CN117577890A - Solar-energy-coupled methanol reforming SOFC system and control method thereof - Google Patents
Solar-energy-coupled methanol reforming SOFC system and control method thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 1137
- 238000002407 reforming Methods 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 claims abstract description 96
- 239000006200 vaporizer Substances 0.000 claims abstract description 86
- 238000006057 reforming reaction Methods 0.000 claims abstract description 51
- 238000010248 power generation Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003546 flue gas Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000002485 combustion reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000008016 vaporization Effects 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011217 control strategy Methods 0.000 description 23
- 238000012546 transfer Methods 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000000446 fuel Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000001276 controlling effect Effects 0.000 description 13
- 238000010586 diagram Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000013461 design Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
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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
- H01M8/04—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
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- 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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04111—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants using a compressor turbine assembly
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- 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
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- 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
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- 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
- H01M8/04537—Electric variables
- H01M8/04544—Voltage
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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
- H01M8/04—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
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- 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
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- 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
- H01M8/04776—Pressure; Flow at auxiliary devices, e.g. reformer, compressor, burner
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- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application provides a solar-energy-coupled methanol reforming SOFC system and a control method thereof, wherein the solar-energy-coupled methanol reforming SOFC system is provided with a preheating section and a superheating section in a methanol vaporizer, a methanol aqueous solution exchanges heat with a heat exchange medium in the preheating section, and is heated by high-temperature flue gas in the superheating section; according to the control method, different control processes are divided according to the temperature of the heat exchange medium, wherein the reforming power generation control process is directly executed when the temperature of the heat exchange medium is lower than the set reforming reaction temperature, and the reforming power generation control process is executed after the heat exchange medium exchanges heat with air participating in the reaction in the SOFC module when the set reforming reaction temperature is reached or exceeded, so that the energy generated by solar energy is fully utilized, the energy consumption is reduced, and the stable operation of methanol reforming and SOFC power generation can be ensured under the condition that the solar energy collection is unstable.
Description
Technical Field
The invention belongs to the fuel cell control technology, and particularly relates to a methanol reforming SOFC system coupled with solar energy and a control method thereof.
Background
A solid oxide fuel cell (Solid Oxide Fuel Cell, abbreviated as SOFC) belongs to a third generation fuel cell, is an all-solid chemical power generation device which directly converts chemical energy stored in fuel and oxidant into electric energy at medium and high temperature with high efficiency and environmental friendliness, and is one of several fuel cells with highest theoretical energy density; hydrogen is one of the most ideal fuels for SOFCs, however, hydrogen has great difficulty in storage and transportation, and based on this, methanol is proposed as a carrier of hydrogen, and methanol is reformed to prepare hydrogen and then participates in SOFC power generation.
At present, the coupling of a methanol reforming system and an SOFC power generation system is a mature study, but the concept of simultaneously coupling solar energy, a methanol reforming system and an SOFC system is quite rare, and the problem of how to couple unstable solar energy with the SOFC system based on methanol reforming is solved because the heat collection temperature of the solar energy is relatively unstable.
Disclosure of Invention
Based on this, the present invention aims to propose a methanol reforming SOFC system coupled with solar energy and a control method thereof, which at least overcome the above-mentioned drawbacks of the prior art.
In a first aspect, the present invention provides a methanol reforming SOFC system coupled to solar energy, comprising a solar collector, a methanol reforming SOFC device;
the methanol reforming SOFC device comprises a methanol reforming module and an SOFC module, wherein the methanol reforming module comprises a methanol storage tank, a buffer tank, a methanol vaporizer, a reformer, a heat exchanger and a condenser, the methanol vaporizer is used for heating and vaporizing a methanol aqueous solution, and the heat exchanger is used for exchanging heat between reformed gas and the methanol aqueous solution;
the outlet of the methanol storage tank is connected with the inlet of the methanol vaporizer, the inlet and the outlet of the methanol vaporizer are respectively connected with the outlet of the buffer tank and the inlet of the reformer, the outlet of the reformer is connected with the inlet of the heat exchanger, the liquid outlet and the gas outlet of the heat exchanger are respectively connected with the inlet of the buffer tank and the inlet of the condenser, and the gas outlet of the condenser is connected with the SOFC module;
The methanol vaporizer comprises a preheating section and a superheating section, a first outlet and a second outlet are respectively arranged, a valve is arranged between the preheating section and the superheating section and used for controlling flow of a methanol aqueous solution in the preheating section and the superheating section, the preheating section is provided with a first pipeline for storing a heat exchange medium, the heat exchange medium enters the first pipeline through heating of a solar heat collector, and the superheating section is provided with a second pipeline for flowing high-temperature flue gas.
Preferably, the preheating section and the superheating section are respectively provided with a first inlet and a second inlet, and the first inlet and the second inlet are both connected with the outlet of the buffer tank.
Preferably, the SOFC module comprises an SOFC electric pile and an afterburner, wherein a gas inlet of the afterburner is connected with the SOFC electric pile, a gas outlet of the condenser is connected with an anode of the SOFC electric pile, tail gas generated by the reaction in the SOFC electric pile enters the afterburner for combustion reaction, and high-temperature flue gas generated by the afterburner enters a superheating section of the methanol vaporizer.
Preferably, the gas outlet of the afterburner is also connected to the inlet of the reformer so that the high temperature flue gas produced by the afterburner heats the reformer.
Preferably, the liquid outlet of the condenser is also connected to the inlet of the methanol storage tank.
