CN111584907A - Solar energy-based medium-temperature fuel cell carbon cycle power generation device and carbon deposition treatment method thereof - Google Patents

Solar energy-based medium-temperature fuel cell carbon cycle power generation device and carbon deposition treatment method thereof Download PDF

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CN111584907A
CN111584907A CN202010527161.1A CN202010527161A CN111584907A CN 111584907 A CN111584907 A CN 111584907A CN 202010527161 A CN202010527161 A CN 202010527161A CN 111584907 A CN111584907 A CN 111584907A
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fuel cell
carbon
solid oxide
reaction chamber
solar
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陆玉正
马李刚
颜森林
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Nanjing Xiaozhuang University
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Nanjing Xiaozhuang University
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Priority to PCT/CN2020/127747 priority patent/WO2021248805A1/en
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    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
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Abstract

The invention discloses a solar energy-based medium-temperature fuel cell carbon cycle power generation device, which comprises a solar energy absorption and conversion device, a carbon reaction chamber, a mixed gas separation device and a solid oxide fuel cell, wherein the solar energy absorption and conversion device is connected with the carbon reaction chamber; the carbon reaction chamber generates carbon monoxide by utilizing heat energy after being charged with carbon dioxide, an exhaust port of the carbon reaction chamber is connected with a mixed gas separation device, the mixed gas separation device separates the carbon monoxide and the carbon dioxide discharged from the carbon reaction chamber, the separated carbon monoxide is sent to the anode of the solid oxide fuel cell, the separated carbon dioxide is output through two branches, a branch I is connected with the carbon reaction chamber, a branch II is connected with the anode of the solid oxide fuel cell, and an electric control valve is arranged on the branch II; the solid oxide fuel cell utilizes carbon monoxide to generate carbon dioxide and electric energy, and the generated carbon dioxide is sent into the carbon reaction chamber; the solid oxide fuel cell system further comprises a controller, the electric control valve is connected with the controller through a cable, and the controller collects voltages at two ends of the solid oxide fuel cell through a voltage sensor.

