WO2010058750A1 - Système de production électrique de mcfc à recyclage d'hydrogène - Google Patents

Système de production électrique de mcfc à recyclage d'hydrogène Download PDF

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WO2010058750A1
WO2010058750A1 PCT/JP2009/069430 JP2009069430W WO2010058750A1 WO 2010058750 A1 WO2010058750 A1 WO 2010058750A1 JP 2009069430 W JP2009069430 W JP 2009069430W WO 2010058750 A1 WO2010058750 A1 WO 2010058750A1
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carbon dioxide
gas
fuel gas
power generation
reaction
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PCT/JP2009/069430
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English (en)
Japanese (ja)
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上松　宏吉
亀山　寛達
昭心 渡部
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東京瓦斯株式会社
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Priority to KR1020117011594A priority Critical patent/KR101210684B1/ko
Priority to JP2010539223A priority patent/JP5282103B2/ja
Priority to EP09827531.6A priority patent/EP2360765A4/fr
Priority to US13/129,809 priority patent/US20110223501A1/en
Publication of WO2010058750A1 publication Critical patent/WO2010058750A1/fr

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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
    • H01M8/14—Fuel cells with fused electrolytes
    • H01M8/144—Fuel cells with fused electrolytes characterised by the electrolyte material
    • H01M8/145—Fuel cells with fused electrolytes characterised by the electrolyte material comprising 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • 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
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/0445—Selective methanation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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. In particular, it contributes to the effective use of energy resources and the improvement of the global environment by improving the power generation efficiency of molten carbonate fuel cells (MCFC) and improving the system to facilitate the recovery of carbon dioxide (CO 2 ). This is the main purpose of the present invention.
  • MCFC molten carbonate fuel cells
  • CO 2 carbon dioxide
  • FIG. 1 is a flowchart of a conventional internal reforming MCFC power generation system.
  • the new fuel gas F supplied from outside such as city gas is first sent to the desulfurizer 1, and after removing the sulfur content in the new fuel gas, it is sent to the fuel humidifier 2.
  • the fuel humidifier 2 is a heat exchanger that heats the new fuel gas F with the cathode exhaust of a molten carbonate fuel cell and simultaneously sprays and evaporates treated water in the fuel gas.
  • the feed water W is pretreated by the water treatment device 3 and supplied to the fuel humidifier 2 by the pump 5 via the treated water tank 4.
  • the mixed gas of high-temperature fuel gas and water vapor that exits the fuel humidifier 2 is then led to the pre-converter 6.
  • the pre-converter 6 is a container containing the reforming catalyst 7, and a part of the hydrocarbon gas in the fuel gas is reformed.
  • the pre-converter outlet gas is heat-exchanged with the cathode exhaust by the fuel gas heater 8 and then supplied to the fuel cell 9.
  • the internal reformer 10 Since the internal reformer 10 is incorporated in the internal reforming fuel cell 9, the fuel gas supplied to the fuel cell 9 is reformed by the internal reformer 10, and mainly H 2 and CO.
  • the reforming catalyst is also arranged in the anode gas passage, and the reforming reaction and the power generation reaction occur in parallel at the anode. About 70% of the total amount of H 2 and CO generated in the fuel cell 9 is used for power generation reaction, but the rest is discharged from the fuel cell 9 as anode exhaust.
  • the anode exhaust containing the combustible component is mixed with the air supplied by the air blower 11a and then guided to the catalyst oxidizer 12, where the combustible component in the anode exhaust is oxidized.
  • air is preheated, and at the same time, carbon dioxide gas contained in the anode exhaust is added to the air and led to the cathode.
  • the operating temperature of the fuel cell 9 is around 600 ° C.
  • Patent Documents 1 to 3 have already been disclosed as prior arts related to the present invention.
  • Patent Documents 1 and 2 relate to a combined power generation of a molten carbonate fuel cell and a gas turbine, and
  • Patent Document 3 relates to a method for producing synthesis gas using an oxygen permeable membrane.
  • the fuel gas mainly containing hydrogen contained in the anode exhaust is combusted for preheating the air. Therefore, there was a problem that power generation efficiency was low.
  • carbon dioxide contained in the anode exhaust is partly used for the power generation reaction at the cathode, but most of it is released into the atmosphere together with the cathode exhaust.
