CN112864438B - High-temperature fuel cell coupling power generation system and method capable of realizing carbon dioxide capture - Google Patents
High-temperature fuel cell coupling power generation system and method capable of realizing carbon dioxide capture Download PDFInfo
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- CN112864438B CN112864438B CN201911193634.2A CN201911193634A CN112864438B CN 112864438 B CN112864438 B CN 112864438B CN 201911193634 A CN201911193634 A CN 201911193634A CN 112864438 B CN112864438 B CN 112864438B
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- 239000000446 fuel Substances 0.000 title claims abstract description 253
- 238000010248 power generation Methods 0.000 title claims abstract description 68
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 23
- 230000008878 coupling Effects 0.000 title description 12
- 238000010168 coupling process Methods 0.000 title description 12
- 238000005859 coupling reaction Methods 0.000 title description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 106
- 239000007787 solid Substances 0.000 claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 225
- 239000002737 fuel gas Substances 0.000 claims description 50
- 238000006477 desulfuration reaction Methods 0.000 claims description 36
- 230000023556 desulfurization Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002485 combustion reaction Methods 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 13
- 238000003487 electrochemical reaction Methods 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 239000007784 solid electrolyte Substances 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
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- 238000011161 development Methods 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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Classifications
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
- H01M8/2495—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies of fuel cells of different types
-
- 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
- H01M8/04082—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
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
-
- 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
The invention relates to the field of fuel cell power generation, and discloses a high-temperature fuel cell coupled power generation system capable of realizing carbon dioxide capture. The cathode oxide of the fuel cell using the solid oxide can be CO-containing2Such that the carbon-containing compounds entering the anode of the solid oxide fuel cell and the anode of the molten carbonate fuel cell are combusted as CO in the combustor2The form of the carbon dioxide enters the cathode of a molten carbonate fuel cell for enrichment, improves the reversible voltage of the molten carbonate fuel cell and simultaneously improves CO2Concentration of (2) of facilitating CO2And (4) trapping. The development requirements of clean, efficient, green and low-carbon fossil energy are met.
Description
Technical Field
The invention belongs to the field of fuel cell power generation, and particularly relates to a high-temperature fuel cell coupling power generation system and method capable of realizing carbon dioxide capture.
Background
The fuel cell power generation technology can convert chemical energy of fossil fuel into electric energy through electrochemical reaction, and the development requirements of clean, efficient, green and low-carbon of fossil energy are met. Current high-temperature fuel cells are classified into Solid Oxide Fuel Cells (SOFC) and Molten Carbonate Fuel Cells (MCFC) according to the kind of electrolyte. The SOFC has high working efficiency, but the system capacity is difficult to amplify, and the SOFC generally works at 700-800 ℃; the MCFC is easy to amplify the system capacity, but the working efficiency is low, and the MCFC generally works at 600-700 ℃.
CN108417876A describes a high-temperature fuel cell coupled power generation system and method, the system includes a fuel purifier, a gas mixer, a heat exchanger, a solid oxide fuel cell, a molten carbonate fuel cell, a fan, a catalytic burner and a DC/AC converter; the invention also discloses a coupling power generation method of the system; the solid oxide fuel cell and the molten carbonate fuel cell are coupled, so that the fuel utilization rate in the fuel cell and the power generation efficiency of a system can be improved to a certain extent; the heat exchanger in the system is arranged to fully utilize heat energy, the power generation efficiency and the comprehensive energy utilization efficiency of the system are improved, secondary fuel and secondary air are adopted as supplements in the system to improve the fuel adaptability of the system, and natural gas, coal gas, low-calorific-value coal bed gas, biomass gas and the like are used as fuels.
The high-temperature fuel cell coupled power generation system is a power generation system in which a solid oxide fuel cell is coupled with a molten carbonate fuel cell, and although the power generation efficiency of the whole system is improved to a certain extent, because the outlet gas of the anode of the solid oxide fuel cell is introduced into the anode of the molten carbonate fuel cell, under the condition of the same fuel gas amount, the effective gas H entering the anode of the molten carbonate fuel cell is reduced2、CO、CH4Such as the partial pressure of the gas, results in a decrease in the power generation efficiency of the molten carbonate fuel cell. The use of air as the burner oxidant will result in ingressCO of molten carbonate fuel cell cathode2The concentration is reduced, and simultaneously, the existence of a large amount of nitrogen in the air reduces CO in the combustion tail gas2In a concentration of increased CO2Difficulty of trapping.
Disclosure of Invention
The invention aims to solve the technical problem that in the prior art, in a solid oxide fuel cell and molten carbonate fuel cell coupled power generation system, when gas at the outlet of the anode of the solid oxide fuel cell is introduced into the anode of the molten carbonate fuel cell, effective gas H entering the anode of the molten carbonate fuel cell can be reduced under the condition of the same fuel air inflow amount2、CO、CH4The partial pressure of the gas, resulting in a reduction in the power generation efficiency of the molten carbonate fuel cell; and due to the presence of large amounts of N in the air2The adoption of air as the oxidant of the burner can reduce CO in the combustion tail gas2Resulting in CO entering the cathode of the molten carbonate fuel cell2Decrease in concentration and increase in CO2The present invention provides a high temperature fuel cell coupled power generation system and method capable of achieving carbon dioxide capture, which can improve the power generation efficiency of the entire system while facilitating the CO capture2And the device can be used for trapping, and can meet the requirements of clean, efficient, green and low-carbon development of fossil energy.