Description

Solar energy-based medium-temperature fuel cell carbon cycle power generation device and carbon deposition treatment method thereof
Technical Field
The invention relates to a new energy power generation device, in particular to a solar-based medium-temperature fuel cell carbon cycle power generation device and a carbon deposition treatment method of the solar-based medium-temperature fuel cell carbon cycle power generation device.
Background
Fuel cells are clean and efficient power generation devices, and among fuel cell systems, solid oxide fuel cells have advantages such as solid-state structures, no need for noble metal catalysts, and wide fuel selection range, and have recently received much attention. However, solid oxide fuel cells have not been commercialized so far, and the most important factor is the high operating temperature of the system, which results in easy chemical reaction between the electrode and electrolyte contact surfaces, and the high temperature causes many problems in the sealing process. Therefore, in recent years, much research has been focused on reducing the operating temperature of solid oxide fuel cells.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a solar energy-based medium-temperature fuel cell carbon circulation power generation device, which starts from a fuel cell technology, carbon is used as a raw material to form a carbon circulation closed loop, and heat energy required in a system is utilized as solar energy, so that a clean and environment-friendly power generation device is obtained.
The invention also aims to solve the technical problem of providing the carbon deposition treatment method of the solar-based intermediate-temperature fuel cell carbon cycle power generation device, which utilizes carbon dioxide to eliminate the carbon deposition of the anode of the solid oxide fuel cell and can ensure the long-term effective and stable operation of the system.
The invention content is as follows: in order to achieve the purpose, the invention adopts the technical scheme that:
a solar energy-based medium-temperature fuel cell carbon cycle power generation device comprises a solar energy absorption and conversion device, a carbon reaction chamber, a mixed gas separation device and a solid oxide fuel cell; the solar energy absorption and conversion device supplies heat energy to the carbon reaction chamber, the mixed gas separation device and the solid oxide fuel cell through the heat exchangers respectively; the carbon reaction chamber generates carbon monoxide by utilizing heat energy after being charged with carbon dioxide, an exhaust port of the carbon reaction chamber is connected with a mixed gas separation device, the mixed gas separation device separates the carbon monoxide and the carbon dioxide discharged from the carbon reaction chamber, the separated carbon monoxide is sent into a solid oxide fuel cell through a carbon monoxide conveying pipeline, the separated carbon dioxide is discharged through a carbon dioxide conveying pipeline, the carbon dioxide conveying pipeline is divided into two branches, the branch I is connected with the carbon reaction chamber, the branch II is connected with the anode of the solid oxide fuel cell, and an electric control valve is arranged on the branch II; the solid oxide fuel cell utilizes carbon monoxide to generate carbon dioxide and electric energy, the generated carbon dioxide is sent into a carbon reaction chamber, and the generated electric energy is supplied to an external load; the solid oxide fuel cell system further comprises a controller, the electric control valve is connected with the controller through a cable, and the controller collects voltages at two ends of the solid oxide fuel cell through a voltage sensor.
The solar energy absorption and conversion device comprises a solar reflector group, a solar thermal collector, a solar heat exchanger and a heat reservoir, solar rays are reflected by the solar reflector group and focused on the solar thermal collector, and heat energy in the solar thermal collector is stored in the heat reservoir through the solar heat exchanger.
The heat exchanger comprises a separation heat exchanger, a fuel cell stack heat exchanger and a carbon reaction chamber heat exchanger, the heat energy output end of the heat reservoir is respectively connected with the heat energy input ends of the separation heat exchanger, the fuel cell stack heat exchanger and the carbon reaction chamber heat exchanger, the heat energy output end of the separation heat exchanger is connected with the mixed gas separation device, the heat energy output end of the fuel cell stack heat exchanger is connected with the solid oxide fuel cell, and the heat energy output end of the carbon reaction chamber heat exchanger is connected with the carbon reaction chamber.
Wherein the carbon reaction chamber contains solid coal, and the filling amount of the coal is more than 3/4 of the volume of the cavity of the carbon reaction chamber.
The mixed gas separation device comprises a molten carbonate fuel cell and a steam-water separator positioned at the gas outlet of the anode plate of the molten carbonate fuel cell; the molten carbonate fuel cell and the solid oxide fuel cell are connected in parallel to supply power to an external load, namely, a cathode of the molten carbonate fuel cell is connected in parallel with a negative electrode of the solid oxide fuel cell through a wire, and an anode of the molten carbonate fuel cell is connected in parallel with a positive electrode of the solid oxide fuel cell through a wire. Steam-water separator for separating CO2、H2O and unreacted H2Unreacted H2And returning the molten carbonate fuel cell anode through the gas path through the anode plate gas inlet for reuse.
Wherein the anode of the molten carbonate fuel cell is metallic nickel; the cathode is lithium nickel oxide; the electrolyte layer is made of carbonate Li2CO3And K2CO3Mixing and preparing; wherein Li2CO3Is 62% by mass, K2CO3Is 38 percent.
Wherein, the exhaust port of the carbon reaction chamber is connected with the cathode plate air inlet of the molten carbonate fuel cell, the cathode plate air inlet is also connected with an external oxygen tank through a branch pipe, and carbon dioxide reacts with oxygen at the cathode of the molten carbonate fuel cell to generate CO3 2-Ion, CO3 2-Ions pass through the electrolyte layer at the anode and H2Reaction to form H2O and CO2，H2O and CO2After being separated by a steam-water separator at the air outlet of the anode plate, CO is separated2Discharging through a carbon dioxide conveying pipeline; unreacted carbon monoxide from meltingThe gas outlet of the cathode plate of the carbonate fuel cell is discharged and sent into the anode of the solid oxide fuel cell through a carbon monoxide conveying pipeline.
The carbon deposition treatment method of the solar-energy-based medium-temperature fuel cell carbon cycle power generation device comprises the following steps: the controller monitors voltage signals at two ends of the solid oxide fuel cell in real time, and controls the electric control valve to be opened if the voltage signals are smaller than a fixed value, so that carbon dioxide is added to the anode of the solid oxide fuel cell, and carbon deposition of the anode is eliminated; after carbon deposition is eliminated, voltage signals at two ends of the solid oxide fuel cell recover to set values, the controller controls the electric control valve to be closed, carbon dioxide supply of the anode of the solid oxide fuel cell is cut off, and carbon monoxide fuel continues to be introduced into the anode of the solid oxide fuel cell.