  • the conventional internal reforming MCFC power generation system has a problem that power generation efficiency is low and carbon dioxide gas cannot be recovered.
  • an object of the present invention is to improve the power generation efficiency by effectively using the fuel gas mainly containing hydrogen contained in the anode exhaust, and to discharge the carbon dioxide by separating and collecting the carbon dioxide.
  • the object is to provide a hydrogen recycling type MCFC power generation system capable of reducing the amount.
  • a molten carbonate fuel cell A carbon dioxide gas separation system for separating the anode exhaust of the fuel cell into recovered carbon dioxide gas, recycled carbon dioxide gas to be recycled, and other recycled fuel gas; A fuel gas heater for branching a part of a mixed fuel gas obtained by mixing a new fuel gas into the recycled fuel gas, preheating to a certain temperature, and adding reforming steam; A fuel gas heater for branching a part of the mixed fuel gas to preheat to a certain temperature and adding reforming steam; A multi-stage preconverter that simultaneously performs the reforming reaction and methanation reaction of the mixed fuel gas, A hydrogen-recycling MCFC power generation system is provided, wherein the mixed fuel gas exiting the multistage pre-converter is supplied to an anode of the fuel cell.
  • the multistage pre-converter has two or more reforming catalyst layers, After each of the reforming catalyst layers is cooled by causing the reforming reaction and the methanation reaction to occur at the same time and mixing a part of the mixed fuel gas and the reforming steam into the outlet gas of each reforming catalyst layer. To the next reforming catalyst layer, Thus, the reforming reaction and the methanation reaction are continued in the reforming catalyst layer of two or more stages without heating or cooling from the outside.
  • the multi-stage pre-converter guides the mixed fuel gas containing the reforming steam preheated by the fuel gas heater to the first reforming catalyst layer, and reforms the hydrocarbon gas contained in the externally supplied fuel gas there Then, the methanation reaction of hydrogen and carbon dioxide contained in the recycled fuel gas is caused to occur simultaneously in the temperature range of 250 to 450 ° C., and the reaction is continued without heating or cooling from the outside.
  • a waste heat recovery boiler having a low temperature shift catalyst layer and generating water vapor from the anode exhaust of the fuel cell, and the shift reaction (CO + H 2 O ⁇ CO 2 in the low temperature shift catalyst layer). + H 2 ) increases the carbon dioxide gas while recovering the heat of reaction.
  • a cathode gas supply system for supplying a cathode gas to the fuel cell
  • the cathode gas supply system includes a closed loop that has a recycle blower and circulates the cathode gas of the fuel cell, an oxygen supply device that supplies oxygen consumed by a power generation reaction to the closed loop, and the recycled carbon dioxide in the closed loop. And a carbon dioxide supply line for supplying.
  • the oxygen supply device includes an air compressor that supplies air and an air separation device that separates oxygen from the supplied air and supplies the air to the closed loop.
  • the oxygen supply device includes an air compressor that supplies air, a low-temperature regenerative heat exchanger that preheats air, and a high-temperature regenerative heat exchanger.
  • the air supplied from the air compressor is first preheated in a low temperature regenerative heat exchanger, then mixed with carbon dioxide supplied from a carbon dioxide supply facility, then heated in a high temperature regenerative heat exchanger, and then recycled. After being mixed with the recycle gas from the blower, it is supplied to the cathode inlet.
  • the carbon dioxide supply line has a recycled carbon dioxide heater that preheats the recycled carbon dioxide by anode exhaust.
  • the carbon dioxide supply line has an oxidation catalyst layer for oxidizing the combustible gas contained in the recycled carbon dioxide gas after adding air to the recycled carbon dioxide gas.
  • the carbon dioxide gas separation system for separating the anode exhaust of the fuel cell into the recovered carbon dioxide gas, the recycled carbon dioxide gas to be recycled, and the remaining recycled fuel gas is provided, the carbon dioxide gas is separated and recovered.
  • the discharge amount of carbon dioxide gas can be reduced.
  • the remaining fuel in the anode exhaust is not burned, but the new fuel gas is mixed with the recycled fuel gas and reused as a mixed fuel gas, so the fuel gas mainly composed of hydrogen contained in the anode exhaust is effectively used.
  • power generation efficiency can be improved.
  • FIG. 1 is an overall configuration diagram showing a first embodiment of a fuel cell power generation system according to the present invention. It is a whole block diagram which shows 2nd Embodiment of the fuel cell power generation system by this invention.
