WO2011118775A1 - 燃料電池システム、改質器システム、及び燃料電池システムの運転方法 - Google Patents
燃料電池システム、改質器システム、及び燃料電池システムの運転方法 Download PDFInfo
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- WO2011118775A1 WO2011118775A1 PCT/JP2011/057367 JP2011057367W WO2011118775A1 WO 2011118775 A1 WO2011118775 A1 WO 2011118775A1 JP 2011057367 W JP2011057367 W JP 2011057367W WO 2011118775 A1 WO2011118775 A1 WO 2011118775A1
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- 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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- 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
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- 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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- H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
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- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
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- H01M8/0432—Temperature; Ambient temperature
- H01M8/04373—Temperature; Ambient temperature of auxiliary devices, e.g. reformers, compressors, burners
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- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0438—Pressure; Ambient pressure; Flow
- H01M8/04425—Pressure; Ambient pressure; Flow at auxiliary devices, e.g. reformers, compressors, burners
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- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
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- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
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- 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
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- 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 reformer system including a reformer that generates a reformed gas by reforming a raw fuel with a reforming catalyst, a fuel cell system further including a fuel cell using the reformed gas as a fuel, and the same It relates to the driving method.
- a fuel cell nitrogen supply facility that supplies nitrogen stored in a liquid nitrogen storage tank to the fuel electrode of the fuel cell when power generation in the solid oxide fuel cell is stopped.
- a fuel cell nitrogen supply facility that supplies nitrogen stored in a liquid nitrogen storage tank to the fuel electrode of the fuel cell when power generation in the solid oxide fuel cell is stopped.
- nickel used for the fuel electrode can be prevented from being oxidized and expanded, As a result, it is possible to avoid damage to the electrolyte made of yttria-stabilized zirconia or the like.
- the present invention has been made to solve the above technical problem, and a fuel cell system, a reformer system, and a fuel cell system capable of avoiding damage to a fuel cell during power generation.
- the purpose is to provide a driving method.
- a fuel cell system includes a reformer that generates a reformed gas containing hydrogen by reforming raw fuel and water with a reforming catalyst, and a reformed gas.
- a fuel cell that generates power in the cell unit, a raw fuel introduction unit that introduces raw fuel into the reforming catalyst, and an unreformed gas generation information acquisition unit that acquires unreformed gas generation information in the reforming catalyst
- a control unit that performs introduction amount reduction control for reducing the introduction amount of the raw fuel with respect to the raw fuel introduction unit based on the unreformed gas generation information acquired by the unreformed gas generation information acquisition unit. It is characterized by providing.
- the reformer system introduces a reformer that generates reformed gas containing hydrogen by reforming raw fuel and water with a reforming catalyst, and introduces the raw fuel into the reforming catalyst.
- the unreformed gas generation information acquisition unit for acquiring the unreformed gas generation information in the reforming catalyst, and the unreformed gas generation information acquisition unit
- a control unit for performing an introduction amount reduction control for reducing the introduction amount of the raw fuel with respect to the raw fuel introduction unit.
- the operating method of the fuel cell system uses a reformer that generates a reformed gas containing hydrogen by reforming raw fuel and water with a reforming catalyst, and the reformed gas.
- a fuel cell that generates power in the cell unit, a raw fuel introduction unit that introduces raw fuel into the reforming catalyst, and an unreformed gas generation information acquisition unit that acquires unreformed gas generation information in the reforming catalyst,
- a fuel cell system operation method comprising: an introduction amount that reduces the introduction amount of raw fuel to the raw fuel introduction unit based on the unreformed gas generation information acquired by the unreformed gas generation information acquisition unit
- a reduction control step is included.
- the unreformed gas generation information in the reforming catalyst is acquired by the unreformed gas generation information acquisition unit, and this unreformed gas generation information
- introduction amount means “amount introduced per unit time”.
- the reaction for generating reformed gas by reforming raw fuel and water with a reforming catalyst is an endothermic reaction. Therefore, by reducing the amount of raw fuel introduced, the endothermic amount decreases with the amount of reformed gas generated. Therefore, it is possible to prevent the temperature of the reforming catalyst from dropping to the unreformed gas generation temperature.
- the unreformed gas generation information is information regarding the possibility of generation of unreformed gas.
- control unit may further perform power generation amount suppression control that suppresses the power generation amount of the fuel cell.
- the amount of raw fuel introduced when the amount of raw fuel introduced is reduced, the amount of reformed gas produced decreases accordingly. At the same time as the amount of raw fuel introduced is reduced, As a result, the power generation amount is suppressed. Therefore, the balance between the reformer and the fuel cell can be suitably maintained.
- the unreformed gas generation information may be a temperature of the reforming catalyst
- the unreformed gas generation information acquisition unit may be a catalyst temperature detection unit that detects the temperature of the reforming catalyst.
- the temperature of the reforming catalyst greatly affects whether or not unreformed gas is generated. According to this fuel cell system, since the temperature of the reforming catalyst is used as unreformed gas generation information, generation of unreformed gas is more reliably prevented.
- control unit reduces the amount of raw fuel introduced to the raw fuel introduction unit when the temperature detected by the catalyst temperature detection unit is equal to or lower than a first threshold value that is higher than the unreformed gas generation temperature. It can be set as the aspect which performs introduction amount reduction
- the introduction amount reduction control of the control unit performs The amount of raw fuel introduced into the fuel introduction part is reduced.
