CN111548826A - Biomass gas boiler transformation method for MCFC circulation loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis - Google Patents
Biomass gas boiler transformation method for MCFC circulation loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
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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
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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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1643—Conversion of synthesis gas to energy
- C10J2300/1646—Conversion of synthesis gas to energy integrated with a fuel cell
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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
- H01M2008/147—Fuel cells with molten carbonates
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- 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
Abstract
A biomass gas boiler transformation method for MCFC circulation loop fuel cell-biomass gas-coal powder coupling and ammonia synthesis relates to a biomass gas boiler transformation method. The purpose is that the problem of coupling failure and unable peak regulation easily appear when clean energy supply is not enough. The invention utilizes the MCFC circulating loop fuel cell to carry out power grid-connected coupling peak regulation for the thermal power plant pulverized coal boiler, the biomass gas boiler carries out high-temperature steam coupling peak regulation for the thermal power plant pulverized coal boiler, and the double-layer coupling structure can simultaneously carry out peak regulation for the thermal power plant pulverized coal boiler and can also independently run to achieve the peak regulation purpose. The direct grid-connected power supply of the MCFC circulation loop fuel cell can solve the problems of coupling failure and incapability of peak regulation caused by untimely straw supply. The invention is suitable for the reformation of the biomass gas boiler.
Description
Technical Field
The invention relates to a method for reforming a biomass gas-fired boiler.
Background
The structure of the conventional coupling boiler is a single coupling form of clean energy and a pulverized coal boiler, but the method is often limited by insufficient supply of clean energy. For example, the problems of insufficient supply of photo-thermal and hot molten salts caused by no illumination at night, unsmooth supply of biomass gas caused by non-straw harvesting seasons, coupling failure and incapability of peak regulation caused by system faults of the single structure and the like. Meanwhile, the conventional transformation scheme cannot realize the product and energy circulation of the system, and the high-temperature tail gas is always discharged to pollute the environment, so that a large amount of heat energy and biological energy are wasted even if the tail gas is clean. In addition, the fuel cell in the traditional coupling mode is of a one-way ventilation non-circulation structure, so that the full utilization of reaction gas cannot be realized, and a great deal of waste of the reaction gas and reaction heat is caused.
Disclosure of Invention
The invention provides a biomass gas boiler transformation method for MCFC circulating loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis, aiming at solving the problems that coupling failure and peak regulation cannot easily occur when clean energy is not sufficiently supplied to the existing coupling boiler.
The invention relates to a biomass gas boiler transformation method for MCFC circulation loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis, which comprises the following steps:
straw gasification gas is generated by using straws as raw materials by using a straw gasification furnace, and the straw gasification gas contains N2、CO、CO2And H2O, inputting the straw gasified gas into a gas pipeline and passing through a burner nozzle on the biomass gas potCombustion in the boiler, wherein combustion products are sequentially conveyed through a horizontal flue, a tail flue and a mixed flue gas descending pipe of the biomass gas boiler for water removal, and a high-temperature steam-water mixture generated after water removal is conveyed to a heat supply pipeline for heat supply or conveyed to a header on a water cooling wall of a pulverized coal boiler of a power plant as boiler water supply; conveying the separated mixed gas generated after water removal to a mixed gas collecting box, wherein the volume fraction of the separated mixed gas is about 56% N2About 43% CO2And the balance of inert gas; conveying a high-temperature steam-water mixture in a main steam pipeline of the biomass gas-fired boiler to a header on a water-cooled wall of a pulverized coal boiler of a power plant;
