WO2022193548A1 - Molten carbonate fuel cell system combining co2 trapping, and operation method thereof - Google Patents

Molten carbonate fuel cell system combining co2 trapping, and operation method thereof Download PDF

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WO2022193548A1
WO2022193548A1 PCT/CN2021/114232 CN2021114232W WO2022193548A1 WO 2022193548 A1 WO2022193548 A1 WO 2022193548A1 CN 2021114232 W CN2021114232 W CN 2021114232W WO 2022193548 A1 WO2022193548 A1 WO 2022193548A1
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unit
heat exchange
fuel cell
outlet
gas
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PCT/CN2021/114232
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Chinese (zh)
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李�昊
程健
张瑞云
卢成壮
许世森
李卫东
王保民
杨冠军
黄华
白发琪
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华能国际电力股份有限公司
中国华能集团清洁能源技术研究院有限公司
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Publication of WO2022193548A1 publication Critical patent/WO2022193548A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • 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
    • H01M8/04—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
    • 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
    • H01M8/04029—Heat exchange using liquids
    • 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
    • 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
    • H01M8/04—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
    • H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
    • H01M8/04164—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by condensers, gas-liquid separators or filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0432—Temperature; Ambient temperature
    • H01M8/04365—Temperature; Ambient temperature of other components of a fuel cell or fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0438—Pressure; Ambient pressure; Flow
    • H01M8/04388—Pressure; Ambient pressure; Flow of anode reactants at the inlet or inside the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0438—Pressure; Ambient pressure; Flow
    • H01M8/04395—Pressure; Ambient pressure; Flow of cathode reactants at the inlet or inside the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0438—Pressure; Ambient pressure; Flow
    • H01M8/04402—Pressure; Ambient pressure; Flow of anode exhausts
    • H—ELECTRICITY
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    • 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
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow 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
    • H01M8/04746—Pressure; Flow
    • H01M8/04761—Pressure; Flow of fuel cell exhausts
    • 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
    • H01M8/14—Fuel cells with fused electrolytes
    • H01M2008/147—Fuel cells with molten carbonates
    • 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 application belongs to the technical field of fuel cells, and in particular relates to a molten carbonate fuel cell system combined with CO 2 capture and a working method thereof.
  • Molten carbonate fuel cell power generation is a clean and efficient power generation method that can achieve near-zero CO2 emissions, can reduce the energy loss caused by the Carnot cycle, and directly convert the chemical energy in the fuel into electrical energy.
  • Molten carbonate fuel cells do not use noble metals such as platinum as catalysts. Therefore, it is not necessary to use 99.99% pure hydrogen as fuel, which has the characteristics of wide fuel sources.
  • the methanol reforming method can be used to produce hydrogen, and then the hydrogen in the reformed gas can be purified to obtain hydrogen-rich gas, which can be used as the fuel cell anode fuel.
  • the methanol reformed gas mainly contains hydrogen and carbon dioxide, but most of the hydrogen separation and purification methods currently in use on the market have problems such as low purification efficiency.
  • the purpose of the present application is to provide a molten carbonate fuel cell system combined with CO2 capture and its working method, which improves the CO2 separation efficiency in methanol reformate gas and the molten carbonate fuel cell fuel Utilization rate, reducing the cost of power generation by molten carbonate fuel cells.
  • the present application discloses a molten carbonate fuel cell system combined with CO2 capture, including a methanol reforming hydrogen production unit, a first heat exchange unit, a gas-liquid separation unit, a mixing device, a CO2 capture unit, a second a heat exchange unit, a third heat exchange unit and a fuel cell unit;
  • the inlet of the methanol reforming hydrogen production unit is connected with a methanol feed pipe
  • the outlet of the methanol reforming hydrogen production unit is connected with the inlet of the mixing device
  • the outlet of the mixing device is connected with the hot side inlet of the first heat exchange unit
  • the first heat exchange The hot side outlet of the unit is connected to the gas-liquid separation unit
  • the liquid-phase outlet of the gas-liquid separation unit is connected with a condensed water discharge pipe
  • the gas-liquid separation unit is connected to the CO2 capture unit
  • the CO2 capture unit is connected to the CO2 capture unit.
  • the outlet is connected to the cold side inlet of the third heat exchange unit, the cold side outlet of the third heat exchange unit is connected to the air intake pipe and then connected to the cathode fuel inlet of the fuel cell unit, and the cathode tail gas outlet of the fuel cell unit is connected to the
  • the hot side inlet of the third heat exchange unit is connected, and the hot side outlet of the third heat exchange unit is connected with a cathode exhaust gas discharge pipe;
  • the H2 outlet of the CO2 capture unit is connected with the cold side inlet of the second heat exchange unit, and the second
  • the cold side outlet of the heat exchange unit is connected with the anode fuel inlet of the fuel cell unit, and the anode tail gas outlet of the fuel cell unit is connected with two branches, one branch is connected with the anode tail gas discharge pipe, and the other branch is connected with the second branch.
  • the hot side inlet of the heat exchange unit is connected, and the hot side outlet of the second heat exchange unit is connected with the inlet of the mixing device.
  • a compression unit is provided on the connecting pipeline between the hot side outlet of the second heat exchange unit and the inlet of the mixing device.
  • the first heat exchange unit is a gas-liquid type heat exchanger
  • the second heat exchange unit and the third heat exchange unit are gas-gas type heat exchangers.
  • the two branches connected to the anode tail gas outlet of the fuel cell unit are provided with flow detection and control devices
  • the fuel cell unit is provided with a pressure sensor
  • the flow detection and control device and the pressure sensor are respectively connected to the control unit of the system .
  • the fuel cell unit is provided with a temperature detection device and an auxiliary heating device, and both the temperature detection device and the auxiliary heating device are respectively connected to the control unit of the system.
  • the condensed water outlet of the gas-liquid separation unit is connected to the cold side inlet of the first heat exchange unit, and a temperature detection device is provided on the connecting pipeline between the outlet of the mixing device and the hot side inlet of the first heat exchange unit.
  • the connection pipeline between the condensate water outlet of the liquid separation unit and the cold side inlet of the first heat exchange unit is provided with a flow detection and control device, and the temperature detection device and the flow detection and control device are respectively connected to the control unit of the system.
  • flow detection and control devices are provided on the air intake pipe, the CO2 outlet connection pipeline of the CO2 capture unit and the H2 outlet connection pipeline of the CO2 capture unit, and all flow detection and control devices are respectively connected with The control unit of the system is connected.
  • the wall surface in the mixing device is a smooth curved surface, and the mixing device is provided with a turbulent component.
  • the working method of the above-mentioned molten carbonate fuel cell system combined with CO capture disclosed in the present application includes:
  • the methanol reforming hydrogen production unit undergoes a methanol reforming reaction, and the generated mixed gas enters the first heat exchange unit through the mixing device for heat exchange and condensation, and then enters the gas-liquid separation unit to remove water vapor to obtain a low-temperature mixed gas containing hydrogen and carbon dioxide,
  • the low-temperature mixed gas is separated and purified in the CO 2 capture unit; the carbon dioxide is heated by the third heat exchange unit and mixed with the air in the air intake pipe, and enters the cathode fuel inlet of the fuel cell unit; the hydrogen is passed through the second heat exchange unit.
  • the heat unit heats up and enters the anode fuel feed port of the fuel cell unit, and part of the anode tail gas enters the second heat exchange unit for heat exchange and cooling, and then enters the mixing device to be mixed with the mixed gas from the methanol reforming hydrogen production unit.
  • the process of the CO2 capture unit is chemical absorption, chemical adsorption, physical adsorption or membrane separation.
