected is preferably selected according to the degree of change in the flow rate of the hydrogen-containing gas detected by the hydrogen generation amount detection unit.
- the controller 4 when operating with control parameters corresponding to 20% propane / 80% methane, the amount of hydrogen-containing gas produced decreases by a predetermined amount (here, the amount of hydrogen-containing gas produced falls by 5% or more)
- the controller 4 is operated with a relatively low calorific value and a control parameter (here, 100% methane) corresponding to an intermediate calorie value among the three.
- Controller 4 when operating with control parameters corresponding to a gas of 20% propane / 80% methane, when the amount of hydrogen-containing gas produced decreases by a predetermined amount greater than the above-mentioned predetermined amount (here, hydrogen-containing gas) Controller 4 is operated by setting a control parameter (in this case, 20% nitrogen / 80% methane) corresponding to the lowest heat quantity among the three. .
- a control parameter in this case, 20% nitrogen / 80% methane
- this modification 1 it shall have three types of control parameters, However, You may set it so that it may have three or more types of control parameters, and may select them suitably.
- the control parameter is given by a function of the composition of the raw material gas, that is, the amount of heat.
- the raw material gas having a relatively low calorific value such that the raw material gas flow rate is large, the water supply amount is small, and the combustion air flow rate is small.
- a control parameter is given as a function with respect to the heat amount of the source gas calculated from the flow rate of the hydrogen-containing gas detected by the hydrogen generation amount detection unit.
- the raw material gas should be increased by 25% ((100 ⁇ 80-1) ⁇ 100) in order to keep the amount of generated hydrogen equal to that before the gas composition change. .
- the rate of decrease can be the flow rate of the hydrogen-containing gas that has decreased in a given time, and is defined here as the rate of decrease in 1 minute. The same can be considered when the flow rate of the hydrogen-containing gas is increased.
- control parameters caused by the raw material gas composition such as the water supply amount or the combustion air flow rate, may be appropriately set by a function.
- the control parameter corresponding to the optimal amount of heat of the source gas that is, the composition
- the control parameter corresponding to the optimal amount of heat of the source gas that is, the composition
- FIG. 8 is a diagram showing a schematic configuration of the hydrogen generator 60 in the second embodiment of the present invention.
- a selective oxidation unit 11 that selectively oxidizes and removes carbon monoxide contained in a hydrogen-containing gas with oxygen, a selective oxidation air supplier 12 that supplies selective oxidation air to the selective oxidation unit 11, It is the structure provided with the selective oxidation air flow rate detector 13 which detects the flow volume of selective oxidation air.
- the selective oxidation unit 11 is maintained in a predetermined temperature (about 160 ° C. in this case) using a Ru-based catalyst, and is supplied into the hydrogen-containing gas by supplying air containing oxygen from the selective oxidation air supply unit 12.
- the carbon monoxide is selectively removed.
- the selective oxidant air supply device 12 is configured to use an air pump to pump air and the selective oxidization air flow rate detector 13 to use a flow meter to measure the supply amount.
- air is supplied so that the selective oxidation air flow volume may be set to 0.7 NLM.
- the selective oxidation air flow rate detector 13 for detecting the flow rate of the selective oxidation air is used as the hydrogen generation amount detection unit.
- the controller 4 operates by setting a control parameter corresponding to the relative low calorific gas, and the flow rate of the selective oxidation air decreases.
- the control parameter corresponding to the relative high calorific gas is set to operate.
- the controller 4 increases the flow rate of the selective oxidation air to the first flow rate (0.8 NLM in this case) or more. If the flow rate of the selective oxidation air has increased by a second flow rate (here, 0.1 NLM / 1 minute) or more within a predetermined time, the control parameter for the low calorific gas is switched. Then, the hydrogen generator 60 is operated.
- a second flow rate here, 0.1 NLM / 1 minute
- the hydrogen generator 60 when the hydrogen generator 60 is operated with the control parameter for the low calorific gas, when the flow rate of the selective oxidation air drops below the third flow rate (here, 0.6 NLM), or is determined in advance.
- the third flow rate here, 0.6 NLM
- the selective oxidation air is supplied to the selective oxidation unit 11, reacted, and then supplied or discharged through the hydrogen-containing gas path.
- the production amount of the hydrogen-containing gas decreases, the amount of fluid flowing through the same path decreases, and the pressure loss of the path decreases accordingly.
- the flow rate is reduced to about 85%, but the pressure loss of the fluid flowing through the pipe or the like is generally proportional to the square of the flow velocity. That is, if the cross-sectional areas of the flow paths are equal, the pressure loss is 0.85 ⁇ 0.85, which is reduced to about 72%.