  • FIG. 3 is a flow diagram around the multistage pre-converter 14 of FIG. 2.
  • FIG. 2 is an overall configuration diagram showing a first embodiment of a fuel cell power generation system according to the present invention.
  • the fuel cell power generation system of the present invention uses an internal reforming type molten carbonate fuel cell 9.
  • the internal reforming type molten carbonate fuel cell 9 is simply referred to as a “fuel cell”.
  • a fuel gas F supplied from the outside such as city gas (hereinafter simply referred to as “new fuel gas F”) is first desulfurized by the desulfurizer 1 and then recycled fuel gas. Mix with RF.
  • the recycle fuel gas RF is a remaining gas obtained by cooling the anode exhaust AE and separating a part of carbon dioxide by the carbon dioxide separation system 20.
  • the mixed fuel gas MF is divided into four equal parts, and the 1/4 mixed fuel gas MF is led to the fuel gas heater 13 and heated by the anode exhaust AE.
  • Water vapor STM is supplied.
  • dividing the mixed fuel gas MF into four equal parts is merely an example, and the gist of the present invention is to divide as appropriate, but it is divided into four equal parts for easy understanding of the explanation.
  • the reforming steam STM is also supplied in an amount commensurate with the amount of the mixed fuel gas MF. This steam is generated in the exhaust heat recovery boiler 17 through the treated water tank 4 and the pump 5 from treated water obtained by pretreating the feed water W with the water treatment device 3.
  • the fuel gas heater 13 1/4 of the mixed fuel gas MF and 1/4 of the reforming steam STM are heated by the anode exhaust AE and guided to the first stage catalyst layer R 1 of the multistage pre-converter 14.
  • the first-stage catalyst layer R1 heavy components of ethane or higher in the new fuel gas F are reformed, and at the same time, H2 and part of the carbon dioxide in the recycled fuel gas RF cause a methanation reaction.
  • the reforming reaction is an endothermic reaction, and the methanation reaction is exothermic. However, as a whole, the exotherm is large, and the temperature of the gas exiting the first stage catalyst layer R1 is considerably higher than the inlet.
  • the outlet gas is supplied with 1 ⁇ 4 of the mixed fuel gas MF having a low temperature and the reforming steam STM corresponding thereto, and the temperature is lowered to lead to the next second-stage catalyst layer R2.
  • the fuel gas exiting the multistage pre-converter 14 is heated by the anode exhaust AE by the fuel gas heater 15, heated to a temperature slightly lower than the operating temperature of the fuel cell 9, and supplied to the fuel cell 9.
  • a thin flat reformer 10 is provided every 6 to 8 cells, and fuel gas is supplied to the reformer 10. Since the heat source for the reforming reaction in the reformer 10 is heat generated by the power generation reaction of the fuel cell 9, the temperature is as low as around 600 ° C., and thus the reforming rate is also low.
  • the fuel gas in which about half of the methane is reformed is supplied to the anode A.
  • a reforming catalyst is also arranged in the gas passage of the anode A, and the reforming reaction and power generation reaction shown below proceed simultaneously in parallel in the anode A.
  • the ratio of the amount of hydrogen when all the fuel gas supplied to the fuel cell is converted to hydrogen and the amount of hydrogen used for the power generation reaction is called the “fuel utilization rate”. Since the fuel utilization rate of the internal reforming type molten carbonate fuel cell 9 (fuel cell) is about 70%, the remaining 30% leaves the fuel cell 9 while being contained in the anode exhaust AE.
  • the anode exhaust AE is substantially the same as the operating temperature of the fuel cell 9, first, a heat source of the fuel gas heater 15 that heats the fuel gas exiting the multistage pre-converter 14 to a temperature slightly lower than the operating temperature of the fuel cell 9. Become. On the other hand, a part of the carbon dioxide separated by the carbon dioxide separation system 20 is recovered and the rest is recycled to the cathode. This carbon dioxide to be recycled is particularly called “recycled carbon dioxide RC”.
  • the anode exhaust AE exiting the fuel gas heater 15 is then led to the recycle carbon dioxide heater 16 to heat the recycle carbon dioxide RC to a certain temperature.
  • the anode exhaust AE is led to the fuel gas heater 13 to heat the 1/4 mixed fuel gas MF and the 1/4 reforming steam STM to a certain temperature.