In order to achieve the foregoing object, an aspect of the present invention provides a high-temperature fuel cell-coupled power generation system capable of achieving carbon dioxide capture, which generates power by coupling a solid oxide fuel cell with a molten carbonate fuel cell, the power generation system including a fine desulfurization tank, a solid oxide fuel cell, a molten carbonate fuel cell, a burner, and a heat exchange unit.
And the fine desulfurization tank is respectively communicated with the solid oxide fuel cell and the molten carbonate fuel cell and provides anode fuel for the solid oxide fuel cell and the molten carbonate fuel cell.
And heat exchange units are arranged between the fine desulfurization tank and the solid oxide fuel cell and between the fine desulfurization tank and the molten carbonate fuel cell, and the cathode outlet of the solid oxide fuel cell and the cathode outlet of the molten carbonate fuel cell are respectively introduced into the heat exchange units.
The solid oxide fuel cell anode outlet and the molten carbonate fuel cell anode outlet are respectively communicated with the combustor, the combustor is communicated with the molten carbonate fuel cell cathode inlet, and a heat exchange unit is arranged between the combustor and the molten carbonate fuel cell cathode inlet.
The heat exchange unit enables heat exchange between pipelines leading to the solid oxide fuel cell and the molten carbonate fuel cell.
Preferably, the heat exchange unit comprises an SOFC anode heater, an SOFC cathode heater and an MCFC anode heater, which are all provided with hot gas channels and cold gas channels separated by heat exchange fins and used for heating the cold gas channels.
The fine desulfurization tank and the anode inlet of the solid oxide fuel cell are respectively communicated with a cold gas channel of the SOFC anode heater, the cathode outlet of the solid oxide fuel cell is communicated with a hot gas channel of the SOFC anode heater, and the hot gas channel of the SOFC anode heater is used for heating the cold gas channel of the SOFC anode heater;
the fine desulfurization tank and the anode inlet of the molten carbonate fuel cell are respectively communicated with a cold gas channel of the MCFC anode heater, the cathode outlet of the MCFC anode heater is communicated with a hot gas channel of the MCFC anode heater, and the cold gas channel of the MCFC anode heater is heated through the hot gas channel of the MCFC anode heater.
The burner and the molten carbonate fuel cell cathode inlet are in communication with the hot gas path of the SOFC cathode heater.
Preferably, the coupled power generation system is provided with a fan, and the fan and the cathode inlet of the solid oxide fuel cell are respectively communicated with the cold gas channel of the SOFC cathode heater.
Preferably, the SOFC anode heater is provided with an SOFC cathode tail gas outlet, and the SOFC cathode tail gas outlet and the solid oxide fuel cell cathode outlet are respectively connected with two ends of the SOFC anode heater hot gas channel;
the MCFC anode heater is provided with an MCFC cathode tail gas outlet, and the MCFC cathode tail gas outlet and the cathode outlet of the molten carbonate fuel cell are respectively connected with two ends of a hot gas channel of the MCFC anode heater.
Preferably, the combustor is provided with a combustion-supporting pipeline, and a steam pipeline is introduced between the fine desulfurization tank and the heat exchange unit.
Preferably, the solid oxide fuel cell comprises a solid electrolyte and a cathode and an anode which are respectively arranged at two sides of the solid electrolyte, fuel enters an anode chamber through an anode inlet of the solid oxide fuel cell, oxidant enters a cathode chamber through a cathode inlet of the solid oxide fuel cell, and electrochemical reaction is carried out to generate electric energy and heat;
the molten carbonate fuel cell comprises a molten electrolyte, and a cathode and an anode which are respectively arranged on two sides of the molten electrolyte, wherein fuel enters an anode chamber through an anode inlet of the molten carbonate fuel cell, oxidant enters a cathode chamber through a cathode inlet of the molten carbonate fuel cell, and electrochemical reaction is generated to generate electric energy and heat.
The second aspect of the present invention provides a high-temperature fuel cell coupled power generation method capable of capturing carbon dioxide, which is performed in the above coupled power generation system, the method comprising the steps of:
s1, introducing fuel gas into the fine desulfurization tank for desulfurization and purification, wherein the fuel gas after desulfurization and purification is divided into SOFC fuel gas and MCFC fuel gas;
s2, mixing the SOFC fuel gas with the water vapor in the water vapor pipeline, and allowing the mixture to enter an anode inlet of the solid oxide fuel cell;
s3, mixing the MCFC fuel gas with the water vapor in the water vapor pipeline, and allowing the mixture to enter an anode inlet of the molten carbonate fuel cell;
s4, introducing SOFC anode tail gas and MCFC anode tail gas into a combustor, mixing and combusting the SOFC anode tail gas and gas in a combustion-supporting pipeline to generate combustion tail gas, wherein the combustion tail gas enters a hot gas channel of an SOFC cathode heater to form MCFC cathode inlet gas, and the MCFC cathode inlet gas enters a cathode inlet of a molten carbonate fuel cell;
and S5, introducing air into the air fan to form air fan outlet gas (the air fan outlet gas exchanges heat with combustion tail gas introduced into the SOFC cathode heater to form SOFC cathode inlet gas and enters the solid oxide fuel cell cathode inlet.