  • the fuel processing unit of the battery system purifies the hydrogen in the methanol reformed gas to a purity of 99.99%, while the gas on the other side still contains A large amount of hydrogen, which cannot be used as cathode fuel (only emptying, catalytic combustion, etc.)
  • the present application discloses a molten carbonate fuel cell system combined with CO capture, the anode fuel required by the fuel cell unit is hydrogen, and the cathode fuel is carbon dioxide and air, which can make full use of the hydrogen produced by the methanol reforming hydrogen production process And carbon dioxide as fuel, methanol reforming hydrogen production process is low in cost; combined with the subsequent CO capture technology, the separation efficiency of methanol reformed gas can be improved, and a higher purity fuel can be provided for molten carbonate fuel cells at the same time.
  • the waste heat of the exhaust gas is comprehensively utilized, the comprehensive thermoelectric efficiency of the fuel cell power generation system is improved, and the energy consumption of the system is reduced.
  • the anode tail gas with similar composition is mixed with methanol reformed gas, and the separation and purification of hydrogen and carbon dioxide are carried out again to improve the utilization rate of fuel.
  • a compression unit is provided on the connecting pipeline between the hot side outlet of the second heat exchange unit and the inlet of the mixing device to control the speed and flow of the circulating exhaust gas.
  • the first heat exchange unit adopts a gas-liquid type heat exchanger
  • the second heat exchange unit and the third heat exchange unit adopt gas-gas type heat exchangers, which have higher heat exchange efficiency and improve the utilization rate of waste heat.
  • the efficiency and stability of the system can be improved.
  • the temperature detection device can monitor the temperature in the fuel cell unit in real time, and achieve or maintain the working temperature of the fuel cell through the auxiliary heating device if necessary, so as to improve the efficiency and stability of the system.
  • the condensed water of the gas-liquid separation unit is used to cool the mixed gas, which improves the energy utilization rate and reduces the energy consumption of the system.
  • the flow detection and control device on the air intake pipe, the CO2 outlet connection pipeline of the CO2 capture unit and the H2 outlet connection pipeline of the CO2 capture unit, real-time adjustment can be made according to the working conditions of the system.
  • the flow of the feed ensures the maximum efficiency and safety and stability of the system.
  • the wall surface in the mixing device adopts a smooth curved surface to ensure the uniform flow of the internal gas without dead angle, and the turbulent component can improve the mixing degree of the gas at the same time.
  • the working method of the above-mentioned molten carbonate fuel cell system combined with CO 2 capture disclosed in the present application has reasonable process flow setting, fully utilizes the reaction products and remaining heat in the system, and has low cost, low energy consumption and comprehensive thermoelectric efficiency of the system. high and has good application prospects.
  • FIG. 1 is a schematic diagram of the overall structure of the system of the application.
  • 1- methanol reforming hydrogen production unit 2- first heat exchange unit; 3- gas-liquid separation unit; 4- mixing device; 5- CO 2 capture unit; 6- second heat exchange unit; 7- Compression unit; 8-third heat exchange unit; 9-fuel cell unit.
  • the molten carbonate fuel cell system combined with CO 2 capture of the present application includes a methanol reforming hydrogen production unit 1, a first heat exchange unit 2, a gas-liquid separation unit 3, a mixing device 4, a CO 2 Capture unit 5 , second heat exchange unit 6 , third heat exchange unit 8 and fuel cell unit 9 .
  • the inlet of the methanol reforming hydrogen production unit 1 is connected with a methanol feed pipe, the outlet of the methanol reforming hydrogen production unit 1 is connected with the inlet of the mixing device 4, and the outlet of the mixing device 4 is connected with the hot side inlet of the first heat exchange unit 2 , the hot-side outlet of the first heat exchange unit 2 is connected to the gas-liquid separation unit 3, the liquid-phase outlet of the gas-liquid separation unit 3 is connected to a condensed water discharge pipe, and the gas-phase outlet of the gas-liquid separation unit 3 is connected to the CO2 capture unit 5
  • the CO2 outlet of the CO2 capture unit 5 is connected to the cold side inlet of the third heat exchange unit 8, and the cold side outlet of the third heat exchange unit 8 is connected to the air intake pipe and then connected to the fuel cell unit 9.
  • Cathode fuel inlet, the cathode tail gas outlet of the fuel cell unit 9 is connected to the hot side inlet of the third heat exchange unit 8, and the hot side outlet of the third heat exchange unit 8 is connected with a cathode tail gas discharge pipe; CO2 capture unit 5
  • the H2 outlet of the second heat exchange unit 6 is connected to the cold side inlet of the second heat exchange unit 6, the cold side outlet of the second heat exchange unit 6 is connected to the anode fuel inlet of the fuel cell unit 9, and the anode tail gas outlet of the fuel cell unit 9 is connected with a Two branches, one branch is connected to the anode tail gas discharge pipe, the other branch is connected to the hot side inlet of the second heat exchange unit 6 , and the hot side outlet of the second heat exchange unit 6 is connected to the inlet of the mixing device 4 .
  • a compression unit 7 is provided on the connecting pipeline between the hot side outlet of the second heat exchange unit 6 and the inlet of the mixing device 4 .
  • the first heat exchange unit 2 is a gas-liquid type heat exchanger
  • the second heat exchange unit 6 and the third heat exchange unit 8 are gas-gas type heat exchangers.
  • the two branches connected to the anode tail gas outlet of the fuel cell unit 9 are provided with flow detection and control devices, and the fuel cell unit 9 is provided with a pressure sensor and a flow detection and control device and the pressure sensor are respectively connected with the control unit of the system.
  • the fuel cell unit 9 is provided with a temperature detection device and an auxiliary heating device, and both the temperature detection device and the auxiliary heating device are respectively connected to the control unit of the system.
  • the condensed water outlet of the gas-liquid separation unit 3 is connected to the cold side inlet of the first heat exchange unit 2
  • the outlet of the mixing device 4 is connected to the hot side inlet of the first heat exchange unit 2
  • a temperature detection device is arranged on the connecting pipeline between the two, and a flow detection and control device is arranged on the connection pipeline between the condensed water outlet of the gas-liquid separation unit 3 and the cold side inlet of the first heat exchange unit 2.
  • the temperature detection device and The flow detection and control devices are respectively connected with the control unit of the system.
  • the air intake pipe, the CO2 outlet connection pipe of the CO2 capture unit 5 and the H2 outlet connection pipe of the CO2 capture unit 5 are all provided with flow detection and control All flow detection and control devices are connected to the control unit of the system respectively.
  • the wall surface in the mixing device 4 is a smooth curved surface, and the mixing device 4 is provided with a spoiler component, such as a spoiler, a spoiler column, and the like.
  • the methanol reforming reaction occurs in the hydrogen production unit 1 of methanol reforming, and the generated mixed gas enters the first heat exchange unit 2 through the mixing device 4 for heat exchange and condensation, and then enters the gas-liquid separation unit 3 to remove water vapor to obtain a mixture containing hydrogen and carbon dioxide.
  • Low-temperature mixed gas the low-temperature mixed gas is separated and purified in the CO2 capture unit 5; carbon dioxide is mixed with the air in the air intake pipe after heat exchange and temperature rise by the third heat exchange unit 8, and enters the cathode fuel feed of the fuel cell unit 9
  • the hydrogen enters the anode fuel feed port of the fuel cell unit 9 after the heat exchange and temperature rise of the second heat exchange unit 6, and a part of the anode tail gas enters the second heat exchange unit 6 after heat exchange and cooling, and then enters the mixing device 4 and comes from the methanol reforming system.
  • the mixed gas of the hydrogen unit 1 is mixed.
