WO2010058749A1 - Système de génération d'énergie mcfc et son procédé de fonctionnement - Google Patents

Système de génération d'énergie mcfc et son procédé de fonctionnement Download PDF

Info

Publication number
WO2010058749A1
WO2010058749A1 PCT/JP2009/069429 JP2009069429W WO2010058749A1 WO 2010058749 A1 WO2010058749 A1 WO 2010058749A1 JP 2009069429 W JP2009069429 W JP 2009069429W WO 2010058749 A1 WO2010058749 A1 WO 2010058749A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
power generation
cathode
temperature
fuel
Prior art date
Application number
PCT/JP2009/069429
Other languages
English (en)
Japanese (ja)
Inventor
上松　宏吉
昭心 渡部
亀山　寛達
Original Assignee
東京瓦斯株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東京瓦斯株式会社 filed Critical 東京瓦斯株式会社
Priority to JP2010539222A priority Critical patent/JP5331819B2/ja
Priority to KR1020117011593A priority patent/KR101352219B1/ko
Priority to US13/129,801 priority patent/US20110223500A1/en
Priority to EP09827530.8A priority patent/EP2360764A4/fr
Publication of WO2010058749A1 publication Critical patent/WO2010058749A1/fr

Links

Images

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04111—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants using a compressor turbine assembly
    • 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
    • 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
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • 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
    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126—Humidifying
    • H01M8/04141—Humidifying by water containing exhaust gases
    • 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
    • H01M8/04701—Temperature
    • H01M8/04708—Temperature of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701—Temperature
    • H01M8/04731—Temperature of other components of a fuel cell or fuel cell stacks
    • 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 belongs to the field of energy conversion devices, and relates to a fuel cell that directly converts chemical energy of a fuel gas into electricity.
  • the present invention relates to an MCFC-gas turbine hybrid system that contributes to the effective use of energy resources and the improvement of the global environment and its operation method.
  • the MCFC-gas turbine hybrid system is simply referred to as “MCFC power generation system”.
  • FIG. 3 is an overall configuration diagram of a conventional MCFC power generation system (MCFC-gas turbine hybrid system).
  • the fuel gas FG such as city gas is desulfurized by the desulfurizing agent 2 in the desulfurizer 1 and then guided to the fuel humidifier 41.
  • the treated water PW is sprayed and evaporated while the fuel gas is heated by the cathode exhaust of the MCFC 12, and the preheated mixed gas of fuel gas and water vapor is then led to the pre-converter 9.
  • the treated water used at this time is obtained by treating the feed water W with the water treatment device 4 and supplying the fuel humidifier 41 with the pump 6 via the treated water tank 5.
  • the pre-converter 9 is a kind of reformer, and a reforming catalyst 10 is disposed inside, but there is no heating source, and heavy components more than ethane are reformed mainly by sensible heat of the gas that it has. Methane is hardly reformed.
  • the gas exiting the preconverter 9 is heated to near the operating temperature of the fuel cell by the fuel heater 11 and supplied to the MCFC 12.
  • the MCFC 12 is an internal reforming type, and an internal reformer 38 is incorporated in the fuel cell.
  • the anode A In the anode A, about 70% of the total of H 2 and CO produced by reforming is used for the power generation reaction (H 2 + CO 3 2 ⁇ ⁇ H 2 O + CO 2 + 2e ⁇ ), but the rest is catalytic combustion as anode exhaust Guided to vessel 14.
  • the anode exhaust is mixed with the air that is the exhaust of the gas turbine, the combustible components in the anode exhaust are combusted by the combustion catalyst 15, and the combustion gas whose temperature has risen is heat-exchanged with the compressed air CA by the high-temperature heat exchanger 16.
  • the combustion gas whose temperature has decreased is supplied to the cathode C.
  • the cathode C At the cathode C, a part of CO 2 and oxygen are consumed and discharged from the cathode C by a power generation reaction (CO 2 + 1 / 2O 2 + 2e ⁇ ⁇ CO 3 2 ⁇ ).
  • the cathode exhaust is heated to the fuel side by the fuel heater 11 and then led to the low-temperature regeneration heat exchanger 32 to preheat the compressed air, and then the fuel humidifier 41 is used to heat the fuel side, To be released.
  • the gas turbine generator 27 has a configuration in which a compressor 28, a turbine 29, and a generator 30 are connected to one shaft, and the air AIR is compressed by the compressor 28 via a filter 31, and the compressed air CA is subjected to low-temperature regenerative heat exchange.
  • the vessel 32 Preheated by the vessel 32, then heated to a predetermined temperature by the high temperature heat exchanger 16 and led to the turbine 29.
  • the turbine 29 works in the process of expanding to near atmospheric pressure, and the exhaust gas is supplied to the cathode via the catalytic combustor 14 and the high temperature heat exchanger 16.
  • the shaft output obtained by subtracting the power of the compressor 28 and the mechanical loss from the output of the turbine 29 is transmitted to the generator 30, whereby an AC output is obtained using the exhaust heat of the fuel cell.
  • FIG. 4 is a configuration diagram of an apparatus for separating and recovering CO 2 from combustion exhaust gas.
  • the combustion exhaust gas CG comes into contact with the absorption liquid LAB in the process from entering the lower part of the absorption tower 42 to being discharged from the upper part, and CO 2 in the combustion exhaust gas is absorbed into the absorption liquid LAB.
  • the absorption liquid RAB that has absorbed CO 2 is pressurized by the pump 43, preheated by the heat exchanger 44, then supplied from the upper part of the regeneration tower 45, and comes into contact with the high-temperature gas rising from the lower part in the process of dropping. To release the absorbed CO 2 .
  • a reboiler 46 is provided at the lower part of the regeneration tower 45, and the absorption liquid is heated by the heat medium HM, CO 2 and water vapor flow from the lower part to the upper part of the regeneration tower, and finally, CO 2 gas from the top of the tower. CO 2 G is recovered.
  • the absorption liquid LAB from which CO 2 has been released is pressurized by a pump 47, cooled by a heat exchanger 44 and a cooler 48, and supplied again from the upper part of the absorption tower. If the above-described CO 2 separation and recovery apparatus is used, CO 2 contained in the combustion exhaust gas can be separated and recovered, but energy consumption such as a reboiler heat source and pump power is large, and the equipment cost is also expensive.
  • Patent Documents 1 and 2 have already been disclosed.
  • FIG. 1 is a third diagram disclosed in Patent Document 1.
  • the combustion gas becomes CO 2 and H 2 O, which is cooled, It has been shown that CO 2 can be easily recovered by separating 2 O. Therefore, it is already disclosed in Patent Document 1 that CO 2 can be recovered by burning the anode exhaust of the fuel cell with oxygen and then cooling to separate the water.
  • SOFC solid oxide fuel cell
  • the fuel cell is a fuel gas oxidation process
  • the anode exhaust is a state in which the fuel gas is partially oxidized. If the fuel gas supplied to the fuel cell is a hydrocarbon fuel or a fuel gas derived therefrom, the anode exhaust is a partially oxidized hydrocarbon fuel. If this is burned with oxygen and cooled to remove water, CO 2 can be recovered.
  • SOFC is used as the fuel cell. Since the SOFC electrolyte has oxygen ion conductivity, even if air is supplied to the air electrode (cathode), only the oxygen in the air moves to the fuel electrode (anode) and reacts with hydrogen at the anode to generate electricity. Therefore, N 2 is not included in the anode exhaust. Therefore, since air can be supplied to the cathode instead of oxygen, oxygen is only needed to burn the anode exhaust with oxygen, and the consumption of oxygen can be reduced.
  • SOFC is used as the fuel cell
  • preheated air 130 obtained by preheating air 120 with the air preheater 110 is supplied to the cathode, and the heat source of the air preheater is cathode exhaust.
  • Gas is supplied to anode A.
  • the supplied fuel gas undergoes an internal reforming reaction in the fuel cell, and a power generation reaction occurs due to the generated H 2 or CO.
  • oxygen is introduced from the outside into the gas discharged from the anode A, which is led to the combustor 360, and the combustion gas is led to the heat exchanger 200, where the water 220 is evaporated, and the steam is converted into the fuel. Used as quality steam. Further, the combustion gas cooled by the heat exchanger 200 is then introduced into a condenser 230, where water is separated and recovered remaining gas as CO 2. The recovered water is used to generate water vapor.
  • FIG. 2 corresponds to FIG. 14 disclosed in Patent Document 2 and is a hybrid system of MCFC, gas turbine, and steam turbine.
  • Oxidizing agent is not air, is a system that enables the CO 2 recovery by using the oxygen.
  • the fuel cell of this system is an MCFC.
  • Methanol is supplied to the anode 407 from a tank, mixed with the recycle gas of the anode exhaust, and supplied to the anode.
  • the cathode 406 is supplied with a mixture of combustion gas obtained by burning anode exhaust with oxygen and gas turbine exhaust.
  • the cathode exhaust is guided to a steam generator 408, and after steam is generated, it is guided to a cooler 410 to separate moisture.
  • the steam generated by the steam generator is guided to the steam turbine 409 to drive the steam turbine and generate electric power.
  • the cathode exhaust from which moisture is separated by the cooler 410 that is, the mixed gas of CO 2 and O 2 is guided to the compressor 411 of the gas turbine, and the compressed gas is heated by the heat exchanger 413, and the combustor Guided to 403.
  • Methanol and oxygen are supplied to the combustor 403, and the combustion gas is supplied to the gas turbine, which works in the process of expanding in the gas turbine and generates power.