Preferably, the gas in the combustion-supporting pipeline in the step S4 is oxygen, preferably pure oxygen.
By controlling the amount of oxygen introduced into the combustion-supporting pipeline, high-purity CO can be obtained in the MCFC cathode tail gas outlet2A gas; preferably the excess of oxygen introduced into the burner is above 5%.
Preferably, the fuel gas in the step S1 contains H as the main component2And CO gas, preferably the hydrogen-carbon ratio of the fuel gas in the step S1 is 1-3: 1.
Preferably, the main components of the SOFC fuel gas and the MCFC fuel gas after desulfurization and purification in the step S1 are CO and H2Gas and small amount of CH4、CO2A gas.
Through the technical scheme, the high-temperature fuel cell coupled power generation system capable of capturing carbon dioxide has the following advantages:
(1) passing the solid oxide fuel cell anode and the molten carbonate fuel cell anode to a combustor such that the solid oxide fuel cell anode off-gas and the molten carbonate fuel cell anode off-gas are CO after combustion in the combustor2The form of the carbon dioxide enters a cathode of a molten carbonate fuel cell for enrichment, and CO is increased2The partial pressure at the cathode of the molten carbonate fuel cell increases the reversible voltage of the molten carbonate fuel cell, thereby improving the efficiency of the whole system;
(2) increasing molten carbonate fuel cell anode with same fuel gas air inputPolar side effective gas H2、CO、CH4The partial pressure of the gas is equal, so that the power generation efficiency of the molten carbonate fuel cell is improved, and the efficiency of the whole system is further improved;
(3) further introducing pure oxygen into the combustor for combustion, and controlling the amount of oxygen to obtain high-purity CO2Facilitating CO2The method meets the requirements of clean, efficient, green and low-carbon development of fossil energy.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention.
In the drawings:
FIG. 1 is a schematic diagram of a high temperature fuel cell coupled power generation system capable of carbon dioxide capture in accordance with the present invention;
figure 2 is a schematic diagram of a CN108417876A system.
Description of the reference numerals
In the attached fig. 1:
1 fine desulfurizing tank 2 SOFC anode heater
3 solid oxide fuel cell 4 air blower
5 SOFC cathode heater 6 MCFC anode heater
7 molten carbonate fuel cell 8 burner
101 fuel gas 102 steam line
103 SOFC anode feed gas mixture 104 SOFC anode feed gas
105 SOFC Anode Tail gas 106 air
107 air blower outlet gas 108 SOFC cathode inlet gas
109 SOFC cathode outlet gas 110 SOFC cathode tail gas outlet
111 SOFC Fuel gas 201 MCFC Fuel gas
203 MCFC anode feed gas mixture 204 MCFC cathode feed gas
205 MCFC anode tail gas 206 combustion-supporting pipeline
207 Combustion exhaust 208 MCFC cathode intake
209 MCFC cathode gas outlet 210 MCFC cathode tail gas outlet
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Referring to fig. 1, the present invention provides a high temperature fuel cell coupled power generation system capable of capturing carbon dioxide, the coupled power generation system generates power by coupling the solid oxide fuel cell 3 with the molten carbonate fuel cell 7, the power generation system comprises a fine desulfurization tank 1, a solid oxide fuel cell 3, a molten carbonate fuel cell 7, a combustor 8 and a heat exchange unit, the fine desulfurization tank 1 is respectively communicated with the solid oxide fuel cell 3 and the molten carbonate fuel cell 7, provides anode fuel for the solid oxide fuel cell 3 and the molten carbonate fuel cell 7, heat exchange units are arranged between the fine desulfurization tank 1 and the solid oxide fuel cell 3 and between the fine desulfurization tank 1 and the molten carbonate fuel cell 7, and the cathode outlet of the solid oxide fuel cell 3 and the cathode outlet of the molten carbonate fuel cell 7 are respectively introduced into the heat exchange unit.
The outlet of the solid oxide fuel cell 3 and the outlet of the molten carbonate fuel cell 7 are respectively communicated with the burner 8, the burner 8 is communicated with the inlet of the molten carbonate fuel cell 7, and a heat exchange unit is arranged between the burner 8 and the inlet of the molten carbonate fuel cell 7.
The heat exchange unit can realize heat exchange between the pipelines which are led into the solid oxide fuel cell 3 and the molten carbonate fuel cell 7.