- the selective oxidation flow rate increases when the pressure loss of the path decreases. Conversely, when the pressure loss of the path increases with the increase in the amount of hydrogen-containing gas produced, the selective oxidation flow rate decreases. By detecting this change in the selective oxidation flow rate, it is possible to detect a change in the production amount of the hydrogen-containing gas, that is, a change in the raw material gas composition.
- a selective oxidized air supply device 12 that supplies selective oxidized air to the selective oxidation unit 11 is used as a hydrogen generation amount detection unit.
- air is supplied so that the selective oxidation air flow rate becomes 0.7 NLM, and the output of the selective oxidation air supplier 12 at this time is 50%.
- the controller 4 When the controller 4 operates the hydrogen generator 60 and controls the selective oxidation air supply device 12 so that the flow rate of the selective oxidation air becomes a predetermined flow rate, the output of the selective oxidation air supply device 12 decreases.
- the control parameter corresponding to the relative low calorific gas is set and operated.
- the control parameter corresponding to the relative high calorific gas is set. Configured to drive.
- the controller 4 controls the control parameter for the low calorific gas. And the hydrogen generator 60 is operated.
- the controller 4 operates the hydrogen generator 60 with the control parameters for the low calorific gas
- the output of the selective oxidation air supplier 12 increases to the third output (here, 60%) or more.
- the output of the selective oxidizing air supply device 12 increases by a fourth output (here, 10% / 1 minute) or more within a predetermined time, switch to the control parameter for the high calorific gas.
- the hydrogen generator 60 is configured to operate.
- FIG. 9 shows the flow of the selected oxidized air flow rate and the selected oxidized air supply device 12 when the gas type is switched (in this case, from the high calorific gas to the low calorific gas) in the modification of the second embodiment of the present invention. It is a figure which shows the comparison of the change of an output, and the change of the temperature of the modification part 1.
- FIG. 9 shows the flow of the selected oxidized air flow rate and the selected oxidized air supply device 12 when the gas type is switched (in this case, from the high calorific gas to the low calorific gas) in the modification of the second embodiment of the present invention. It is a figure which shows the comparison of the change of an output, and the change of the temperature of the modification part 1.
- FIG. 9 shows the flow of the selected oxidized air flow rate and the selected oxidized air supply device 12 when the gas type is switched (in this case, from the high calorific gas to the low calorific gas) in the modification of the second embodiment of the present invention. It is a figure which shows
- the change in the selective oxidation air flow rate or the output of the selective oxidation air supplier 12 can be detected instantaneously as compared with the temperature change in the reforming section 1 having a large heat capacity. For this reason, stable operation is possible by applying control according to switching of gas types.
- the output of the selective oxidized air supply device 12 accompanying the change in the pressure of the path due to the change in the amount of hydrogen-containing gas generated is, a change in the composition of the source gas can be detected instantaneously by detecting a change in the manipulated variable.
- the composition of the source gas can be determined using a general selective oxidation flow rate in the hydrogen generator 60, a simple device can be realized at low cost.
- FIG. 10 is a diagram showing a schematic configuration of the hydrogen generator 70 in the third embodiment of the present invention.
- the present embodiment is configured to include a pressure detector 14 that detects the pressure of a path including the reforming unit 1 downstream from the raw material supplier 2 as a hydrogen production amount detection unit.
- the pressure detector 14 is installed at the inlet of the reforming unit 1, and the measured pressure during operation is 3.0 kPa. Note that the installation position of the pressure detector 14 is not limited to this example as long as the pressure resulting from the generation amount of the hydrogen-containing gas can be detected. The structure which detects the pressure of 1 exit may be sufficient.
- the controller 4 When the pressure of the pressure detector 14 decreases, the controller 4 operates by setting a control parameter corresponding to the relative low calorific gas, and when the pressure of the pressure detector 14 increases, the controller 4 It is configured to operate by setting control parameters corresponding to the high calorific gas.
- the controller 4 switches to a control parameter for low calorific gas and supplies hydrogen.
- the generator 70 is operated.
- the controller 4 operates the hydrogen generator 70 with the control parameters for the low calorific gas
- the pressure of the pressure detector 14 increases to the third pressure (here 3.5 kPa) or more
- a fourth pressure in this case, 0.5 kPa / 1 minute
- the hydrogen generation device is switched to the control parameter for the high calorific gas. Drive 70.
- control parameter setting the same method as in the first embodiment can be used.