In a second aspect, the present invention provides a control method of the above-mentioned solar-coupled methanol reforming SOFC system, including:
Controlling the solar heat collector to heat the heat exchange medium to a first temperature;
when the first temperature is lower than the set reforming reaction temperature, directly executing a reforming power generation control process, otherwise, enabling the heat exchange medium to exchange heat with air participating in the reaction in the SOFC module, and then executing the reforming power generation control process:
the reforming power generation control process includes:
s1, introducing a heat exchange medium into a first pipeline of a preheating section of a methanol vaporizer to enable a first methanol aqueous solution to be heated to a second temperature in the methanol vaporizer and then release the methanol vaporizer;
s2, controlling a first methanol aqueous solution at a second temperature to enter a reformer for reaction to obtain reformed gas;
s3, enabling the reformed gas to enter a heat exchanger to exchange heat with a second methanol aqueous solution, and enabling the second methanol aqueous solution after heat exchange and the reformed gas to enter a buffer tank and a condenser respectively;
and S4, introducing the reformed gas condensed in the condenser into an SOFC module for power generation, and introducing the second methanol aqueous solution in the buffer tank into a methanol vaporizer for heat exchange.
Preferably, when the first temperature is lower than the set reforming reaction temperature, step S1 includes:
the first methanol aqueous solution is heated to a third temperature through heat exchange with a heat exchange medium in the preheating section, a valve between the preheating section and the superheating section is controlled to be opened, so that the first methanol aqueous solution with the third temperature enters the superheating section, and the first methanol aqueous solution is heated to a second temperature by high-temperature flue gas in the superheating section and releases the methanol vaporizer from a second outlet.
Preferably, when the first temperature reaches or exceeds the set reforming reaction temperature, step S1 includes:
the first methanol aqueous solution is subjected to heat exchange with a heat exchange medium in a preheating section to be heated to a second temperature, and the methanol vaporizer is released from a first outlet.
Preferably, passing the second aqueous methanol solution in the buffer tank to the methanol vaporizer for heat exchange in step S4 includes:
judging whether the flow of the second methanol aqueous solution in the buffer tank is greater than the set reforming reaction flow, if so, adjusting the flow of the second methanol aqueous solution in the buffer tank to be the set reforming reaction flow and introducing the second methanol aqueous solution into the methanol vaporizer, and if not, preparing the third methanol aqueous solution in the buffer tank to enable the flow of the third methanol aqueous solution to reach the set reforming reaction flow and then introducing the third methanol aqueous solution into the methanol vaporizer.
Preferably, when the first temperature reaches or exceeds the set reforming reaction temperature and the methanol reforming SOFC system includes at least two sets of methanol reforming SOFC devices, the at least two sets of methanol reforming SOFC devices include a first methanol reforming SOFC device and a second methanol reforming SOFC device, and the reforming power generation control process further includes:
controlling a heat exchange medium to exchange heat with air participating in the reaction in the SOFC module, and then introducing the heat exchange medium into a first methanol vaporizer of a first methanol reforming SOFC device, wherein the heat exchange medium exchanges heat with a methanol aqueous solution in the first methanol vaporizer and then enters a second methanol vaporizer of a second methanol reforming SOFC device;
The reforming power generation control process is performed in the first methanol reforming SOFC device and the second methanol reforming SOFC device.
Preferably, when the first temperature reaches or exceeds the set reforming reaction temperature and the methanol reforming SOFC system includes at least two sets of methanol reforming SOFC devices, the at least two sets of methanol reforming SOFC devices include a first methanol reforming SOFC device and a second methanol reforming SOFC device, and the reforming power generation control process further includes:
enabling a heat exchange medium to enter a first methanol vaporizer of the first methanol reforming SOFC device and a second methanol vaporizer of the second methanol reforming SOFC device simultaneously;
steps S1 to S4 are performed simultaneously in the first methanol reforming SOFC device and the second methanol reforming SOFC device.
From the above technical scheme, the invention has the following beneficial effects:
the invention provides a methanol reforming SOFC system coupled with solar energy and a control method thereof, wherein the methanol reforming SOFC system is provided with a preheating section and a superheating section in a methanol vaporizer, so that the energy generated by solar energy is fully utilized, the energy consumption is reduced, and the control method for the system is further provided, so that the stable operation of methanol reforming and SOFC power generation can be ensured under the condition that the solar energy collection is unstable.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a methanol vaporizer according to an embodiment of the present invention;
fig. 2 is a block diagram of a system for reforming a methanol with coupling solar energy according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a control strategy for controlling a solar-coupled methanol reforming SOFC system according to an embodiment of the invention;
fig. 4 is a schematic diagram of a control strategy for controlling a solar-coupled methanol reforming SOFC system according to an embodiment of the present invention;
fig. 5 is a schematic diagram of a control strategy for controlling a solar-coupled methanol reforming SOFC system according to an embodiment of the present invention;
fig. 6 is a schematic diagram of a control strategy for controlling a solar-coupled methanol reforming SOFC system according to an embodiment of the present invention;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Solid oxide fuel cells (Solid Oxide Fuel Cell, SOFCs for short) are a type of fuel cell that use a solid oxide electrolyte that conducts negative oxygen ions from the cathode to the anode. The negative oxygen ions oxidize hydrogen or carbon monoxide electrochemically at the anode. The hydrogen in the fuel is mainly derived from reforming natural gas, methanol and other fuels, while the oxygen is derived from air, and typically the fuel undergoes a reforming reaction in a device upstream of the SOFC anode, and the reformed product includes hydrogen (H 2 ) Carbon monoxide (CO), carbon dioxide (CO) 2 ) Etc. SOFCs can provide this endothermic reaction for steam reforming by tail gas combustion, improving efficiency. The reaction temperature of the methanol reforming hydrogen production is 200-300 ℃, and compared with other fuel reforming hydrogen production routes, the reaction is quicker and milder.
The heat collection temperature of the solar heat collector is unstable, the range is about 300-1500 ℃, the heat collection temperature is changed along with the change of the solar radiation intensity, the heat collection temperature is generally increased and then reduced, the common temperature of the methanol reforming reaction is about 250 ℃, and the working temperature of the SOFC is more than 600 ℃, so that the heat energy of the solar heat collector can not ensure that the temperature required by the reforming reaction can be always reached after the methanol aqueous solution is vaporized, and the power generation efficiency of the SOFC is further influenced.