  • the methanol reforming hydrogen production unit 1 undergoes a methanol reforming reaction, and the generated mixed gas is condensed by heat exchange to remove excess water vapor that does not participate in the reaction in the mixed gas, and obtain a low-temperature mixed gas mainly containing hydrogen and carbon dioxide.
  • the low-temperature mixed gas is then used to separate and purify carbon dioxide through carbon dioxide capture technology.
  • the main component of the remaining gas is hydrogen, which is used as anode fuel.
  • carbon dioxide is used as the cathode.
  • the fuel is mixed with air and passed into the cathode of the molten carbonate fuel cell after completing heat exchange with the high temperature cathode exhaust gas.
  • the fuel cell unit 9 mainly includes a molten carbonate fuel cell stack, a fuel cell inlet and outlet gas control system, a fuel cell temperature system, an auxiliary heating system, and the like.
  • the molten carbonate fuel cell stack operates at 650°C, the anode uses hydrogen as fuel, and the cathode uses carbon dioxide and oxygen (from air) as raw materials, and an electrochemical reaction occurs inside the fuel cell, as shown in the following formula:
  • the fuel cell inlet and outlet control system mainly monitors and adjusts the inlet and outlet parameters of the molten carbonate fuel cell in real time.
  • the fuel cell temperature control system and auxiliary heating device mainly monitor and adjust the temperature of the molten carbonate fuel cell stack body in real time, and achieve or maintain the working temperature of the fuel cell through auxiliary heating if necessary.
  • the anode tail gas circulation and waste heat recovery and utilization system mainly includes an anode tail gas circulation unit and a waste heat recovery and utilization unit.
  • the anode tail gas circulation unit recycles part of the anode tail gas.
  • the anode tail gas mainly includes carbon dioxide and high-temperature water vapor generated by the anode reaction and hydrogen that does not participate in the reaction.
  • the anode tail gas is recycled to the methanol reforming hydrogen production unit, and then reformed with methanol.
  • the hydrogen production tail gas is mixed, and after further water vapor condensation separation, carbon dioxide absorption/analytical separation, hydrogen and carbon dioxide are purified, the utilization rate of hydrogen is fully improved, and carbon dioxide is recycled.
  • the waste heat in the exhaust gas is fully utilized by means of heat exchange.

Abstract

The present application relates to the technical field of fuel cells. Disclosed are a molten carbonate fuel cell system combining CO2 trapping, and an operation method thereof. The system mainly comprises a methanol-reforming hydrogen production unit, a first heat exchange unit, a gas-liquid separation unit, a mixing apparatus, a CO2 trapping unit, a second heat exchange unit, a third heat exchange unit, and a fuel cell unit. By using a methanol reformed gas as a fuel, and utilizing a CO2 trapping technique in combination with anode tail gas circulation, the CO2 separation efficiency and the utilization rate of the fuel can be improved, and the power generation cost of the molten carbonate fuel cell is reduced. Moreover, waste heat of the tail gas can be used to preheat an intake gas, such that the thermoelectric comprehensive efficiency of a molten carbonate fuel cell power generation system is improved, and the power generation cost of the molten carbonate fuel cell is reduced. The system has a good application prospect.

Description

一种结合CO 2捕集的熔融碳酸盐燃料电池系统及其工作方法 a combined CO 2 Captured molten carbonate fuel cell system and method of operation 技术领域technical field
本申请属于燃料电池技术领域，具体涉及一种结合CO 2捕集的熔融碳酸盐燃料电池系统及其工作方法。 The present application belongs to the technical field of fuel cells, and in particular relates to a molten carbonate fuel cell system combined with CO 2 capture and a working method thereof.
背景技术Background technique
熔融碳酸盐燃料电池发电是一种可以实现CO 2近零排放的清洁高效发电方式，可以减少由于卡诺循环造成的能量损失，直接将燃料中的化学能转化为电能。 Molten carbonate fuel cell power generation is a clean and efficient power generation method that can achieve near-zero CO2 emissions, can reduce the energy loss caused by the Carnot cycle, and directly convert the chemical energy in the fuel into electrical energy.
熔融碳酸盐燃料电池不使用铂等贵金属作为催化剂，因此，不必使用99.99％的纯氢作为燃料，具有燃料来源广的特点。比如，可以使用甲醇重整制氢的方式，然后对重整气中的氢气进行提纯来获得富氢气体，作为燃料电池阳极燃料。甲醇重整气中主要包含氢气和二氧化碳，但是目前市面上大多数正在使用的氢气分离提纯方式，都存在提纯效率偏低等问题。Molten carbonate fuel cells do not use noble metals such as platinum as catalysts. Therefore, it is not necessary to use 99.99% pure hydrogen as fuel, which has the characteristics of wide fuel sources. For example, the methanol reforming method can be used to produce hydrogen, and then the hydrogen in the reformed gas can be purified to obtain hydrogen-rich gas, which can be used as the fuel cell anode fuel. The methanol reformed gas mainly contains hydrogen and carbon dioxide, but most of the hydrogen separation and purification methods currently in use on the market have problems such as low purification efficiency.
发明内容SUMMARY OF THE INVENTION
为了解决上述问题，本申请的目的在于提供一种结合CO 2捕集的熔融碳酸盐燃料电池系统及其工作方法，提高了甲醇重整气中CO 2分离效率和熔融碳酸盐燃料电池燃料利用率，降低了熔融碳酸盐燃料电池发电成本。 In order to solve the above problems, the purpose of the present application is to provide a molten carbonate fuel cell system combined with CO2 capture and its working method, which improves the CO2 separation efficiency in methanol reformate gas and the molten carbonate fuel cell fuel Utilization rate, reducing the cost of power generation by molten carbonate fuel cells.
本申请是通过以下技术方案来实现：This application is achieved through the following technical solutions:
本申请公开了一种结合CO 2捕集的熔融碳酸盐燃料电池系统，包括甲醇重整制氢单元、第一换热单元、气液分离单元、混合装置、CO 2捕集单元、第二换热单元、第三换热单元和燃料电池单元； The present application discloses a molten carbonate fuel cell system combined with CO2 capture, including a methanol reforming hydrogen production unit, a first heat exchange unit, a gas-liquid separation unit, a mixing device, a CO2 capture unit, a second a heat exchange unit, a third heat exchange unit and a fuel cell unit;
甲醇重整制氢单元的进口连接有甲醇进料管，甲醇重整制氢单元的出口与混合装置的进口连接，混合装置的出口与第一换热单元的热侧进口连接，第一换热单元的热侧出口与气液分离单元连接，气液分离单元的液相出口连接有冷 凝水排出管，气液分离单元的气相出口与CO 2捕集单元的连接，CO 2捕集单元的CO 2出口与第三换热单元的冷侧进口连接，第三换热单元的冷侧出口与空气进气管连通后共同连接至燃料电池单元的阴极燃料进料口，燃料电池单元的阴极尾气出口与第三换热单元的热侧进口连接，第三换热单元的热侧出口连接有阴极尾气排出管；CO 2捕集单元的H 2出口与第二换热单元的冷侧进口连接，第二换热单元的冷侧出口与燃料电池单元的阳极燃料进料口连接，燃料电池单元的阳极尾气出口连接有两条支路，一条支路连接有阳极尾气排出管，另一条支路与第二换热单元的热侧进口连接，第二换热单元的热侧出口与混合装置的进口连接。 The inlet of the methanol reforming hydrogen production unit is connected with a methanol feed pipe, the outlet of the methanol reforming hydrogen production unit is connected with the inlet of the mixing device, the outlet of the mixing device is connected with the hot side inlet of the first heat exchange unit, and the first heat exchange The hot side outlet of the unit is connected to the gas-liquid separation unit, the liquid-phase outlet of the gas-liquid separation unit is connected with a condensed water discharge pipe, the gas-liquid separation unit is connected to the CO2 capture unit, and the CO2 capture unit is connected to the CO2 capture unit. 2 The outlet is connected to the cold side inlet of the third heat exchange unit, the cold side outlet of the third heat exchange unit is connected to the air intake pipe and then connected to the cathode fuel inlet of the fuel cell unit, and the cathode tail gas outlet of the fuel cell unit is connected to the The hot side inlet of the third heat exchange unit is connected, and the hot side outlet of the third heat exchange unit is connected with a cathode exhaust gas discharge pipe; the H2 outlet of the CO2 capture unit is connected with the cold side inlet of the second heat exchange unit, and the second The cold side outlet of the heat exchange unit is connected with the anode fuel inlet of the fuel cell unit, and the anode tail gas outlet of the fuel cell unit is connected with two branches, one branch is connected with the anode tail gas discharge pipe, and the other branch is connected with the second branch. The hot side inlet of the heat exchange unit is connected, and the hot side outlet of the second heat exchange unit is connected with the inlet of the mixing device.