- an appropriate control parameter may be selected, or a continuous parameter setting may be configured as a function of heat quantity. .
- the composition of the raw material gas to be supplied changes during operation of the hydrogen generator 70, the composition of the raw material gas is detected by detecting a change in the path pressure caused by the change in the amount of hydrogen-containing gas produced. Changes can be detected instantly.
- the controller 4 controls the raw material supplier 2 so that the flow rate of the raw material becomes a predetermined flow rate, and when the output of the raw material supplier 2 decreases, the control parameter corresponding to the relative low calorific gas is set.
- control parameters corresponding to relative high calorific gas are set and operated.
- the output of the raw material supplier 2 when the raw material gas is supplied at 3.0 NLM is 70%.
- the controller 4 switches to the control parameter for the low calorific gas and switches the hydrogen generator. drive.
- the controller 4 switches to the control parameter for the high calorific gas and operates the hydrogen generator.
- control parameter setting the same method as in the first embodiment can be used. It should be noted that control parameters corresponding to three or more gas types may be provided, and an appropriate control parameter may be selected, or continuous parameter setting may be configured as a function of heat quantity.
- the output of the raw material supplier 2 accompanying the change in the path pressure caused by the change in the amount of hydrogen-containing gas produced that is, By detecting a change in the operation amount, a change in the composition of the source gas can be detected instantaneously.
- the composition of the raw material gas can be determined using the output of the general raw material supplier 2 in the hydrogen generator, a simple device can be realized at low cost.
- FIG. 11 is a diagram showing a schematic configuration of a fuel cell system 80 according to the fifth embodiment of the present invention.
- the present embodiment is configured to include a fuel cell 20 that generates power using the hydrogen-containing gas supplied from the hydrogen generator 50. Further, an anode flow meter 3b that detects the flow rate at the anode inlet of the fuel cell 20 is provided as a hydrogen generation amount detection unit.
- a polymer electrolyte fuel cell (PEFC) is used as the fuel cell 20. Since the voltage of the fuel cell 20 is generally lowered by carbon monoxide, it is necessary to reduce the carbon monoxide to approximately 10 ppm or less in the selective oxidation unit 11.
- the hydrogen-containing gas containing carbon monoxide obtained in the reforming unit 1 may be supplied to the selective oxidation unit 11 after reducing the carbon monoxide stepwise through the shift catalyst.
- the controller 4 supplies the hydrogen-containing gas to the anode of the fuel cell 20 as the fuel gas of the fuel cell 20.
- the fuel gas supplied to the anode and the power generation air supplied to the cathode react electrochemically to generate electricity, heat, and water.
- the electricity obtained by the fuel cell 20 is used by being supplied to a power load (not shown).
- heat generated with power generation is recovered by a heat recovery means (not shown), supplied to a heat load, and used for various purposes.
- unreacted fuel gas hereinafter referred to as off-gas
- off-gas unreacted fuel gas
- the controller 4 controls the combustion air supplier 7 and supplies combustion air necessary for burning off gas supplied to the combustor 6.
- off gas and the combustion air supplied from the combustion air supplier 7 are mixed and burned, and heat necessary for the steam reforming reaction in the reforming unit 1 is supplied.
- the flow rate of the combustion air is controlled to be 1.7 as an air ratio representing the supply air flow rate with respect to the theoretical air flow rate.
- the controller 4 generates an amount of generated hydrogen from the raw material flow rate detected by the raw material flow rate detector 8 and the hydrocarbon conversion rate calculated from the temperature detected by the reforming temperature detector (not shown). And the power generation amount in the fuel cell 20 is instructed so that power generation can be performed within a predetermined hydrogen utilization rate range.
- the hydrogen utilization rate is preferably set to be between 70% and 85% for stable operation.
- the hydrogen generation amount detection unit is configured to include an anode flow meter 3b in the anode path. Then, as a method for determining whether or not the production amount has decreased, for example, when the production amount of the hydrogen-containing gas has decreased by a predetermined value within a predetermined time or when it has decreased to a predetermined flow rate threshold value. In consideration of the behavior when the amount of change under normal operating conditions and the gas composition change, it is preferable to select appropriately so that the change in composition can be detected more reliably.
- the production amount of the hydrogen-containing gas has increased by a predetermined value within a predetermined time, or when the production amount has increased to a predetermined flow rate threshold. It can be determined that the generation amount has increased. You may compare these values taking the average value for every predetermined time.
- the method of directly detecting the amount of hydrogen-containing gas produced using the anode flow meter 3b is used.