In order to solve the technical problems, the application provides a methanol reforming SOFC system coupled with solar energy and a control method thereof through a series of embodiments, and the system ensures stable operation of methanol reforming and SOFC power generation while fully utilizing the heat energy of the solar energy through control strategies of different temperature intervals.
In one embodiment, the present embodiment provides a methanol reforming SOFC system coupled with solar energy, a solar collector, and a methanol reforming SOFC device;
the methanol reforming SOFC device comprises a methanol reforming module and an SOFC module, wherein the methanol reforming unit comprises a methanol storage tank, a buffer tank, a methanol vaporizer, a reformer, a heat exchanger and a condenser, the methanol vaporizer is used for heating and vaporizing a methanol aqueous solution, and the heat exchanger is used for exchanging heat between reformed gas and the methanol aqueous solution.
The outlet of the methanol storage tank is connected with the inlet of the methanol vaporizer, the inlet and the outlet of the methanol vaporizer are respectively connected with the outlet of the buffer tank and the inlet of the reformer, the outlet of the reformer is connected with the inlet of the heat exchanger, the liquid outlet and the gas outlet of the heat exchanger are respectively connected with the inlet of the buffer tank and the inlet of the condenser, and the gas outlet of the condenser is connected with the SOFC module.
The methanol vaporizer comprises a preheating section and a superheating section, a first outlet and a second outlet are respectively arranged, a valve is arranged between the preheating section and the superheating section and used for controlling flow of a methanol aqueous solution in the preheating section and the superheating section, the preheating section is provided with a first pipeline for storing a heat exchange medium, the heat exchange medium enters the first pipeline through heating of a solar heat collector, and the superheating section is provided with a second pipeline for flowing high-temperature flue gas.
Specifically, the methanol aqueous solution in the methanol vaporizer is directly provided by the methanol storage tank, and can also be recovered from the buffer tank after heat exchange in the heat exchanger, the methanol aqueous solution flows in a gap formed by the first pipeline, exchanges heat with a heat exchange medium in the first pipeline to raise the temperature to a certain temperature, and then passes through a gap formed by the second pipeline to be heated to the temperature required by reforming by high-temperature flue gas in the pipeline.
It will be readily appreciated that if the aqueous methanol solution has reached the desired reforming temperature after heat exchange in the first conduit, the valve may be controlled to close so that the aqueous methanol solution does not flow through the second conduit and may be released through the first outlet of the first conduit directly into the reforming reactor.
In a possible design, the preheating section and the superheating section are provided with a first inlet and a second inlet, respectively, which are both connected to the outlet of the buffer tank.
Specifically, when the temperature of the aqueous methanol solution recovered in the buffer tank is higher than the temperature of the heat exchange medium, namely the heat exchange medium cannot overcome the heat transfer fort, the aqueous methanol solution does not need to exchange heat with the heat exchange medium, and at the moment, the aqueous methanol solution can directly enter the superheating section from the second inlet without passing through the preheating section and is heated to the temperature required by reforming by high-temperature flue gas in the superheating section, or the first pipeline is not led in with the heat exchange medium, and the aqueous methanol solution still sequentially passes through the preheating section and the superheating section, and at the moment, no heat exchange occurs in the preheating section.
In a possible design, the liquid outlet of the condenser is further connected to the inlet of the methanol storage tank for recovering the unreacted complete methanol and water after condensation by the condenser, i.e. the unreacted complete methanol and water recovered after condensation of the reformed gas by the condenser may be returned to the methanol storage tank, and in some examples, the liquid recovered after condensation may be stored by another recovery vessel and mixed with the aqueous methanol solution in the methanol storage tank.
In a possible design, the SOFC module comprises an SOFC electric pile and an afterburner, wherein a gas inlet of the afterburner is connected with the SOFC electric pile, a gas outlet of the condenser is connected with an anode of the SOFC electric pile, tail gas generated by the reaction in the SOFC electric pile enters the afterburner for combustion reaction, and high-temperature flue gas generated by the afterburner enters a superheating section of the methanol vaporizer for heat exchange with the aqueous solution of methanol.
Specifically, the SOFC stack performs oxidation reaction at the anode, the generated anode tail gas is mainly hydrogen and water vapor which are not completely reacted, the generated cathode tail gas is mainly air (oxygen-containing) which is not completely reacted, at this time, an anode tail gas treatment unit can be further arranged in the SOFC module, the cathode tail gas and a part of anode tail gas enter an afterburner to perform combustion reaction, and the other part of anode tail gas is treated by the anode tail gas treatment unit and recycled to the anode of the SOFC stack to participate in SOFC power generation.
In a possible design, the gas outlet of the afterburner is also connected to the inlet of the reformer, so that the high temperature flue gas generated by the afterburner heats the reformer.
Specifically, in order to fully utilize the heat energy, the high-temperature flue gas generated by the combustion reaction of the afterburner can be used for heating a heat source of a superheating section of the methanol vaporizer, heating a reformer and preheating air.
In a possible design, a combustion heating channel is arranged in the reformer, and high-temperature flue gas combusted by the afterburner can be introduced into the combustion heating channel to maintain the stability of the temperature of the reforming reactor.
By way of example, fig. 1 provides a design of a methanol vaporizer, the methanol vaporizer 100 shown in fig. 1 includes a preheating section 102 and a superheating section 104, which is of a circular double-section structure, a first pipeline 106 is arranged in the preheating section 102, a heat exchange medium can flow in the first pipeline 106, a methanol aqueous solution flows between gaps formed by the first pipeline 106, heat exchange is performed between the methanol aqueous solution and the heat exchange medium so as to raise the temperature of the methanol aqueous solution, and an outlet a is arranged at the end of heat exchange of the preheating section 102 so that the heat exchanged methanol aqueous solution can be released into the reformer from the outlet a; the superheating section 104 is provided with a high-temperature flue gas channel, the high-temperature flue gas flows in the channel to heat the methanol aqueous solution, and an outlet B is arranged at the heat exchange end of the superheating section 104, so that the heat exchanged methanol aqueous solution can be released from the outlet B to enter the reformer.