  • the anode exhaust AE is guided to the exhaust heat recovery boiler 17 to generate steam.
  • a part of the exhaust heat recovery boiler 17 is provided with a low temperature shift catalyst layer, which reacts carbon monoxide (CO) in the anode exhaust with water vapor to convert it into carbon dioxide (CO 2 ) and hydrogen (H 2 ). To do. Since this reaction is an exothermic reaction, the exhaust heat recovery boiler 17 can effectively recover this reaction heat, and at the same time, carbon dioxide is converted to carbon dioxide so that the carbon dioxide separation system 20 can recover carbon dioxide more effectively. It has been converted.
  • CO carbon monoxide
  • the anode exhaust AE exiting the exhaust heat recovery boiler 17 is led to a cooler 18 to be cooled, and a part of moisture is separated and recovered by a knockout drum 19.
  • the anode exhaust AE that has exited the knockout drum 19 is guided to the carbon dioxide separation system 20, where a part of the carbon dioxide is separated and recovered.
  • the carbon dioxide separation method For the carbon dioxide separation system 20, an adsorption method using a molecular sieve, an absorption method using an absorbent, a liquefaction separation method, and the like are known, but the carbon dioxide separation method is not specified here. A part of the carbon dioxide separated by the carbon dioxide separation system 20 is recovered, and the rest is recycled to the cathode as recycled carbon dioxide RC. Further, the remaining gas from which the carbon dioxide gas is separated is mixed with the new fuel gas F as the recycled fuel RF as described above, and is effectively used as the fuel of the fuel cell 9.
  • a line that supplies carbon dioxide from the carbon dioxide separation system 20 to the cathode of the fuel cell 9 through the catalytic oxidizer 22 and the recycled carbon dioxide heater 16 is referred to as a “carbon dioxide supply line”.
  • the fuel cell power generation system of the present invention further includes a cathode gas supply system that supplies a cathode gas to the fuel cell 9.
  • the cathode gas supply system includes a closed loop that has a recycle blower 26 and circulates the cathode gas of the fuel cell 9, an oxygen supply device that supplies oxygen consumed by the power generation reaction to the closed loop, and a power generation reaction to the closed loop.
  • a carbon dioxide supply facility for supplying carbon dioxide consumed by the gas generator.
  • oxygen consumed by the power generation reaction (CO 2 + 1 / 2O 2 + 2e ⁇ ⁇ CO 3 2 ⁇ ) was generated by an oxygen supply device (that is, the air compressor 27 and the air separation device 28). Replenished with oxygen O 2 .
  • the carbon dioxide consumed by the power generation reaction is separated by the carbon dioxide separation system 20 and replenished by the recycled carbon dioxide RC recycled to the cathode.
  • the cathode gas has a higher outlet temperature than the inlet due to the power generation reaction, it can be returned to the inlet temperature by replenishing and mixing nearly normal temperature oxygen and recycled carbon dioxide RC preheated to a constant temperature. It can be.
  • the cathode is closed loop, and only the anode exhaust AE takes away energy from the fuel cell, and the energy of the anode exhaust AE is recovered as much as possible by various heat exchangers.
  • hydrogen H2 and carbon dioxide CO 2 which is a main component of recycle fuel gas RF by methanation reaction, effectively using the heat of reaction. Since the methanation reaction is an exothermic reaction, it can be used as a heat source.
  • the calorific value is also the same.
  • the fuel cell is cooled by the reforming reaction, the sensible heat of the gas flowing through the anode and the cathode, and heat loss. These sums must be balanced with the fuel cell heat generation. Of these, the heat loss depends on the fuel cell itself and does not change depending on the system.
  • the cathode of the present invention is a closed loop, if the flow rate, composition, and fuel cell inlet / outlet temperature are the same as those of the conventional system, the cooling effect is the same.
  • the temperature of the cathode gas increases from the inlet toward the outlet, and consumes carbon dioxide and oxygen in the power generation reaction.
  • oxygen O 2 that has been consumed is supplied from the air separation device 28, and carbon dioxide is replenished with recycled carbon dioxide RC.
  • oxygen is at room temperature and recycled carbon dioxide RC is preheated to about 400 ° C. and mixed and replenished to return the cathode outlet temperature to the cathode inlet temperature. Therefore, the cooling effect of the cathode is the same as that of the conventional system. For the rest, if the reforming cooling and the sensible heat of the anode gas are the same, the cooling effect of the fuel cell is also the same.