- a change in pressure loss is detected using a pressure detector, the flow rate of the selective oxidation flow meter and
- the composition of the raw material gas is detected by indirectly detecting the change in pressure caused by the change in the flow rate of the anode passage by using the output of the selective oxidizing air supplier 12 or the output of the raw material supplier 2.
- the change of may be detected.
- the setting may be changed if the output of the fuel cell 20 is within a predetermined range. Alternatively, if the amount of change per predetermined time of the output of the fuel cell 20 is within a predetermined range, the setting may be changed. On the other hand, the generated power may be varied according to the load, for example.
- the controller 4 may correct the production amount of the hydrogen-containing gas detected by the hydrogen production amount detector based on the output of the fuel cell 20. Further, the same effect can be obtained by correcting the threshold value for changing the control parameter.
- FIG. 12 is a diagram showing a hydrogen-containing gas generation amount correction image corresponding to a change in the output of the fuel cell 20 in the fifth embodiment of the present invention.
- control parameters parameters related to the operation of the fuel cell 20 are set in addition to the parameters of the hydrogen generator 50 in the first embodiment.
- the flow rate of the combustion gas combusted in the combustor 6 decreases as the hydrogen amount decreases. . That is, when the combustion air flow rate is the same, the combustion air flow rate may be excessive with respect to the combustion gas flow rate.
- the combustion air ratio becomes excessive, proper combustion cannot be maintained and carbon monoxide may be generated.
- the flow rate of the combustion gas combusted in the combustor 6 increases as the hydrogen amount increases. Become. That is, when the combustion air flow rate is the same, the combustion air flow rate may be too small with respect to the combustion gas flow rate. If the combustion air ratio is too low, proper combustion cannot be maintained and carbon monoxide may be generated.
- the control parameter corresponding to the relatively low heat quantity is set and operated.
- the control parameter corresponding to the relatively high heat amount is set and the operation is performed.
- the power generation amount of the fuel cell 20 may be reduced, and conversely, when the generated hydrogen amount increases, the generated power amount of the fuel cell 20 is increased. Also good.
- the power generation amount is controlled to be reduced to 600 W.
- the fuel cell 20 needs to be operated with the hydrogen utilization rate kept in an appropriate range.
- the power generation amount is reduced to stabilize the operation. Is possible. Further, as the amount of off-gas of the fuel cell 20 decreases, the combustion air becomes excessive and the combustibility may deteriorate, but the combustibility can be maintained by reducing the power generation amount in the same manner.
- the power generation amount may be returned to the original state.
- the amount of generated hydrogen is increased based on a command to increase the power generation output. After correcting the amount of hydrogen produced by this external input (command), it is determined whether or not the amount of hydrogen-containing gas detected by the hydrogen production amount detector has changed, and control parameters are set. You may comprise as follows.
- control parameters corresponding to three or more gas types may be provided, and an appropriate control parameter may be selected, or continuous parameter setting may be configured as a function of heat quantity.
- control parameters corresponding to the composition of the raw material gas are set, and in particular, the power generation amount is set corresponding to the heat amount of the raw material gas, thereby realizing the fuel cell system 80 capable of stable operation. can do. Further, stable combustion can be maintained while suppressing generation of carbon monoxide.
- FIG. 13 is a diagram showing a schematic configuration of a fuel cell system 80 in Modification 1 of the fifth embodiment of the present invention.
- This modification is configured to include a cathode air supplier 21 that sends air to the cathode of the fuel cell 20. Further, the cathode air supply branching from the cathode air supply path of the fuel cell 20 is supplied to the selective oxidation unit 11 so that the flow rate detected by the selective oxidation air flow rate detector 13 becomes a predetermined flow rate. 21 is controlled. Note that an air blower is used as the cathode air supplier 21.
- the power generation performance may be deteriorated due to carbon monoxide adsorbed on the anode during the power generation of the fuel cell 20. Therefore, a part of the air supplied from the cathode air supplier 21 may be added to the hydrogen-containing gas and supplied to the anode of the fuel cell 20.
- the hydrogen generation amount detection unit detects a change in pressure caused by a change in the flow rate of the anode path of the fuel cell 20. Specifically, a change in pressure is detected from the output of the cathode air supplier 21, the change in the selective oxidation air flow rate or the anode air flow rate.
- the controller 4 sets the control parameter corresponding to the relative low calorific gas. Set and drive. Conversely, when the output of the cathode air supply 21 increases, when the selective oxidation air flow rate decreases, or when the anode air flow rate decreases, control parameters corresponding to relative high calorific gas are set. Configured to drive.