优选地，第二换热单元的热侧出口与混合装置的进口之间的连接管路上设有压缩单元。Preferably, a compression unit is provided on the connecting pipeline between the hot side outlet of the second heat exchange unit and the inlet of the mixing device.
优选地，第一换热单元为气-液型换热器，第二换热单元和第三换热单元为气-气型换热器。Preferably, the first heat exchange unit is a gas-liquid type heat exchanger, and the second heat exchange unit and the third heat exchange unit are gas-gas type heat exchangers.
优选地，燃料电池单元的阳极尾气出口连接的两条支路上均设有流量检测及控制装置，燃料电池单元内设有压力传感器，流量检测及控制装置和压力传感器均分别与系统的控制单元连接。Preferably, the two branches connected to the anode tail gas outlet of the fuel cell unit are provided with flow detection and control devices, the fuel cell unit is provided with a pressure sensor, and the flow detection and control device and the pressure sensor are respectively connected to the control unit of the system .
优选地，燃料电池单元内设有温度检测装置和辅助加热装置，温度检测装置和辅助加热装置均分别与系统的控制单元连接。Preferably, the fuel cell unit is provided with a temperature detection device and an auxiliary heating device, and both the temperature detection device and the auxiliary heating device are respectively connected to the control unit of the system.
优选地，气液分离单元的冷凝水出口与第一换热单元的冷侧入口连接，混合装置的出口与第一换热单元的热侧进口之间的连接管路上设有温度检测装置，气液分离单元的冷凝水出口与第一换热单元的冷侧入口之间的连接管路上设有流量检测及控制装置，温度检测装置和流量检测及控制装置均分别与系统的控制单元连接。Preferably, the condensed water outlet of the gas-liquid separation unit is connected to the cold side inlet of the first heat exchange unit, and a temperature detection device is provided on the connecting pipeline between the outlet of the mixing device and the hot side inlet of the first heat exchange unit. The connection pipeline between the condensate water outlet of the liquid separation unit and the cold side inlet of the first heat exchange unit is provided with a flow detection and control device, and the temperature detection device and the flow detection and control device are respectively connected to the control unit of the system.
优选地，空气进气管、CO 2捕集单元的CO 2出口连接管路和CO 2捕集单元的H 2出口连接管路上均设有流量检测及控制装置，所有流量检测及控制装置均 分别与系统的控制单元连接。 Preferably, flow detection and control devices are provided on the air intake pipe, the CO2 outlet connection pipeline of the CO2 capture unit and the H2 outlet connection pipeline of the CO2 capture unit, and all flow detection and control devices are respectively connected with The control unit of the system is connected.
优选地，混合装置内的壁面为圆滑曲面，混合装置内设有扰流部件。Preferably, the wall surface in the mixing device is a smooth curved surface, and the mixing device is provided with a turbulent component.
本申请公开的上述结合CO 2捕集的熔融碳酸盐燃料电池系统的工作方法，包括： The working method of the above-mentioned molten carbonate fuel cell system combined with CO capture disclosed in the present application includes:
甲醇重整制氢单元发生甲醇重整反应，生成的混合气体经混合装置进入第一换热单元换热冷凝后，进入气液分离单元中除去水蒸汽，得到含有氢气和二氧化碳的低温混合气体，低温混合气体在CO 2捕集单元中完成分离提纯；二氧化碳经第三换热单元换热升温后与空气进气管内的空气混合，进入燃料电池单元的阴极燃料进料口；氢气经第二换热单元换热升温后进入燃料电池单元的阳极燃料进料口，一部分阳极尾气进入第二换热单元换热降温后进入混合装置与来自甲醇重整制氢单元的混合气体混合。 The methanol reforming hydrogen production unit undergoes a methanol reforming reaction, and the generated mixed gas enters the first heat exchange unit through the mixing device for heat exchange and condensation, and then enters the gas-liquid separation unit to remove water vapor to obtain a low-temperature mixed gas containing hydrogen and carbon dioxide, The low-temperature mixed gas is separated and purified in the CO 2 capture unit; the carbon dioxide is heated by the third heat exchange unit and mixed with the air in the air intake pipe, and enters the cathode fuel inlet of the fuel cell unit; the hydrogen is passed through the second heat exchange unit. The heat unit heats up and enters the anode fuel feed port of the fuel cell unit, and part of the anode tail gas enters the second heat exchange unit for heat exchange and cooling, and then enters the mixing device to be mixed with the mixed gas from the methanol reforming hydrogen production unit.
优选地，CO 2捕集单元的工艺为化学吸收法、化学吸附法、物理吸附法或膜分离法。 Preferably, the process of the CO2 capture unit is chemical absorption, chemical adsorption, physical adsorption or membrane separation.
与现有技术相比，本申请具有以下有益的技术效果：Compared with the prior art, the present application has the following beneficial technical effects:
由于传统的质子交换膜燃料电池燃料需要的氢气纯度为99.99％，因此，该电池系统的燃料处理单元是将甲醇重整气中的氢气提纯至99.99％的纯度，而另一侧气体中仍含有大量氢气，不能作为阴极燃料使用(只能排空、催化燃烧等)Since the traditional proton exchange membrane fuel cell fuel requires a hydrogen purity of 99.99%, the fuel processing unit of the battery system purifies the hydrogen in the methanol reformed gas to a purity of 99.99%, while the gas on the other side still contains A large amount of hydrogen, which cannot be used as cathode fuel (only emptying, catalytic combustion, etc.)
本申请公开的一种结合CO 2捕集的熔融碳酸盐燃料电池系统，燃料电池单元所需的阳极燃料为氢气，阴极燃料为二氧化碳和空气，可以充分利用甲醇重整制氢工艺产生的氢气和二氧化碳作为燃料，甲醇重整制氢工艺成本低；结合后续的CO 2捕集技术，能够提高甲醇重整气的分离效率，为熔融碳酸盐燃料电池同时提供纯度更高的燃料。综合利用了尾气的余热，提高了燃料电池发电系统综合热电效率，减少了系统能耗。采用成分组成接近的阳极尾气循环与甲醇重整气混合，重新进行氢气和二氧化碳的分离提纯，提高燃料的利用率，同时，不采用催化燃烧技术处理阳极尾气，成本较低。 The present application discloses a molten carbonate fuel cell system combined with CO capture, the anode fuel required by the fuel cell unit is hydrogen, and the cathode fuel is carbon dioxide and air, which can make full use of the hydrogen produced by the methanol reforming hydrogen production process And carbon dioxide as fuel, methanol reforming hydrogen production process is low in cost; combined with the subsequent CO capture technology, the separation efficiency of methanol reformed gas can be improved, and a higher purity fuel can be provided for molten carbonate fuel cells at the same time. The waste heat of the exhaust gas is comprehensively utilized, the comprehensive thermoelectric efficiency of the fuel cell power generation system is improved, and the energy consumption of the system is reduced. The anode tail gas with similar composition is mixed with methanol reformed gas, and the separation and purification of hydrogen and carbon dioxide are carried out again to improve the utilization rate of fuel.