  • the exhaust of the gas turbine is supplied to the cathode.
  • the anode exhaust is guided to the combustor 412, oxygen is supplied to the combustor, and combustible components in the anode exhaust are combusted.
  • This combustion gas gives heat to the compressed gas in the heat exchanger 413, and then is divided into two systems. In one system, moisture is separated by the cooler 414, and CO 2 gas is recovered. The other system is supplied to the cathode.
  • Patent Document 2 is a very complex system consisting of a combination of MCFC, gas turbine, and steam turbine, and the subsystems affect each other, making it difficult to operate and control. It is not possible to change the composition freely.
  • problems that are not solved by the system of Patent Document 2 will be described in detail.
  • the power generation reaction of MCFC is as follows. About half of the reaction heat of hydrogen is changed to electricity, and the rest is heat. Cathode reaction: CO 2 + 1 / 2O 2 + 2e ⁇ ⁇ CO 3 2 ⁇ Anode reaction: H 2 + CO 3 2 ⁇ ⁇ H 2 O + CO 2 + 2e ⁇ Overall reaction: H 2 + 1 / 2O 2 ⁇ H 2 O Therefore, the fuel cell needs to be cooled according to the heat generated by the power generation reaction. In the case of the external reforming type MCFC, it is cooled by sensible heat of the cathode gas and the anode gas, and in the case of the internal reforming type, the cathode gas and the anode are cooled.
  • the cathode In addition to the sensible heat of the gas, it is also cooled by a reforming reaction. Therefore, the flow rate of the gas flowing through the cathode and the temperatures of the inlet and outlet are determined by the heat balance of the fuel cell.
  • the cathode is supplied with exhaust from a gas turbine, and after the cathode exhaust has separated moisture, it is supplied to a compressor of the gas turbine, methanol and oxygen are added, and the combustion gas is supplied to the gas turbine. That is, the cathode and the gas turbine are integrated and cannot be freely adjusted individually. It is quite difficult to maintain the fuel cell thermal balance between the amount of gas flowing through the cathode and the cathode inlet and outlet temperatures.
  • the amount corresponding to the amount of CO 2 and O 2 consumed by the power generation reaction of the cathode must be replenished from the outside.
  • CO 2 is replenished from methanol and by recycling the gas from the anode exhaust burned with oxygen, but this amount must exactly match the power generation reaction. Since the amounts of methanol and oxygen determine the temperature at the cathode inlet and at the same time determine the CO 2 balance, it is quite difficult to satisfy this condition.
  • the amount of CO 2 produced from methanol cannot exceed the amount of power generation reaction, and oxygen cannot enter more than is consumed in the power generation reaction.
  • the sum of the CO 2 and O 2 coming from the anode exhaust combustion gas and the CO 2 and O 2 coming from the methanol combustor must always closely match the amount consumed by the power generation reaction.
  • the gas turbine outlet temperature which is determined by the combustion of methanol, also determines the gas turbine outlet temperature, that is, the cathode inlet temperature. Therefore, there is a factor that determines the methanol flow rate separately from the CO 2 balance. Both fuel cells and gas turbines can only be operated under conditions that satisfy these conditions.
  • the power generation load is lowered from 100% of the rated value to, for example, 50%
  • the heat generation in the fuel cell is reduced to less than half
  • the cathode inlet and outlet temperatures are kept constant
  • the flow rate through the gas turbine is less than half.
  • the pressure ratio of the gas turbine also changes depending on the flow rate, in order to maintain the cathode inlet temperature constant, the amount of methanol, that is, the combustion temperature must be changed in accordance with the flow rate.
  • the amount of CO 2 consumed by the power generation reaction is less than half, the amount of methanol must be less than half.
  • both the gas turbine and the fuel cell are operated while satisfying the cathode gas circulation amount, the cathode inlet / outlet temperature, and the CO 2 balance that influence the thermal balance of the fuel cell, and the load It is very difficult to change freely.
  • Nickel short-circuiting means that nickel oxide constituting the cathode dissolves in the form of ions in the electrolyte (NiO + CO 2 ⁇ Ni 2+ + CO 3 2 ⁇ ), and is reduced by hydrogen. This is a phenomenon in which nickel is deposited (Ni 2+ + H 2 + CO 3 2 ⁇ ⁇ Ni + H 2 O + CO 2 ). When the amount of nickel deposited increases, the anode and cathode of the electrolyte plate, which must be an insulator, become conductive. This is a fatal problem for fuel cells.
  • methanol is supplied to the anode as fuel, but no steam necessary for reforming is supplied from the outside, and all is provided by recycling of the anode exhaust.
  • the anode exhaust includes the CO 2 mass besides H 2 O, since CO 2 is also recycled, lower the anodes of hydrogen partial pressure, whereby the voltage of the fuel cell decreases, the power generation efficiency decreases .
  • the fuel methanol is a system that cannot be operated unless it is supplied not only for the MCFC but also for the gas turbine, and its power generation efficiency is lower than a system that supplies fuel only to the MCFC having the highest power generation efficiency.
  • an oxygen plant is required to supply oxygen, and the oxygen consumption of both the methanol for the fuel cell and the methanol for the gas turbine.
  • the amount of combustion is required, and the power consumption becomes very large, which is a major factor for reducing power generation efficiency.
  • MCFC has a factor that can improve power generation efficiency by using oxygen, but gas turbine is determined by the flow rate flowing through the gas turbine, inlet temperature and pressure ratio, so there is no particular merit of using oxygen, so it corresponds to gas turbine use
  • the power consumed by the oxygen plant is a factor that reduces power generation efficiency.
  • the system disclosed in FIG. 2 does not recover heat at all and tries to convert as much of the energy of fuel as possible into electric power, which is used as a large-scale commercial power generation facility.
  • it is not suitable for small and medium distributed power sources that require both heat and power.
  • the distributed power supply requires a load change, and the required ratio of heat and electricity is not constant, and so-called thermoelectric variable operation is also required.
  • the entire system is integrated, and it seems that the flexibility of the system for performing load change, thermoelectric variable operation, adjustment of cathode gas composition, and the like is lacking.
  • the present invention has been developed to solve the above-described conventional problems. That is, the object of the present invention is to minimize the equipment added to the normal power generation equipment, greatly reduce or not substantially release CO 2 into the atmosphere, and at the same time provide high power generation efficiency and heat recovery efficiency. It is to provide an MCFC power generation system capable of obtaining the above and a method for operating the same. That is, an object of the present invention is to provide an MCFC power generation system having substantially no generation of CO 2 into the atmosphere and having high power generation efficiency and heat recovery efficiency, and an operation method thereof.
  • an object of the present invention is to adjust the gas composition of the cathode so that the voltage and output of the fuel cell can be adjusted within a certain range, and the ratio of heat to electricity can be greatly changed, so-called thermoelectric variable operation. It is to provide an MCFC power generation system that can be operated and an operation method thereof.
  • the present invention has a fuel gas supply system for supplying fuel gas to a molten carbonate fuel cell
  • the fuel gas supply system has a fuel heater connected to the anode outlet, anode exhaust at the fuel heater outlet divided into two systems, one system connected to the anode exhaust circulation blower, and the blower outlet gas connected to the fuel cell Is mixed with the fuel gas supplied from the outside, then mixed with the reforming steam, and then introduced into the catalyst layer of the pre-converter, and after pre-processing the mixed gas, the temperature is raised by the fuel heater to the fuel cell.
  • An MCFC power generation system is provided.
  • the mixing temperature of the outlet gas of the anode exhaust circulation blower, the fuel gas supplied from the outside, and the reforming steam is in the range of 250 to 400 ° C.
  • the anode recycle amount was controlled, thereby increasing the methane concentration of the preconverter outlet gas.
  • the present invention has a cathode gas circulation system for circulating the cathode gas of a molten carbonate fuel cell
  • the cathode gas circulation system has a closed circulation loop in which the suction side of the cathode gas circulation blower is connected to the cathode outlet and the discharge side is connected to the cathode inlet.
  • the cathode outlet side is divided into two systems, and one system has a flow control valve.
  • the other system is connected to a check valve, and an oxygen supply line having a flow control valve and a CO 2 supply line having a flow control valve are connected downstream of the check valve.
  • a featured MCFC power generation system is provided.
  • the CO 2 supply line is provided with a heat exchanger having a temperature adjustment function, and the CO 2 supply temperature is adjusted, whereby the cathode that has passed through the check valve.
  • the cathode inlet temperature can be adjusted only by supplying and mixing oxygen and CO 2 to the outlet gas.
  • the energy recovery system recovers energy from the anode exhaust of the molten carbonate fuel cell
  • the energy recovery system guides at least part of the anode exhaust to a mixer, while the mixer is connected to an oxygen supply line and a combustion gas recycle line, and the mixed gas at the outlet of the mixer is guided to a catalytic oxidizer and oxidized.