  • the cooling effect of the fuel cell is the same if the flow rate of methane supplied to the fuel cell is the same.
  • about 30% is recycled fuel gas RF, the main components of which are H 2 and carbon dioxide, and only 70% of new fuel gas F is supplied from outside such as city gas containing methane.
  • the cooling effect cannot be obtained. Therefore, methanation of the recycled fuel gas RF is required. Since methanation is exothermic, if this heat can be used, the thermal balance of the system and the thermal balance of the fuel cell can both be achieved.
  • the invention of the multistage preconverter 14 that achieves this is the point of the present invention. Details will be described below.
  • Multistage pre-converter 14 a. Power Generation Reaction and Fuel Gas
  • the fuel cell 9 undergoes the following power generation reaction, and the overall reaction is hydrogen combustion.
  • the new fuel gas F such as city gas contains ethane as the main component and contains ethane, propane, butane and the like.
  • the main components of the recycled fuel gas RF are hydrogen (H 2 ) and carbon dioxide (CO 2 ), and depending on the carbon dioxide separation system 20, water vapor (H 2 O) is contained.
  • the operating temperature of the pre-converter 6 is preferably around 300 ° C., in the case of the new fuel gas F, methane is hardly reformed on the chemical equilibrium, and heavy components of ethane or higher are reformed almost 100%. Since the pre-converter 6 does not have a heating source, the fuel gas needs to be preheated to about 400 ° C. and supplied to the pre-converter 6 in order to cause reforming only by the sensible heat of the gas. Need a lot.
  • the recycled fuel gas RF is exothermic due to the methanation reaction, but in order to start the reaction, it needs to be preheated to about 250 ° C., so a heat source is required.
  • the system of the present invention shown in FIG. 2 requires preheating of the recycled carbon dioxide RC, so that heating each fuel gas alone requires more heat sources, The anode exhaust alone is not sufficient, and the system cannot be established.
  • Multistage pre-converter 14 of the present invention In order to solve the above-mentioned problems, a new fuel gas F supplied from the outside and a recycled fuel gas RF are mixed in advance, and a reforming steam corresponding to the mixture is added to lead to the multistage preconverter 14.
  • This provides an advantage that the endothermic heat of the reforming reaction and a part of the exothermic heat of the methanation reaction can be offset.
  • in order to preheat these gases to the reaction start temperature of about 250 ° C. many heat sources are still required, and the final reaction temperature becomes too high, and the methane concentration does not increase. .
  • cooling from the outside is necessary, and the preconverter becomes expensive and the operation becomes difficult.
  • the ratio of the amount of hydrogen when all the fuel gas supplied to the fuel cell is converted to hydrogen and the amount of hydrogen used for the power generation reaction is called the “fuel utilization rate”.
  • this is about 70%. That is, 30% of the hydrogen is recycled, which means that the fuel gas is 70%, and the mixed fuel gas MF supplied to the multistage pre-converter 14 is considered to be in a state where about 30% is reformed. it can. Since this is an excessively reformed state, the reaction in the multistage preconverter 14 proceeds in the direction of methanation. That is, as a whole, the temperature rises due to heat generation.
  • the degree of temperature rise is mitigated.
  • the temperature is lowered by supplying 1/4 of each of the mixed fuel gas MF at approximately normal temperature and the reforming steam STM at saturation temperature to the gas whose temperature has gone out of the first-stage catalyst layer R1, and the second stage Lead to the catalyst layer R2.
  • the power generation efficiency is remarkably increased and carbon dioxide gas is hardly released into the atmosphere, so that it can greatly contribute to the effective use of resources and the improvement of the global environment.
  • a heat exchanger for oxygen-containing gas and fuel gas a fuel gas heater 8 and a fuel humidifier 2.
  • a heat exchanger is included. It has not been improved, and it has also been improved in terms of safety.
  • the cathode gas has a very simple configuration with only a closed loop circulating in the cathode recycling blower 26.
  • the cathode gas also has the effect of cooling the fuel cell, so the outlet temperature is higher than the inlet temperature, but the outlet gas is supplemented with and mixed with oxygen at about room temperature and carbon dioxide preheated to about 400 ° C. , Can be returned to the inlet temperature.