By way of example, fig. 2 provides one embodiment of a solar-coupled methanol reforming SOFC system, and fig. 2 shows a system 200 comprising a solar collector 201, a methanol vaporizer 202, a reformer 203, a heat exchanger 204, a condenser 205, a buffer tank 206, a methanol aqueous solution storage tank 207, an SOFC stack 208, an afterburner 209, an air preheater 210, and an anode tail gas treatment unit 211.
After the solar heat collector 201 collects heat of the heat exchange medium, heat energy of solar energy is supplied to the methanol vaporizer 202 through the heat exchange medium, the methanol aqueous solution in the methanol aqueous solution storage tank 207 is vaporized in the methanol vaporizer 202, and the vaporized methanol aqueous solution undergoes a reforming reaction in the reformer 203 to generate a liquid containing H 2 、CO 2 The temperature of the outlet of the reformed gas is close to the temperature required by reforming, the reformed gas firstly passes through a heat exchanger 204 and exchanges heat with the aqueous methanol solution to heat the aqueous methanol solution so as to recover part of heat in the reformed gas, the heated aqueous methanol solution enters a buffer tank 206, the reformed gas is then introduced into a condenser 205 to condense the methanol and water which are not completely reacted in the reformed gas, so that the pipeline is prevented from being blocked by condensed liquid and the performance of a galvanic pile is prevented from being influenced, the condensed methanol and water are recycled to a methanol aqueous solution storage tank 207, and the hydrogen-containing gas after removing the methanol and the water is introduced into the anode of the galvanic pile 208 for oxidation reaction.
The heat of the solar heat collector 201 preheats air through the air preheater 210, the preheated air is introduced into the cathode of the SOFC stack 208 for reduction reaction, unreacted cathode tail gas and part of anode tail gas are introduced into the afterburner 209, and the other part of anode tail gas is mixed with hydrogen-containing gas after being treated by the anode tail gas treatment unit 211 and introduced into the anode of the SOFC stack 208 for oxidation reaction.
The method of controlling the solar-coupled methanol reforming SOFC system provided in the above embodiments will be described below.
In one embodiment, the present embodiment provides a control method of the above-mentioned solar-coupled methanol reforming SOFC system, including the following steps:
controlling the solar heat collector to heat the heat exchange medium to a first temperature;
when the first temperature is lower than the set reforming reaction temperature, directly executing a reforming power generation control process, and when the first temperature reaches or exceeds the set reforming reaction temperature, enabling the heat exchange medium to exchange heat with air participating in the reaction in the SOFC module, and then executing the reforming power generation control process:
the reforming power generation control process includes:
s1, introducing a heat exchange medium into a first pipeline of a preheating section of a methanol vaporizer, performing heat exchange between a first methanol aqueous solution and the heat exchange medium in the methanol vaporizer, and heating to a second temperature to release the methanol vaporizer;
s2, controlling a first methanol aqueous solution at a second temperature to enter a reformer for reaction to obtain reformed gas;
s3, enabling the reformed gas to enter a heat exchanger to exchange heat with a second methanol aqueous solution, and enabling the second methanol aqueous solution after heat exchange and the reformed gas to enter a buffer tank and a condenser respectively;
and S4, introducing the reformed gas condensed in the condenser into an SOFC module for power generation, and introducing the second methanol aqueous solution in the buffer tank into a methanol vaporizer for heat exchange.
In some embodiments, when the first temperature is lower than the set reforming reaction temperature, step S1 includes:
the first methanol aqueous solution sequentially passes through a preheating section and a superheating section, exchanges heat with a heat exchange medium in the preheating section and rises to a third temperature, a valve between the preheating section and the superheating section is controlled to be opened so that the first methanol aqueous solution at the third temperature enters the superheating section, and is heated to the second temperature by high-temperature flue gas in the superheating section and is released from a second outlet.
Specifically, when the temperature of the heat exchange medium is lower than the set reforming reaction temperature, the heat exchange between the heat exchange medium and the aqueous methanol solution is insufficient to heat the aqueous methanol solution to the set reforming reaction temperature, so that the aqueous methanol solution needs to exchange heat with the heat exchange medium in the preheating section, the aqueous methanol solution after heat exchange enters the superheating section for secondary heating, the aqueous methanol solution is heated to the set reforming reaction temperature by high-temperature flue gas in the superheating section, and then the vaporized aqueous methanol solution enters the reformer for reforming reaction.
In some embodiments, when the first temperature reaches or exceeds the set reforming reaction temperature, step S1 includes:
the first methanol aqueous solution is heated to a second temperature by heat exchange with a heat exchange medium in a preheating section and is released from a first outlet.
Specifically, the heat exchange medium reaches or exceeds the set reforming reaction temperature, which means that the solar heat collection temperature is higher, so that the temperature of the heat exchange medium is also higher, the heat exchange medium directly enters the methanol vaporizer to cause energy waste, and in order to fully utilize the heat energy, the heat exchange medium is not directly introduced into the preheating section at the moment, but part of the heat exchange medium is firstly recovered, so that the heat exchange is firstly carried out with the air which participates in the reaction in the SOFC module to heat the air, but the air which is subjected to primary heating at the moment cannot reach the temperature required by SOFC power generation, and the secondary heating is also required before the heat is introduced into the SOFC module.
In some embodiments, passing the second aqueous methanol solution in the buffer tank to the methanol vaporizer for heat exchange at step S4 comprises:
judging whether the flow of the second methanol aqueous solution in the buffer tank is greater than the set reforming reaction flow, if so, adjusting the flow of the second methanol aqueous solution in the buffer tank to be the set reforming reaction flow and introducing the second methanol aqueous solution into the methanol vaporizer, and if not, preparing the third methanol aqueous solution in the buffer tank to enable the flow of the third methanol aqueous solution to reach the set reforming reaction flow and then introducing the third methanol aqueous solution into the methanol vaporizer.