straw is used as raw material to ferment in a straw fermentation tank, and the main component of fermentation gas generated by fermentation is CH4The fermentation gas is conveyed to a carbon monoxide shift converter to react to obtain CO and H2The reaction in the carbon monoxide shift converter is as follows: 2CH4+O2＝2CO+4H2A portion of the CO and H produced by the carbon monoxide shift converter2Delivering the CO to a pressure absorption device for pressure reduction absorption, delivering CO obtained by pressure reduction absorption to a gas pipeline of a biomass gas boiler to be used as fuel, and obtaining pure high-temperature H by pressure reduction absorption2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; another part of CO and H produced by the carbon monoxide shift converter2To the anode of the fuel cell, the anode reaction of the fuel cell is: 2H2+2CO3 2--4e-＝2H2O+2CO2And CO-2e-+2H2O＝CO3 2-+4H+The anode tail gas of the fuel cell generates a large amount of high-temperature H2O and high temperature CO2For high temperature H2O and high temperature CO2The mixed gas is subjected to water removal, the high-temperature steam-water mixture generated after water removal is conveyed to a heat supply pipeline for heat supply, or conveyed to a header on a water-cooled wall of a pulverized coal boiler of a power plant as the water supply of the boiler, and the high-temperature CO generated after water removal is used2Inputting the compressed air into a mixed gas collecting box, and simultaneously inputting the compressed air in a compressed air storage tank into the mixed gas collecting box, wherein the high-temperature CO in the mixed gas collecting box2The separated gas mixture and the compressed air are mixed and then are conveyed to a cathode of the fuel cell asA cathode reactant;
the MCFC circulating loop fuel cell is composed of a fuel cell stack, a low-temperature molten salt storage tank and a high-temperature molten salt storage tank; the fuel battery pack is composed of a plurality of molten carbonate fuel cells, wherein a high-temperature molten salt electrolyte inlet of each molten carbonate fuel cell is communicated with an outlet of the high-temperature molten salt storage tank, a high-temperature molten salt electrolyte outlet of each molten carbonate fuel cell is communicated with an inlet of the low-temperature molten salt storage tank, and an inlet of the high-temperature molten salt storage tank and an outlet of the low-temperature molten salt storage tank are communicated through molten K2CO3Loop pipe connection, melting K2CO3The middle part of the loop pipeline is communicated with a biomass gas boiler, and tail gas generated by the cathode of the fuel cell is pure high-temperature high-pressure N2Is a reaction of N2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; the electric energy generated by the fuel cell is merged into a power grid, so that grid-connected coupling is realized and the power generation of the pulverized coal boiler of the thermal power plant is assisted.
The principle and the beneficial effects of the invention are as follows:
in the invention, the MCFC circulating loop fuel cell is used for carrying out power grid-connected coupling peak regulation on a thermal power plant pulverized coal boiler, the biomass gas boiler is used for carrying out high-temperature steam coupling peak regulation on the thermal power plant pulverized coal boiler, and the double-layer coupling structure can simultaneously carry out peak regulation on the thermal power plant pulverized coal boiler and can also independently run to achieve the peak regulation purpose. The direct grid-connected power supply of the MCFC circulation loop fuel cell can solve the problems of coupling failure and incapability of peak regulation caused by untimely straw supply.
The invention can simultaneously realize the circulation loop reaction of the MCFC fuel cell, the reaction of biomass gas participating in fermentation and gasification, and the process of finally synthesizing additional product ammonia, fully improve the operating efficiency of the coupling unit, and realize energy utilization. Wherein, the high-temperature water in the fuel cell tail gas and the high-temperature water in the biomass gas boiler tail gas are recycled as heating water or boiler feed water; high-temperature CO in anode tail gas of fuel cell2The combustion products of the biomass gas boiler and the air are mixed and then used as the cathode high-temperature reaction gas of the fuel cell to form a loop, so that the waste of biological energy and heat energy is greatly reduced, and the environmental pollution is reduced. Straw is subjected to two reactions of gasification and fermentationThe mode is participated in production, gasified gas is used as the supply gas of the biomass gas-fired boiler, and fermentation gas is simultaneously used as the anode reaction gas of the fuel cell and the reaction gas of the synthetic ammonia, thereby greatly improving the utilization rate of the straw and reducing the environmental pollution. The high-temperature steam-water mixture obtained by dewatering through the condenser can be mixed with the steam-water mixture of the pulverized coal boiler to increase the working medium flow of the pulverized coal boiler.
Drawings
FIG. 1 is a process flow diagram of a portion of the method of reforming a biomass gas boiler according to example 1;
FIG. 2 is another part of the process flow diagram of the method for reforming the biomass gas boiler in example 1.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and any reasonable combination of the specific embodiments is included.
