WO2012091037A1 - 燃料電池システム - Google Patents

燃料電池システム Download PDF

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Publication number
WO2012091037A1
WO2012091037A1 PCT/JP2011/080268 JP2011080268W WO2012091037A1 WO 2012091037 A1 WO2012091037 A1 WO 2012091037A1 JP 2011080268 W JP2011080268 W JP 2011080268W WO 2012091037 A1 WO2012091037 A1 WO 2012091037A1
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WO
WIPO (PCT)
Prior art keywords
fuel
unit
hydrogen
cell stack
value
Prior art date
Application number
PCT/JP2011/080268
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English (en)
French (fr)
Japanese (ja)
Inventor
環樹 水野
Original Assignee
Ｊｘ日鉱日石エネルギー株式会社
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Filing date
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Application filed by Ｊｘ日鉱日石エネルギー株式会社 filed Critical Ｊｘ日鉱日石エネルギー株式会社
Publication of WO2012091037A1 publication Critical patent/WO2012091037A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—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
    • H01M8/04537—Electric variables
    • H01M8/04544—Voltage
    • H01M8/04559—Voltage of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H01M8/04865—Voltage
    • H01M8/0488—Voltage of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • H01M8/14—Fuel cells with fused electrolytes
    • H01M2008/147—Fuel cells with molten carbonates
    • 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
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/086—Phosphoric acid fuel cells [PAFC]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a fuel cell system.
  • a fuel cell system including a hydrogen generation unit that generates a hydrogen-containing gas using a fuel containing hydrogen and a cell stack that generates power using the hydrogen-containing gas is known.
  • a hydrogen generation unit that generates a hydrogen-containing gas using a fuel containing hydrogen
  • a cell stack that generates power using the hydrogen-containing gas
  • the temperature of the cell stack repeatedly increases and decreases, and as a result, the deterioration of the cell stack may be accelerated. In any case, deterioration of the cell stack occurs with the operation of the fuel cell system. Therefore, in addition to the technique for suppressing the deterioration of the cell stack, there is a need for a technique for operating the fuel cell system without any trouble according to the degree of deterioration of the cell stack even when the cell stack is deteriorated.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a fuel cell system that can be operated in accordance with the degree of deterioration of the cell stack.
  • a fuel cell system includes a hydrogen generation unit that generates a hydrogen-containing gas using a fuel containing hydrogen, a cell stack that generates power using the hydrogen-containing gas, and A voltage detection unit that detects a voltage output from the cell stack, an operation state determination unit that determines whether or not the fuel cell system is in a rated operation state, and an operation determination unit A fuel utilization rate variation unit that varies the fuel utilization rate of the fuel cell system when it is determined that the fuel cell system is in a rated operation state, and a voltage for each value of the fuel utilization rate that varies depending on the fuel utilization rate variation unit.
  • a value is obtained from the voltage detection unit, a comparison unit that compares each value of the voltage with a reference value, and the comparison unit determines that each value of the voltage has dropped below a threshold value with respect to the reference value If it, and a fuel utilization rate controller for reducing the upper limit value of the fuel utilization rate in a predetermined ratio at rated operating conditions.
  • the fluctuation of the voltage from the cell stack with respect to the fluctuation of the fuel utilization rate is acquired, and the deterioration of the cell stack is detected by comparing the voltage value with the reference value. Then, the upper limit value of the fuel utilization rate in the rated operation state is reduced at a predetermined rate, and the operation according to the degree of deterioration of the cell stack is realized.
  • This fuel cell system can be operated according to the degree of deterioration of the cell stack.
  • FIG. 1 is a diagram showing an embodiment of a fuel cell system according to the present invention. It is a figure which shows the functional component of a control part. It is a figure which shows the mode of the fluctuation
  • the fuel cell system 1 includes a desulfurization unit 2, a water vaporization unit 3, a hydrogen generation unit 4, a cell stack 5, an off-gas combustion unit 6, a hydrogen-containing fuel supply unit 7, The water supply part 8, the oxidizing agent supply part 9, the power conditioner 10, and the control part 11 are provided.
  • the fuel cell system 1 generates power in the cell stack 5 using a hydrogen-containing fuel and an oxidant.
  • the type of the cell stack 5 in the fuel cell system 1 is not particularly limited, and examples thereof include a polymer electrolyte fuel cell (PEFC), a solid oxide fuel cell (SOFC), and phosphoric acid.
  • a fuel cell (PAFC: Phosphoric Acid Fuel Cell), a molten carbonate fuel cell (MCFC: Molten Carbonate Fuel Cell), and other types can be employed. 1 may be appropriately omitted depending on the type of cell stack 5, the type of hydrogen-containing fuel, the reforming method, and the like.