- control parameters corresponding to three or more gas types may be provided, and an appropriate control parameter may be selected, or continuous parameter setting may be configured as a function of heat quantity.
- FIG. 14 is a diagram showing a schematic configuration of a fuel cell system 80 according to Modification 2 of the fifth embodiment of the present invention.
- the hydrogen generation amount detection unit includes an offgas flow meter 3c as a hydrogen generation amount detection unit in the offgas path at the anode outlet of the fuel cell 20.
- FIG. 15 shows the fuel cell 20 when the gas of 100% methane is supplied and the gas of 20% nitrogen / 80% methane is supplied in the second modification of the fifth embodiment of the present invention. It is a figure which shows the change of an off-gas flow rate when the electric power generation output, ie, an electric current value, and the amount of consumed hydrogen are the same.
- the off-gas flow rate decreases to about 61%.
- the pressure loss of the flow path is 0.61 ⁇ 0.61 and is reduced to about 37%. That is, as shown in FIG. 15, when an inert gas containing 20% nitrogen / 80% methane, which is a relatively low calorie gas, is supplied, the amount of generated hydrogen is reduced, but the amount of power generation is reduced. In the same case, the flow rate of the off-gas of the fuel cell 20 and the pressure loss of the path resulting therefrom are significantly reduced.
- the offgas flow rate is directly detected using the offgas flow meter 3c.
- a change in pressure is detected, the flow rate of the selective oxidation flow meter, the output of the selective oxidation air supply device 12, and the raw material supply device.
- a change in the composition of the raw material gas may be detected by indirectly detecting a change in pressure caused by a change in the flow rate of the off-gas path using the output of No. 2 or the like.
- control parameters corresponding to three or more gas types may be provided, and an appropriate control parameter may be selected, or continuous parameter setting may be configured as a function of heat quantity.
- the hydrogen generator of the first aspect of the embodiment includes a reforming unit that reforms a raw material to generate a hydrogen-containing gas, a raw material supplier that supplies the raw material to the reforming unit, A hydrogen generation amount detection unit that detects the generation amount of the hydrogen-containing gas.
- the control parameter corresponding to the relative low calorific gas is set to operate the raw material feeder, and when the production amount of the hydrogen-containing gas increases,
- a controller configured to set a control parameter corresponding to the high heat quantity gas and operate the raw material supplier.
- a selective oxidation unit that selectively oxidizes and removes carbon monoxide contained in a hydrogen-containing gas with oxygen, and selective oxidation air is supplied to the selective oxidation unit.
- a selective oxidizing air supply device and a selective oxidizing air flow rate detector for detecting a flow rate of the selective oxidizing air.
- the hydrogen generation amount detection unit is a selective oxidation air flow rate detector, and the controller sets the control parameter corresponding to the relative low calorific gas when the flow rate of the selective oxidation air increases and supplies the raw material.
- the raw material supplier is operated by setting control parameters corresponding to the relative high calorific gas.
- a selective oxidation unit that selectively oxidizes and removes carbon monoxide contained in the hydrogen-containing gas with oxygen, and selective oxidation air in the selective oxidation unit.
- a selective oxidized air supply device to be supplied and a selective oxidized air flow rate detector for detecting a flow rate of the selective oxidized air are provided.
- the controller controls the selective oxidation air supply so that the flow rate of the selective oxidation air becomes a predetermined flow rate, and when the output of the selective oxidation air supply decreases, a control parameter corresponding to the relative low calorific gas.
- the control parameter corresponding to a relative high calorific gas is set and the raw material supply device is operated.
- the output of the selective oxidant air supply device accompanying the change in the pressure of the path caused by the change in the amount of hydrogen-containing gas produced That is, the change in the composition of the raw material gas can be detected instantaneously by detecting the change in the operation amount. Further, by setting control parameters corresponding to the composition of the raw material gas based on the result, it is possible to realize a hydrogen generator capable of maintaining a proper amount of generated hydrogen and performing stable operation.
- the fourth aspect includes a pressure detector that detects the pressure of the path including the reforming section downstream from the raw material supplier in the hydrogen generator of the first aspect.
- the hydrogen generation amount detector is a pressure detector, and the controller sets the control parameter corresponding to the relative low calorific gas and operates the raw material supplier when the pressure of the pressure detector decreases. And when the pressure of a pressure detector increases, it is comprised so that the control parameter corresponding to relative high calorific gas may be set and a raw material supply device may be operated.