In a preferred embodiment of the invention the heat exchange unit comprises a SOFC anode heater 2, a SOFC cathode heater 5 and an MCFC anode heater 6. The SOFC anode heater 2, the SOFC cathode heater 5 and the MCFC anode heater 6 are respectively provided with a hot gas channel and a cold gas channel, and the hot gas channel and the cold gas channel are separated by a heat exchange sheet and are used for heating the cold gas channel.
Specifically, the anode inlets of the fine desulfurization tank 1 and the solid oxide fuel cell 3 are respectively communicated with the cold gas channel of the SOFC anode heater 2, the cathode outlet of the solid oxide fuel cell 3 is communicated with the hot gas channel of the SOFC anode heater 2, and the SOFC anode heater 2 cold gas channel is heated by the hot gas channel of the SOFC anode heater 2.
The anode inlets of the fine desulfurization tank 1 and the molten carbonate fuel cell 7 are respectively communicated with a cold gas channel of the MCFC anode heater 6, the cathode outlet of the MCFC anode heater 6 is communicated with a hot gas channel of the MCFC anode heater 6, and the hot gas channel of the MCFC anode heater 6 is used for heating the cold gas channel of the MCFC anode heater 6.
The outlet of the burner 8 and the cathode inlet of the molten carbonate fuel cell 7 are respectively communicated with two ends of the hot gas channel of the SOFC cathode heater 5.
In a preferred embodiment of the invention, the coupled power generation system is provided with an air fan 4, and the air fan 4 and the cathode inlet of the solid oxide fuel cell 3 are respectively communicated with two ends of a cold gas channel of the SOFC cathode heater 5.
In a preferred embodiment of the present invention, the SOFC anode heater 2 is provided with an SOFC cathode tail gas outlet 110, and the SOFC cathode tail gas outlet 110 and the solid oxide fuel cell 3 cathode outlet are respectively connected to two ends of the SOFC anode heater 2 hot gas channel;
the MCFC anode heater 6 is provided with an MCFC cathode tail gas outlet 210, and the MCFC cathode tail gas outlet 210 and the cathode outlet of the molten carbonate fuel cell 7 are respectively connected with two ends of a hot gas channel of the MCFC anode heater 6.
In an embodiment of the present invention, a combustion-supporting pipeline 206 is disposed on the combustor 8, the combustion-supporting of gas in the combustion-supporting pipeline 206 is utilized to fully oxidize and burn the material in the combustor 8, and a steam pipeline 102 is introduced between the fine desulfurization tank 1 and the heat exchange unit.
The solid oxide fuel cell 3 comprises a solid electrolyte, and a cathode and an anode which are respectively arranged on two sides of the solid electrolyte, wherein fuel enters an anode chamber through an anode inlet of the solid oxide fuel cell 3, oxidant enters a cathode chamber through a cathode inlet of the solid oxide fuel cell 3, and electrochemical reaction is generated to generate electric energy and heat.
The molten carbonate fuel cell 7 includes a molten electrolyte and a cathode and an anode respectively disposed at both sides of the molten electrolyte, and a fuel is introduced into an anode chamber through an anode inlet of the molten carbonate fuel cell 7, and an oxidant is introduced into a cathode chamber through a cathode inlet of the molten carbonate fuel cell 7, and an electrochemical reaction occurs to generate electric energy and heat.
According to the invention, in the technical scheme, the heat of the gas at the outlet of the cathode and the anode of the solid oxide fuel cell 3 and the molten carbonate fuel cell 7 is fully recovered by the SOFC anode heater 2, the SOFC cathode heater 5 and the MCFC anode heater 6 to exchange heat for the cold material flow at the inlet of the cathode and the anode of the cell, so that the heat management of the whole coupling power generation system is realized, the complete gas starting can be realized in the starting process of the coupling power generation system, the energy is saved, and the power generation efficiency of the coupling power generation system is improved.
In the invention, the fine desulfurization tank is used for desulfurizing and purifying the fuel gas, has no special requirement on other unit structures, and adopts the structure and design which are commonly used in the field.
The invention also provides a high-temperature fuel cell coupled power generation method capable of realizing carbon dioxide capture, which is carried out in the coupled power generation system and comprises the following steps:
s1, introducing fuel gas 101 into the fine desulfurization tank 1 for desulfurization and purification, wherein the desulfurized and purified fuel gas 101 is divided into an SOFC fuel gas 111 and an MCFC fuel gas 201;
s2, SOFC fuel gas 111 and the water vapor in the water vapor pipeline 102 are mixed and enter the anode inlet of the solid oxide fuel cell 3;
s3, MCFC fuel gas 201 is mixed with the water vapor in the water vapor pipeline 102 and enters the anode inlet of the molten carbonate fuel cell 7;
s4, SOFC anode tail gas 105 and MCFC anode tail gas 205 are introduced into a combustor 8 and then mixed with gas in a combustion-supporting pipeline 206 to be combusted to generate combustion tail gas 207, the combustion tail gas 207 enters a hot gas channel of an SOFC cathode heater 5 to form MCFC cathode inlet gas 208, and the MCFC cathode inlet gas 208 enters a cathode inlet of a molten carbonate fuel cell 7;
s5, introducing air 106 into the air fan 4 to form air fan outlet gas 107, allowing the air fan outlet gas 107 to enter a SOFC cathode heater 5 cold gas channel and exchange heat with combustion tail gas 207 introduced into a SOFC cathode heater 5 hot gas channel to form SOFC cathode inlet gas 108, and allowing the SOFC cathode inlet gas 108 to enter a solid oxide fuel cell 3 cathode inlet.