  • hydrocarbon fuel a compound containing carbon and hydrogen in the molecule (may contain other elements such as oxygen) or a mixture thereof is used.
  • hydrocarbon fuels include hydrocarbons, alcohols, ethers, and biofuels. These hydrocarbon fuels are derived from conventional fossil fuels such as petroleum and coal, and synthetic systems such as synthesis gas. Those derived from fuel and those derived from biomass can be used as appropriate. Specific examples of hydrocarbons include methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, town gas, gasoline, naphtha, kerosene, and light oil. Examples of alcohols include methanol and ethanol. Examples of ethers include dimethyl ether. Examples of biofuels include biogas, bioethanol, biodiesel, and biojet.
  • oxygen-enriched air for example, air, pure oxygen gas (which may contain impurities that are difficult to remove by a normal removal method), or oxygen-enriched air is used.
  • the desulfurization unit 2 desulfurizes the hydrogen-containing fuel supplied to the hydrogen generation unit 4.
  • the desulfurization part 2 has a desulfurization catalyst for removing sulfur compounds contained in the hydrogen-containing fuel.
  • a desulfurization method of the desulfurization unit 2 for example, an adsorptive desulfurization method that adsorbs and removes sulfur compounds and a hydrodesulfurization method that removes sulfur compounds by reacting with hydrogen are employed.
  • the desulfurization unit 2 supplies the desulfurized hydrogen-containing fuel to the hydrogen generation unit 4.
  • the water vaporization unit 3 generates water vapor supplied to the hydrogen generation unit 4 by heating and vaporizing water.
  • heat generated in the fuel cell system 1 such as recovering the heat of the hydrogen generation unit 4, the heat of the off-gas combustion unit 6, or the heat of the exhaust gas may be used.
  • FIG. 1 only heat supplied from the off-gas combustion unit 6 to the hydrogen generation unit 4 is described as an example, but the present invention is not limited to this.
  • the water vaporization unit 3 supplies the generated water vapor to the hydrogen generation unit 4.
  • the hydrogen generation unit 4 generates a hydrogen rich gas using the hydrogen-containing fuel from the desulfurization unit 2.
  • the hydrogen generator 4 has a reformer that reforms the hydrogen-containing fuel with a reforming catalyst.
  • the reforming method in the hydrogen generating unit 4 is not particularly limited, and for example, steam reforming, partial oxidation reforming, autothermal reforming, and other reforming methods can be employed.
  • the hydrogen generator 4 may have a configuration for adjusting the properties in addition to the reformer reformed by the reforming catalyst depending on the properties of the hydrogen rich gas required for the cell stack 5.
  • the hydrogen generation unit 4 is configured to remove carbon monoxide in the hydrogen-rich gas. (For example, a shift reaction part and a selective oxidation reaction part).
  • the hydrogen generation unit 4 supplies a hydrogen rich gas to the anode 12 of the cell stack 5.
  • the cell stack 5 generates power using the hydrogen rich gas from the hydrogen generation unit 4 and the oxidant from the oxidant supply unit 9.
  • the cell stack 5 includes an anode 12 to which a hydrogen-rich gas is supplied, a cathode 13 to which an oxidant is supplied, and an electrolyte 14 disposed between the anode 12 and the cathode 13.
  • the cell stack 5 supplies power to the outside via the power conditioner 10.
  • the cell stack 5 supplies the hydrogen rich gas and the oxidant, which have not been used for power generation, to the off gas combustion unit 6 as off gas.
  • a combustion section for example, a combustor that heats the reformer
  • the hydrogen generation section 4 may be shared with the off-gas combustion section 6.
  • the off gas combustion unit 6 burns off gas supplied from the cell stack 5.
  • the heat generated by the off-gas combustion unit 6 is supplied to the hydrogen generation unit 4 and used for generation of a hydrogen rich gas in the hydrogen generation unit 4.
  • the hydrogen-containing fuel supply unit 7 supplies hydrogen-containing fuel to the desulfurization unit 2.
  • the water supply unit 8 supplies water to the water vaporization unit 3.
  • the oxidant supply unit 9 supplies an oxidant to the cathode 13 of the cell stack 5.
  • the hydrogen-containing fuel supply unit 7, the water supply unit 8, and the oxidant supply unit 9 are configured by a pump, for example, and are driven based on a control signal from the control unit 11.
  • the power conditioner 10 adjusts the power from the cell stack 5 according to the external power usage state. For example, the power conditioner 10 performs a process of converting a voltage and a process of converting DC power into AC power.