  • This temperature control is possible by controlling the preheating temperature of the carbon dioxide gas.
  • oxygen and carbon dioxide contain impure gas a certain amount of purge is required, but the amount of purge is very small compared to the amount of replenishment. It doesn't matter.
  • combustible gas may be included in the recycled carbon dioxide RC, but in this case, it is about twice as much as oxygen necessary for oxidation of the combustible gas.
  • Combustible gas can be treated by adding the corresponding air and passing through the oxidation catalyst layer.
  • the amount of nitrogen mixed at this time is very small and hardly affects the composition of the cathode gas.
  • water can be recovered at the final stage of cooling the anode exhaust AE, so that it is not necessary to replenish water for reforming steam from outside except at the time of startup. There are fewer restrictions.
  • FIG. 3 is an overall configuration diagram showing a second embodiment of the fuel cell power generation system according to the present invention. This embodiment is a system that supplies oxygen to the cathode by air.
  • the fuel pretreatment system is exactly the same as in FIG.
  • the difference from the first embodiment is that the amount of carbon dioxide recovered from the carbon dioxide separated by the carbon dioxide separation system 20 is about half that of the case of FIG.
  • the carbon dioxide gas separated by the carbon dioxide separation system 20 is the sum of the carbon dioxide gas moved from the cathode to the anode by the power generation reaction and the carbon produced in the fuel gas, but is produced from the new fuel gas F supplied from the outside. If all the carbon dioxide is recovered, the carbon dioxide at the cathode outlet becomes zero and the power generation reaction does not proceed, so only about half of the carbon dioxide generated from the fuel gas can be recovered.
  • this system does not require the air separation device 28 of FIG. 2, there is a merit that the in-site power is reduced by the difference between the power of the air blower and the power of the air blower, and the power generation efficiency is improved.
  • the amount released is about 1/3 of the system of FIG.
  • Air AIR is supplied by an air blower 23. This air is heated by the cathode exhaust in the low temperature regeneration heat exchanger 24 and then mixed with the preheated recycled carbon dioxide RC. The air mixed with the recycle carbon dioxide RC is heated again by the cathode exhaust in the high temperature regenerative heat exchanger 25, and then mixed with the cathode recycle gas and supplied to the cathode inlet. At the cathode, carbon dioxide gas and oxygen are consumed by the power generation reaction to become cathode exhaust.
  • this cathode gas system does not change the fuel cell cooling effect of the cathode gas.
  • this cathode gas system does not include a heat exchanger with fuel gas, and is a highly safe system.
  • FIG. 4 is a flow diagram around the multistage preconverter 14 of FIG. Table 1 shows an example of the heat balance and material balance in FIG.
  • Table 1 shows that the mixed gas MF and the reforming steam STM are divided into four equal parts, and the reaction of the first stage R1 is started by the fuel gas heater 13 in the example of the multistage preconverter 14 having four stages of catalyst layers R1 to R4. It is the calculation result which made temperature 250 degreeC.
  • the numbers surrounded by ⁇ ⁇ ⁇ ⁇ ⁇ are the stream numbers in this flowchart, and Table 1 shows the state and composition of each gas at the main positions.
  • the outlet temperature of the first stage catalyst R1 is 416 ° C. under these conditions, but the outlet temperatures of the 2nd to 4th stage catalyst layers are all 400 ° C. or less, and there is no significant temperature increase due to the methanation reaction. It can also be seen that the outlet temperature of the final catalyst layer R4 is 350 ° C. and the methane concentration is sufficiently high. Further, under this condition, the value converted into the reforming rate of methane is about 5%, and there is no problem with the cooling effect of the fuel cell. It can be seen that the fluctuation range of the operating temperature is 250 to 416 ° C., and a very stable operation is possible.
  • the above-described fuel cell power generation system of the present invention has high power generation efficiency, is suitable as a distributed power source that can significantly reduce carbon dioxide emission into the atmosphere, and is considered to be widely used as a new power generation facility from the viewpoint of effective use of resources and improvement of the global environment. .
  • improvement of power generation efficiency and reduction of atmospheric emissions of carbon dioxide have been studied, but in reality there are many distributed power sources, and it is difficult to reduce carbon dioxide for these. It did not progress.
  • the present invention has made it possible to reduce the carbon dioxide gas of the distributed power source.