- the reaction for generating reformed gas by reforming raw fuel and water with a reforming catalyst is an endothermic reaction. Therefore, by reducing the amount of raw fuel introduced, the endothermic amount decreases with the amount of reformed gas generated. Therefore, it is possible to prevent the temperature of the reforming catalyst from dropping to the unreformed gas generation temperature. Thereby, generation
- control unit performs power generation amount suppression control that suppresses the power generation amount for the fuel cell when the temperature detected by the catalyst temperature detection unit is equal to or lower than a first threshold value that is higher than the unreformed gas generation temperature. It can be set as the mode to perform.
- the amount of raw fuel introduced when the amount of raw fuel introduced is reduced, the amount of reformed gas produced decreases accordingly. At the same time as the amount of raw fuel introduced is reduced, As a result, the power generation amount is suppressed. Therefore, the balance between the reformer and the fuel cell can be suitably maintained.
- the first threshold value can be set in advance according to the introduction amount of the raw fuel into the reforming catalyst when the introduction amount reduction control is not performed.
- the unreformed gas generation temperature is determined by the amount of raw fuel introduced into the reforming catalyst when the introduction amount reduction control is not performed. According to this reformer system, since the first threshold value is determined in advance according to the amount of raw fuel introduced into the reforming catalyst when the introduction amount reduction control is not performed, the generation of unreformed gas is further reduced. It can be effectively prevented.
- the control unit detects a second temperature detected by the catalyst temperature detection unit that is higher than the unreformed gas generation temperature and lower than the first threshold value. When it is less than the threshold, it is possible to perform an introduction stop control for stopping the introduction of the raw fuel to the raw fuel introduction unit.
- the introduction stop control is performed by the control unit to introduce the raw fuel. Is stopped.
- the introduction of the raw fuel is stopped in this way, the reformed gas production reaction in the reformer stops and the generation of unreformed gas is prevented. Therefore, damage to the fuel cell can be avoided.
- the second threshold value can be set in a predetermined manner in accordance with the amount of raw fuel introduced into the reforming catalyst when the introduction amount reduction control is performed.
- the second threshold value is determined in advance according to the amount of raw fuel introduced into the reforming catalyst when the introduction amount reduction control is performed, the generation of unreformed gas is more effective. Can be prevented.
- the control unit detects a temperature detected by the catalyst temperature detection unit that is equal to or higher than the third threshold higher than the first threshold. In such a case, the introduction amount reduction control can be canceled.
- the control unit cancels the raw fuel introduction amount reduction control.
- the control unit cancels the raw fuel introduction amount reduction control.
- the apparatus further includes a cell part temperature detection unit that detects the temperature of the cell part, and the control unit starts the introduction amount reduction control and then the catalyst temperature detection unit performs the second time following the first time.
- the detection temperature is equal to or higher than the third threshold higher than the first threshold and the temperature detected by the cell temperature detector is equal to or higher than a predetermined fourth threshold, the introduction amount reduction control is canceled. It can be set as an aspect.
- the temperature detected by the catalyst temperature detection unit is equal to or higher than the third threshold higher than the first threshold, and the temperature detected by the cell unit temperature detection unit is a predetermined fourth threshold.
- the control unit cancels the raw fuel introduction amount reduction control.
- the reformer can recover the amount of reformed gas while preventing the generation of unreformed gas, and the reformed gas whose amount is recovered is used in the fuel cell. Therefore, suitable power generation can be performed in the cell portion. Therefore, the power generation amount in the fuel cell can be recovered without damaging the fuel cell.
- the third threshold value can be set in a predetermined manner according to the introduction amount of the raw fuel into the reforming catalyst when the introduction amount reduction control is performed.
- the third threshold value is determined in advance according to the amount of raw fuel introduced into the reforming catalyst when the introduction amount reduction control is performed, the generation of unreformed gas is more effective. Can be prevented.
- the fourth threshold value can be set in advance according to the amount of raw fuel introduced into the reforming catalyst when the introduction amount reduction control is not performed.
- the fourth threshold value is determined in advance according to the amount of raw fuel introduced into the reforming catalyst when the introduction amount reduction control is not performed, the generation of unreformed gas is more effective. Can be prevented.
- FIG. 1 is a block diagram schematically showing one embodiment of a fuel cell system according to the present invention.
- 2 is a flowchart showing a control procedure in the fuel cell system shown in FIG. 1. It is a flowchart which shows the control procedure following FIG.
- a fuel cell system 1 includes a reformer 2 that generates a reformed gas containing hydrogen by reforming raw fuel with a reforming catalyst 2a, and a reforming process. And a solid oxide fuel cell 12 using gas as fuel.
- the reformer 2 generates a reformed gas by subjecting the raw fuel and steam (water) to a steam reforming reaction with the reforming catalyst 2a. Since the steam reforming reaction is an endothermic reaction, the reformer 2 uses the exhaust heat of the fuel cell 12 for the steam reforming reaction.
- a catalyst known as a steam reforming catalyst can be used as the reforming catalyst 2a.
- the raw fuel is a hydrocarbon-based fuel known in the field of solid oxide fuel cells as a raw material for reformed gas, that is, a compound containing carbon and hydrogen in its molecule (containing other elements such as oxygen). Or a mixture thereof may be used as appropriate.
- a compound containing carbon and hydrogen in the molecule such as hydrocarbons, alcohols and ethers. More specifically, methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, hydrocarbons such as gasoline, naphtha, kerosene and light oil, alcohols such as methanol and ethanol, dimethyl ether, etc. Ethers and the like.