  • the control unit 11 performs control processing for the entire fuel cell system 1.
  • the control unit 11 is configured by a device including a CPU (Central Processing Unit), a ROM (Read Only Memory), a RAM (Random Access Memory), and an input / output interface, for example.
  • the control unit 11 is electrically connected to a hydrogen-containing fuel supply unit 7, a water supply unit 8, an oxidant supply unit 9, a power conditioner 10, and other sensors and auxiliary equipment not shown.
  • the control unit 11 acquires various signals generated in the fuel cell system 1 and outputs a control signal to each device in the fuel cell system 1.
  • control executed by the control unit 11 will be described in more detail.
  • the control unit 11 is a part that outputs a control signal to each device in the fuel cell system 1, and in addition, executes a diagnostic process for diagnosing the deterioration of the cell stack 5.
  • control unit 11 includes, as functional components, a diagnosis start condition determination unit 101, an operation state determination unit 102, a voltage detection unit 103, and a fuel utilization rate variation unit. 104, a comparison unit 105, and a fuel utilization rate control unit 106.
  • the diagnosis start condition determination unit 101 is a part that determines whether or not to start execution of diagnosis processing. Various conditions can be applied as the diagnosis start condition. For example, whether or not a predetermined time has elapsed since the fuel cell system 1 started power generation, or a hot water tank (not shown) connected to the fuel cell system 1 The remaining amount of water is small and there is a demand for hot water (the fuel cell system 1 is in a state of recovering heat).
  • the predetermined time after starting the power generation is set to 1000 hours, for example.
  • the operation state determination unit 102 is a part that determines whether or not the fuel cell system 1 is in a rated operation state.
  • the rated operation state is an operation state in which the power generated by the cell stack 5 is the maximum power in the specification, and is a state in which the voltage / current operates stably.
  • the operation state determination unit 102 determines that the fuel cell system 1 is in the rated operation state when, for example, the change in the moving average value of the voltage output from the cell stack 5 is equal to or less than the threshold value for a certain time (for example, 15 minutes). to decide.
  • the voltage detection unit 103 is a part that detects a voltage output from the cell stack 5 to the power conditioner 10.
  • the voltage detector 103 constantly detects the voltage output from the cell stack 5 to the power conditioner 10 while the fuel cell system 1 is generating power.
  • the fuel usage rate changing unit 104 is a part that changes the fuel usage rate of the fuel cell system 1.
  • the fuel utilization rate is a ratio of the flow rate of the fuel used for the power generation reaction in the cell stack 5 with respect to the flow rate of the fuel supplied from the hydrogen-containing fuel supply unit 7.
  • the fuel usage rate change unit 104 controls the hydrogen-containing fuel supply unit 7 when the operation determination unit 102 determines that the fuel cell system 1 is in the rated operation state, and changes the fuel usage rate of the fuel cell system 1. .
  • the comparison unit 105 is a part that acquires each value of the voltage with respect to each value of the fuel utilization rate fluctuated by the fuel utilization rate variation unit 104 from the voltage detection unit 103, and compares each value of the voltage with a reference value.
  • the reference value may be a preset voltage value stored in the comparison unit 105, or may be a voltage value acquired when a past diagnosis process is executed.
  • the comparison unit 105 determines that the cell stack 5 has not deteriorated when the decrease in each value of the voltage with respect to each value of the fuel utilization rate is less than the threshold (graph A). On the other hand, the comparison unit 105 determines that the cell stack 5 has deteriorated when the decrease in each value of the voltage with respect to each value of the fuel utilization rate exceeds the threshold (graph B).
  • the fuel utilization rate control unit 106 is a part that controls the fuel utilization rate in the rated operation state of the fuel cell system 1.
  • the fuel utilization rate control unit 106 sets a predetermined upper limit value of the fuel utilization rate in a rated operation state when the comparison unit 105 determines that each value of the voltage is lower than a reference value. Decrease by rate. For example, when the upper limit value of the fuel usage rate is set from 70% to 65%, the fuel usage rate control unit 106 starts from the hydrogen-containing fuel supply unit 7 so that the fuel usage rate during rated operation does not exceed 65%. Increase the flow rate of the supplied fuel compared to before the setting change.
  • FIG. 4 is a flowchart illustrating an example of diagnosis processing by the control unit.
  • step S01 when the fuel cell system 1 starts power generation, detection of the voltage output from the cell stack 5 is started (step S01). Next, based on the amount of change in the moving average value of the voltage output from the cell stack 5, it is determined whether or not the fuel cell system 1 is in the rated operation state (step S02). In step S02, when it is determined that the fuel cell system 1 is in the rated operation state, the diagnosis start condition is determined (step S03, step S04).