The first embodiment is as follows: the modification method of the biomass gas boiler for MCFC circulation loop fuel cell-biomass gas-coal powder coupling and ammonia synthesis comprises the following steps:
straw gasification gas is generated by using straws as raw materials by using a straw gasification furnace, and the straw gasification gas contains N2、CO、CO2And H2O, inputting straw gasified gas into a gas pipeline, burning the straw gasified gas in a biomass gas boiler through a burner nozzle, removing water after the combustion products are conveyed through a horizontal flue, a tail flue and a mixed flue gas descending pipe of the biomass gas boiler in sequence, conveying a high-temperature steam-water mixture generated after water removal to a heat supply pipeline for heat supply, or conveying the high-temperature steam-water mixture to a header on a water-cooled wall of a pulverized coal boiler of a power plant as boiler water supply; conveying the separated mixed gas generated after water removal to a mixed gas collecting box, wherein the volume fraction of the separated mixed gas is about 56% N2About 43% CO2And the balance of inert gas; conveying a high-temperature steam-water mixture in a main steam pipeline of the biomass gas-fired boiler to a header on a water-cooled wall of a pulverized coal boiler of a power plant;
straw is used as raw material to ferment in a straw fermentation tank, and the main component of fermentation gas generated by fermentation is CH4The fermentation gas is conveyed to a carbon monoxide shift converter for reaction to obtainTo CO and H2The reaction in the carbon monoxide shift converter is as follows: 2CH4+O2＝2CO+4H2A portion of the CO and H produced by the carbon monoxide shift converter2Delivering the CO to a pressure absorption device for pressure reduction absorption, delivering CO obtained by pressure reduction absorption to a gas pipeline of a biomass gas boiler to be used as fuel, and obtaining pure high-temperature H by pressure reduction absorption2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; another part of CO and H produced by the carbon monoxide shift converter2To the anode of the fuel cell, the anode reaction of the fuel cell is: 2H2+2CO3 2--4e-＝2H2O+2CO2And CO-2e-+2H2O＝CO3 2-+4H+The anode tail gas of the fuel cell generates a large amount of high-temperature H2O and high temperature CO2For high temperature H2O and high temperature CO2The mixed gas is subjected to water removal, the high-temperature steam-water mixture generated after water removal is conveyed to a heat supply pipeline for heat supply, or conveyed to a header on a water-cooled wall of a pulverized coal boiler of a power plant as the water supply of the boiler, and the high-temperature CO generated after water removal is used2Inputting the compressed air into a mixed gas collecting box, and simultaneously inputting the compressed air in a compressed air storage tank into the mixed gas collecting box, wherein the high-temperature CO in the mixed gas collecting box2The separated mixed gas and the compressed air are mixed and then are conveyed to the cathode of the fuel cell to be used as a cathode reactant;
the MCFC circulating loop fuel cell is composed of a fuel cell stack, a low-temperature molten salt storage tank and a high-temperature molten salt storage tank; the fuel battery pack is composed of a plurality of molten carbonate fuel cells, wherein a high-temperature molten salt electrolyte inlet of each molten carbonate fuel cell is communicated with an outlet of the high-temperature molten salt storage tank, a high-temperature molten salt electrolyte outlet of each molten carbonate fuel cell is communicated with an inlet of the low-temperature molten salt storage tank, and an inlet of the high-temperature molten salt storage tank and an outlet of the low-temperature molten salt storage tank are communicated through molten K2CO3Loop pipe connection, melting K2CO3The middle part of the loop pipeline is communicated with a biomass gas boiler, and tail gas generated by the cathode of the fuel cell is pure high-temperature high-pressure N2Is a reaction of N2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; will be provided withThe electricity generated by the fuel cell is merged into a power grid, so that grid-connected coupling is realized and the power generation of the pulverized coal boiler of the thermal power plant is assisted.
In the embodiment, the MCFC circulating loop fuel cell is used for carrying out power grid-connected coupling peak shaving for the thermal power plant pulverized coal boiler, the biomass gas boiler is used for carrying out high-temperature steam coupling peak shaving for the thermal power plant pulverized coal boiler, and the double-layer coupling structure can simultaneously carry out peak shaving for the thermal power plant pulverized coal boiler and can also independently run to achieve the peak shaving purpose. The direct grid-connected power supply of the MCFC circulation loop fuel cell can solve the problems of coupling failure and incapability of peak regulation caused by untimely straw supply.