- kerosene and LPG are preferable because they are easily available. Moreover, since kerosene and LPG can be stored independently, they are useful in areas where city gas lines are not widespread. Furthermore, a solid oxide fuel cell using kerosene or LPG is useful as an emergency power source.
- the fuel cell 12 uses the reformed gas generated in the reformer 2 as fuel, and generates power in a cell stack 13 formed by stacking a plurality of cells called SOFC (Solid Oxide Fuel Cells).
- SOFC Solid Oxide Fuel Cells
- Each cell is configured by disposing an electrolyte, which is a solid oxide, between a fuel electrode and an air electrode.
- the electrolyte is made of, for example, yttria stabilized zirconia (YSZ), and conducts oxide ions at a temperature of 800 ° C. to 1000 ° C.
- the fuel electrode is made of, for example, a mixture of nickel and YSZ, and generates electrons and water by reacting oxide ions with hydrogen in the reformed gas.
- the air electrode is made of lanthanum strontium manganite, for example, and reacts oxygen in the air with electrons to generate oxide ions.
- the fuel cell system 1 includes a raw fuel introduction device (raw fuel introduction portion) 3 for introducing raw fuel into the reforming catalyst 2a, a water introduction device 4 for introducing water vapor into the reforming catalyst 2a, and a cathode (air electrode). And a cathode air introducing device (not shown) for introducing air into the air.
- the raw fuel introduction device 3 has a raw fuel introduction pipe for introducing the raw fuel, an introduction amount adjusting valve for adjusting the introduction amount of the raw fuel, and the like.
- the cathode air introduction device has an air introduction pipe for introducing air, an introduction amount adjusting valve for adjusting the introduction amount of air, and the like.
- the water introduction device 4 includes a water introduction pipe for introducing water, an introduction amount adjusting valve for adjusting the amount of water introduced, and the like.
- the water introduction device 4 introduces water into the reformer 2. This water is vaporized by a vaporizer provided separately from the reformer 2 or the reformer 2, and is introduced into the reforming catalyst 2a as water vapor.
- the fuel cell system 1 includes a control device (control unit) 5 that controls the entire system, a catalyst temperature detector (catalyst temperature detection unit) 6 that detects the temperature of the reforming catalyst 2a, and a cell stack of the fuel cell 12. And a cell stack temperature detector (cell part temperature detector) 14 for detecting the temperature of 13.
- the temperature of the reforming catalyst 2a corresponds to unreformed gas generation information that is information relating to the possibility of generation of unreformed gas.
- the catalyst temperature detector 6 corresponds to an unreformed gas generation information acquisition unit.
- the temperature detectors 6 and 14 are, for example, thermocouples.
- the catalyst temperature detector 6 is provided at a plurality of positions in the reformer 2, and the temperature measuring contact of each catalyst temperature detector 6 is the central axis of the flow path of the raw fuel introduced by the raw fuel introduction device 3. It is arranged on the line.
- the cell stack temperature detectors 14 are provided at a plurality of positions in the cell stack 13, and the temperature measuring contacts of each cell stack temperature detector 14 are arranged on or in the vicinity of the cells constituting the cell stack 13. Yes.
- the control device 5 performs control to activate the entire system in response to an operation by the operator. Further, the control device 5 acquires the temperature of the reforming catalyst 2a detected by the catalyst temperature detector 6 and the temperature of the cell stack 13 detected by the cell stack temperature detector 14, and based on the acquired temperature of each part. The raw fuel introduction device 3, the water introduction device 4, and the fuel cell 12 are controlled.
- the control device 5 performs a predetermined process based on the temperature of the reforming catalyst 2 a and the temperature of the cell stack 13, so that the reformer 2 is applied to the raw fuel introduction device 3 and the fuel cell 12. And instructing to suppress the load in the fuel cell 12 (hereinafter, this instruction is referred to as “load suppression instruction of the reformer 2 and the fuel cell 12”). That is, the control device 5 performs control (introduction amount reduction control) to reduce the introduction amount of the raw fuel to the raw fuel introduction device 3. Further, the control device 5 performs control (power generation amount suppression control) for suppressing the power generation amount with respect to the fuel cell 12 together with reduction control of the introduction amount of raw fuel.
- control device 5 may perform control to shift to a so-called “hot standby” in which the fuel cell system 1 is on standby while the temperature of the cell stack 13 is at the operating temperature. Good. Further, the control device 5 may perform control for reducing the amount of water introduced into the water introduction device 4 together with the reduction control of the amount of raw fuel introduced.
- control device 5 stops the system by executing a predetermined process based on the temperature of the reforming catalyst 2a and the temperature of the cell stack 13. That is, the control device 5 performs control (introduction stop control) for stopping the introduction of raw fuel to the raw fuel introduction device 3.
- control device 5 controls the fuel cell 12 to stop power generation together with the raw fuel introduction stop control. In stopping the system, it is preferable to perform reforming while the fuel cell 12 is cooled down to a temperature zone that does not require hydrogen-containing gas. For this reason, the control device 5 operates by lowering the amount of raw fuel introduced in the raw fuel introduction device 3 stepwise or continuously (gradually) from the normal operation or hot standby state.
- the control device 5 may perform control for stopping the water introduction device 4 to introduce water together with the raw fuel introduction stop control.
- the control device 5 operates by reducing the amount of water introduced in the water introduction device 4 stepwise or continuously (gradually) from a normal operation or hot standby state.
- control device 5 performs a predetermined process based on the temperature of the reforming catalyst 2a and the temperature of the cell stack 13, so that the reformer 2 and the fuel are supplied to the raw fuel introduction device 3 and the fuel cell 12.