- the composition of the raw material gas is detected by detecting a change in the pressure of the path caused by the change in the amount of hydrogen-containing gas produced. Changes can be detected instantly. Further, by setting control parameters corresponding to the composition of the raw material gas based on the result, it is possible to realize a hydrogen generator capable of maintaining a proper amount of generated hydrogen and performing stable operation.
- the fifth aspect includes a raw material flow rate detector for detecting the flow rate of the raw material in the hydrogen generator of the first aspect.
- the controller controls the raw material supplier so that the flow rate of the raw material becomes a predetermined flow rate, and when the output of the raw material supplier decreases, sets the control parameter corresponding to the relative low calorific gas and supplies the raw material When the output of the raw material supplier increases, the control parameter corresponding to the relative high calorific gas is set to operate the raw material supplier.
- the low calorific gas contains more inert gas than the high calorific gas.
- the flow rate of the raw material gas that does not contribute to hydrogen generation increases with respect to the flow rate of the raw material gas. It can be detected.
- the controller in the hydrogen generator of any one of the first to sixth aspects has a parameter that contributes to the production amount of the hydrogen-containing gas within a predetermined range
- the hydrogen-containing gas In the case where the production amount of the raw material decreases, the control parameter corresponding to the relative low calorific gas is set to operate the raw material supplier. And when the production
- the controller in the hydrogen generation device when the controller in the hydrogen generation device according to any one of the first to sixth aspects has a change amount of a parameter that contributes to the generation amount of the hydrogen-containing gas within a predetermined range,
- the raw material supplier When the production amount of the hydrogen-containing gas decreases, the raw material supplier is operated by setting control parameters corresponding to the relative low calorific gas. And when the production
- the hydrogen generator detected by the hydrogen generation amount detection unit is based on a parameter that contributes to the generation amount of the hydrogen-containing gas by the controller in the hydrogen generation apparatus according to any one of the first to sixth aspects.
- the gas generation amount is corrected.
- the tenth aspect is a configuration including a water supply device for supplying water to the reforming unit in the hydrogen generator according to any one of the first to ninth aspects. And, when the amount of hydrogen-containing gas produced decreases, the controller sets the control parameter corresponding to the relative low calorific gas, operates the water supply device, and the amount of hydrogen-containing gas produced increases In addition, a control parameter corresponding to the relative high calorific gas is set to operate the water supply device.
- the amount of hydrogen-containing gas produced changes with the change in the composition of the raw material gas.
- the change in the composition of the raw material gas can be detected instantaneously. Also, based on the result, by setting the control parameters of the water supply device corresponding to the composition of the raw material gas, it is possible to realize a hydrogen generator capable of maintaining a proper amount of generated hydrogen and performing stable operation. .
- a combustor that combusts the hydrogen-containing gas discharged from the reforming unit, and combustion air is supplied to the combustor. And an air supply for combustion.
- the controller sets the control parameter corresponding to the relative low calorific gas, operates the combustion air supply device, and increases the production amount of the hydrogen-containing gas.
- the combustion air supply unit is operated by setting control parameters corresponding to the relative high calorific gas.
- the amount of hydrogen-containing gas produced changes with the change in the composition of the raw material gas.
- the change in the composition of the raw material gas can be detected instantaneously.
- the control parameters of the combustion air supply corresponding to the composition of the raw material gas are set, thereby realizing a hydrogen generator that can maintain the amount of generated hydrogen properly and can be operated stably. Can do.
- a twelfth aspect is a fuel cell system comprising the hydrogen generator according to any of the first to eleventh aspects and a fuel cell that generates power using a hydrogen-containing gas supplied from the hydrogen generator. It is.
- the controller of the fuel cell system according to the twelfth aspect is relatively low when the amount of hydrogen-containing gas produced decreases when the output of the fuel cell is within a predetermined output range.
- the controller of the fuel cell system performs a relative operation when the amount of hydrogen-containing gas produced decreases when the amount of change in the output of the fuel cell is within a predetermined output range.
- Set the control parameters corresponding to the typical low calorific gas operate the raw material feeder, and set the control parameters corresponding to the relative high calorific gas when the amount of hydrogen-containing gas generated increases and supply the raw material Is configured to operate the vessel.
- the controller of the fuel cell system in the twelfth aspect is configured so as to correct the production amount of the hydrogen-containing gas detected by the hydrogen production amount detector based on the output of the fuel cell.
- a sixteenth aspect is the fuel cell system according to any one of the twelfth aspect to the fifteenth aspect, and includes a water supplier that supplies water to the reforming unit.