The implementation mode can simultaneously realize the circulation loop reaction of the MCFC fuel cell, the reaction of the biomass gas participating in fermentation and gasification, and the process of finally synthesizing the additional product ammonia, fully improves the operating efficiency of the coupling unit, and realizes energy utilization. Wherein, the high-temperature water in the fuel cell tail gas and the high-temperature water in the biomass gas boiler tail gas are recycled as heating water or boiler feed water; high-temperature CO in anode tail gas of fuel cell2Combustion products of biomass gas boiler (N)2+CO2+H2O) and air (N)2+O2+CO2) After being mixed, the mixture is used as the cathode high-temperature reaction gas of the fuel cell to form a loop, thereby greatly reducing the waste of biological energy and heat energy and reducing the environmental pollution. The straw is produced by two modes of gasification and fermentation reaction, the gasified gas is used as the supply gas of the biomass gas-fired boiler, and the fermentation gas is simultaneously used as the anode reaction gas of the fuel cell and the reaction gas of the synthetic ammonia, so that the utilization rate of the straw is greatly improved, and the environmental pollution is reduced. The high-temperature steam-water mixture obtained by dewatering through the condenser can be mixed with the steam-water mixture of the pulverized coal boiler to increase the working medium flow of the pulverized coal boiler.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: k near the inlet of the high-temperature molten salt storage tank2CO3The loop pipeline is provided with a pipeline for conveying the melting K2CO3The molten salt pump of (1). Other steps and parameters are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment and toolEmbodiments one or two differ in that: h in the ammonia converter2And N2The reaction temperature is 500 deg.C and the pressure is 30Mpa in the process of synthesizing ammonia, and iron is used for catalytic reaction. Other steps and parameters are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the water removal is carried out in a condenser. Other steps and parameters are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the combustion product generated after the straw gasification gas is combusted is about 50 percent of N according to volume fraction2About 38% CO2About 10% of H2O and the balance of inert gas.
Other steps and parameters are the same as in one of the first to fourth embodiments.
Example 1:
straw gasification gas is generated by using straws as raw materials by using a straw gasification furnace, and the straw gasification gas contains N2、CO、CO2And H2O, inputting the straw gasified gas into a gas pipeline, burning the straw gasified gas in a biomass gas boiler through a burner nozzle, and generating a combustion product with 50 percent of N 238% of CO2And 10% of H2O, the combustion products are sequentially conveyed through a horizontal flue, a tail flue and a mixed flue gas downcomer of the biomass gas boiler to remove water, and a high-temperature steam-water mixture generated after water removal is conveyed to a heat supply pipeline to supply heat or conveyed to a header on a water cooling wall of a pulverized coal boiler of a power plant to serve as boiler feed water; conveying the separated mixed gas generated after water removal to a mixed gas collecting box, wherein the volume fraction of the separated mixed gas is about 56% N2About 43% CO2And the balance of inert gas; conveying a high-temperature steam-water mixture in a main steam pipeline of the biomass gas-fired boiler to a header on a water-cooled wall of a pulverized coal boiler of the thermal power plant;
straw is used as raw material to ferment in a straw fermentation tank, and the main component of fermentation gas generated by fermentation is CH4The fermentation gas is delivered to the carbon monoxide converterReacting in the furnace change to obtain CO and H2The reaction in the carbon monoxide shift converter is as follows: 2CH4+O2＝2CO+4H2A portion of the CO and H produced by the carbon monoxide shift converter2Delivering the CO to a pressure absorption device for pressure reduction absorption, delivering CO obtained by pressure reduction absorption to a gas pipeline of a biomass gas boiler to be used as fuel, and obtaining pure high-temperature H by pressure reduction absorption2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; another part of CO and H produced by the carbon monoxide shift converter2To the anode of the fuel cell, the anode reaction of the fuel cell is: 2H2+2CO3 2--4e-＝2H2O+2CO2And CO-2e-+2H2O＝CO3 2-+4H+The anode tail gas of the fuel cell generates a large amount of high-temperature H2O and high temperature CO2For high temperature H2O and high temperature CO2The mixed gas is subjected to water removal, the high-temperature steam-water mixture generated after water removal is conveyed to a heat supply pipeline for heat supply, or conveyed to a header on a water-cooled wall of a pulverized coal boiler of a power plant as the water supply of the boiler, and the high-temperature CO generated after water removal is used2Inputting the compressed air into a mixed gas collecting box, and simultaneously inputting the compressed air in a compressed air storage tank into the mixed gas collecting box, wherein the high-temperature CO in the mixed gas collecting box2The separated mixed gas and the compressed air are mixed and then are conveyed to the cathode of the fuel cell to be used as a cathode reactant;