- An instruction is given to cancel the suppression of the load on the battery 12 (hereinafter, this instruction is referred to as “load suppression cancellation of the reformer 2 and the fuel cell 12”). That is, the control device 5 controls the raw fuel introduction device 3 to increase the amount of raw fuel introduced. Further, the control device 5 controls the fuel cell 12 to increase the power generation amount together with the increase control of the introduction amount of the raw fuel.
- the control device 5 may perform control to increase the amount of water introduced into the water introduction device 4 together with increase control of the amount of raw fuel introduced.
- control device 5 stores a plurality of threshold values (first threshold value to fourth threshold value) that serve as criteria for determining whether or not to shift to each control described above.
- the plurality of threshold values are threshold values related to the temperature of the reforming catalyst 2 a or the temperature of the cell stack 13. Further, the control device 5 stores a plurality of times (first time to third time) for regulating the time for determining whether or not to shift to each control described above.
- the first threshold value is a value determined in advance according to the amount of raw fuel introduced into the reforming catalyst 2a during normal power generation operation.
- the second threshold value and the third threshold value are determined in advance according to the amount of raw fuel introduced into the reforming catalyst 2a when a load suppression instruction for the reformer 2 and the fuel cell 12 is given (that is, after load suppression). Value.
- the fourth threshold T 4 is a value depending on the power generation amount of the in the introduction amount and the fuel cell 12 to the raw fuel of the reforming catalyst 2a at the time of normal power generation operation is predetermined.
- a reformer system 10 is configured by the reformer 2, the raw fuel introduction device 3, the water introduction device 4, the control device 5, and the catalyst temperature detector 6.
- the entire system is started according to the operation by the operator. That is, the control device 5 instructs the reformer 2, the raw fuel introduction device 3, the water introduction device 4, and the fuel cell 12 to complete the startup process. Thereby, the whole system shifts to a normal power generation operation mode (steady operation mode).
- the first threshold value T 1 is a temperature between the unreformed gas generation temperature and the temperature of the reforming catalyst 2a during normal power generation operation. For example, when the raw fuel is kerosene, the temperature is 400 ° C. to 700 ° C. It is. In other words, the first thresholds T 1 is higher than the non-reformed gas generation temperature a temperature lower than the temperature of the reforming catalyst 2a at the time of normal power generation operation.
- the temperature of the reforming catalyst 2a used for the determination process here may be an average value of a plurality of temperatures detected by each catalyst temperature detector 6, or may be detected by a specific catalyst temperature detector 6. It may be temperature. The same applies to the determination process (S4, S7) regarding the temperature of the reforming catalyst 2a.
- the unreformed gas generation temperature is a hydrocarbon gas having 2 or more carbon atoms that can damage the cells constituting the cell stack 13 of the fuel cell 12 because the raw fuel is not completely reformed by the reforming catalyst 2a. It means the temperature at which (unreformed gas) is generated and begins to be mixed into the reformed gas (the slip temperature that is the starting point at which so-called reformed slip occurs).
- These unmodified gas generation temperature and the first thresholds T 1 when the load restriction instruction of the reformer 2 and the fuel cell 12 is not performed, i.e., the raw fuel at the time of normal power generation operation to the reforming catalyst 2a It is preset according to the introduction amount.
- step S1 If the temperature of the reforming catalyst 2a is higher than the first threshold value T 1, the determination processing in step S1 is repeated.
- the load restriction instruction of the reformer 2 and the fuel cell 12 is performed (step S2). That is, based on the temperature of the reforming catalyst 2a that is unreformed gas generation information, the raw fuel introduction device 3 is controlled to reduce the amount of raw fuel introduced.
- the water introduction device 4 may be controlled to reduce the introduction amount of water. In this case, the amount of water vapor introduced is reduced according to the reduction in the amount of raw fuel introduced.
- control is performed to suppress the power generation amount for the fuel cell 12. By such control, the endothermic amount accompanying the steam reforming reaction (endothermic reaction) in the reformer 2 is reduced, so that the heat balance in the reformer 2 is improved (returned) to a good state.
- steps S1 and S2 correspond to an introduction amount reduction control step and a power generation amount suppression step.
- control may be performed to increase the amount of steam introduced according to the amount of raw fuel introduced.
- step S3 it is determined whether or not the first time has elapsed since the load suppression instruction for the reformer 2 and the fuel cell 12 is started (step S3).
- the first time is set in advance according to, for example, the amount of raw fuel introduced into the reforming catalyst 2a during normal power generation operation or the amount of power generated by the fuel cell 12.
- the first time may be set as appropriate based on the amount of reduction in the amount of raw fuel introduced in step S2, the amount of reduction in the amount of water introduced, or the amount of power generation suppression in the fuel cell 12.
- the determination process in step S3 is repeated.
- the second threshold value T 2 are an index for determining the goodness of the heat balance in the reformer 2, similarly to the first threshold value T 1, unreformed gas generation temperature and the modification of the normal power generation operation
- the temperature is between the temperature of the catalyst 2a.
- the second threshold value T 2 are higher than the non-reformed gas generation temperature a temperature lower than the first threshold value T 1.
- the second threshold value T 2 are are suitably set for each catalyst temperature detector 6.
- step S5 control for stopping the introduction of raw fuel to the raw fuel introduction device 3 is performed.
- the water introduction device 4 may be controlled to stop the introduction of water. Further, power generation in the fuel cell 12 is stopped.