- the controller sets the control parameter corresponding to the relative low calorific gas, operates the water supply device, and the amount of hydrogen-containing gas produced increases
- a control parameter corresponding to the relative high calorific gas is set to operate the water supply device.
- the amount of hydrogen-containing gas produced changes with the change in the composition of the raw material gas.
- the change in the composition of the raw material gas can be detected instantaneously. Also, based on the result, by setting the control parameters of the water supply device corresponding to the composition of the raw material gas, it is possible to realize a hydrogen generator capable of maintaining a proper amount of generated hydrogen and performing stable operation. .
- a seventeenth aspect is the fuel cell system according to any one of the twelfth aspect to the sixteenth aspect, wherein the combustor combusts the hydrogen-containing gas discharged from the fuel cell, and the combustor combusts.
- Combustion air supply device for supplying industrial air is provided. Then, when the production amount of the hydrogen-containing gas decreases, the controller sets the control parameter corresponding to the relative low calorific gas, operates the combustion air supply device, and increases the production amount of the hydrogen-containing gas. In this case, the combustion air supply unit is operated by setting control parameters corresponding to the relative high calorific gas.
- the amount of hydrogen-containing gas produced changes with the change in the composition of the raw material gas.
- the change in the composition of the raw material gas can be detected instantaneously.
- the control parameters of the combustion air supply corresponding to the composition of the raw material gas are set, thereby realizing a hydrogen generator that can maintain the amount of generated hydrogen properly and can be operated stably. Can do.
- the eighteenth aspect is a method for operating a hydrogen generator, comprising a reforming unit that reforms a raw material to generate a hydrogen-containing gas, and a raw material supplier that supplies the raw material to the reforming unit. And when the production amount of the hydrogen-containing gas decreases, when the production parameter of the hydrogen-containing gas increases, the step of setting the control parameter corresponding to the relative low calorific gas and operating the raw material feeder, And setting a control parameter corresponding to the relative high calorific gas to operate the raw material supplier.
- the present invention is particularly useful when the composition of the raw material gas can change over time, and reforms the raw material gas containing hydrocarbons such as a dispersed solid polymer form or solid oxide form to produce hydrogen. It is useful as a fuel cell system equipped with a fuel cell that generates electricity using a hydrogen-containing gas obtained by the hydrogen generator and a method for operating the same, and a hydrogen-containing gas obtained by the hydrogen generator.
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Abstract
Description
まず、本発明の第1の実施の形態について説明する。
まず、本実施の形態における水素含有ガスの生成量の検知方法について説明する。
次に、本実施の形態における水素生成装置50の制御パラメータの設定方法について説明する。
次に、本発明の第1の実施の形態における水素生成装置50の変形例1について説明する。
次に、本変形例1における水素生成装置50の制御パラメータの設定方法について説明する。
次に、本発明の第1の実施の形態における水素生成装置50の変形例2について説明する。
次に、本発明の第2の実施の形態における水素生成装置60について説明する。
次に、本発明の第2の実施の形態における水素生成装置60の変形例について説明する。
次に、本発明の第3の実施の形態における水素生成装置70について説明する。
次に、本発明の第4の実施の形態における水素生成装置について説明する。
次に、本発明の第5の実施の形態における燃料電池システム80について説明する。
まず、本発明における燃料電池システム80の水素含有ガスの生成量の検知方法について説明する。