  • the combustible component in the anode exhaust gas is burned with oxygen by the catalyst, and the combustion gas exiting the catalytic oxidizer first heats the compressed air of the gas turbine using the separately provided air as the working medium, and then recycles CO 2.
  • An exhaust heat recovery boiler where steam is generated, and the combustion gas exiting the evaporation section of the exhaust heat recovery boiler is divided into two systems, and one system is connected to a combustion gas recycling blower and cooled.
  • An MCFC power generation system is provided that recycles the generated combustion gas into a mixer and supplies the other system to the feed water heating section of the exhaust heat recovery boiler. Is done.
  • a gas turbine that uses air that receives heat from the high-temperature combustion gas from the catalytic oxidizer via an air heater as a working medium, and the air that is the working medium is a gas turbine. And is not mixed with any other fluid.
  • the thermal energy of the turbine exhaust it is configured so that the compressed air is first heated by the regenerative heat exchanger and then steam is generated by the exhaust heat recovery boiler.
  • the outlet temperature of the regenerative heat exchanger was controlled so that the necessary steam could be generated.
  • the rotational speed of the combustion gas recycle blower was controlled so that the outlet temperature of the catalyst oxidizer was made constant according to the set value.
  • it has a damper that can switch the combustion gas recycling position from the low temperature part to the high temperature part.
  • the combustion gas recycling position is switched from the low temperature portion to the high temperature portion, thereby increasing the flow rate of the combustion gas passing through the air heater and increasing the amount of heat given to the compressed air.
  • the circulating flow rate of the combustion gas recycle blower is gradually increased by gradually decreasing the set value of the outlet temperature of the catalyst oxidizer.
  • the outlet temperature is lowered, the amount of heat given to the compressed air through the air heater is reduced, and as a result, the output of the gas turbine is reduced, and conversely, the generated steam amount of the exhaust heat recovery boiler is increased.
  • the reforming steam supply is switched from the exhaust heat recovery boiler on the gas turbine side to the exhaust heat recovery boiler on the combustion gas side. Stop and maximize the amount of steam generated in the exhaust heat recovery boiler.
  • the CO 2 and O 2 concentrations in the cathode circulation system are increased by the amount corresponding to the voltage deterioration in response to the voltage deterioration with time of the fuel cell, so that the voltage of the fuel cell is increased.
  • a method for operating the MCFC power generation system is provided, characterized in that the power consumption of the MCFC is maintained substantially constant during the lifetime.
  • the cathode gas circulation system is provided, the cathode gas is circulated by the cathode gas circulation blower, forms a closed loop, and oxygen consumed by the power generation reaction is supplied from the oxygen supply plant. Since it is replenished and CO 2 is replenished with recycled CO 2 , the amount and composition of the cathode circulation gas can be maintained in a necessary state, and basically there is no exhaust from the cathode gas circulation system. Therefore, it can be said that it is a power generation facility that does not substantially release CO 2 into the atmosphere or a power generation facility that is extremely reduced.
  • the amount of fuel gas supplied from the outside can be reduced.
  • the temperature of the fuel gas and reforming water vapor can be raised to the operating temperature of the pre-converter by mixing with a part of the high-temperature anode exhaust, so that a fuel humidifier is not required.
  • the anode exhaust contains water vapor generated by the power generation reaction of the anode, the amount of reforming water vapor to be newly supplied can be significantly reduced.
  • the MCFC of the present invention is an internal reforming type, in which a part of anode exhaust and a fuel gas such as city gas supplied from the outside are mixed, and reforming steam is added to form one reforming catalyst layer.
  • a part of anode exhaust and a fuel gas such as city gas supplied from the outside are mixed, and reforming steam is added to form one reforming catalyst layer.
  • the medium of the gas turbine is air and does not pollute the atmosphere by exhaust. Further, when the gas turbine is operated, the electric output increases, but when the gas turbine is stopped, the exhaust heat recovery becomes large, so that the thermoelectric ratio variable operation becomes possible. (7) When oxygen is supplied instead of air as an oxidant supplied to the MCFC cathode, not only CO 2 can be recovered, but the fuel cell voltage can be increased by increasing the CO 2 and O 2 concentration of the cathode. Can be increased. As a result, the output of the fuel cell can be increased and the power generation efficiency can be improved.
  • FIG. 1 is a configuration diagram of a power generation system disclosed in Patent Document 1.
  • FIG. It is a block diagram of the electric power generation system disclosed by patent document 2.
  • FIG. It is a whole block diagram of a conventional MCFC power generation system.
  • It is a schematic diagram of an apparatus for separating and recovering CO 2 from flue gas.
  • 1 is an overall configuration diagram of an MCFC power generation system of the present invention.
  • FIG. 6 is a detailed view of the cathode gas circulation system of FIG. 5.
  • FIG. 6 is a detailed view of the fuel gas supply system of FIG. 5.
  • FIG. 6 is a detailed view of the energy recovery system of FIG. 5.
  • It is a relationship diagram of the combustion gas recycle amount, the inlet temperature of the gas turbine, and the output. It is data at the time of constant voltage operation.
  • FIG. 5 is an overall configuration diagram of the MCFC power generation system of the present invention.
  • the fuel gas FG such as city gas supplied from the outside is desulfurized by the desulfurizing agent 2 in the desulfurization apparatus 1 and supplied to the pre-converter 9 through the filter 3. Mixed in state.
  • the city gas supplied from the outside At the same time as the heavy component of ethane or higher contained in the fuel gas is reformed, H 2 , CO, and CO 2 in the anode exhaust gas to be recycled cause a methanation reaction.
  • the order of mixing fuel gas such as city gas supplied from the outside and part of the anode exhaust and reforming steam is as shown in FIG. 5 or after mixing part of the anode exhaust and reforming steam.
  • fuel gas such as city gas supplied from the outside and part of the anode exhaust and reforming steam
  • FIG. 5 shows only one example.
  • the gas exiting the preconverter is guided to the fuel heater 11, heated to a temperature slightly lower than the operating temperature of the fuel cell by the anode exhaust, and supplied to the fuel cell 12.
  • the fuel cell 12 is an internal reforming type MCFC, and a reformer 38 is incorporated in the fuel cell.
  • the fuel gas is reformed in the fuel cell, and H 2 and CO serving as fuel for the MCFC are generated.
  • part of H 2 and CO in the fuel gas is consumed by the power generation reaction, and the rest is discharged from the fuel cell as anode exhaust. Since direct current electricity is generated in the fuel cell, it is converted into alternating current by the inverter 37 and output.
  • the anode exhaust is heated by the fuel heater 11 to the pre-converter outlet gas, and then a part of the anode exhaust is pressurized by the anode exhaust circulation blower 8 and mixed with fuel gas such as city gas supplied from the outside. The remainder is mixed with oxygen and the recycle combustion gas RCG by the mixer 13 and led to the catalytic combustor 14.
  • the catalytic combustor 14 is provided with a combustion catalyst layer 15 so that combustible components in the anode exhaust are combusted.
  • the combustion gas leaving the catalytic combustor 14 is guided to the high temperature heat exchanger 16 to heat the compressed air CA to the turbine inlet temperature.
  • the CO 2 heater 17 heats the RCO 2 that is the recycled CO 2 , and the heat is guided to the exhaust heat recovery boiler 18.
  • the exhaust heat recovery boiler 18 is composed of an evaporation unit EVA and a feed water heating unit ECO, and the heat source is the same combustion gas, but the recycled combustion gas RCG is branched from the outlet of the evaporation unit of the exhaust heat recovery boiler 18, The flow rate of the combustion gas is different between the evaporation unit and the feed water heating unit.
  • the position where the combustion gas is recycled is used as the outlet of the evaporation section of the exhaust heat recovery boiler.
  • it can be used as the outlet of the CO 2 heater 17 or the outlet of the high-temperature heat exchanger 16, and the recycling position is high.
  • the power generation efficiency becomes, the power generation efficiency increases, but the exhaust heat recovery efficiency decreases, and each has its own characteristics.
  • the recycled combustion gas is pressurized by the combustion gas recycling blower 19 and sent to the mixer 13.
  • FIG. 5 it is described in FIG. 5 that mixing is performed on the oxygen line, there is a method of mixing the anode exhaust, oxygen, and recycle combustion gas in the mixer 13 and other methods, and FIG. 5 is drawn in a specific sense. is not.
  • the combustion gas exiting the feed water heating section of the exhaust heat recovery boiler 18 is cooled by the cooler 20, and the condensed water is separated by the KO drum 21.
  • the dehumidifying system 22 includes a refrigerator 23, a heat exchanger 24, and a KO drum 25.
  • the CO 2 gas exiting the KO drum 25 has a CO 2 concentration increased to about 95%.
  • a part of the pressure is increased by the CO 2 recycle blower 26, preheated by the CO 2 heater 17, and then supplied to the cathode gas circulation system.
  • the remaining CO 2 gas is recovered by the high-concentration CO 2 recovery device 70 in a high-concentration state, and is almost never released to the atmosphere.