- stop controls may be control to shift to so-called “cold standby” in which the fuel cell system 1 stands by while the temperature of the cell stack 13 is at room temperature, or when the temperature of the cell stack 13 is at the operating temperature. Control that shifts to a so-called “hot standby” in which the fuel cell system 1 waits may be performed.
- the second threshold value T 2 are, also has the meaning as operating minimum temperature.
- the second threshold value T2 indicates whether or not the risk of unreformed gas generation (reformed slip) is extremely high without losing the heat balance even when the load on the reformer 2 is reduced. It is a threshold value for determining whether or not.
- Step S5 is a step of stopping the system because it is determined that there is a high risk of generating unreformed gas.
- step S5 it is preferable to perform reforming while the fuel cell 12 is cooled down to a temperature range that does not require a hydrogen-containing gas. For this reason, the process shifts to a stopping process in which the amount of raw fuel introduced in the raw fuel introduction device 3 is lowered in a stepwise manner or continuously (gradually) from a normal operation or a hot standby state. In addition, when it is difficult to shift to such a stopping process, the amount of raw fuel introduced in the raw fuel introduction device 3 can be stopped immediately.
- step S6 whether further second time from the time lapse of the first time has elapsed. That is, it is determined whether or not the second time following the first time has elapsed since the load suppression instruction for the reformer 2 and the fuel cell 12 is started. This second time is appropriately set according to the amount of raw fuel introduced into the reforming catalyst 2a during normal power generation operation, the amount of power generated by the fuel cell 12, and the like. If the second time has not elapsed, the process returns to the determination process in step S4.
- the reformer load amount and the power generation amount are temporarily suppressed within the second time period by the processing in steps S4 to S6. Furthermore, while monitoring whether the heat balance of the reforming catalyst 2a has been critically disrupted, the standby state for the independent operation (independent standby state) is maintained, and the good thermal balance is maintained within the second time. Deciding. And when it is not in a predetermined heat balance state, a system stop process is carried out. Moreover, when it is in the predetermined
- step S6 the process proceeds to the process shown in FIG. 3, whether the temperature of the reforming catalyst 2a detected by the catalyst temperature detector 6 is equal to the third threshold value T 3 or more Is determined (step S7).
- the third threshold value T 3 is an index for determining the goodness of the heat balance in the reformer 2, similarly to the second threshold value T 2, unreformed gas generation temperature and the normal reforming during the power generation operation of the The temperature is between the temperature of the catalyst 2a.
- the third threshold T 3 is higher than the first threshold T 1 and is equal to or lower than the temperature of the reforming catalyst 2a during normal power generation operation.
- the third threshold T 3 is set as appropriate for each catalyst temperature detector 6.
- the temperature of the reforming catalyst 2a is the third threshold value T 3 or more, whether the temperature of the cell stack 13 detected by the cell stack temperature detector 14 is equal to the fourth threshold value T 4 or more is judged (step S8).
- the fourth threshold value T 4 is a temperature lower than the temperature of normal power generation operation when the cell stack 13.
- the fourth threshold T 4 is appropriately set in accordance with the power generation amount of the in the introduction amount and the fuel cell 12 to the raw fuel of the reforming catalyst 2a at the time of normal power generation operation.
- the temperature of the cell stack 13 used for the determination process here may be an average value of a plurality of temperatures detected by each cell stack temperature detector 14 or may be determined by a specific cell stack temperature detector 14. It may be the detected temperature.
- step S9 the load derepression of the reformer 2 and the fuel cell 12 is performed (step S9). That is, control for increasing the amount of raw fuel introduced into the raw fuel introduction device 3 is performed. In addition to the increase control of the introduction amount of the raw fuel, the water introduction device 4 may be controlled to increase the introduction amount of water. Further, control for increasing the power generation amount is performed on the fuel cell 12. By such control, the fuel cell system 1 returns to the normal power generation operation mode. In addition, when the control which increases the introduction amount of water vapor
- step S10 if the temperature of the reforming catalyst 2a is lower than the third threshold value T 3 in step S7, the system is stopped (step S10).
- the stop control here is the same as the stop control in step S5.
- the third threshold T 3 also has meaning as operating minimum temperature.
- step S11 The temperature of the cell stack 13 in step S8 if a fourth less than the threshold value T 4, whether further third time from the time lapse of the second time has elapsed (step S11).
- the third time is appropriately set according to the amount of raw fuel introduced into the reforming catalyst 2a during normal power generation operation, the amount of power generated by the fuel cell 12, and the like. If the third time has not elapsed, the process returns to the determination process in step S7.
- the system is stopped (step S12).
- the stop control here is the same as the stop control in steps S5 and S10.
- the fourth threshold value T 4 also has meaning as operating minimum temperature.
- the third time has a meaning as a time limit for returning to the normal power generation operation mode.
- the reformer load amount and the power generation amount are temporarily suppressed within the third time period by the processing in steps S7, S8, and S11. Further, while monitoring whether the heat balance of the reforming catalyst 2a has been critically broken, the self-sustaining standby state is maintained, and the goodness of the heat balance is determined within the third time. And when it is not in a predetermined heat balance state, a system stop process is carried out. When the predetermined heat balance state is reached within the third time, the determination (countdown) of whether or not the third time has ended is cancelled, and the process returns to the normal power generation process.
- the temperature of the reforming catalyst 2a detected by the catalyst temperature detector 6 is higher than the unreformed gas generation temperature. If it is thresholds T 1 or less, the control unit 5, a load restriction instruction of the reformer 2 and the fuel cell 12 is performed.