the MCFC circulating loop fuel cell is composed of a fuel cell stack, a low-temperature molten salt storage tank and a high-temperature molten salt storage tank; the fuel battery pack is composed of a plurality of molten carbonate fuel cells, wherein a high-temperature molten salt electrolyte inlet of each molten carbonate fuel cell is communicated with an outlet of the high-temperature molten salt storage tank, a high-temperature molten salt electrolyte outlet of each molten carbonate fuel cell is communicated with an inlet of the low-temperature molten salt storage tank, and an inlet of the high-temperature molten salt storage tank and an outlet of the low-temperature molten salt storage tank are communicated through molten K2CO3Loop pipe connection, melting K2CO3The middle part of the loop pipeline is communicated with a biomass gas boiler, and the electrolyte in the high-temperature molten salt electrolyte tank is K2CO3Hot molten salt, anodic reaction is 2H2+2CO3 2--4e-＝2H2O+2CO2The cathode reaction is: o is2+2CO2+4e-＝2CO3 2-Although a large amount of CO is consumed in the anode reaction3 2-But at the same time the cathodic reaction continues to produce CO3 2-Can maintain the ion concentration and the conductivity of the electrolyte to ensure that the anode reaction is carried out smoothly. Melting K between low-temperature molten salt storage tank and high-temperature molten salt storage tank2CO3The loop pipeline is arranged in a horizontal flue of the biomass gas boiler and is melted K2CO3K in the return line2CO3The hot molten salt is heated and then returns to the high-temperature molten salt storage tank to participate in power generation, so that waste heat utilization is realized; the tail gas generated by the cathode of the fuel cell is pure N with high temperature and high pressure2Is a reaction of N2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; the electric energy generated by the fuel cell is merged into a power grid to realize grid-connected coupling and assist the pulverized coal boiler of the thermal power plant to generate electricity;
k near the inlet of the high-temperature molten salt storage tank2CO3The loop pipeline is provided with a pipeline for conveying the melting K2CO3The molten salt pump of (2); h in the ammonia converter2And N2In the process of synthesizing ammonia, the reaction temperature is 500 ℃, the pressure is 30Mpa, and iron is adopted to contact coal for catalysis; the water removal is carried out in a condenser;
in the embodiment, the flow of the method for reforming the biomass gas-fired boiler by coupling the MCFC circulation loop fuel cell with the biomass gas and the pulverized coal and synthesizing ammonia is formed by combining the flow charts shown in fig. 1 and fig. 2, wherein fig. 1 comprises the operation of the biomass gas-fired boiler and the operation of the MCFC circulation loop fuel cell; figure 2 contains straw fermentation operation, industrial ammonia synthesis operation, and MCFC circulation loop fuel cell operation.
In this embodiment, the MCFC circulation loop fuel cell performs grid-connected coupled peak regulation for the thermal power plant pulverized coal boiler, the biomass gas boiler performs high-temperature steam coupled peak regulation for the thermal power plant pulverized coal boiler, and the double-layer coupling structure can simultaneously perform peak regulation for the thermal power plant pulverized coal boiler and also can independently operate to achieve the peak regulation purpose. The direct grid-connected power supply of the MCFC circulation loop fuel cell can solve the problems of coupling failure and incapability of peak regulation caused by untimely straw supply.
The embodiment can simultaneously realize the circulation loop reaction of the MCFC fuel cell, the reaction of the biomass gas participating in fermentation and gasification, and the process of finally synthesizing the additional product ammonia, fully improve the operating efficiency of the coupling unit, and realize energy utilization. Wherein, the high-temperature water in the fuel cell tail gas and the high-temperature water in the biomass gas boiler tail gas are recycled as heating water or boiler feed water; high-temperature CO in anode tail gas of fuel cell2Combustion products of biomass gas boiler (N)2+CO2+H2O) and air (N)2+O2+CO2) After being mixed, the mixture is used as the cathode high-temperature reaction gas of the fuel cell to form a loop, thereby greatly reducing the waste of biological energy and heat energy and reducing the environmental pollution. The straw is produced by two modes of gasification and fermentation reaction, the gasified gas is used as the supply gas of the biomass gas-fired boiler, and the fermentation gas is simultaneously used as the anode reaction gas of the fuel cell and the reaction gas of the synthetic ammonia, so that the utilization rate of the straw is greatly improved, and the environmental pollution is reduced. The high-temperature steam-water mixture obtained by dewatering through the condenser can be mixed with the steam-water mixture of the pulverized coal boiler to increase the working medium flow of the pulverized coal boiler.