  • the cathode gas circulation system forms a closed cycle that is circulated by the cathode gas circulation blower 36, and oxygen consumed by the power generation reaction (CO 2 + 1 / 2O 2 + 2e ⁇ ⁇ CO 3 2 ⁇ ) of the cathode is oxygen.
  • the oxygen supply plant 33 is composed of an air compressor 34 and a separation device 35.
  • the oxygen supply plant has several types such as PSA (Pressure Swing Adsorber) and liquefaction separation, and the present invention is an oxygen supply plant. It does not specify the details.
  • the CO 2 consumed by the power generation reaction is replenished to the cathode gas circulation system after the anode exhaust gas is burned with oxygen, and the cooled and dehumidified recycled CO 2 is preheated.
  • the temperature of the cathode gas becomes higher at the outlet than the inlet due to the heat generated by the power generation reaction in the fuel cell, but it can be adjusted to the inlet by mixing oxygen near normal temperature and recycled CO 2 preheated to 250 to 450 ° C. it can.
  • This temperature control is performed by controlling the outlet temperature of the CO 2 heater 17.
  • the above is the basic configuration of the MCFC power generation equipment portion of the present invention.
  • a gas turbine generator using air as a working medium is added thereto.
  • the air is guided to the compressor 28 of the gas turbine generator 27 through the filter 31, and the compressed air CA is first heated by the exhaust of the turbine 29 in the regenerative heat exchanger 32, and then the anode by the high temperature heat exchanger 16.
  • the compressed air that is heat-exchanged with the combustion gas CG of the exhaust gas and heated to the turbine inlet temperature is guided to the turbine 29.
  • Work is performed in the process of expanding to a pressure close to atmospheric pressure by the turbine 29, and the AC power is taken out by the generator 30 as AC output.
  • the turbine exhaust is led to the regenerative heat exchanger 32 where heat is supplied to the compressed air, and then to the exhaust heat recovery boiler 7.
  • the exhaust heat recovery boiler 7 generates low-pressure steam necessary for reforming, and the turbine exhaust discharged from the exhaust heat recovery boiler is released to the atmosphere.
  • the MCFC power generation system of the present invention described above has the following effects.
  • Cathode gas is circulated by a cathode gas circulation blower to form a closed loop.
  • Oxygen consumed by the power generation reaction (CO 2 + 1 / 2O 2 + 2e ⁇ ⁇ CO 3 2 ⁇ ) is replenished from the oxygen supply plant, and CO 2 is replenished with recycled CO 2.
  • the composition can also be maintained as required and there is essentially no exhaust from the cathode gas circulation system.
  • oxygen or CO 2 to be replenished contains impurities, a certain purge is required.
  • the amount of nitrogen contained in oxygen and the amount of H 2 O contained in CO 2 is small, a part of this CO 2 is recycled to the cathode, and the rest is almost recovered as high-concentration CO 2 gas. Almost no CO 2 emissions from the atmosphere.
  • carbonate ions (CO 3 2 ⁇ ) generated at the cathode pass through the electrolyte to the anode, and are generated by the power generation reaction (H 2 + CO 3 2 ⁇ ⁇ H 2 O + CO 2 + 2e ⁇ ) of the anode.
  • the anode exhaust contains CH 4 , H 2 , CO, CO 2 , H 2 O, but when combustible components are burned with oxygen, it becomes CO 2 and H 2 O, and if water is removed by cooling. Only CO 2 will remain. However, if the oxygen includes nitrogen contains nitrogen traces in the CO 2, if the oxygen has been excessively charged also includes a small amount of oxygen.
  • CO 2 cannot be completely removed by cooling to remove moisture, CO 2 contains a small amount of nitrogen, oxygen, water vapor, etc., but this impurity is recycled. The recovery is not particularly harmful. Since a portion of this CO 2 is recovered and the rest is recycled to the cathode, the atmospheric release of CO 2 from the anode is zero.
  • the fuel humidifier becomes unnecessary. Furthermore, since the anode exhaust contains water vapor generated by the power generation reaction of the anode, the amount of reforming water vapor to be newly supplied can be significantly reduced. A decrease in the amount of fuel gas such as city gas supplied from the outside is also a factor that can reduce the supply amount of reforming steam.
  • the MCFC of the present invention is an internal reforming type, and utilizes a reforming reaction (CH 4 + H 2 O ⁇ CO + 3H 2 ) that is an endothermic reaction for cooling the fuel cell. Therefore, it is preferable that the methane concentration in the fuel gas supplied to the fuel cell is high. However, the main components in the anode exhaust are H 2 , CO, CO 2 , H 2 O, and almost no methane is contained. Therefore, it is necessary to proceed with the methanation reaction (CO 2 + 4H 2 ⁇ CH 4 + 2H 2 O) which is the reverse reaction of the reforming reaction. This reaction can be achieved by adjusting the temperature with the same reforming catalyst.
  • a reforming reaction CH 4 + H 2 O ⁇ CO + 3H 2
  • the methanation reaction is an exothermic reaction, and when a part of the anode exhaust is methanated alone, the temperature rises too much and the methane concentration does not increase in equilibrium. If the temperature becomes too high, the catalyst will be deteriorated.
  • fuel gas such as city gas supplied from the outside contains ethane, propane, butane, etc. in addition to methane.
  • the reforming temperature is low, heavy components above ethane are almost reformed. Methane is hardly reformed. This reforming reaction is an endothermic reaction and needs to be preheated in advance to proceed alone.
  • the reforming reaction and the methanation reaction proceed simultaneously by mixing a part of the anode exhaust and a fuel gas such as city gas supplied from the outside, adding reforming steam and passing through one reforming catalyst layer.
  • a fuel gas such as city gas supplied from the outside
  • the temperature change is moderated and the reaction temperature can be easily maintained at the target temperature.
  • operations such as gas preheating and reactor cooling are unnecessary.
  • Fuel gas such as city gas supplied from the outside is at room temperature, and when this is mixed with saturated steam, drainage is generated. Therefore, after mixing fuel gas with a part of the hot anode exhaust, is steam mixed? Alternatively, after mixing a portion of the high-temperature anode exhaust gas and water vapor, mixing can be performed without generating drainage by mixing the fuel gas.
  • the medium of the gas turbine is air, does not pollute the atmosphere by exhaust, and only receives heat from the MCFC power generation system via the heat exchanger, so even if the gas turbine stops, the MCFC power generation system Can continue. Accordingly, the electric output increases when the gas turbine is operated, but the exhaust heat recovery increases when the gas turbine is stopped, so that the thermoelectric ratio variable operation becomes possible. As a process of this change, increase the amount of combustion gas recycled and lower the catalyst oxidizer outlet temperature to reduce the amount of heat exchanged in the high-temperature heat exchanger, lower the output of the gas turbine and at the same time generate steam in the exhaust heat recovery boiler The amount can be increased and the final form is a gas turbine shutdown. Details thereof will be described in Examples.
  • the amount of circulating gas at the cathode can be easily increased or decreased by changing the rotation speed of the blower. Even considering the heat balance of the battery, the CO 2 and O 2 concentrations of the cathode gas can be easily and accurately adjusted in consideration of a nickel short circuit. This will be described in detail in the embodiments.
  • FIG. 6 shows only the portion of the cathode gas circulation system of FIG. 5 and describes it in detail. It is necessary to replenish CO 2 and O 2 consumed by the cathode power generation reaction (CO 2 + 1 / 2O 2 + 2e ⁇ ⁇ CO 3 2 ⁇ ) and purge.
  • the reaction amount can be calculated from the direct current of the fuel cell, and the purge amount can be confirmed by the flow control valve 53.
  • O 2 is controlled by a flow rate control valve 51 from an oxygen plant provided outside the MCFC power plant, and is supplied at a temperature near room temperature.
  • CO 2 combusts the anode exhaust with oxygen, recycling the CO 2 dropped water was cooled (RCO 2) to control the flow rate at a flow rate regulating valve 52, a temperature regulating valve 40 provided in the CO 2 heater 36
  • RCO 2 the cathode gas circulation system
  • the cathode gas circulation system is replenished. Since the gas passing through the cathode has a higher temperature at the outlet than the inlet due to heat generated by the power generation reaction, the gas is controlled to return to the inlet temperature by replenishment and mixing of CO 2 and O 2 .
  • the replenishment temperature of the recycled CO 2 is adjusted with a CO 2 heater so that the temperature after adiabatic compression of the mixed gas with the cathode gas circulation blower becomes the cathode inlet temperature.
  • the cathode gas circulation blower controls the circulation amount so that the cathode outlet gas temperature becomes constant.
  • the cathode outlet of the cathode circulation system is divided into two systems, and one system is equipped with a flow control valve 53.
  • the system is connected to the purge line, the other system is connected to the check valve 54, and the CO 2 and O 2 supply lines are connected downstream of the check valve 54.
  • the cathode gas circulation system of the present invention can freely change the gas composition of the cathode, and can freely increase or decrease the amount of circulation according to the degree of heat generation of the fuel cell. In addition, it does not affect other subsystems.
  • Table 1 shows the plant performance when the cathode gas composition of the present invention is changed.
  • the CO 2 and O 2 concentrations in Table 1 do not mean the highest concentrations, but are concentrations that take into account the influence of nickel short-circuiting, and the power generation efficiency is still improved by 5%.