Specifically, the inlet of the fine desulfurization tank 1 is connected with a fuel gas 101, and the outlet gas of the fine desulfurization tank 1 is divided into two streams, one stream is an SOFC fuel gas 111 and the other stream is an MCFC fuel gas 201. The feed gas 101 of the coupling power generation system can be carbon-based fuel such as synthesis gas, natural gas and the like, and meets the development requirements of clean, efficient, green and low-carbon of fossil energy.
The SOFC fuel gas 111 and the water vapor are mixed and then introduced into a cold gas channel of the SOFC anode heater 2 and finally enter the anode inlet of the solid oxide fuel cell 3, the MCFC fuel gas 201 and the water vapor are mixed and then introduced into a cold gas channel of the MCFC anode heater 6 and finally enter the anode inlet of the molten carbonate fuel cell 7.
Specifically, the SOFC fuel gas 111 and the water vapor are mixed and then introduced into a cold gas channel inlet of the SOFC anode heater 2, a cold gas channel outlet of the SOFC anode heater 2 is introduced into an anode inlet of the solid oxide fuel cell 3, a cathode outlet of the solid oxide fuel cell 3 is connected to a hot gas channel of the SOFC anode heater 2, and the fuel introduced into the anode inlet of the solid oxide fuel cell 3 is heated by heat exchange between the hot gas channel of the SOFC anode heater 2 and the cold gas channel, so that the fuel utilization rate in the solid oxide fuel cell 3 is improved, and the power generation efficiency and the comprehensive heat utilization rate of the coupled power generation system are improved.
The MCFC fuel gas 201 and the water vapor are mixed and then are introduced into a cold gas channel inlet of the MCFC anode heater 6, a cold gas channel outlet of the MCFC anode heater 6 is introduced into an anode inlet of the molten electrolyte fuel cell 7, a cathode outlet of the molten electrolyte fuel cell 7 is connected to a hot gas channel of the MCFC anode heater 6, and the fuel introduced into the anode inlet of the molten electrolyte fuel cell 7 is heated through heat exchange between the hot gas channel of the MCFC anode heater 6 and the cold gas channel, so that the fuel utilization rate in the molten electrolyte fuel cell 7 is improved, and the power generation efficiency and the comprehensive utilization rate of heat of a coupled power generation system are improved.
The SOFC anode tail gas 105 and the MCFC anode tail gas 205 are introduced into the combustor 8 and then mixed with gas in a combustion-supporting pipeline 206 to be combusted to generate combustion tail gas 207, the combustion tail gas 207 is introduced into a hot gas channel inlet of the SOFC cathode heater 5, a hot gas channel outlet of the SOFC cathode heater 5 is introduced into a cathode inlet of the molten carbonate fuel cell 7, air fan outlet gas 107 of the air fan 4 is introduced into a cold gas channel inlet of the SOFC cathode heater 5, a cold gas channel outlet of the SOFC cathode heater 5 is introduced into a cathode inlet of the solid oxide fuel cell 3, and the oxidant introduced into the cathode inlet of the solid oxide fuel cell 3 is heated by utilizing heat exchange between the hot gas channel of the SOFC cathode heater 5 and the cold gas channel.
Under the condition of the same air input of the fuel gas 101, the effective gas CH is increased4、CO、H2Partial pressure at the anode of the molten carbonate fuel cell 7, anode of the solid oxide fuel cell 3The carbon-containing compound fuel of the electrode and the anode of the molten carbonate fuel cell 7 are all burnt with CO2The form of the carbon dioxide enters the cathode of the molten carbonate fuel cell 7 for enrichment, increases the reversible voltage of the molten carbonate fuel cell 7, improves the power generation efficiency of the molten carbonate fuel cell 7, and further improves the power generation efficiency of the whole coupling power generation system.
In order to increase the pressure of the air blower outlet 107 of the air blower 4, the air blower 4 is any one of an axial fan, a turbo fan, or a centrifugal fan.
In a preferred embodiment of the present invention, in step S4, the gaseous oxygen in the combustion-supporting pipeline 206, preferably pure oxygen, is introduced into the combustor 8, and the SOFC anode tail gas 105 and the MCFC anode tail gas 205 are combusted with pure oxygen to facilitate CO combustion2The collection of (2).
In a preferred embodiment of the present invention, in step S4, the amount of oxygen introduced into the combustion-supporting line 206 is controlled, so that CO with high purity can be obtained at the MCFC cathode off-gas outlet 2102The gas, preferably oxygen, is introduced into the burner 8 in an excess of 5% or more.