Claims (5)
1. A biomass gas boiler transformation method for MCFC circulation loop fuel cell-biomass gas-coal powder coupling and ammonia synthesis is characterized in that: the method comprises the following steps:
straw gasification gas is generated by using straws as raw materials by using a straw gasification furnace, and the straw gasification gas contains N2、CO、CO2And H2O, inputting straw gasified gas into a gas pipeline, burning the straw gasified gas in a biomass gas boiler through a burner nozzle, removing water after the combustion products are conveyed through a horizontal flue, a tail flue and a mixed flue gas descending pipe of the biomass gas boiler in sequence, conveying a high-temperature steam-water mixture generated after water removal to a heat supply pipeline for heat supply, or conveying the high-temperature steam-water mixture to a header on a water-cooled wall of a pulverized coal boiler of a power plant as boiler water supply; the separated mixed gas generated after water removal is conveyed to a mixed gas collection box, and the separated mixed gas is separated from N2、CO2And the balance of inert gas; conveying a high-temperature steam-water mixture in a main steam pipeline of the biomass gas-fired boiler to a header on a water-cooled wall of a pulverized coal boiler of a power plant;
straw is used as raw material to ferment in a straw fermentation tank, and the main component of fermentation gas generated by fermentation is CH4The fermentation gas is conveyed to a carbon monoxide shift converter to react to obtain CO and H2The reaction in the carbon monoxide shift converter is as follows: 2CH4+O2＝2CO+4H2A portion of the CO and H produced by the carbon monoxide shift converter2Delivering the CO to a pressure absorption device for pressure reduction absorption, delivering CO obtained by pressure reduction absorption to a gas pipeline of a biomass gas boiler to be used as fuel, and obtaining pure high-temperature H by pressure reduction absorption2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; another part of CO and H produced by the carbon monoxide shift converter2To the anode of the fuel cell, the anode reaction of the fuel cell is: 2H2+2CO3 2--4e-＝2H2O+2CO2And CO-2e-+2H2O＝CO3 2-+4H+The anode tail gas of the fuel cell generates a large amount of high-temperature H2O and high temperature CO2For high temperature H2O and high temperature CO2The mixed gas is subjected to water removal, the high-temperature steam-water mixture generated after water removal is conveyed to a heat supply pipeline for heat supply, or conveyed to a header on a water-cooled wall of a pulverized coal boiler of a power plant as the water supply of the boiler, and the high-temperature CO generated after water removal is used2Inputting the compressed air into a mixed gas collecting box, and simultaneously inputting the compressed air in a compressed air storage tank into the mixed gas collecting box, wherein the high-temperature CO in the mixed gas collecting box2The separated mixed gas and the compressed air are mixed and then are conveyed to the cathode of the fuel cell to be used as a cathode reactant;
the MCFC circulating loop fuel cell is composed of a fuel cell stack, a low-temperature molten salt storage tank and a high-temperature molten salt storage tank; the fuel battery pack is composed of a plurality of molten carbonate fuel cells, a high-temperature molten salt electrolyte inlet of each molten carbonate fuel cell is communicated with an outlet of the high-temperature molten salt storage tank, a high-temperature molten salt electrolyte outlet of each molten carbonate fuel cell is communicated with an inlet of the low-temperature molten salt storage tank,the inlet of the high-temperature molten salt storage tank and the outlet of the low-temperature molten salt storage tank are melted through K2CO3Loop pipe connection, melting K2CO3The middle part of the loop pipeline is communicated with a biomass gas boiler, and tail gas generated by the cathode of the fuel cell is pure high-temperature high-pressure N2Is a reaction of N2Conveying to an ammonia synthesis tower for industrial ammonia synthesis; the electric energy generated by the fuel cell is merged into a power grid, so that grid-connected coupling is realized and the power generation of the pulverized coal boiler of the thermal power plant is assisted.
2. The method for reforming the biomass gas-fired boiler for the MCFC circulation loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis according to claim 1, characterized in that:
k near the inlet of the high-temperature molten salt storage tank2CO3The loop pipeline is provided with a pipeline for conveying the melting K2CO3The molten salt pump of (1).
3. The method for reforming the biomass gas-fired boiler for the MCFC circulation loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis according to claim 1, characterized in that:
h in the ammonia converter2And N2The reaction temperature is 500 deg.C and the pressure is 30Mpa in the process of synthesizing ammonia, and iron is used for catalytic reaction.
4. The method for reforming the biomass gas-fired boiler for the MCFC circulation loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis according to claim 1, characterized in that: the water removal is carried out in a condenser.
5. The method for reforming the biomass gas-fired boiler for the MCFC circulation loop fuel cell-biomass gas-pulverized coal coupling and ammonia synthesis according to claim 1, characterized in that: the combustion product generated after the straw gasified gas is combusted is composed of N2、CO2、H2O and the balance of inert gas.
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