次に、本実施の形態における燃料電池システム80の制御パラメータの設定方法について説明する。
次に、本発明の第5の実施の形態における燃料電池システム80の変形例1について説明する。
次に、本発明の第5の実施の形態における燃料電池システム80の変形例2について説明する。
2 原料供給器
3a 水素含有ガス流量計
3b アノード流量計
3c オフガス流量計
4 制御器
5 水供給器
6 燃焼器
7 燃焼用空気供給器
8 原料流量検知器
11 選択酸化部
12 選択酸化空気供給器
13 選択酸化空気流量検知器
14 圧力検知器
20 燃料電池
21 カソード空気供給器
50,60,70 水素生成装置
80 燃料電池システム
Claims (18)
- 原料を改質して水素含有ガスを生成する改質部と、
前記改質部に前記原料を供給する原料供給器と、
前記水素含有ガスの生成量を検知する水素生成量検知部と、
前記水素含有ガスの生成量が減少した場合に、相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記水素含有ガスの生成量が増加した場合に、相対的な高熱量ガスに対応する制御パラメータを設定して、前記原料供給器を運転するように構成された制御器と、
を備えた、水素生成装置。 - 前記水素含有ガスに含まれる一酸化炭素を、酸素によって選択的に酸化除去する選択酸化部と、
前記選択酸化部に選択酸化空気を供給する選択酸化空気供給器と、
前記選択酸化空気の流量を検知する選択酸化空気流量検知器と、
を備え、
前記水素生成量検知部は、前記選択酸化空気流量検出器であり、
前記制御器は、前記選択酸化空気の流量が増加した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記選択酸化空気の流量が減少した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、請求項1に記載の水素生成装置。 - 前記水素含有ガスに含まれる一酸化炭素を、酸素によって選択的に酸化除去する選択酸化部と、
前記選択酸化部に選択酸化空気を供給する選択酸化空気供給器と、
前記選択酸化空気の流量を検知する選択酸化空気流量検知器と、
を備え、
前記制御器は、前記選択酸化空気の流量が所定の流量となるように前記選択酸化空気供給器を制御し、前記選択酸化空気供給器の出力が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記選択酸化空気供給器の出力が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、
請求項1に記載の水素生成装置。 - 前記原料供給器より下流の前記改質部を含む経路の圧力を検知する圧力検知器を備え、
前記水素生成量検知部は、前記圧力検知器であり、
前記制御器は、前記圧力検知器の圧力が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記圧力検知器の圧力が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、
請求項1に記載の水素生成装置。 - 前記原料の流量を検知する原料流量検知器を備え、
前記制御器は、前記原料の流量が所定の流量となるように前記原料供給器を制御し、前記原料供給器の出力が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記原料供給器の出力が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、
請求項1に記載の水素生成装置。 - 前記低熱量ガスは、前記高熱量ガスよりも不活性ガスが多く含まれる、
請求項1から請求項5までのいずれか1項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に寄与するパラメータが所定の範囲内であるときに、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、
請求項1から請求項6までのいずれか1項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に寄与するパラメータの変化量が所定の範囲内であるときに、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、
請求項1から請求項6までのいずれか1項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に寄与するパラメータに基づき、前記水素生成量検知部が検知する水素含有ガスの生成量を補正するように構成された、請求項1から請求項6までのいずれか1項に記載の水素生成装置。
- 前記改質部に水を供給する水供給器を備え、
前記制御器は、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記水供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して、前記水供給器を運転するように構成された、請求項1から請求項9までのいずれか1項に記載の水素生成装置。 - 前記改質部から排出された前記水素含有ガスを燃焼する燃焼器と、
前記燃焼器に燃焼用空気を供給する燃焼用空気供給器とを備え、
前記制御器は、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記燃焼用空気供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して、前記燃焼用空気供給器を運転するように構成された、
請求項1から請求項10までのいずれか1項に記載の水素生成装置。 - 請求項1から請求項11までのいずれか1項に記載の水素生成装置と、
前記水素生成装置から供給される水素含有ガスを用いて発電する燃料電池と、を備えた、
燃料電池システム。 - 前記制御器は、前記燃料電池の出力が所定の出力範囲内であるときに、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、
請求項12に記載の燃料電池システム。 - 前記制御器は、前記燃料電池の出力の変化量が所定の出力範囲内であるときに、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するように構成された、
請求項12に記載の燃料電池システム。 - 前記制御器は、前記燃料電池の出力に基づき、前記水素生成量検知部が検知する水素含有ガスの生成量を補正するように構成された、
請求項12に記載の燃料電池システム。 - 前記改質部に水を供給する水供給器を備え、
前記制御器は、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記水供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して、前記水供給器を運転するように構成された、
請求項12から請求項15までのいずれか1項に記載の燃料電池システム。 - 前記燃料電池から排出された前記水素含有ガスを燃焼する燃焼器と、
前記燃焼器に燃焼用空気を供給する燃焼用空気供給器を備え、
前記制御器は、前記水素含有ガスの生成量が減少した場合に、前記相対的な低熱量ガスに対応する制御パラメータを設定して前記燃焼用空気供給器を運転し、前記水素含有ガスの生成量が増加した場合に、前記相対的な高熱量ガスに対応する制御パラメータを設定して、前記燃焼用空気供給器を運転するように構成された、
請求項12から請求項16までのいずれか1項に記載の燃料電池システム。 - 原料を改質して水素含有ガスを生成する改質部と、前記改質部に前記原料を供給する原料供給器と、を備えた、水素生成装置の運転方法であって、
前記水素含有ガスの生成量が減少した場合に、相対的な低熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するステップと、
前記水素含有ガスの生成量が増加した場合に、相対的な高熱量ガスに対応する制御パラメータを設定して前記原料供給器を運転するステップとを備えた、
水素生成装置の運転方法。
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