- the reaction for generating the reformed gas by reforming the raw fuel and water with the reforming catalyst 2a is an endothermic reaction. Therefore, the amount of heat absorption decreases with the amount of reformed gas produced by reducing the amount of raw fuel and water introduced. Therefore, it is possible to prevent the temperature of the reforming catalyst 2a from dropping to the unreformed gas generation temperature. As a result, generation of unreformed gas is prevented, and the reformed gas is supplied to the fuel cell 12. Therefore, damage to the fuel cell 12 during power generation can be avoided.
- the temperature of the reforming catalyst 2a greatly affects whether or not unreformed gas is generated. According to the fuel cell system 1, since the temperature of the reforming catalyst 2a is used as unreformed gas generation information, generation of unreformed gas is more reliably prevented.
- the amount of raw fuel introduced is reduced, the amount of reformed gas produced decreases accordingly, but at the same time as the amount of raw fuel introduced is reduced, the amount of power generation is suppressed for the fuel cell 12. Be made. Therefore, the balance between the reformer 2 and the fuel cell 12 can be suitably maintained.
- the system is controlled by the control device 5. Is stopped.
- the reformed gas production reaction in the reformer 2 is stopped and the generation of unreformed gas is prevented. Therefore, damage to the fuel cell 12 can be avoided.
- the stability of the system can be improved by providing the second time as a time reference for performing such stop control.
- the temperature detected by the catalyst temperature detector 6 is equal to or higher than the third threshold T 3 higher than the first threshold T 1 within the third time after the second time elapses, and the cell stack temperature detector 14 If the temperature detected is a fourth threshold value T 4 than the predetermined, the control device 5, the load derepression of the reformer 2 and the fuel cell 12 is performed. By such control, the reformer 2 can recover the amount of reformed gas generated while preventing the generation of unreformed gas, and the reformed gas whose generated amount has been recovered in the fuel cell 12.
- the cell stack 13 can be used to generate suitable power. Therefore, the power generation amount in the fuel cell 12 can be recovered without damaging the fuel cell 12.
- the system is stopped by the control device 5.
- the control device 5 When the system is thus stopped, the reformed gas production reaction in the reformer 2 is stopped and the generation of unreformed gas is prevented. Therefore, damage to the fuel cell 12 can be avoided. Further, by providing the third time as a time reference for performing such stop control, the stability of the system can be further enhanced.
- the first threshold value T 1 is determined in advance according to the introduction amount to the reforming catalyst 2a of the raw fuel at the time of normal power generation operation, it is possible to prevent the occurrence of non-reformed gas more effectively .
- the second threshold value T 2 and the third threshold value T 3 is determined in advance according to the introduction amount of the raw fuel of the reforming catalyst 2a in the afterload suppressed the reformer 2 and the fuel cell 12, unreformed gas Can be more effectively prevented.
- the fourth threshold T 4 are determined in advance according to the introduction amount to the reforming catalyst 2a of the raw fuel at the time of normal power generation operation, it is possible to prevent the occurrence of the non-reformed gas more effectively it can.
- the present invention is not limited to the above embodiment.
- the case of using a solid oxide fuel cell has been described, but the present invention can also be applied to a fuel cell system using a solid polymer fuel cell or a molten carbonate fuel cell.
- the temperature of the reforming catalyst 2a in the third time, is a third threshold T 3 or more, it is determined whether the temperature of the cell stack 13 is the fourth threshold value T 4 or more Although the case has been described, the determination regarding the temperature of the cell stack 13 in step S8 can be omitted. Namely, within the third hour, when the temperature of the reforming catalyst 2a is the third threshold value T 3 or more, it may be performed generation amount derepression control in step S9.
- the reformer 2 may realize an autothermal reforming reaction (ATR) or a partial oxidation reforming reaction. Also in those cases, the amount of raw fuel introduced into the reforming catalyst 2a of the reformer 2 is decreased, and before the temperature of the reforming catalyst 2a falls to the unreformed gas generation temperature, the reforming catalyst 2a If the temperature is raised, the generation of unreformed gas can be prevented with a simple structure when power generation in the fuel cell 12 is stopped, and damage to the fuel cell 12 can be avoided. Is possible. In these cases, a known catalyst can be used as the reforming catalyst 2a as an autothermal reforming (autothermal reforming) catalyst or a partial oxidation reforming catalyst.
- ATR autothermal reforming reaction
- a partial oxidation reforming reaction a partial oxidation reforming reaction
- the fuel cell system 1 can be provided with known components of the indirect internal SOFC as necessary.
- a vaporizer for vaporizing liquid a pump for pressurizing various fluids, a pressure increasing means such as a compressor, a blower, etc., a valve for adjusting the flow rate of the fluid, or for blocking / switching the fluid flow
- flow control means flow path blocking / switching means
- heat exchanger for heat exchange / recovery
- condenser for condensing gas
- heating / heat retaining means for externally heating various devices with steam, etc.
- hydrocarbon system include fuel and combustible storage means, instrument air and electrical systems, control signal systems, control devices, output and power electrical systems, and the like.
- the control unit 5 when the temperature of the reforming catalyst 2a detected by the catalyst temperature detector 6 is high first thresholds T 1 less than unreformed gas generation temperature, the control unit 5, the reformed
- the criterion for executing the load suppression instruction is not limited to the temperature of the reforming catalyst 2a.