In a preferred embodiment of the present invention, the fuel gas 101 in the step S1 contains H as a main component2And CO gas, preferably the hydrogen-to-carbon ratio of the fuel gas 101 in step S1 is 1-3: 1.
In the above-described embodiment, the SOFC fuel gas 111 and the MCFC fuel gas 201 after the desulfurization and purification in step S1 preferably contain CO and H as main components2Gas, further comprising a small amount of CH4And CO2A gas.
The coupling power generation method is suitable for normal pressure and pressurization operation, and particularly, the main reactions occurring in the solid oxide fuel cell 3 are as follows:
anode:
H2+O2-→H2O+2e
CO+O2-→CO2+2e
cathode:
O2+4e→2O2-
the main reactions taking place inside the molten carbonate fuel cell 7 are:
anode:
H2+CO3 2-→H2O+CO2+2e
CO+CO3 2-→2CO2+2e
cathode:
CO2+1/2O2+2e→CO3 2-
example 1
The above-described coupled power generation system and method is used in this embodiment, in which the fuel gas 101 has a composition of H2CO, hydrogen to carbon ratio of 1.6:1, and the inlet gas ratio of solid oxide fuel cell 3 and molten carbonate fuel cell 7 was 1: 1.
Referring to fig. 1, the fuel gas 101 is introduced into the fine desulfurization tank 1, and the desulfurized and purified syngas is divided into two streams, one stream is SOFC fuel gas 111, and the other stream is MCFC fuel gas 201.
The other stream of desulfurized and purified MCFC fuel gas 201 is also mixed with the water vapor in the water vapor pipeline 102 to form an MCFC anode feed gas mixture 203, the MCFC anode feed gas mixture enters the MCFC anode heater 6, the MCFC cathode outlet gas 209 at the cathode outlet of the molten carbonate fuel cell 7 is heated to form an MCFC anode feed gas 204, the MCFC anode feed gas 204 enters the anode inlet of the molten carbonate fuel cell 7, and the MCFC anode tail gas 205 at the anode outlet of the molten carbonate fuel cell 7 enters the burner 8.
The SOFC anode tail gas 105 and the MCFC anode tail gas 205 are mixed and combusted with oxygen in the combustor 8 to generate a combustion tail gas 207, wherein the main gas of the combustion tail gas 207 is CO2Said CO is2After the gas exchanges heat with the air blower outlet gas 107 of the cold gas channel leading into the SOFC cathode heater 5,entering the cathode inlet of the molten carbonate fuel cell 7, enriching at the cathode of the molten carbonate fuel cell 7, increasing the CO2The partial pressure at the cathode of the molten carbonate fuel cell 7 increases the reversible voltage of the molten carbonate fuel cell 7, improves the power generation efficiency of the molten carbonate fuel cell 7, and further improves the power generation efficiency of the whole coupled power generation system.
The parameters of the coupled power generation system of the present embodiment are shown in table 1.
TABLE 1
| Single pass conversion of solid |
80％ |
| Molten |
80％ |
The efficiency of the coupled power generation system of the present embodiment is shown in table 2.
TABLE 2
| Electric energy production | 100kw |
| Electric efficiency | 55％ |
Comparative example 1
In fig. 2, 1 is a first fuel purifier, 2 is a second fuel purifier, 3 is a first gas mixer, 4 is a first heat exchanger, 5 is a second heat exchanger, 6 is a solid oxide fuel cell, 7 is a second gas mixer, 8 is a molten carbonate fuel cell, 9 is a third gas mixer, 10 is a second blower, 11 is a third heat exchanger, 12 is a fourth heat exchanger, 13 is a first blower, 14 is a fifth heat exchanger, 15 is a sixth heat exchanger, 16 is a catalytic combustor, 17 is a first DC/AC converter, and 18 is a second DC/AC converter.