进一步地，第二换热单元的热侧出口与混合装置的进口之间的连接管路上设有压缩单元，控制循环尾气的速度及流量。Further, a compression unit is provided on the connecting pipeline between the hot side outlet of the second heat exchange unit and the inlet of the mixing device to control the speed and flow of the circulating exhaust gas.
进一步地，第一换热单元采用气-液型换热器，第二换热单元和第三换热单元采用气-气型换热器，具有较高的换热效率，提高余热利用率。Further, the first heat exchange unit adopts a gas-liquid type heat exchanger, and the second heat exchange unit and the third heat exchange unit adopt gas-gas type heat exchangers, which have higher heat exchange efficiency and improve the utilization rate of waste heat.
进一步地，通过燃料电池单元内的压力数值，对阳极尾气的循环和排空的比例进行实时调节，能够提高系统的效率和稳定性。Further, by adjusting the ratio of the anode tail gas circulation and evacuation in real time through the pressure value in the fuel cell unit, the efficiency and stability of the system can be improved.
进一步地，温度检测装置能够对燃料电池单元内的温度进行实时监控，必要时通过辅助加热装置达到或维持燃料电池工作温度，提高系统的效率和稳定性。Further, the temperature detection device can monitor the temperature in the fuel cell unit in real time, and achieve or maintain the working temperature of the fuel cell through the auxiliary heating device if necessary, so as to improve the efficiency and stability of the system.
进一步地，利用气液分离单元的冷凝水对混合气进行降温，提高了能源利用率，减少了系统能耗。Further, the condensed water of the gas-liquid separation unit is used to cool the mixed gas, which improves the energy utilization rate and reduces the energy consumption of the system.
进一步地，通过在空气进气管、CO 2捕集单元的CO 2出口连接管路和CO 2捕集单元的H 2出口连接管路上设置流量检测及控制装置，能够根据系统的工况，实时调节进料的流量，保证系统的最大效率和安全稳定性。 Further, by setting the flow detection and control device on the air intake pipe, the CO2 outlet connection pipeline of the CO2 capture unit and the H2 outlet connection pipeline of the CO2 capture unit, real-time adjustment can be made according to the working conditions of the system. The flow of the feed ensures the maximum efficiency and safety and stability of the system.
进一步地，混合装置内的壁面采用圆滑曲面，保证内部气体的均匀流动无死角，同时扰流部件能够提高气体的混合程度。Further, the wall surface in the mixing device adopts a smooth curved surface to ensure the uniform flow of the internal gas without dead angle, and the turbulent component can improve the mixing degree of the gas at the same time.
本申请公开的上述结合CO 2捕集的熔融碳酸盐燃料电池系统的工作方法，工艺流程设置合理，充分利用了系统中反应产物及其余热，系统的成本低、能耗低、综合热电效率高，具有良好的应用前景。 The working method of the above-mentioned molten carbonate fuel cell system combined with CO 2 capture disclosed in the present application has reasonable process flow setting, fully utilizes the reaction products and remaining heat in the system, and has low cost, low energy consumption and comprehensive thermoelectric efficiency of the system. high and has good application prospects.
附图说明Description of drawings
图1为本申请的系统整体结构示意图。FIG. 1 is a schematic diagram of the overall structure of the system of the application.
图中：1-甲醇重整制氢单元；2-第一换热单元；3-气液分离单元；4-混合装置；5-CO 2捕集单元；6-第二换热单元；7-压缩单元；8-第三换热单元；9-燃料电池单元。 In the figure: 1- methanol reforming hydrogen production unit; 2- first heat exchange unit; 3- gas-liquid separation unit; 4- mixing device; 5- CO 2 capture unit; 6- second heat exchange unit; 7- Compression unit; 8-third heat exchange unit; 9-fuel cell unit.
具体实施方式Detailed ways
下面结合附图对本申请做进一步详细描述，其内容是对本申请的解释而不是限定：The application will be described in further detail below in conjunction with the accompanying drawings, and its content is to explain rather than limit the application:
如图1，为本申请的结合CO 2捕集的熔融碳酸盐燃料电池系统，包括甲醇重整制氢单元1、第一换热单元2、气液分离单元3、混合装置4、CO 2捕集单元5、第二换热单元6、第三换热单元8和燃料电池单元9。 As shown in Fig. 1, the molten carbonate fuel cell system combined with CO 2 capture of the present application includes a methanol reforming hydrogen production unit 1, a first heat exchange unit 2, a gas-liquid separation unit 3, a mixing device 4, a CO 2 Capture unit 5 , second heat exchange unit 6 , third heat exchange unit 8 and fuel cell unit 9 .
甲醇重整制氢单元1的进口连接有甲醇进料管，甲醇重整制氢单元1的出口与混合装置4的进口连接，混合装置4的出口与第一换热单元2的热侧进口连接，第一换热单元2的热侧出口与气液分离单元3连接，气液分离单元3的液相出口连接有冷凝水排出管，气液分离单元3的气相出口与CO 2捕集单元5的连接，CO 2捕集单元5的CO 2出口与第三换热单元8的冷侧进口连接，第三换热单元8的冷侧出口与空气进气管连通后共同连接至燃料电池单元9的阴极燃料进料口，燃料电池单元9的阴极尾气出口与第三换热单元8的热侧进口连接，第三换热单元8的热侧出口连接有阴极尾气排出管；CO 2捕集单元5的H 2出口与第二换热单元6的冷侧进口连接，第二换热单元6的冷侧出口与燃料电池单元9的阳极燃料进料口连接，燃料电池单元9的阳极尾气出口连接有两条支路，一条支路连接有阳极尾气排出管，另一条支路与第二换热单元6的热侧进口连接，第二换热单元6的热侧出口与混合装置4的进口连接。 The inlet of the methanol reforming hydrogen production unit 1 is connected with a methanol feed pipe, the outlet of the methanol reforming hydrogen production unit 1 is connected with the inlet of the mixing device 4, and the outlet of the mixing device 4 is connected with the hot side inlet of the first heat exchange unit 2 , the hot-side outlet of the first heat exchange unit 2 is connected to the gas-liquid separation unit 3, the liquid-phase outlet of the gas-liquid separation unit 3 is connected to a condensed water discharge pipe, and the gas-phase outlet of the gas-liquid separation unit 3 is connected to the CO2 capture unit 5 The CO2 outlet of the CO2 capture unit 5 is connected to the cold side inlet of the third heat exchange unit 8, and the cold side outlet of the third heat exchange unit 8 is connected to the air intake pipe and then connected to the fuel cell unit 9. Cathode fuel inlet, the cathode tail gas outlet of the fuel cell unit 9 is connected to the hot side inlet of the third heat exchange unit 8, and the hot side outlet of the third heat exchange unit 8 is connected with a cathode tail gas discharge pipe; CO2 capture unit 5 The H2 outlet of the second heat exchange unit 6 is connected to the cold side inlet of the second heat exchange unit 6, the cold side outlet of the second heat exchange unit 6 is connected to the anode fuel inlet of the fuel cell unit 9, and the anode tail gas outlet of the fuel cell unit 9 is connected with a Two branches, one branch is connected to the anode tail gas discharge pipe, the other branch is connected to the hot side inlet of the second heat exchange unit 6 , and the hot side outlet of the second heat exchange unit 6 is connected to the inlet of the mixing device 4 .