  • the operation at a high concentration may be performed only when it is desired to increase the power generation efficiency, and it can be easily returned to the standard operation condition.
  • the lifetime of the fuel cell is defined as when the cell voltage has deteriorated by 10%. Assuming that the operating time for one year is 8000 hours and the life of the fuel cell is 5 years and 40000 hours, it will deteriorate by 1% every six months.
  • the output of the fuel cell is proportional to the voltage of the fuel cell. However, the power generation efficiency will decrease by 1% every six months.
  • the CO 2 and O 2 concentrations of the cathode can be gradually increased in accordance with the deterioration of the fuel cell, whereby the voltage of the fuel cell can always be kept constant.
  • FIG. 10 shows data at a constant voltage operation.
  • This figure shows an example of changes in the CO 2 and O 2 concentrations of the cathode to maintain the same performance as standard operating conditions for 5 years.
  • the output of the fuel cell and the power generation efficiency can be improved by an average of 5%.
  • this operating method the period during which the partial pressure of CO 2 at the cathode is very high is short, and the accumulated amount of metallic nickel leading to a nickel short circuit can be suppressed. Therefore, this operation method is one operating method that increases power generation efficiency while suppressing the nickel short circuit.
  • FIG. 7 is a detailed view showing only the fuel gas supply system of FIG. 5.
  • the anode outlet is connected to the fuel heater 11, and the outlet gas of the pre-converter 9 is made close to the operating temperature of the fuel cell using the anode exhaust as a heat source. Heat.
  • the anode exhaust whose temperature has dropped is divided into two systems, one system is connected to the anode exhaust circulation blower, and the blower outlet gas is mixed with fuel gas such as city gas supplied from the outside.
  • a fuel gas such as city gas is supplied with its flow rate adjusted by a flow rate control valve 56.
  • the city gas and the like are mixed with steam for reforming.
  • the steam is supplied with its flow rate adjusted by a flow control valve 57.
  • This mixed gas is then guided to the reforming catalyst layer 10 of the pre-converter 9.
  • lighter components than ethane in the city gas are reformed, and CO, CO 2 and H 2 O in the anode recycle gas cause a methanation reaction.
  • the reforming reaction is an endothermic reaction
  • the methanation reaction is an exothermic reaction
  • the two reactions occur at the same time, which has the effect of suppressing temperature changes between each other, and maintains the operating temperature of the preconverter at the desired temperature. It becomes easy.
  • the preconverter outlet gas has a methane concentration.
  • a reforming reaction CH 4 + H 2 O ⁇ CO + 3H 2
  • the temperature controller 58 equipped with anode exhaust circulation blower according to the flow rate of city gas etc. and the flow rate of reforming steam by the temperature controller 58 so that the catalyst layer outlet temperature of the pre-converter is in the range of 250-450 ° C
  • the recycle amount is controlled by the speed controller 39.
  • the constituent elements of the fuel supply system of the present invention are that the anode outlet and the fuel heater are connected, the temperature of the anode exhaust is lowered, the anode exhaust line whose temperature is lowered is divided into two systems, and the one system is anode exhausted.
  • the circulation blower By connecting to the circulation blower, mixing the outlet gas of the anode exhaust circulation blower, fuel gas such as city gas, and reforming water vapor, the temperature can be adjusted without using a heat exchanger up to the supply gas temperature to the pre-converter.
  • the mixed gas is guided to the reforming catalyst layer of the pre-converter having no heat source, and the pre-converter operating temperature is in the range of 250 to 450 ° C. so that the methane concentration of the pre-converter outlet gas is increased.
  • the recycling rate of the anode exhaust is in the range of about 20-40%.
  • Table 2 shows a comparison of performance with and without recycling of the anode exhaust.
  • the power generation efficiency does not change, but the heat recovery rate is greatly improved.
  • the power generation efficiency of the entire plant does not change greatly, but individual factors have changed in various ways.
  • Increasing the anode recycling rate reduces the amount of city gas supplied, the amount of reforming steam supplied decreases, the fuel cell voltage decreases, and therefore the output of the fuel cell also decreases, the output of the gas turbine decreases, and the in-house power also decreases. Go down. These fluctuation factors have the effect of changing the operating conditions of the plant.
  • the fuel cell heat balance is maintained while maintaining the power generation efficiency by lowering the fuel cell voltage by increasing the anode recycling rate and reducing the city gas supply amount instead. Can take. In addition, it is effective in adjusting the specifications of the component devices.
  • FIG. 8 is a diagram showing the details of an energy recovery system that effectively burns the anode exhaust in FIG. 5 with oxygen and uses the heat of combustion through various heat exchangers.
  • the anode exhaust AEG is mixed with oxygen OXG and recycle combustion gas RCG in the mixer 13.
  • the amount of the combustible component in the anode exhaust can be calculated from the fuel supply amount, the fuel utilization rate, the direct current of the fuel cell, etc., so that the required oxygen amount is calculated based on that, and is controlled and supplied by the flow control valve 59 Is done.
  • the combustion gas RCG is recycled to the mixer by the combustion gas recycling blower. If the anode exhaust gas is simply burned with oxygen, the temperature becomes too high. Therefore, it is considered that the outlet temperature of the catalytic combustor can be adjusted by recycling the low-temperature combustion gas.
  • the combustible gas in the anode exhaust is burned by the combustion catalyst of the catalytic combustor 14 as the mixed gas of the anode exhaust, oxygen, and recycled combustion gas, and the temperature rises.
  • the speed controller 61 of the combustion gas recycle blower controls the flow rate so that the outlet temperature of the catalyst combustor matches the set value. This set value is changed as necessary.
  • the combustion gas exiting the catalytic combustor 14 first heats the compressed air by the high-temperature heat exchanger 16, then heats the recycled CO 2 by the CO 2 heater, and then generates steam by the exhaust heat recovery boiler 18. .
  • the combustion gas is recycled when it leaves the evaporation section EVA of the exhaust heat recovery boiler.
  • the remaining combustion gas is sent to the feed water heating unit ECO of the exhaust heat recovery boiler.
  • the combustion gas is recycled from the outlet of the high temperature heat exchanger 16. This switching is performed by gradually switching the opening degree of the damper 62 from the low temperature side to the high temperature side.
  • the flow rate of the combustion gas recycle blower increases so as to maintain the catalyst combustor outlet temperature at the set value. Accordingly, the amount of combustion gas passing through the high temperature heat exchanger 16 increases, and the amount of heat given to the compressed air increases.
  • the amount of air in the gas turbine is increased by the speed controller 64 of the gas turbine generator.
  • the output of the gas turbine is increased, but the amount of heat that goes to the exhaust heat recovery boiler is reduced accordingly, so the amount of steam generated is reduced.
  • Table 3 shows a comparison between standard operating conditions and high-power operating modes.
  • the power generation efficiency is improved by 2 points, but the heat recovery rate is reduced by 6 points. What mode of operation is desirable depends on the balance of heat demand and power demand at that time.
  • This gas turbine recovers the exhaust heat of the fuel cell and generates power, and the amount of exhaust heat changes depending on the load on the MCFC side. Therefore, the generator is a motor / generator and the rotation speed is variable. Consideration is given so that the air flow rate can be changed according to the operating conditions.
  • thermoelectric operation is possible by using the energy recovery system in Fig. 8.
  • the condition for maximizing the electrical output is the operation mode in which the recycle position of the combustion gas is switched to the high temperature heat exchanger outlet.
  • the operation method for maximizing heat recovery is as described below.
  • the recycle position of the combustion gas is set to the place where the evaporation part of the exhaust heat recovery boiler is left, and the set value of the outlet temperature of the catalytic oxidizer is gradually lowered in that state. This increases the flow rate of the combustion gas recycle blower.
  • the outlet temperature of the catalytic oxidizer decreases, the amount of heat given to the compressed air via the high-temperature heat exchanger 16 decreases, and the gas turbine inlet temperature decreases. As a result, the gas turbine output decreases.
  • no change is the amount of heat for heating the recycled CO 2 in the process in a CO 2 heater, the amount of evaporation in the heat recovery steam by the amount of reduced heat to be applied to the gas turbine increases.
  • Fig. 9 shows the relationship between the combustion gas recycle amount and the gas turbine inlet temperature and output.
  • the catalyst combustor outlet temperature falls below a certain temperature, the output of the gas turbine becomes zero.
  • the supply of reforming steam is switched from the exhaust heat recovery boiler on the gas turbine side to the exhaust heat recovery boiler on the combustion gas side, and the gas turbine is stopped.
  • the gas turbine is stopped, all the heat that entered the gas turbine during standard operation enters the exhaust gas heat recovery boiler on the combustion gas side, so the heat recovery amount is maximized.
  • Table 4 shows a comparison between standard operation and maximum heat recovery.