Specifically, the temperature of the second aqueous methanol solution subjected to heat exchange in the heat exchanger was raised, and the flow rate was denoted as V1. If the flow of the second methanol aqueous solution is V1 to be more than or equal to V0, the buffer tank can provide enough methanol aqueous solution for reforming reaction, and at the moment, the second methanol aqueous solution is introduced into the methanol vaporizer for heat exchange and temperature rise after the flow is regulated to V0 in the buffer tank; if the flow V1 of the second aqueous methanol solution is smaller than V0, the amount of the second aqueous methanol solution is insufficient to meet the flow of the aqueous methanol solution required by the reforming reaction, and a new aqueous methanol solution needs to be prepared or supplemented in the buffer tank at the moment, so that the flow of the aqueous methanol solution in the buffer tank can reach V0, and then the aqueous methanol solution is fed into the methanol vaporizer for heat exchange and temperature rise.
The temperature of the aqueous methanol solution flowing out of the buffer tank is possibly higher than the temperature of the heat exchange medium due to heat exchange and temperature rise in the heat exchanger, so that the temperature of the aqueous methanol solution and the temperature of the aqueous methanol solution can be determined through temperature monitoring, if the temperature of the aqueous methanol solution flowing out of the buffer tank is higher than the temperature of the heat exchange medium, the aqueous methanol solution does not need to be introduced into the preheating section and is heated by high-temperature flue gas, or the first pipeline of the preheating section is not introduced with the heat exchange medium, the aqueous methanol solution passes through the preheating section and is then introduced into the superheating section, and at the moment, the aqueous methanol solution does not undergo heat exchange in the preheating section.
In some embodiments, when the first temperature reaches or exceeds the set reforming reaction temperature and the methanol reforming SOFC system includes at least two sets of methanol reforming SOFC devices, the at least two sets of methanol reforming SOFC devices include a first methanol reforming SOFC device and a second methanol reforming SOFC device, the performing the reforming power generation control process by exchanging heat between the heat exchange medium and air involved in the reaction in the SOFC module further includes:
controlling a heat exchange medium to exchange heat with air participating in the reaction in the SOFC module, and then introducing the heat exchange medium into a first methanol vaporizer of a first methanol reforming SOFC device, wherein the heat exchange medium exchanges heat with a methanol aqueous solution in the first methanol vaporizer and then enters a second methanol vaporizer of a second methanol reforming SOFC device;
The reforming power generation control process is performed in the first methanol reforming SOFC device and the second methanol reforming SOFC device.
Specifically, when the solar heat collection efficiency is high, so that the temperature of the heat exchange medium is sufficient to supply more than one group of methanol reforming devices, at least two groups of methanol reforming SOFC devices can be started, at this time, the heat exchange medium firstly heats the air participating in the reaction in the SOFC module for one time, so that the temperature of the heat exchange medium is reduced, the heat of the cooled heat exchange medium still can meet the requirement that the methanol aqueous solution of the two groups of methanol reforming SOFC devices is heated to the set reforming reaction temperature, then the cooled heat exchange medium firstly enters the first methanol vaporizer in the first methanol reforming SOFC device to exchange heat with the methanol aqueous solution so as to start the methanol reforming reaction and SOFC power generation of the devices, then the heat exchange medium is led out from the first methanol vaporizer and is introduced into the second methanol vaporizer in the second methanol reforming SOFC device to exchange heat with the other path of methanol aqueous solution so as to start the methanol reforming reaction and SOFC power generation of the second group of methanol reforming SOFC devices. The reforming control process in the two-group methanol reforming SOFC device is similar to that provided in the above embodiment, and will not be repeated here.
For a system comprising two sets of methanol reforming SOFC devices, only one set of air preheater may be provided, and the preheated air of the air preheater may simultaneously supply two sets of methanol reforming SOFC devices, or two sets of air preheaters may be provided, which respectively correspond to different methanol reforming SOFC devices.
In some embodiments, when the first temperature reaches or exceeds the set reforming reaction temperature and the methanol reforming SOFC system includes at least two sets of methanol reforming SOFC devices, the at least two sets of methanol reforming SOFC devices include a first methanol reforming SOFC device and a second methanol reforming SOFC device, the reforming power generation control process further includes:
enabling a heat exchange medium to enter a first methanol vaporizer of the first methanol reforming SOFC device and a second methanol vaporizer of the second methanol reforming SOFC device simultaneously;
steps S1 to S4 of the reforming power generation control process described above are performed simultaneously in the first methanol reforming SOFC device and the second methanol reforming SOFC device.
Specifically, for the heat exchange medium with higher temperature, besides heat exchange with the methanol aqueous solution in different sets of devices in sequence, the heat exchange medium heated by the solar heat collector can be split and simultaneously exchanges heat with the methanol aqueous solution of a plurality of sets of devices, two sets of devices are taken as an example, the high-temperature heat exchange medium is divided into two sets, the flow is halved, and simultaneously, two sets of methanol reforming SOFC devices are introduced to start two sets of methanol reforming reactions and SOFC power generation, so that compared with the situation of starting in sequence provided by the embodiment, the response speed of the whole system is faster.
In other embodiments, when the solar heat collection temperature is higher, 3 groups, 4 groups or even more methanol reforming SOFC devices can be started simultaneously or sequentially, and different control strategies provided by the above embodiments, that is, the combination of the control strategies, can be adopted for the methanol reforming SOFC devices of different groups, and specific implementation logic can refer to the related description of the control strategies provided by the above embodiments and is not repeated herein.
To further illustrate the control method described above, the control method provided in the present application will be described in specific scenarios with reference to fig. 3 to 6 based on the methanol vaporizer 100 shown in fig. 1 and the methanol reforming SOFC system 200 schematically shown in fig. 2.
In the scenario provided below, the heat transfer oil is used as a heat exchange medium, the reforming reaction temperature is set to 250 ℃, the solar collector heats the heat transfer oil to a temperature T1, and the temperature interval length is divided by 250 ℃.