在本申请的一个较优的实施例中，第二换热单元6的热侧出口与混合装置4的进口之间的连接管路上设有压缩单元7。In a preferred embodiment of the present application, a compression unit 7 is provided on the connecting pipeline between the hot side outlet of the second heat exchange unit 6 and the inlet of the mixing device 4 .
在本申请的一个较优的实施例中，第一换热单元2为气-液型换热器，第二换热单元6和第三换热单元8为气-气型换热器。In a preferred embodiment of the present application, the first heat exchange unit 2 is a gas-liquid type heat exchanger, and the second heat exchange unit 6 and the third heat exchange unit 8 are gas-gas type heat exchangers.
在本申请的一个较优的实施例中，燃料电池单元9的阳极尾气出口连接的两条支路上均设有流量检测及控制装置，燃料电池单元9内设有压力传感器，流量检测及控制装置和压力传感器均分别与系统的控制单元连接。In a preferred embodiment of the present application, the two branches connected to the anode tail gas outlet of the fuel cell unit 9 are provided with flow detection and control devices, and the fuel cell unit 9 is provided with a pressure sensor and a flow detection and control device and the pressure sensor are respectively connected with the control unit of the system.
在本申请的一个较优的实施例中，燃料电池单元9内设有温度检测装置和 辅助加热装置，温度检测装置和辅助加热装置均分别与系统的控制单元连接。In a preferred embodiment of the present application, the fuel cell unit 9 is provided with a temperature detection device and an auxiliary heating device, and both the temperature detection device and the auxiliary heating device are respectively connected to the control unit of the system.
在本申请的一个较优的实施例中，气液分离单元3的冷凝水出口与第一换热单元2的冷侧入口连接，混合装置4的出口与第一换热单元2的热侧进口之间的连接管路上设有温度检测装置，气液分离单元3的冷凝水出口与第一换热单元2的冷侧入口之间的连接管路上设有流量检测及控制装置，温度检测装置和流量检测及控制装置均分别与系统的控制单元连接。In a preferred embodiment of the present application, the condensed water outlet of the gas-liquid separation unit 3 is connected to the cold side inlet of the first heat exchange unit 2 , and the outlet of the mixing device 4 is connected to the hot side inlet of the first heat exchange unit 2 A temperature detection device is arranged on the connecting pipeline between the two, and a flow detection and control device is arranged on the connection pipeline between the condensed water outlet of the gas-liquid separation unit 3 and the cold side inlet of the first heat exchange unit 2. The temperature detection device and The flow detection and control devices are respectively connected with the control unit of the system.
在本申请的一个较优的实施例中，空气进气管、CO 2捕集单元5的CO 2出口连接管路和CO 2捕集单元5的H 2出口连接管路上均设有流量检测及控制装置，所有流量检测及控制装置均分别与系统的控制单元连接。 In a preferred embodiment of the present application, the air intake pipe, the CO2 outlet connection pipe of the CO2 capture unit 5 and the H2 outlet connection pipe of the CO2 capture unit 5 are all provided with flow detection and control All flow detection and control devices are connected to the control unit of the system respectively.
在本申请的一个较优的实施例中，混合装置4内的壁面为圆滑曲面，混合装置4内设有扰流部件，如扰流板、扰流柱等。In a preferred embodiment of the present application, the wall surface in the mixing device 4 is a smooth curved surface, and the mixing device 4 is provided with a spoiler component, such as a spoiler, a spoiler column, and the like.
上述系统的工作方法如下：The working method of the above system is as follows:
甲醇重整制氢单元1发生甲醇重整反应，生成的混合气体经混合装置4进入第一换热单元2换热冷凝后，进入气液分离单元3中除去水蒸汽，得到含有氢气和二氧化碳的低温混合气体，低温混合气体在CO 2捕集单元5中完成分离提纯；二氧化碳经第三换热单元8换热升温后与空气进气管内的空气混合，进入燃料电池单元9的阴极燃料进料口；氢气经第二换热单元6换热升温后进入燃料电池单元9的阳极燃料进料口，一部分阳极尾气进入第二换热单元6换热降温后进入混合装置4与来自甲醇重整制氢单元1的混合气体混合。 The methanol reforming reaction occurs in the hydrogen production unit 1 of methanol reforming, and the generated mixed gas enters the first heat exchange unit 2 through the mixing device 4 for heat exchange and condensation, and then enters the gas-liquid separation unit 3 to remove water vapor to obtain a mixture containing hydrogen and carbon dioxide. Low-temperature mixed gas, the low-temperature mixed gas is separated and purified in the CO2 capture unit 5; carbon dioxide is mixed with the air in the air intake pipe after heat exchange and temperature rise by the third heat exchange unit 8, and enters the cathode fuel feed of the fuel cell unit 9 The hydrogen enters the anode fuel feed port of the fuel cell unit 9 after the heat exchange and temperature rise of the second heat exchange unit 6, and a part of the anode tail gas enters the second heat exchange unit 6 after heat exchange and cooling, and then enters the mixing device 4 and comes from the methanol reforming system. The mixed gas of the hydrogen unit 1 is mixed.
本申请的工作原理如下：This application works as follows:
甲醇重整制氢单元1发生甲醇重整反应，生成的混合气体通过换热冷凝，除去混合气体中未参与反应的过量的水蒸气，得到主要含有氢气和二氧化碳的低温混合气体。该低温混合气体再通过二氧化碳捕集技术完成二氧化碳的分离提纯，剩余气体主要成分为氢气，作为阳极燃料，经过与高温阳极尾气换热后通入熔融碳酸盐燃料电池阳极，同时，二氧化碳作为阴极燃料，与空气混合后 并与高温阴极尾气完成换热后通入熔融碳酸盐燃料电池阴极。The methanol reforming hydrogen production unit 1 undergoes a methanol reforming reaction, and the generated mixed gas is condensed by heat exchange to remove excess water vapor that does not participate in the reaction in the mixed gas, and obtain a low-temperature mixed gas mainly containing hydrogen and carbon dioxide. The low-temperature mixed gas is then used to separate and purify carbon dioxide through carbon dioxide capture technology. The main component of the remaining gas is hydrogen, which is used as anode fuel. After heat exchange with the high-temperature anode tail gas, it is passed to the anode of the molten carbonate fuel cell. At the same time, carbon dioxide is used as the cathode. The fuel is mixed with air and passed into the cathode of the molten carbonate fuel cell after completing heat exchange with the high temperature cathode exhaust gas.
燃料电池单元9主要包括熔融碳酸盐燃料电池堆、燃料电池进出气控制系统和燃料电池温度系统及辅助加热系统等。The fuel cell unit 9 mainly includes a molten carbonate fuel cell stack, a fuel cell inlet and outlet gas control system, a fuel cell temperature system, an auxiliary heating system, and the like.
熔融碳酸盐燃料电池堆工作于650℃，阳极采用氢气为燃料，阴极采用二氧化碳和氧气(来自空气)为原料，并在燃料电池内部发生电化学反应，如下式所示：The molten carbonate fuel cell stack operates at 650°C, the anode uses hydrogen as fuel, and the cathode uses carbon dioxide and oxygen (from air) as raw materials, and an electrochemical reaction occurs inside the fuel cell, as shown in the following formula:
阳极反应：H 2+CO 3 2-→H 2O+CO 2+2e - Anodic reaction: H 2 +CO 3 2- →H 2 O+CO 2 +2e -
阴极反应：1/2O 2+CO 2+2e -→CO 3 2- Cathodic reaction: 1/2O 2 +CO 2 +2e - →CO 3 2-
总反应：H 2+1/2O 2→H 2O Overall reaction: H 2 +1/2O 2 →H 2 O
燃料电池进出气控制系统主要对熔融碳酸盐燃料电池进气参数和出气参数进行实时监控和调节。The fuel cell inlet and outlet control system mainly monitors and adjusts the inlet and outlet parameters of the molten carbonate fuel cell in real time.