Abstract

La présente invention concerne un système de génération d'énergie MCFC et son procédé de fonctionnement, qui permettent une réduction significative des émissions de CO2 ou de ne produire quasiment pas d'émission de CO2 par réduction au minimum de la facilité ajoutée à une facilité de génération d'énergie générale, qui permettent une forte efficacité de génération d'énergie et de récupération de chaleur, qui permettent l'ajustement de la tension et la sortie de la pile à combustible dans une certaine plage par ajustement de la composition du gaz de cathode, qui permettent une grande variation du rapport entre la chaleur et l'électricité et qui permettent donc un fonctionnement avec chaleur/électricité variable. Le système de génération MCFC comprend un système de circulation du gaz de cathode, dans lequel le gaz de cathode circule grâce à un souffleur de recyclage de gaz de cathode et où une boucle fermée est constituée. L'oxygène consommé dans la génération d'énergie est fourni par une usine d'alimentation en oxygène et le CO2 est fourni par le CO2 recyclé. Les composants combustibles dans un échappement d'anode sont brûlés avec l'oxygène, le gaz de résultat est refroidi et l'eau est retirée. Les gaz combustibles dans l'échappement d'anode sont recyclés.
PCT/JP2009/069429 2008-11-18 2009-11-16 Système de génération d'énergie mcfc et son procédé de fonctionnement WO2010058749A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2010539222A JP5331819B2 (ja) 2008-11-18 2009-11-16 Ｍｃｆｃ発電システム
KR1020117011593A KR101352219B1 (ko) 2008-11-18 2009-11-16 Ｍｃｆｃ 발전 시스템과 그 운전 방법
US13/129,801 US20110223500A1 (en) 2008-11-18 2009-11-16 Mcfc power generation system and method for operating same
EP09827530.8A EP2360764A4 (fr) 2008-11-18 2009-11-16 Système de génération d'énergie mcfc et son procédé de fonctionnement