When T1 < 250 ℃, it means that the temperature of the heat exchange medium is insufficient to raise the temperature of the aqueous methanol solution to the set reforming reaction temperature, as illustrated in fig. 3, the control process of the solar energy coupled methanol reforming SOFC system is the following control strategy one:
The first pipeline 106 of the preheating section 102 is filled with heat conduction oil, the heat conduction oil exchanges heat with the methanol aqueous solution in the preheating section 102, at this time, the methanol aqueous solution in the methanol vaporizer 100 comes from a methanol aqueous solution storage tank, the warmed methanol aqueous solution enters the superheating section 104 to be secondarily heated to the preset reforming reaction temperature of 250 ℃, and the vaporized methanol aqueous solution warmed to 250 ℃ is released from the outlet B to enter the reformer to be reformed to produce hydrogen.
The reformed gas obtained by the reforming reaction exchanges heat with a certain flow of methanol aqueous solution through a heat exchanger, so that the methanol aqueous solution in the heat exchanger is heated, the heated methanol aqueous solution enters a buffer tank, and the reformed gas subjected to certain cooling enters a condenser.
It should be noted that, the critical heat transfer oil temperature T01 required by the aqueous methanol solutions with different volume flows and different temperature differences is different, that is, the heat transfer oil needs to reach a certain temperature to have heat transfer value, and not only the heat transfer barrier with the aqueous methanol solution needs to be overcome, for example, the heat transfer oil at 50 ℃ and the aqueous methanol solution at 20 ℃ cannot fully utilize heat, so when the actual temperature T1 of the heat transfer oil is greater than T01, the aqueous methanol solution flowing out of the buffer tank enters the preheating section to exchange heat with the heat transfer oil, and if T1 is less than or equal to T01, the aqueous methanol solution flowing out of the buffer tank does not exchange heat in the preheating section and is directly heated by the high-temperature flue gas of the superheating section.
The reformed gas comprises partial unreacted methanol and water, and is condensed into liquid in a condenser, and the boiling point of the methanol is about 65 ℃, so that the outlet temperature of the condenser can be set to 30 ℃, the unreacted methanol is ensured to be completely condensed, the methanol aqueous solution generated after the condensation enters a methanol aqueous solution storage tank for storage, the reformed gas condensed by the condenser is hydrogen-containing gas, and the hydrogen-containing gas can directly enter an SOFC stack for reaction with preheated air.
The hydrogen-containing gas and air generate cathode tail gas and anode tail gas after oxidation-reduction reaction in the SOFC stack, the anode tail gas is mainly unreacted complete hydrogen and water vapor, the cathode tail gas is mainly unreacted complete air (oxygen-containing gas), the cathode tail gas and a part of anode tail gas enter a afterburner to carry out combustion reaction, the other part of anode tail gas is treated and recycled to the SOFC stack anode by an anode tail gas treatment unit to participate in SOFC power generation, and high-temperature flue gas generated by the afterburner can be used for being supplied to a superheating section of a methanol vaporizer, heating or heat preservation of a reformer and preheating air.
When the temperature of the heat exchange medium is more than or equal to 250 ℃ and less than or equal to T1 and less than 500 ℃, the temperature of the heat exchange medium is enough to enable the aqueous methanol solution to be heated to the set reforming reaction temperature, as shown in the schematic diagram of fig. 4, at the moment, the control process of the solar energy coupled methanol reforming SOFC system is the following second control strategy:
And the heat conduction oil exchanges heat with the air participating in the reaction in the SOFC stack for one time, so that the temperature of the heat conduction oil is reduced from T1 to T2, and the T2 is slightly higher than 250 ℃. The air is preheated for the first time by heat exchange with the heat conducting oil, and then is preheated for the second time by high-temperature flue gas generated by the afterburner to the temperature required by SOFC electric pile reaction, for example, 700 ℃.
The heat transfer oil which exchanges heat with the air is introduced into the preheating section of the methanol vaporizer, and the temperature of the heat transfer oil is T2 at this moment, which is still sufficient to raise the temperature of the aqueous methanol solution to the set reforming reaction temperature, so that the aqueous methanol solution does not need to enter the superheating section, but is released from the outlet A of the methanol vaporizer 100 to enter the reformer.
The temperature of the aqueous methanol solution flowing out of the buffer tank is necessarily smaller than the temperature T2 of the heat transfer oil, so that the aqueous methanol solution only needs to flow back to the preheating section 102 of the methanol vaporizer 100 and can reach the set reforming reaction temperature of 250 ℃ after heat exchange with the heat transfer oil, and the aqueous methanol solution does not need to be heated for the second time through the heating section 104.
The process from the reformer to the SOFC module is similar to the first control strategy, and reference may be made to the related description of the first control strategy, which is not repeated here.
When the temperature of the heat exchange medium is higher than or equal to 500 ℃ and lower than 750 ℃, the temperature of the heat exchange medium is enough to enable the two groups of methanol aqueous solutions to rise to the set reforming reaction temperature, and the two groups of methanol reforming SOFC devices can be started, as shown in the schematic diagram of fig. 5, at the moment, the control process of the solar energy coupled methanol reforming SOFC system is as follows:
And the heat conduction oil exchanges heat with the air participating in the reaction in the SOFC stack for one time, so that the temperature of the heat conduction oil is reduced from T1 to T3, and the T3 is slightly higher than 500 ℃. The air is preheated for the first time by heat exchange with the heat conducting oil, and then is preheated for the second time by high-temperature flue gas generated by the afterburner to the temperature required by SOFC electric pile reaction, for example, 700 ℃.
The heat transfer oil with the temperature of T3 is firstly subjected to heat exchange with the methanol aqueous solution required by the first reformer through the preheating section of the first methanol vaporizer so as to start the first group of methanol reforming SOFC devices. And the temperature of the heat conduction oil led out by the first methanol vaporizer is T4, the temperature of the T4 is slightly higher than 250 ℃, and the heat conduction oil with the temperature of T4 is led into a preheating section of the second methanol vaporizer to exchange heat with the methanol aqueous solution required by the second reformer so as to start the second group of methanol reforming SOFC devices.