According to the flow shown in fig. 2, the primary fuel is introduced into the inlet of the first fuel purifier 1, and the secondary fuel is introduced into the inlet of the second fuel purifier 2; deionized water is introduced into the first heat exchanger 4 and converted into water vapor; after being fully mixed in the first gas mixer 3, the water vapor at the outlet of the first heat exchanger 4 and the fuel at the outlet of the first fuel purifier 1 are heated to over 600 ℃ through the second heat exchanger 5, and then are introduced into the anode inlet of the solid oxide fuel cell 6, an internal reforming reaction is generated in the anode chamber of the solid oxide fuel cell 6, an electrochemical reaction is generated in the anode of the solid oxide fuel cell 6, and electric energy is generated; the temperature of the product of the solid oxide fuel cell 6 after the anode reaction is higher than 800 ℃; introducing the anode outlet gas of the solid oxide fuel cell 6 into a second inlet of a second gas mixer 7, and fully mixing the anode outlet gas with the fuel and the deionized water at the outlet of the second fuel purifier 2 in the second gas mixer 7, wherein the mixing temperature is reduced to 600 ℃; the gas at the outlet of the second gas mixer 7 is introduced into the inlet of the anode of the molten carbonate fuel cell 8 and enters the anode of the molten carbonate fuel cell 8 to carry out reforming reaction; electrochemical reactions occur in the anode of the molten carbonate fuel cell 8 and generate electrical energy; the molten carbonate fuel cell 8 anode outlet gas is fed into the first inlet of the third gas mixer 9;
introducing primary air into a first fan 13, wherein the air pressure at the outlet of the fan is more than 1.5atm, heating to more than 200 ℃ after passing through a fifth heat exchanger 14, heating to more than 600 ℃ after passing through a sixth heat exchanger 15, and finally introducing the primary air into the cathode inlet of the solid oxide fuel cell 6, wherein oxygen in the air generates electrochemical reaction at the cathode of the solid oxide fuel cell 6, and the tail gas temperature of the solid oxide fuel cell 6 after the reaction is 800 ℃; the temperature of the gas at the cathode outlet of the solid oxide fuel cell 6 is reduced to below 400 ℃ through the fourth heat exchanger 12, and is reduced to below 200 ℃ through the fifth heat exchanger 14, and finally, the waste gas is discharged outwards;
the secondary air is introduced into the second fan 10, the air pressure is raised to be more than 1.5atm, then the temperature is raised to be more than 150 ℃ through the third heat exchanger 11, the temperature is raised to be more than 400 ℃ through the fourth heat exchanger 12, and finally the secondary air is introduced into the second inlet of the third gas mixer 9; in the third gas mixer 9, the secondary air is fully mixed with the anode outlet gas of the molten carbonate fuel cell 8, and then is introduced into the catalytic combustor 16 to fully react in the catalytic combustor 16; the temperature of the gas at the outlet of the catalytic combustor 16 is reduced to 550 ℃ through a sixth heat exchanger 15, and then the gas is introduced into the cathode inlet of the molten carbonate fuel cell 8; electrochemical reactions take place in the cathode of the molten carbonate fuel cell 8; the temperature of the gas at the cathode outlet of the molten carbonate fuel cell 8 is reduced to below 400 ℃ through the second heat exchanger 5, the gas is subjected to heat exchange through the third heat exchanger 11 to below 200 ℃, the gas is reduced to below 100 ℃ through the first heat exchanger 4, and finally, waste gas is discharged outwards; the solid oxide fuel cell 6 outputs direct current power, and outputs alternating current power to a user through the first DC/AC converter 17; the molten carbonate fuel cell 8 outputs direct current power and alternating current power to the user through the second DC/AC converter 18, see fig. 2.
Referring to FIG. 2, comparative example 1 employs a high temperature fuel cell coupled power generation system as shown in FIG. 2, with a feed gas composition of H2CO, hydrogen to carbon ratio of about 1.6:1, and the inlet gas ratio of the solid oxide fuel cell and the molten carbonate fuel cell is 1: 1.
Comparative example 1 the power generation system setting parameters are shown in table 3.
TABLE 3
| Single pass conversion of solid oxide fuel cell | 80％ |
| Molten carbonate fuel cell single pass conversion | 80％ |
The efficiency of the power generation system of comparative example 1 is shown in table 4.
TABLE 4
| Electric energy production | 90kw |
| Electrical efficiency | 50％ |
As can be seen from the results of tables 1 to 4, example 1, which employs the high temperature fuel cell coupled power generation system and method capable of capturing carbon dioxide according to the present invention, has advantages of large power generation capacity and significantly better power generation efficiency than comparative example 1.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (7)
1. A high-temperature fuel cell coupled power generation method capable of realizing carbon dioxide capture is characterized in that the method is carried out in a power generation system, and the power generation system comprises a fine desulfurization tank (1),
A solid oxide fuel cell (3), a molten carbonate fuel cell (7), a burner (8) and a heat exchange unit;
the fine desulfurization tank (1) is respectively connected with the solid oxide fuel cell (3) and the molten carbon
The acid salt fuel cell (7) is communicated with the solid oxide fuel cell (3) and the molten carbonic acid
A salt fuel cell (7) provides anode fuel;
heat exchange units are arranged between the fine desulfurization tank (1) and the solid oxide fuel cell (3) and between the fine desulfurization tank (1) and the molten carbonate fuel cell (7), and a cathode outlet of the solid oxide fuel cell (3) and a cathode outlet of the molten carbonate fuel cell (7) are respectively connected with the heat exchange units;