- a temperature information acquisition unit that acquires information on the temperature of the reforming catalyst 2a detected by the catalyst temperature detector 6 is provided, and a load suppression instruction by the control device 5 is based on the temperature information acquired by the temperature information acquisition unit. It is good also as performing.
- the second threshold value and the third threshold value are determined in advance according to the amount of raw fuel introduced into the reforming catalyst 2a after the load suppression of the reformer 2 and the fuel cell 12 is suppressed.
- the second threshold value and the third threshold value may be fixed values regardless of the amount of raw fuel introduced after load suppression.
- the load suppression instruction by the control device 5 can be based not only on the information on the temperature of the reforming catalyst 2a and the like but also on other information.
- a reformed gas composition detection device unreformed gas generation information acquisition unit
- the introduction amount reduction control and the power generation amount suppression control by the control device 5 may be performed based on the detection result of the reformed gas composition by the reformed gas composition detection device.
- the composition of the reformed gas detected by the reformed gas composition detection device corresponds to unreformed gas generation information.
- Information regarding the temperature of the reforming catalyst 2a and the cell stack 13 and the composition of the reformed gas are acquired as unreformed gas generation information, and introduction amount reduction control and power generation amount suppression control are performed based on these information. You may do it.
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Abstract
Description
Claims (14)
- 原燃料及び水を改質触媒で改質することにより、水素を含有する改質ガスを生成する改質器と、
前記改質ガスを用いて、セル部で発電を行う燃料電池と、
前記改質触媒に前記原燃料を導入する原燃料導入部と、
前記改質触媒における未改質ガス発生情報を取得する未改質ガス発生情報取得部と、
前記未改質ガス発生情報取得部によって取得された前記未改質ガス発生情報に基づいて、前記原燃料導入部に対して前記原燃料の導入量を減少させる導入量減少制御を行う制御部と、を備えることを特徴とする燃料電池システム。 - 前記制御部は、前記燃料電池に対して発電量を抑制させる発電量抑制制御を更に行うことを特徴とする請求項1記載の燃料電池システム。
- 前記未改質ガス発生情報は前記改質触媒の温度であり、前記未改質ガス発生情報取得部は前記改質触媒の温度を検出する触媒温度検出部であることを特徴とする請求項1又は2記載の燃料電池システム。
- 前記制御部は、前記触媒温度検出部によって検出される前記温度が、未改質ガス発生温度よりも高い第1閾値以下である場合に、前記原燃料導入部に対して前記原燃料の導入量を減少させる導入量減少制御を行うことを特徴とする請求項3記載の燃料電池システム。
- 前記制御部は、前記触媒温度検出部によって検出される前記温度が、未改質ガス発生温度よりも高い第1閾値以下である場合に、前記燃料電池に対して発電量を抑制させる発電量抑制制御を行うことを特徴とする請求項3又は4記載の燃料電池システム。
- 前記第1閾値は、前記導入量減少制御が行われない場合における前記原燃料の前記改質触媒への導入量に応じて、予め定められていることを特徴とする請求項4又は5記載の燃料電池システム。
- 前記制御部は、前記導入量減少制御を開始してから第1時間が経過した後、前記触媒温度検出部によって検出される前記温度が前記未改質ガス発生温度よりも高く前記第1閾値よりも低い第2閾値未満である場合に、前記原燃料導入部に対して前記原燃料の導入を停止させる導入停止制御を行うことを特徴とする請求項4~6のいずれか一項記載の燃料電池システム。
- 前記第2閾値は、前記導入量減少制御が行われた場合における前記原燃料の前記改質触媒への導入量に応じて、予め定められていることを特徴とする請求項7記載の燃料電池システム。
- 前記制御部は、前記導入量減少制御を開始してから、前記第1時間に続く第2時間が経過した後、前記触媒温度検出部によって検出される前記温度が前記第1閾値よりも高い第3閾値以上である場合に、前記導入量減少制御を解除することを特徴とする請求項4~8のいずれか一項記載の燃料電池システム。
- 前記セル部の温度を検出するセル部温度検出部を更に備え、
前記制御部は、前記導入量減少制御を開始してから、前記第1時間に続く第2時間が経過した後、前記触媒温度検出部によって検出される前記温度が前記第1閾値よりも高い第3閾値以上であり、且つ前記セル部温度検出部によって検出される前記温度が予め定められた第4閾値以上である場合に、前記導入量減少制御を解除することを特徴とする請求項4~8のいずれか一項記載の燃料電池システム。 - 前記第3閾値は、前記導入量減少制御が行われた場合における前記原燃料の前記改質触媒への導入量に応じて、予め定められていることを特徴とする請求項9又は10記載の燃料電池システム。
- 前記第4閾値は、前記導入量減少制御が行われない場合における前記原燃料の前記改質触媒への導入量に応じて、予め定められていることを特徴とする請求項10記載の燃料電池システム。
- 原燃料及び水を改質触媒で改質することにより、水素を含有する改質ガスを生成する改質器と、
前記改質触媒に前記原燃料を導入する原燃料導入部と、
前記改質触媒における未改質ガス発生情報を取得する未改質ガス発生情報取得部と、
前記未改質ガス発生情報取得部によって取得された前記未改質ガス発生情報に基づいて、前記原燃料導入部に対して前記原燃料の導入量を減少させる導入量減少制御を行う制御部と、を備えることを特徴とする改質器システム。 - 原燃料及び水を改質触媒で改質することにより、水素を含有する改質ガスを生成する改質器と、前記改質ガスを用いて、セル部で発電を行う燃料電池と、前記改質触媒に前記原燃料を導入する原燃料導入部と、前記改質触媒における未改質ガス発生情報を取得する未改質ガス発生情報取得部と、を備える燃料電池システムの運転方法であって、