Because the temperature of the heat transfer oil is high at this time, the aqueous methanol solution does not need to enter the superheating section, but is released from the outlet a of the methanol vaporizer 100 into the reformer.
For systems where there is more than one methanol reforming SOFC device, only one set of air preheaters may be provided, and the preheated air of the air preheaters may be supplied to both sets of devices at the same time, or it may be provided that each set of devices is provided with a single set of air preheaters.
The process from the reformer to the SOFC module is similar to the first control strategy, and reference may be made to the related description of the first control strategy, which is not repeated here.
For the case that T1 is less than or equal to 500 ℃ and less than 750 ℃, the heat conduction oil can supply heat to two groups of methanol aqueous solutions, so that in addition to the control strategy III, different groups of methanol evaporators can be sequentially introduced, and the heat conduction oil can be separated, and different groups of methanol evaporators are simultaneously introduced, and then the control strategy IV as shown in fig. 6 is provided, and the following process is provided:
the high temperature heat conduction oil is divided into two groups according to the formula q=v1t1=v2t2, i.e. in practice, when the heat collection temperature of solar energy is higher than 500 ℃, the flow VD of the heat conduction oil can be reduced to VD 1/2 (half of the original flow of conduction oil) it is also possible to ensure heating of the aqueous methanol solution to 250 ℃. Therefore, the same flow of heat transfer oil can start 2 groups of methanol reforming SOFC devices at the same time, and each group of methanol aqueous solution can be directly released from the outlet of the preheating section of the methanol vaporizer, taking the methanol vaporizer 100 shown in fig. 1 as an example, that is, different groups of methanol aqueous solutions are released from the outlet A of the methanol vaporizer.
The process from the reformer to the SOFC module is similar to the first control strategy, and reference may be made to the related description of the first control strategy, which is not repeated here.
And the control strategy IV can simultaneously start 2 groups of devices, and compared with the control strategy III, the system response speed is faster.
In some embodiments, the fourth control strategy described above may also be used to simultaneously start 3 groups of methanol reforming SOFC devices, wherein the first 2 groups of devices use the third control strategy and the 3 rd groups of devices use the first control strategy
In some embodiments, 3 sets of methanol reforming SOFC devices may be started simultaneously when the temperature of the solar collector, i.e., the temperature of the heat transfer oil, satisfies 750 ℃ to less than or equal to T1 < 1000 ℃, and 4 sets of methanol reforming SOFC devices may be started simultaneously when 1000 ℃ to less than or equal to T1 < 1250 ℃.
In some embodiments, the heat exchange medium may also be other solar heat collection media such as molten salt.
In some embodiments, the main fuel of the afterburner is SOFC anode tail gas, and the high-temperature flue gas combusted by the tail gas can be used for heat preservation of the SOFC stack, heat preservation of the reformer, air preheating, and heat source of the overheating section of the methanol vaporizer, so that the demand for the anode tail gas is larger, and if the anode tail gas cannot meet the heat energy demand of the system, the fuel such as methanol can be supplemented in the afterburner for combustion to compensate.
The embodiments described above have described the invention in particular detail with respect to possible scenarios, and those skilled in the art will recognize that the invention can be practiced with other embodiments. No particular naming of the components, case of terminology, attribute, data structure, or any other programming or structural aspect is mandatory or significant, and the mechanisms that implement the invention or its features may have different names, forms, or procedures. The system may be implemented by a combination of hardware and software (as described), entirely by hardware elements or entirely by software elements. The specific division of functionality between the various system components described herein is exemplary only and not mandatory; in contrast, functions performed by a single system component may be performed by multiple components, or functions performed by multiple components may be performed by a single component.
It will be appreciated by those skilled in the art that the various steps of the disclosed methods may be implemented by general purpose computing devices, they may be concentrated on a single computing device, or distributed across a network of computing devices, or they may alternatively be implemented in program code executable by computing devices, such that they may be stored in storage devices for execution by computing devices, or they may be separately fabricated into individual integrated circuit modules, or multiple modules or steps within them may be fabricated into a single integrated circuit module. Thus, the present disclosure is not limited to any specific combination of hardware and software.
The programs (also referred to as programs, software applications, or code) executable by these computing devices include machine instructions for a programmable processor, and may be implemented in a high-level procedural and/or object-oriented programming language, and/or in assembly/machine language. As used herein, the terms "machine-readable medium" and "computer-readable medium" refer to any computer program product, apparatus, and/or device (e.g., magnetic discs, optical disks, memory, programmable Logic Devices (PLDs)) used to provide machine instructions and/or data to a programmable processor, including a machine-readable medium that receives machine instructions as a machine-readable signal. The term "machine-readable signal" refers to any signal used to provide machine instructions and/or data to a programmable processor.
Certain aspects of the invention include the process steps and instructions described herein in the form of algorithms. It should be noted that the process steps and instructions of the present invention may be embodied in software, firmware, and/or hardware, which when implemented in software, can be downloaded to reside on and be operated from different platforms used by a variety of operating systems.