燃料电池温度控制系统及辅助加热装置主要对熔融碳酸盐燃料电池堆本体的温度进行实时监控和调节，必要时通过辅助加热达到或维持燃料电池工作温度。The fuel cell temperature control system and auxiliary heating device mainly monitor and adjust the temperature of the molten carbonate fuel cell stack body in real time, and achieve or maintain the working temperature of the fuel cell through auxiliary heating if necessary.
阳极尾气循环及余热回收利用系统主要包括阳极尾气循环单元和余热回收利用单元。阳极尾气循环单元将部分阳极尾气做循环处理，阳极尾气主要包括阳极反应生成的二氧化碳和高温水蒸气以及未参与反应的氢气，将该阳极尾气循环至甲醇重整制氢单元之后，与甲醇重整制氢尾气进行混合，在经过进一步水蒸气冷凝分离、二氧化碳吸收/解析分离，提纯氢气和二氧化碳，充分提高氢气的利用率并循环使用二氧化碳。同时，通过换热方式充分利用尾气中的余热。The anode tail gas circulation and waste heat recovery and utilization system mainly includes an anode tail gas circulation unit and a waste heat recovery and utilization unit. The anode tail gas circulation unit recycles part of the anode tail gas. The anode tail gas mainly includes carbon dioxide and high-temperature water vapor generated by the anode reaction and hydrogen that does not participate in the reaction. The anode tail gas is recycled to the methanol reforming hydrogen production unit, and then reformed with methanol. The hydrogen production tail gas is mixed, and after further water vapor condensation separation, carbon dioxide absorption/analytical separation, hydrogen and carbon dioxide are purified, the utilization rate of hydrogen is fully improved, and carbon dioxide is recycled. At the same time, the waste heat in the exhaust gas is fully utilized by means of heat exchange.
以上所述，仅为本申请实施方式中的部分，本申请中虽然使用了部分术语，但并不排除使用其它术语的可能性。使用这些术语仅仅是为了方便的描述和解释本申请的本质，把它们解释成任何一种附加的限制都是与本申请精神相违背的。以上所述仅以实施例来进一步说明本申请的内容，以便于更容易理解，但不代表本申请的实施方式仅限于此，任何依本申请所做的技术延伸或再创造， 均受本申请的保护。The above descriptions are only part of the embodiments of the present application. Although some terms are used in the present application, the possibility of using other terms is not excluded. These terms are only used for convenience in describing and explaining the essence of the present application, and it is contrary to the spirit of the present application to interpret them as any kind of additional limitations. The above is only to further illustrate the content of this application with examples, so as to make it easier to understand, but it does not mean that the embodiments of this application are limited to this. protection of.

Claims (10)

  1. 一种结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，包括甲醇重整制氢单元(1)、第一换热单元(2)、气液分离单元(3)、混合装置(4)、CO 2捕集单元(5)、第二换热单元(6)、第三换热单元(8)和燃料电池单元(9)； A molten carbonate fuel cell system combined with CO capture, characterized in that it comprises a methanol reforming hydrogen production unit (1), a first heat exchange unit (2), a gas-liquid separation unit (3), a mixing device (4), a CO2 capture unit (5), a second heat exchange unit (6), a third heat exchange unit (8) and a fuel cell unit (9);
    甲醇重整制氢单元(1)的进口连接有甲醇进料管，甲醇重整制氢单元(1)的出口与混合装置(4)的进口连接，混合装置(4)的出口与第一换热单元(2)的热侧进口连接，第一换热单元(2)的热侧出口与气液分离单元(3)连接，气液分离单元(3)的液相出口连接有冷凝水排出管，气液分离单元(3)的气相出口与CO 2捕集单元(5)的连接，CO 2捕集单元(5)的CO 2出口与第三换热单元(8)的冷侧进口连接，第三换热单元(8)的冷侧出口与空气进气管连通后共同连接至燃料电池单元(9)的阴极燃料进料口，燃料电池单元(9)的阴极尾气出口与第三换热单元(8)的热侧进口连接，第三换热单元(8)的热侧出口连接有阴极尾气排出管；CO 2捕集单元(5)的H 2出口与第二换热单元(6)的冷侧进口连接，第二换热单元(6)的冷侧出口与燃料电池单元(9)的阳极燃料进料口连接，燃料电池单元(9)的阳极尾气出口连接有两条支路，一条支路连接有阳极尾气排出管，另一条支路与第二换热单元(6)的热侧进口连接，第二换热单元(6)的热侧出口与混合装置(4)的进口连接。 The inlet of the methanol reforming hydrogen production unit (1) is connected with a methanol feed pipe, the outlet of the methanol reforming hydrogen production unit (1) is connected with the inlet of the mixing device (4), and the outlet of the mixing device (4) is connected with the first changer. The hot-side inlet of the heat unit (2) is connected, the hot-side outlet of the first heat exchange unit (2) is connected with the gas-liquid separation unit (3), and the liquid-phase outlet of the gas-liquid separation unit (3) is connected with a condensed water discharge pipe , the gas phase outlet of the gas-liquid separation unit (3) is connected to the CO2 capture unit (5), the CO2 outlet of the CO2 capture unit (5) is connected to the cold side inlet of the third heat exchange unit (8), The cold side outlet of the third heat exchange unit (8) is communicated with the air intake pipe and then jointly connected to the cathode fuel inlet of the fuel cell unit (9). The cathode exhaust outlet of the fuel cell unit (9) is connected to the third heat exchange unit. The hot side inlet of (8) is connected, and the hot side outlet of the third heat exchange unit (8) is connected with a cathode tail gas discharge pipe; the H2 outlet of the CO2 capture unit (5) is connected to the outlet of the second heat exchange unit (6). The cold side inlet is connected, the cold side outlet of the second heat exchange unit (6) is connected with the anode fuel inlet of the fuel cell unit (9), and the anode tail gas outlet of the fuel cell unit (9) is connected with two branches, one The branch is connected with an anode tail gas discharge pipe, the other branch is connected with the hot side inlet of the second heat exchange unit (6), and the hot side outlet of the second heat exchange unit (6) is connected with the inlet of the mixing device (4).
  2. 根据权利要求1所述的结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，第二换热单元(6)的热侧出口与混合装置(4)的进口之间的连接管路上设有压缩单元(7)。 The molten carbonate fuel cell system combined with CO capture according to claim 1, characterized in that the connecting pipe between the hot side outlet of the second heat exchange unit (6) and the inlet of the mixing device (4) A compression unit (7) is provided on the road.
  3. 根据权利要求1所述的结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，第一换热单元(2)为气-液型换热器，第二换热单元(6)和第三换热单元(8)为气-气型换热器。 The molten carbonate fuel cell system combined with CO capture according to claim 1, characterized in that the first heat exchange unit (2) is a gas-liquid type heat exchanger, and the second heat exchange unit (6) And the third heat exchange unit (8) is a gas-gas type heat exchanger.
  4. 根据权利要求1所述的结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，燃料电池单元(9)的阳极尾气出口连接的两条支路上均设有流量检测及控制装置，燃料电池单元(9)内设有压力传感器，流量检测及控制装置和压 力传感器均分别与系统的控制单元连接。 The molten carbonate fuel cell system combined with CO2 capture according to claim 1, characterized in that, the two branches connected to the anode tail gas outlet of the fuel cell unit (9) are provided with flow detection and control devices, The fuel cell unit (9) is provided with a pressure sensor, and the flow detection and control device and the pressure sensor are respectively connected with the control unit of the system.