Abstract

La présente invention concerne un système de production électrique de pile à combustible à carbonate fondu (MCFC) à recyclage d'hydrogène, capable d'améliorer l'efficacité de la production électrique grâce à l'utilisation efficace d'un gaz combustible dont l'hydrogène est inclus dans un échappement d'anode en tant que composant principal, et capable de réduire la quantité de dioxyde de carbone évacué grâce à la séparation et la récupération du dioxyde de carbone. Ledit système est pourvu des éléments suivants : une pile à combustible à carbonate fondu (9) ; un système de séparation du dioxyde de carbone (20) qui sépare et récupère une partie du dioxyde de carbone provenant de l'échappement de l'anode (AE) depuis la pile à combustible ; un mélangeur de gaz qui mélange le gaz combustible recyclé (RF) après qu'une partie du dioxyde de carbone a été séparée de l'échappement d'anode avec un nouveau gaz combustible (F) qui est fourni depuis l'extérieur pour réaliser un gaz combustible mélangé (MF) ; un appareil de réchauffement du gaz combustible (13) qui dévie une partie du gaz combustible mélangé, le préchauffe à une température constante et ajoute une vapeur de reformage (STM) ; et un pré-convertisseur multi-étage (14) qui réalise simultanément une réaction de reformage et une réaction de méthanation du gaz combustible mélangé. Le gaz combustible mélangé sortant du pré-convertisseur multi-étage est fourni à l'anode (A) de la pile à combustible.
PCT/JP2009/069430 2008-11-18 2009-11-16 Système de production électrique de mcfc à recyclage d'hydrogène WO2010058750A1 (fr)

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JP2010539223A JP5282103B2 (ja) 2008-11-18 2009-11-16 水素リサイクル型ｍｃｆｃ発電システム
EP09827531.6A EP2360765A4 (fr) 2008-11-18 2009-11-16 Système de production électrique de mcfc à recyclage d'hydrogène
US13/129,809 US20110223501A1 (en) 2008-11-18 2009-11-16 Hydrogen-recycling mcfc power-generating system

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JP2016514226A (ja) * 2013-02-21 2016-05-19 エクソンモービル アップストリーム リサーチ カンパニー ガスタービン排気ガスの処理のための酸素貯蔵成分を含む触媒
JP2017133701A (ja) * 2016-01-25 2017-08-03 株式会社Ihi 燃焼ガス供給システム
JP2018536979A (ja) * 2015-10-08 2018-12-13 １３０４３４２ アルバータ リミテッド 燃料電池を使用する加圧及び加熱された流体の生成
CN113958933A (zh) * 2021-09-26 2022-01-21 西安交通大学 一种集多能存储与碳氢燃料制备的复合能量系统及方法
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JP2023541660A (ja) 2020-09-16 2023-10-03 フュエルセル エナジー， インコーポレイテッド 炭酸塩燃料電池からの二酸化炭素生成
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KR101309558B1 (ko) 2010-08-10 2013-09-24 한국전력공사 화력발전 시스템과 용융 탄산염 연료전지발전 시스템을 연계한 복합발전 시스템
JP2016514226A (ja) * 2013-02-21 2016-05-19 エクソンモービル アップストリーム リサーチ カンパニー ガスタービン排気ガスの処理のための酸素貯蔵成分を含む触媒
JP2016512917A (ja) * 2013-03-15 2016-05-09 エクソンモービル リサーチ アンド エンジニアリング カンパニーＥｘｘｏｎ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｏｍｐａｎｙ 燃料電池を使用する集積化された発電および炭素捕捉
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JP2018536979A (ja) * 2015-10-08 2018-12-13 １３０４３４２ アルバータ リミテッド 燃料電池を使用する加圧及び加熱された流体の生成
JP2017133701A (ja) * 2016-01-25 2017-08-03 株式会社Ihi 燃焼ガス供給システム
WO2017130758A1 (fr) * 2016-01-25 2017-08-03 株式会社Ihi Système de distribution de gaz de combustion
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CN113958933A (zh) * 2021-09-26 2022-01-21 西安交通大学 一种集多能存储与碳氢燃料制备的复合能量系统及方法
CN113958933B (zh) * 2021-09-26 2022-06-07 西安交通大学 一种集多能存储与碳氢燃料制备的复合能量系统及方法

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