the outlet of the solid oxide fuel cell (3) and the outlet of the molten carbonate fuel cell (7) are respectively communicated with the combustor (8), the outlet of the combustor (8) is communicated with the inlet of the molten carbonate fuel cell (7) and a heat exchange unit is arranged between the combustor (8) and the inlet of the molten carbonate fuel cell (7);
the heat exchange unit enables heat exchange between pipelines leading to the solid oxide fuel cell (3) and the molten carbonate fuel cell (7);
the heat exchange unit comprises an SOFC cathode heater (5); the SOFC cathode heater (5) is provided with a hot gas channel and a cold gas channel which are separated by a heat exchange sheet and used for heating the cold gas channel;
the combustor (8) and the cathode inlet of the molten carbonate fuel cell (7) are respectively communicated with two ends of a hot gas channel of the SOFC cathode heater (5);
the power generation system is provided with an air fan (4), and the air fan (4) and the cathode inlet of the solid oxide fuel cell (3) are respectively communicated with a cold gas channel of the SOFC cathode heater (5);
the method comprises the following steps:
s1, introducing fuel gas (101) into the fine desulfurization tank (1) for desulfurization and purification, wherein the fuel gas (101) after desulfurization and purification is divided into SOFC fuel gas (111) and MCFC fuel gas (201);
s2, SOFC fuel gas (111) and water vapor in the water vapor pipeline (102) are mixed and enter the anode inlet of the solid oxide fuel cell (3);
s3, MCFC fuel gas (201) and water vapor in a water vapor pipeline (102) are mixed and enter an anode inlet of the molten carbonate fuel cell (7);
s4, introducing SOFC anode tail gas (105) and MCFC anode tail gas (205) into a combustor (8), mixing and combusting the gas with gas in a combustion-supporting pipeline (206) to generate combustion tail gas (207), wherein the combustion tail gas (207) enters a hot gas channel of an SOFC cathode heater (5) to form MCFC cathode inlet gas (208), and the MCFC cathode inlet gas (208) enters a cathode inlet of a molten carbonate fuel cell (7);
s5, introducing air (106) into the air fan (4) to form air fan outlet gas (107), wherein the air fan outlet gas (107) enters a cold gas channel of the SOFC cathode heater (5) to exchange heat with combustion tail gas (207) introduced into a hot gas channel of the SOFC cathode heater (5) to form SOFC cathode inlet gas (108), and the SOFC cathode inlet gas (108) enters a cathode inlet of the solid oxide fuel cell (3);
the hydrogen-carbon ratio of the fuel gas (101) in the step S1 is 1-3: 1;
the gas in the combustion-supporting pipeline (206) in the step S4 is pure oxygen; the excess of pure oxygen introduced into the burner (8) is more than 5%.
2. The coupled power generation method of claim 1, wherein the heat exchange unit comprises
SOFC anode heater (2) and MCFC anode heater (6), the SOFC anode being provided with
The heater (2) and the MCFC anode heater (6) are both provided with a hot gas channel and a cold gas channel which are separated by a heat exchange sheet and used for heating the cold gas channel;
the anode inlets of the fine desulfurization tank (1) and the solid oxide fuel cell (3) are respectively communicated with a cold gas channel of the SOFC anode heater (2), the cathode outlet of the solid oxide fuel cell (3) is communicated with a hot gas channel of the SOFC anode heater (2), and the cold gas channel of the SOFC anode heater (2) is heated through the hot gas channel of the SOFC anode heater (2);
the fine desulfurization tank (1) and the anode inlet of the molten carbonate fuel cell (7) are respectively communicated with a cold gas channel of the MCFC anode heater (6), the cathode outlet of the MCFC anode heater (6) is communicated with a hot gas channel of the MCFC anode heater (6), and the cold gas channel of the MCFC anode heater (6) is heated through the hot gas channel of the MCFC anode heater (6).
3. The coupled power generation method of claim 2,
the SOFC anode heater (2) is provided with an SOFC cathode tail gas outlet (110), and the SOFC cathode tail gas outlet (110) and the cathode outlet of the solid oxide fuel cell (3) are respectively connected with two ends of a hot gas channel of the SOFC anode heater (2);
the MCFC anode heater (6) is provided with an MCFC cathode tail gas outlet (210), and the MCFC cathode tail gas outlet (210) and the cathode outlet of the molten carbonate fuel cell (7) are respectively connected with two ends of a hot gas channel of the MCFC anode heater (6).
4. The coupled power generation method according to claim 1, wherein the burner (8) is provided with a combustion-supporting line (206), and a line between the fine desulfurization tank (1) and the heat exchange unit is communicated with a steam line (102).
5. The coupled power generation method of claim 1,
the solid oxide fuel cell (3) comprises a solid electrolyte and a solid electrolyte respectively arranged on the solid electrolyte
A cathode and an anode on both sides of the electrolyte, through which the fuel passes
An inlet into the anode chamber and an oxidant through the cathode of the solid oxide fuel cell (3)
The inlet enters the cathode chamber and generates electrochemical reaction to generate electric energy and heat;
the molten carbonate fuel cell (7) comprises molten electrolyte and electrodes respectively arranged on the molten electrolyte
Cathode and anode on both sides of a electrolyte through which fuel passes to the anode of the molten carbonate fuel cell (7)
An inlet into the anode chamber and an oxidant through the cathode of the molten carbonate fuel cell (7)
The inlet enters the cathode chamber and an electrochemical reaction occurs to generate electrical energy and heat.
6. The coupled power generation method according to claim 1, wherein the fuel gas (101) in the step S1 contains H as a main component2And CO gas.
7. The coupled power generation method of claim 1, wherein the SOFC fuel gas (111) and the MCFC fuel gas (201) subjected to desulfurization and purification in the step S1 have main components of CO and H2Gas and small amount of CH4、CO2A gas.
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