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-294106 2008-11-18
JP2008294106 2008-11-18

Publications (1)

Publication Number Publication Date
WO2010058749A1 true WO2010058749A1 (fr) 2010-05-27

Family

ID=42198189

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/069429 WO2010058749A1 (fr) 2008-11-18 2009-11-16 Système de génération d'énergie mcfc et son procédé de fonctionnement

Country Status (5)

Country Link
US (1) US20110223500A1 (fr)
EP (1) EP2360764A4 (fr)
JP (3) JP5331819B2 (fr)
KR (1) KR101352219B1 (fr)
WO (1) WO2010058749A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9435230B2 (en) 2011-12-27 2016-09-06 Posco Energy Co., Ltd. Fuel cell hybrid system
CN108321416A (zh) * 2018-03-29 2018-07-24 中国华能集团清洁能源技术研究院有限公司 Co2近零排放的整体煤气化燃料电池发电系统及方法
CN113540504A (zh) * 2021-07-16 2021-10-22 中国科学院上海应用物理研究所 热泵式-氢能复合储能发电方法及装置
CN114371745A (zh) * 2021-12-29 2022-04-19 徐州捷科思网络科技有限公司 一种温度控制系统
CN114635815A (zh) * 2022-04-01 2022-06-17 招商局重工(深圳)有限公司 一种甲醇燃料供给系统及其控制方法

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2491562A (en) * 2011-05-23 2012-12-12 Alstom Technology Ltd Fossil fuel power plant with gas turbine and MCFC arrangements
WO2013100714A1 (fr) * 2011-12-30 2013-07-04 두산중공업 주식회사 Système de récupération de dioxyde de carbone utilisant une pile à combustible
KR101408139B1 (ko) * 2011-12-30 2014-06-17 두산중공업 주식회사 연료전지를 이용한 이산화탄소 회수 시스템
KR101401451B1 (ko) * 2012-02-14 2014-05-29 두산중공업 주식회사 열교환형 촉매 산화기 및 이를 이용한 고농도 이산화탄소 회수장치
KR101451839B1 (ko) * 2012-12-18 2014-10-16 두산중공업 주식회사 연료 전지 시스템 및 그 제어 방법
KR101397091B1 (ko) * 2012-12-28 2014-05-19 포스코에너지 주식회사 연료 전지 시스템
KR20150129790A (ko) 2013-03-15 2015-11-20 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 통합형 발전에서 NOx의 경감
US9077008B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
CN103410614B (zh) * 2013-08-21 2015-12-23 华北电力大学 用两级常压mcfc回收燃气轮机排气中co2的复合动力系统
US9556753B2 (en) 2013-09-30 2017-01-31 Exxonmobil Research And Engineering Company Power generation and CO2 capture with turbines in series
US9819042B2 (en) 2013-09-30 2017-11-14 Exxonmobil Research And Engineering Company Fuel cell integration within a heat recovery steam generator
US9755258B2 (en) 2013-09-30 2017-09-05 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using solid oxide fuel cells
CN104196582B (zh) * 2014-07-03 2015-10-21 华北电力大学 基于mcfc电化学法捕集igcc系统中co2的复合动力系统
KR101511100B1 (ko) 2015-01-27 2015-04-10 (주)지케이홀딩스 연료전지시스템에서 발생한 고온배출가스를 이용한 발전시스템 및 발전방법
BR112018002616B1 (pt) 2015-08-10 2022-09-20 Nissan Motor Co., Ltd. Sistema de células a combustível de óxido sólido
JP6483598B2 (ja) * 2015-12-21 2019-03-13 本田技研工業株式会社 燃料電池システム
DK178834B1 (en) * 2016-03-15 2017-03-06 Mogens Skou Nielsen A system and method to generate power using dry ice
US10770741B2 (en) * 2016-08-31 2020-09-08 Toshiba Energy Systems & Solutions Corporation Fuel cell module with hydrodesulfurizer and preheating
US10854899B2 (en) * 2016-11-04 2020-12-01 Cummins Enterprise Llc Power generation system using cascaded fuel cells and associated methods thereof
JP7108848B2 (ja) * 2016-11-28 2022-07-29 パナソニックＩｐマネジメント株式会社 燃料電池システム
CN108301922A (zh) * 2017-01-12 2018-07-20 华北电力大学（保定） 基于燃气轮机和熔融碳酸盐燃料电池的混合供能系统
CN108301923A (zh) * 2017-01-13 2018-07-20 华北电力大学（保定） 一种富氧燃烧与熔融碳酸盐燃料电池混合发电系统
CN107221695B (zh) * 2017-06-30 2023-05-30 北京理工大学 一种以生物质气化制氢的燃料电池系统及其发电方法
US10622656B2 (en) 2017-10-11 2020-04-14 Saudi Arabian Oil Company Method and system for capturing high-purity CO2 in a hydrocarbon facility
CN109148919B (zh) * 2018-10-11 2023-06-09 中国华能集团清洁能源技术研究院有限公司 一种利用煤气高温显热的整体煤气化燃料电池发电系统及方法
CN109346744B (zh) * 2018-11-15 2023-04-25 中国华能集团清洁能源技术研究院有限公司 一种采用超临界co2底循环的天然气燃料电池发电系统及方法
US11424469B2 (en) 2018-11-30 2022-08-23 ExxonMobil Technology and Engineering Company Elevated pressure operation of molten carbonate fuel cells with enhanced CO2 utilization
WO2020112812A1 (fr) 2018-11-30 2020-06-04 Exxonmobil Research And Engineering Company Fonctionnement de piles à combustible à carbonate fondu présentant une utilisation du co2 améliorée
WO2020112806A1 (fr) 2018-11-30 2020-06-04 Exxonmobil Research And Engineering Company Cathode en couches pour pile à combustible à carbonate fondu
CN113228361B (zh) * 2018-11-30 2023-09-22 燃料电池能有限公司 具有提高的co2利用率的熔融碳酸盐燃料电池的高压操作
WO2020112895A1 (fr) 2018-11-30 2020-06-04 Exxonmobil Research And Engineering Company Motif de catalyseur de reformage pour pile à combustible fonctionnant avec une utilisation améliorée du co2
US11211621B2 (en) 2018-11-30 2021-12-28 Exxonmobil Research And Engineering Company Regeneration of molten carbonate fuel cells for deep CO2 capture
KR102610184B1 (ko) 2018-11-30 2023-12-04 퓨얼셀 에너지, 인크 용융 탄산염 연료 전지를 위한 연료 전지 스테이징
WO2021107933A1 (fr) 2019-11-26 2021-06-03 Exxonmobil Research And Engineering Company Ensemble module de pile à combustible et systèmes utilisant ledit ensemble module de pile à combustible
CA3162231A1 (fr) 2019-11-26 2021-06-03 Exxonmobile Research And Engineering Company Fonctionnement de piles a combustible a carbonate fondu presentant un niveau de remplissage d'electrolyte eleve
US20210300788A1 (en) * 2020-03-29 2021-09-30 Chaac Holdings, Inc. Atmospheric water and power generation compression apparatus, system and method
CN111874863B (zh) * 2020-08-07 2023-05-30 华北电力大学（保定） 一种太阳能光催化制氢燃料电池发电系统
US11978931B2 (en) 2021-02-11 2024-05-07 ExxonMobil Technology and Engineering Company Flow baffle for molten carbonate fuel cell
CN113530677A (zh) * 2021-07-30 2021-10-22 中国华能集团清洁能源技术研究院有限公司 一种前置燃料电池的天然气联合循环发电系统及方法
CN113464279A (zh) * 2021-07-30 2021-10-01 中国华能集团清洁能源技术研究院有限公司 一种采用燃料电池调制合成气成分的igcc系统及工作方法
CN114094242B (zh) * 2021-12-29 2023-09-15 重庆大学 处理脱硫废水同时还原二氧化碳的流动式光电化学电池
CN115466637B (zh) * 2022-09-15 2024-03-22 西安交通大学 一种耦合生物质能及太阳能的燃料电池发电系统及方法
CN117599607A (zh) * 2023-11-14 2024-02-27 常熟荣瑞灭菌技术有限公司 一种新型高效节能eog处理系统