前記未改質ガス発生情報取得部によって取得された前記未改質ガス発生情報に基づいて、前記原燃料導入部に対して前記原燃料の導入量を減少させる導入量減少制御ステップを含むことを特徴とする燃料電池システムの運転方法。
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US13/636,822 US20130040215A1 (en) | 2010-03-26 | 2011-03-25 | Fuel cell system, reformer system, and method for driving fuel cell system |
CN2011800161313A CN102834960A (zh) | 2010-03-26 | 2011-03-25 | 燃料电池系统、重整器系统以及燃料电池系统的运转方法 |
JP2012507086A JP5690812B2 (ja) | 2010-03-26 | 2011-03-25 | 燃料電池システム及び燃料電池システムの運転方法 |
KR1020127023616A KR20130040172A (ko) | 2010-03-26 | 2011-03-25 | 연료 전지 시스템, 개질기 시스템, 및 연료 전지 시스템의 운전 방법 |
EP11759579.3A EP2555301A4 (en) | 2010-03-26 | 2011-03-25 | FUEL CELL SYSTEM, REFORMER SYSTEM AND METHOD FOR DRIVING THE FUEL CELL SYSTEM |
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US (1) | US20130040215A1 (ja) |
EP (1) | EP2555301A4 (ja) |
JP (1) | JP5690812B2 (ja) |
KR (1) | KR20130040172A (ja) |
CN (1) | CN102834960A (ja) |
TW (1) | TW201143198A (ja) |
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KR20140106704A (ko) * | 2012-04-26 | 2014-09-03 | 제이엑스 닛코닛세키 에네루기 가부시키가이샤 | 미세 패턴 전사용 몰드의 제조 방법 및 이것을 사용한 요철 구조를 가지는 기판의 제조 방법, 및 상기 요철 구조를 가지는 기판을 가지는 유기 el 소자의 제조 방법 |
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JP2001332284A (ja) * | 2000-05-23 | 2001-11-30 | Nissan Motor Co Ltd | 燃料電池用改質システム |
JP2004220942A (ja) | 2003-01-15 | 2004-08-05 | Tokyo Electric Power Co Inc:The | 固体酸化物形燃料電池システムおよび燃料電池コンバインドサイクル発電プラント |
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JP2005190917A (ja) * | 2003-12-26 | 2005-07-14 | Fuji Electric Holdings Co Ltd | 原燃料制御装置および原燃料制御方法 |
JP2008171707A (ja) * | 2007-01-12 | 2008-07-24 | Casio Comput Co Ltd | 反応装置及びそれを備える発電装置並びに反応装置の動作方法 |
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JP5037214B2 (ja) * | 2007-05-01 | 2012-09-26 | Jx日鉱日石エネルギー株式会社 | 改質器システム、燃料電池システム、及びその運転方法 |
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2011
- 2011-03-25 JP JP2012507086A patent/JP5690812B2/ja active Active
- 2011-03-25 EP EP11759579.3A patent/EP2555301A4/en not_active Withdrawn
- 2011-03-25 KR KR1020127023616A patent/KR20130040172A/ko not_active Application Discontinuation
- 2011-03-25 WO PCT/JP2011/057367 patent/WO2011118775A1/ja active Application Filing
- 2011-03-25 US US13/636,822 patent/US20130040215A1/en not_active Abandoned
- 2011-03-25 TW TW100110481A patent/TW201143198A/zh unknown
- 2011-03-25 CN CN2011800161313A patent/CN102834960A/zh active Pending
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JP2001520576A (ja) * | 1997-04-15 | 2001-10-30 | インターナショナル フュエル セルズ コーポレイション | ガスを生成するための装置及び方法 |
JP2001165431A (ja) * | 1999-12-02 | 2001-06-22 | Osaka Gas Co Ltd | 燃料電池用改質器の空燃比制御装置 |
JP2001332284A (ja) * | 2000-05-23 | 2001-11-30 | Nissan Motor Co Ltd | 燃料電池用改質システム |
JP2004220942A (ja) | 2003-01-15 | 2004-08-05 | Tokyo Electric Power Co Inc:The | 固体酸化物形燃料電池システムおよび燃料電池コンバインドサイクル発電プラント |
JP2005174745A (ja) * | 2003-12-11 | 2005-06-30 | Ebara Ballard Corp | 燃料電池システムの運転方法及び燃料電池システム |
JP2005190917A (ja) * | 2003-12-26 | 2005-07-14 | Fuji Electric Holdings Co Ltd | 原燃料制御装置および原燃料制御方法 |
JP2008171707A (ja) * | 2007-01-12 | 2008-07-24 | Casio Comput Co Ltd | 反応装置及びそれを備える発電装置並びに反応装置の動作方法 |
JP2008177059A (ja) * | 2007-01-18 | 2008-07-31 | Nippon Oil Corp | 改質器システム、燃料電池システム、及びその運転方法 |
Also Published As
Publication number | Publication date |
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EP2555301A1 (en) | 2013-02-06 |
JPWO2011118775A1 (ja) | 2013-07-04 |
JP5690812B2 (ja) | 2015-03-25 |
TW201143198A (en) | 2011-12-01 |
EP2555301A4 (en) | 2015-08-05 |
US20130040215A1 (en) | 2013-02-14 |
CN102834960A (zh) | 2012-12-19 |
KR20130040172A (ko) | 2013-04-23 |
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