  • diagnosis start condition for example, as shown in FIG. 5, it is first determined whether or not a predetermined time has elapsed since the start of power generation (step S11). Next, it is determined whether or not the demand for hot water is large (step S12). If both steps S11 and S12 are satisfied, it is determined that the diagnosis start condition is satisfied (step S13). If either of steps S11 and S12 is not satisfied, it is determined that the diagnosis start condition is not satisfied (step S14). If it is determined that the diagnosis start condition is not satisfied, the processes from step S02 to step S04 are repeated.
  • the fuel utilization rate variation unit 104 performs the variation of the fuel utilization rate (step S05). Next, each value of the voltage of the cell stack 5 is acquired for each value of the fuel utilization rate (step S06). After each voltage value is acquired, a comparison with a reference value is performed (step S07), and it is determined whether or not each voltage value has dropped below a threshold value (step S08).
  • step S08 if the decrease in each value of the voltage is less than the threshold value, it is determined that the cell stack 5 has not deteriorated, and the diagnosis process ends. On the other hand, when the decrease in each voltage value exceeds the threshold value, it is determined that the cell stack 5 has deteriorated, and the upper limit value of the fuel utilization rate in the rated operation state is decreased at a predetermined rate. . (Step S09).
  • the fluctuation of the voltage from the cell stack 5 with respect to the fluctuation of the fuel utilization rate is acquired, and the deterioration of the cell stack 5 is detected by comparing the voltage value with the reference value. Then, the upper limit value of the fuel utilization rate in the rated operation state is decreased at a predetermined rate, and the operation according to the degree of deterioration of the cell stack 5 is realized.
  • the deterioration of the cell stack 5 is judged based on the voltage fluctuation of the cell stack 5. Yes. Thereby, the configuration necessary for determining the deterioration of the cell stack 5 can be simplified.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
PCT/JP2011/080268 2010-12-28 2011-12-27 燃料電池システム WO2012091037A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-292699 2010-12-28
JP2010292699A JP2012142125A (ja) 2010-12-28 2010-12-28 燃料電池システム

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10593974B2 (en) 2016-05-27 2020-03-17 Cummins Enterprise Llc Fuel cell system and operating method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0896825A (ja) * 1994-09-28 1996-04-12 Toshiba Corp 燃料電池発電装置
JP2004164909A (ja) * 2002-11-11 2004-06-10 Denso Corp 燃料電池システム
JP2007172855A (ja) * 2005-12-19 2007-07-05 Casio Comput Co Ltd 電源システム、電源システムの制御装置及び電源システムの制御方法
JP2007193951A (ja) * 2006-01-17 2007-08-02 Mitsubishi Heavy Ind Ltd 燃料電池及びその運転方法
JP2009163940A (ja) * 2007-12-28 2009-07-23 Nissan Motor Co Ltd 燃料電池システムおよび燃料電池システムの制御方法
JP2010027580A (ja) * 2008-07-24 2010-02-04 Osaka Gas Co Ltd 燃料電池システム

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4942386B2 (ja) * 2006-04-26 2012-05-30 京セラ株式会社 発電・給湯コジェネレーションシステム
JP5148072B2 (ja) * 2006-05-17 2013-02-20 Ｊｘ日鉱日石エネルギー株式会社 燃料電池コージェネレーションシステム用液体原燃料及び燃料電池コージェネレーションシステム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0896825A (ja) * 1994-09-28 1996-04-12 Toshiba Corp 燃料電池発電装置
JP2004164909A (ja) * 2002-11-11 2004-06-10 Denso Corp 燃料電池システム
JP2007172855A (ja) * 2005-12-19 2007-07-05 Casio Comput Co Ltd 電源システム、電源システムの制御装置及び電源システムの制御方法
JP2007193951A (ja) * 2006-01-17 2007-08-02 Mitsubishi Heavy Ind Ltd 燃料電池及びその運転方法
JP2009163940A (ja) * 2007-12-28 2009-07-23 Nissan Motor Co Ltd 燃料電池システムおよび燃料電池システムの制御方法
JP2010027580A (ja) * 2008-07-24 2010-02-04 Osaka Gas Co Ltd 燃料電池システム

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10593974B2 (en) 2016-05-27 2020-03-17 Cummins Enterprise Llc Fuel cell system and operating method thereof
US10892506B2 (en) 2016-05-27 2021-01-12 Cummins Enterprise Llc Fuel cell system and operating method thereof

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