It will be appreciated by persons skilled in the art that the structures shown in the various figures are block diagrams of only some of the structures associated with the aspects of the present application and are not intended to limit the terminal device to which the aspects of the present application may be applied, and that a particular terminal device may include more or less components than those shown, or may combine some of the components, or have a different arrangement of components.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "examples," "specific examples," or "possible designs," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Finally, it is further noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The methanol reforming SOFC system coupled with solar energy is characterized by comprising a solar heat collector and a methanol reforming SOFC device;
the methanol reforming SOFC device comprises a methanol reforming module and an SOFC module, wherein the methanol reforming module comprises a methanol storage tank, a buffer tank, a methanol vaporizer, a reformer, a heat exchanger and a condenser, the methanol vaporizer is used for heating and vaporizing a methanol aqueous solution, and the heat exchanger is used for exchanging heat between reformed gas and the methanol aqueous solution;
the outlet of the methanol storage tank is connected with the inlet of the methanol vaporizer, the inlet and the outlet of the methanol vaporizer are respectively connected with the outlet of the buffer tank and the inlet of the reformer, the outlet of the reformer is connected with the inlet of the heat exchanger, the liquid outlet and the gas outlet of the heat exchanger are respectively connected with the inlet of the buffer tank and the inlet of the condenser, and the gas outlet of the condenser is connected with the SOFC module;
the methanol vaporizer comprises a preheating section and a superheating section, a first outlet and a second outlet are respectively arranged, a valve is arranged between the preheating section and the superheating section and used for controlling flow of a methanol aqueous solution in the preheating section and the superheating section, the preheating section is provided with a first pipeline for storing a heat exchange medium, the heat exchange medium enters the first pipeline through heating of a solar heat collector, and the superheating section is provided with a second pipeline for flowing high-temperature flue gas.
2. The methanol reforming SOFC system of claim 1, wherein the preheating section and the superheating section are provided with a first inlet and a second inlet, respectively, each of the first inlet and the second inlet being connected to an outlet of the buffer tank.
3. The methanol reforming SOFC system of claim 1, wherein the SOFC module comprises an SOFC stack and an afterburner, a gas inlet of the afterburner is connected with the SOFC stack, a gas outlet of the condenser is connected with an anode of the SOFC stack, tail gas generated by reaction in the SOFC stack enters the afterburner to perform combustion reaction, and high-temperature flue gas generated by the afterburner enters the superheating section.
4. A methanol reforming SOFC system according to claim 3, wherein the gas outlet of the afterburner is further connected to the inlet of the reformer such that the high temperature flue gas produced by the afterburner heats the reformer.
5. A control method for controlling the solar-coupled methanol reforming SOFC system of any one of claims 1-4, the control method comprising:
controlling the solar heat collector to heat the heat exchange medium to a first temperature;
the first temperature is lower than the set reforming reaction temperature, and the reforming power generation control process is directly executed, otherwise, the heat exchange medium exchanges heat with the air participating in the reaction in the SOFC module, and then the reforming power generation control process is executed:
The reforming power generation control process includes:
s1, introducing a heat exchange medium into a preheating section of a methanol vaporizer to enable a first methanol aqueous solution to be heated to a second temperature in the methanol vaporizer and released from the methanol vaporizer;
s2, controlling a first methanol aqueous solution at a second temperature to enter a reformer for reforming reaction to obtain reformed gas;
s3, enabling the reformed gas to enter a heat exchanger to exchange heat with a second methanol aqueous solution, and enabling the second methanol aqueous solution and the reformed gas after heat exchange to enter a buffer tank and a condenser respectively;
and S4, introducing the reformed gas condensed in the condenser into an SOFC module for power generation, and introducing the second methanol aqueous solution in the buffer tank into a methanol vaporizer for heat exchange.
6. The control method according to claim 5, wherein when the first temperature is lower than the set reforming reaction temperature, the step S1 includes:
and the first methanol aqueous solution is subjected to heat exchange with a heat exchange medium in the preheating section to be heated to a third temperature, a valve between the preheating section and the superheating section is controlled to be opened, so that the first methanol aqueous solution with the third temperature enters the superheating section, and the first methanol aqueous solution is heated to a second temperature by high-temperature flue gas in the superheating section and is released from a second outlet.
7. The control method according to claim 5, wherein when the first temperature reaches or exceeds the set reforming reaction temperature, the step S1 includes:
the first methanol aqueous solution is subjected to heat exchange with a heat exchange medium in a preheating section to be heated to a second temperature, and the methanol vaporizer is released from a first outlet.
8. The control method according to claim 5, wherein passing the second aqueous methanol solution in the buffer tank to the methanol vaporizer for heat exchange in step S4 includes:
judging whether the flow of the second methanol aqueous solution in the buffer tank is greater than the set reforming reaction flow, if so, adjusting the flow of the second methanol aqueous solution in the buffer tank to be the set reforming reaction flow and introducing the second methanol aqueous solution into the methanol vaporizer, and if not, preparing the third methanol aqueous solution in the buffer tank to enable the flow of the third methanol aqueous solution to reach the set reforming reaction flow and then introducing the third methanol aqueous solution into the methanol vaporizer.
9. The control method according to claim 5, wherein when the first temperature reaches or exceeds a set reforming reaction temperature and the methanol reforming SOFC system includes at least two sets of methanol reforming SOFC devices, the at least two sets of methanol reforming SOFC devices include a first methanol reforming SOFC device and a second methanol reforming SOFC device, the heat exchange medium exchanging heat with air involved in a reaction in the SOFC module and then performing a reforming power generation control process further includes:
Controlling a heat exchange medium to exchange heat with air participating in the reaction in the SOFC module, and then introducing the heat exchange medium into a first methanol vaporizer of a first methanol reforming SOFC device, wherein the heat exchange medium exchanges heat with a methanol aqueous solution in the first methanol vaporizer and then enters a second methanol vaporizer of a second methanol reforming SOFC device;
the reforming power generation control process is performed in the first and second methanol reforming SOFC devices.
10. The control method according to claim 5, wherein when the first temperature reaches or exceeds a set reforming reaction temperature and the methanol reforming SOFC system includes at least two sets of methanol reforming SOFC devices, the at least two sets of methanol reforming SOFC devices include a first methanol reforming SOFC device and a second methanol reforming SOFC device, the reforming power generation control process further includes:
enabling a heat exchange medium to enter a first methanol vaporizer of the first methanol reforming SOFC device and a second methanol vaporizer of the second methanol reforming SOFC device simultaneously;
the steps S1 to S4 are performed simultaneously in the first and second methanol reforming SOFC devices.
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