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63141268A (ja) * 1986-12-03 1988-06-13 Ishikawajima Harima Heavy Ind Co Ltd 天然ガス改質溶融炭酸塩型燃料電池発電装置
JPH04108A (ja) 1990-03-14 1992-01-06 Mitsubishi Heavy Ind Ltd 燃焼装置
JPH05101839A (ja) * 1991-05-13 1993-04-23 Mitsubishi Electric Corp 溶融炭酸塩型燃料電池発電装置
JPH065298A (ja) * 1992-06-19 1994-01-14 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池発電装置
JPH1126004A (ja) 1997-07-02 1999-01-29 Toshiba Corp 発電システム
JPH11176455A (ja) * 1997-12-15 1999-07-02 Yoyu Tansanengata Nenryo Denchi Hatsuden System Gijutsu Kenkyu Kumiai 燃料電池複合発電装置
JP2000228208A (ja) * 1999-02-05 2000-08-15 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池とガスタービンの複合装置
JP2000331698A (ja) * 1999-05-19 2000-11-30 Ishikawajima Harima Heavy Ind Co Ltd ガスタービン排ガスを用いた燃料電池発電装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62276764A (ja) * 1986-05-26 1987-12-01 Hitachi Ltd 燃料電池の運転法
JPS63174282A (ja) * 1987-01-12 1988-07-18 Hitachi Ltd 燃料電池発電方法
JPH0896824A (ja) * 1994-09-29 1996-04-12 Ishikawajima Harima Heavy Ind Co Ltd 溶融炭酸塩型燃料電池発電装置
JPH10302820A (ja) * 1997-04-24 1998-11-13 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池発電設備
US7285350B2 (en) * 2002-09-27 2007-10-23 Questair Technologies Inc. Enhanced solid oxide fuel cell systems
US20050221137A1 (en) * 2004-03-31 2005-10-06 Todd Bandhauer Fuel humidifier and pre-heater for use in a fuel cell system

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63141268A (ja) * 1986-12-03 1988-06-13 Ishikawajima Harima Heavy Ind Co Ltd 天然ガス改質溶融炭酸塩型燃料電池発電装置
JPH04108A (ja) 1990-03-14 1992-01-06 Mitsubishi Heavy Ind Ltd 燃焼装置
JPH05101839A (ja) * 1991-05-13 1993-04-23 Mitsubishi Electric Corp 溶融炭酸塩型燃料電池発電装置
JPH065298A (ja) * 1992-06-19 1994-01-14 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池発電装置
JPH1126004A (ja) 1997-07-02 1999-01-29 Toshiba Corp 発電システム
JPH11176455A (ja) * 1997-12-15 1999-07-02 Yoyu Tansanengata Nenryo Denchi Hatsuden System Gijutsu Kenkyu Kumiai 燃料電池複合発電装置
JP2000228208A (ja) * 1999-02-05 2000-08-15 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池とガスタービンの複合装置
JP2000331698A (ja) * 1999-05-19 2000-11-30 Ishikawajima Harima Heavy Ind Co Ltd ガスタービン排ガスを用いた燃料電池発電装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2360764A4 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9435230B2 (en) 2011-12-27 2016-09-06 Posco Energy Co., Ltd. Fuel cell hybrid system
CN108321416A (zh) * 2018-03-29 2018-07-24 中国华能集团清洁能源技术研究院有限公司 Co2近零排放的整体煤气化燃料电池发电系统及方法
CN108321416B (zh) * 2018-03-29 2023-09-29 中国华能集团清洁能源技术研究院有限公司 Co2近零排放的整体煤气化燃料电池发电系统及方法
CN113540504A (zh) * 2021-07-16 2021-10-22 中国科学院上海应用物理研究所 热泵式-氢能复合储能发电方法及装置
CN114371745A (zh) * 2021-12-29 2022-04-19 徐州捷科思网络科技有限公司 一种温度控制系统
CN114371745B (zh) * 2021-12-29 2022-09-27 徐州捷科思网络科技有限公司 一种温度控制系统
CN114635815A (zh) * 2022-04-01 2022-06-17 招商局重工(深圳)有限公司 一种甲醇燃料供给系统及其控制方法
CN114635815B (zh) * 2022-04-01 2023-04-28 招商局重工(深圳)有限公司 一种甲醇燃料供给系统及其控制方法

Also Published As

Publication number Publication date
EP2360764A4 (fr) 2014-03-12
JPWO2010058749A1 (ja) 2012-04-19
EP2360764A1 (fr) 2011-08-24
KR20110086110A (ko) 2011-07-27
JP5331819B2 (ja) 2013-10-30
US20110223500A1 (en) 2011-09-15
JP2013191572A (ja) 2013-09-26
KR101352219B1 (ko) 2014-01-15
JP2013219034A (ja) 2013-10-24

Similar Documents

Publication Publication Date Title
JP5331819B2 (ja) Ｍｃｆｃ発電システム
Lanzini et al. Experimental investigation of direct internal reforming of biogas in solid oxide fuel cells
JP5282103B2 (ja) 水素リサイクル型ｍｃｆｃ発電システム
US9373856B2 (en) Method of recycling and tapping off hydrogen for power generation apparatus
JP7155241B2 (ja) 燃料電池システム及び燃料電池システムの運転方法
JP2009048854A (ja) 燃料電池発電装置およびその制御方法
JPWO2003038934A1 (ja) 燃料電池システム
JP4342172B2 (ja) エネルギー併給システム
JP5066020B2 (ja) 燃料電池発電システムおよびその動作方法
JPH07230819A (ja) 自己熱交換型断熱プレリフォーマを有する内部改質型固体電解質燃料電池システム
JP2004171802A (ja) 燃料電池システム
JP4578787B2 (ja) ハイブリッド型燃料電池システム
JP2009176659A (ja) 燃料電池発電システムおよびその制御方法
JP5134309B2 (ja) 燃料電池発電装置およびその制御方法
JP2001143731A (ja) 燃料電池システム
JP3872006B2 (ja) 燃料電池発電システム
JP4938299B2 (ja) 燃料電池発電装置の運転方法
JP2006100197A (ja) 固体酸化物形燃料電池を用いたコンバインド発電システム
KR101295237B1 (ko) 연료전지 시스템
JP4467929B2 (ja) 燃料電池発電システム
JP3886887B2 (ja) 燃料電池発電システム
WO2022113397A1 (fr) Système de pile à combustible
JPH08339815A (ja) 燃料電池発電装置
JP2010044960A (ja) 燃料電池発電システムおよび燃料電池発電方法
KR101324112B1 (ko) 연료전지 시스템

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09827530

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2010539222

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2009827530

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13129801

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20117011593

Country of ref document: KR

Kind code of ref document: A