  5. 根据权利要求1所述的结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，燃料电池单元(9)内设有温度检测装置和辅助加热装置，温度检测装置和辅助加热装置均分别与系统的控制单元连接。 The molten carbonate fuel cell system combined with CO capture according to claim 1, characterized in that a temperature detection device and an auxiliary heating device are provided in the fuel cell unit (9), and both the temperature detection device and the auxiliary heating device are provided. They are respectively connected with the control unit of the system.
  6. 根据权利要求1所述的结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，气液分离单元(3)的冷凝水出口与第一换热单元(2)的冷侧入口连接，混合装置(4)的出口与第一换热单元(2)的热侧进口之间的连接管路上设有温度检测装置，气液分离单元(3)的冷凝水出口与第一换热单元(2)的冷侧入口之间的连接管路上设有流量检测及控制装置，温度检测装置和流量检测及控制装置均分别与系统的控制单元连接。 The molten carbonate fuel cell system combined with CO capture according to claim 1, characterized in that the condensed water outlet of the gas-liquid separation unit (3) is connected to the cold side inlet of the first heat exchange unit (2) , a temperature detection device is provided on the connecting pipeline between the outlet of the mixing device (4) and the hot side inlet of the first heat exchange unit (2), and the condensed water outlet of the gas-liquid separation unit (3) is connected to the first heat exchange unit (2) The connection pipeline between the cold side inlets is provided with a flow detection and control device, and the temperature detection device and the flow detection and control device are respectively connected with the control unit of the system.
  7. 根据权利要求1所述的结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，空气进气管、CO 2捕集单元(5)的CO 2出口连接管路和CO 2捕集单元(5)的H 2出口连接管路上均设有流量检测及控制装置，所有流量检测及控制装置均分别与系统的控制单元连接。 The molten carbonate fuel cell system combined with CO 2 capture according to claim 1, characterized in that the air intake pipe, the CO 2 outlet of the CO 2 capture unit (5) are connected to the pipeline and the CO 2 capture unit (5) The H2 outlet connection pipeline is equipped with flow detection and control devices, and all flow detection and control devices are respectively connected with the control unit of the system.
  8. 根据权利要求1所述的结合CO 2捕集的熔融碳酸盐燃料电池系统，其特征在于，混合装置(4)内的壁面为圆滑曲面，混合装置(4)内设有扰流部件。 The molten carbonate fuel cell system combined with CO 2 capture according to claim 1, characterized in that the wall surface in the mixing device (4) is a smooth curved surface, and the mixing device (4) is provided with a turbulent component.
  9. 根据权利要求1～8任意一项所述的结合CO 2捕集的熔融碳酸盐燃料电池系统的工作方法，其特征在于，包括： The working method of the molten carbonate fuel cell system combined with CO capture according to any one of claims 1 to 8, characterized in that, comprising:
    甲醇重整制氢单元(1)发生甲醇重整反应，生成的混合气体经混合装置(4)进入第一换热单元(2)换热冷凝后，进入气液分离单元(3)中除去水蒸汽，得到含有氢气和二氧化碳的低温混合气体，低温混合气体在CO 2捕集单元(5)中完成分离提纯；二氧化碳经第三换热单元(8)换热升温后与空气进气管内的空气混合，进入燃料电池单元(9)的阴极燃料进料口；氢气经第二换热单元(6)换热升温后进入燃料电池单元(9)的阳极燃料进料口，一部分阳极尾气进入第二换热单元(6)换热降温后进入混合装置(4)与来自甲醇重整制氢单元(1) 的混合气体混合。 The methanol reforming hydrogen production unit (1) undergoes a methanol reforming reaction, and the generated mixed gas enters the first heat exchange unit (2) after heat exchange and condensation through the mixing device (4), and then enters the gas-liquid separation unit (3) to remove water. steam to obtain a low-temperature mixed gas containing hydrogen and carbon dioxide, and the low-temperature mixed gas is separated and purified in the CO 2 capture unit (5); Mixed and enter the cathode fuel feed port of the fuel cell unit (9); the hydrogen enters the anode fuel feed port of the fuel cell unit (9) after being heated and heated by the second heat exchange unit (6), and a part of the anode tail gas enters the second heat exchange unit (6). The heat exchange unit (6) enters the mixing device (4) after heat exchange and cooling down, and is mixed with the mixed gas from the methanol reforming hydrogen production unit (1).
  10. 根据权利要求9所述的结合CO 2捕集的熔融碳酸盐燃料电池系统的工作方法，其特征在于，CO 2捕集单元(5)的工艺为化学吸收法、化学吸附法、物理吸附法或膜分离法 The working method of a molten carbonate fuel cell system combined with CO 2 capture according to claim 9, wherein the process of the CO 2 capture unit (5) is chemical absorption method, chemical adsorption method, physical adsorption method or membrane separation
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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
CN112820915A (en) * 2021-03-15 2021-05-18 华能国际电力股份有限公司 Combined CO2Trapped molten carbonate fuel cell system and method of operating same
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106898794A (en) * 2017-04-20 2017-06-27 武汉理工大学 A kind of electricity-generating method and TRT based on methanol steam reforming system
CN109326805A (en) * 2018-09-04 2019-02-12 新地能源工程技术有限公司 A kind of solid oxide fuel cell power generating system and technique
CN109361001A (en) * 2018-09-04 2019-02-19 新地能源工程技术有限公司 A kind of integral coal gasification solid oxide fuel cell power generating system and technique
CN111480254A (en) * 2017-10-11 2020-07-31 沙特阿拉伯石油公司 For capturing high purity CO in hydrocarbon facilities2Method and system of
CN111525166A (en) * 2020-06-04 2020-08-11 中国华能集团清洁能源技术研究院有限公司 Hybrid high-temperature fuel cell power generation system and method
CN111952642A (en) * 2020-08-21 2020-11-17 清华大学 High-efficiency low-vibration noise fuel cell power generation system
CN112820915A (en) * 2021-03-15 2021-05-18 华能国际电力股份有限公司 Combined CO2Trapped molten carbonate fuel cell system and method of operating same
CN214378520U (en) * 2021-03-15 2021-10-08 华能国际电力股份有限公司 Combined CO2Trapped molten carbonate fuel cell system

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106898794A (en) * 2017-04-20 2017-06-27 武汉理工大学 A kind of electricity-generating method and TRT based on methanol steam reforming system
CN111480254A (en) * 2017-10-11 2020-07-31 沙特阿拉伯石油公司 For capturing high purity CO in hydrocarbon facilities2Method and system of
CN109326805A (en) * 2018-09-04 2019-02-12 新地能源工程技术有限公司 A kind of solid oxide fuel cell power generating system and technique
CN109361001A (en) * 2018-09-04 2019-02-19 新地能源工程技术有限公司 A kind of integral coal gasification solid oxide fuel cell power generating system and technique
CN111525166A (en) * 2020-06-04 2020-08-11 中国华能集团清洁能源技术研究院有限公司 Hybrid high-temperature fuel cell power generation system and method
CN111952642A (en) * 2020-08-21 2020-11-17 清华大学 High-efficiency low-vibration noise fuel cell power generation system
CN112820915A (en) * 2021-03-15 2021-05-18 华能国际电力股份有限公司 Combined CO2Trapped molten carbonate fuel cell system and method of operating same
CN214378520U (en) * 2021-03-15 2021-10-08 华能国际电力股份有限公司 Combined CO2Trapped molten carbonate fuel cell system

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