The carbon deposition treatment method of the solar-based medium-temperature fuel cell carbon cycle power generation device specifically adopts a fuzzy control method to control:
the control structure of the fuzzy controller is a 2-input and 1-output structure:
input variable x 1: the difference value of the anode and cathode voltages of the solid oxide fuel cell and the standard transformation voltage;
input variable x 2: a rate of change of the difference;
output variable u 1: opening time of the electric control valve;
input and output variable discourse domain
The basic domain of input variables x1 and x2 is designed to be (0, 1), then the two input variables are divided into 3 linguistic variables, namely positive large (PB), Zero (ZE) and negative large (NB), and the membership function of the 3 linguistic variables of the two input variables in the basic domain of discourse (0, 1) is a triangle and trapezoid combined membership function;
the basic domain of output variable U1 is (0, 1), and the output variable is divided into 3 linguistic variables U, namely positive large (PB), Zero (ZE) and negative large (NB);
the membership function of the output variable u1 in the basic discourse domain is (0, 1) is a triangle and trapezoid combined membership function;
designing a fuzzy control rule:
the principle of designing the fuzzy control rule is that when the error is large or large, the control quantity is selected to eliminate the error as soon as possible, and when the error is small or small, the control quantity is selected to control the overshoot, and the fuzzy control rule of the typical working condition is as follows:
rule 1: if x1 and x2 are PB, then u1 is PB;
rule 2: if x1 ═ PB, x2 ═ ZE, then u1 ═ ZE;
rule 3: if x1 is PB and x2 is NB, then u1 is NB;
rule 4: if x1 ═ ZE, x2 ═ PB, then u1 ═ ZE;
rule 5: if x1 ═ ZE, x2 ═ ZE, then u1 ═ ZE;
rule 6: if x1 ═ ZE, x2 ═ NB, then u1 ═ NB;
rule 7: if x 1-NB, x 2-PB, then u 1-NB;
rule 8: if x1 ═ NB, x2 ═ ZE, then u1 ═ NB;
rule 9: if x 1-NB, x 2-NB, then u 1-NB;
and (3) a fuzzy resolving process:
and the solution of the fuzzy is carried out by adopting a maximum membership method.
The invention relates to a working principle of a solar energy-based medium-temperature fuel cell carbon cycle power generation device, which comprises the following steps: in the device, the molten carbonate fuel cell, the solid oxide fuel cell and the carbon reaction chamber all need to operate at high temperature, the operating temperature is about 700 ℃ (the specific operating temperature depends on materials adopted in all links), the required high temperature is from solar energy, the solar energy is focused on the solar heat collector through the solar reflector group, the heat energy is stored in the heat reservoir through the solar heat exchanger, the heat reservoir provides heat energy for the molten carbonate fuel cell through the separation heat exchanger, the solid oxide fuel cell is provided with heat energy through the fuel cell stack heat exchanger, and the carbon reaction chamber is provided with heat energy through the carbon reaction chamber heat exchanger. The carbon reaction chamber is filled with a large amount of solid carbon, carbon dioxide is introduced into the carbon reaction chamber, the solid carbon can be converted into gaseous carbon monoxide, and the carbon dioxide which does not participate in the reaction and the generated carbon monoxide form mixed gas at an outlet, and the carbon reaction chamber is used for storing carbon dioxideThe mixed gas passes through the mixed gas separation device, the carbon monoxide/carbon dioxide mixed gas enters from the air inlet of the cathode plate of the molten carbonate fuel cell, and the carbon dioxide in the mixed gas reacts with oxygen at the cathode of the molten carbonate fuel cell to generate CO3 2-The unreacted carbon monoxide in the mixed gas is discharged from a gas outlet of a cathode plate of the molten carbonate fuel cell and is conveyed into the solid oxide fuel cell through a carbon monoxide conveying pipeline; CO 23 2-Ions pass through the electrolyte layer at the anode and H2Reaction to form H2O and CO2，H2O and CO2After being separated by a steam-water separator at the air outlet of the anode plate of the molten carbonate fuel cell, CO is separated2Discharging through a carbon dioxide conveying pipeline; carbon dioxide is returned and sent to the carbon reaction chamber to participate in the cyclic reaction; the invention judges whether the anode generates carbon deposition by detecting the voltage at the two ends of the solid oxide fuel cell, if the carbon deposition is generated, the voltage at the two ends of the solid oxide fuel cell can generate obvious reduction, at the moment, the controller controls the carbon dioxide electric control valve to be opened, the carbon dioxide gas discharged by the mixed gas separation device is sent to the anode of the solid oxide fuel cell to eliminate the carbon deposition, and when the voltage at the two ends of the solid oxide fuel cell is recovered, the controller controls the carbon dioxide electric control valve to be closed to stop the supply of the carbon dioxide to the solid oxide fuel cell.
Has the advantages that: firstly, the solar energy is used as a heat energy source required by the system, other power sources are not needed, and the solar energy heat pump system has the advantages of energy conservation and environmental protection; secondly, the solid carbon is gasified, the obtained carbon monoxide is used as the fuel of the solid oxide fuel cell, and the exhausted carbon dioxide of the solid oxide fuel cell is returned to the carbon gasification chamber again, so that a closed loop is formed in the whole capacity production process, any gas and substance do not need to be discharged outside, and the problem of environmental pollution is effectively avoided; thirdly, the invention effectively separates the mixed gas of carbon monoxide and carbon dioxide by using the molten carbonate fuel cell; finally, carbon dioxide is used for eliminating carbon deposition of the anode of the solid oxide fuel cell, and long-term stable operation of the system can be guaranteed.
Drawings
FIG. 1 is a system schematic diagram of a solar-based medium-temperature fuel cell carbon cycle power plant according to the present invention;
FIG. 2 is a schematic diagram of gas separation for a molten carbonate fuel cell;
fig. 3 is a schematic diagram of a molten carbonate fuel cell.
Detailed Description
As shown in fig. 1 to 3, the intermediate-temperature fuel cell carbon cycle power generation device based on solar energy of the present invention includes a solar reflector group 1, a solar heat collector 2, a solar heat exchanger 3, a heat reservoir 4, a separation heat exchanger 5, a mixed gas separation device 6, an electric control valve 7, a solid oxide fuel cell 8, a controller 9, an inverter 10, a fuel cell stack heat exchanger 11, a carbon reaction chamber 12, and a carbon reaction chamber heat exchanger 13; the solar reflector group 1 reflects solar rays and focuses the solar rays on the solar heat collector 2, a working medium in the solar heat collector 2 is heated to a high temperature, the working medium in the solar heat collector 2 stores heat energy in the heat reservoir 4 through the solar heat exchanger 3, and the heat reservoir 4 provides heat energy for the mixed gas separation device 6, the solid oxide fuel cell 8 and the carbon reaction chamber 12 through the separation heat exchanger 5, the fuel cell stack heat exchanger 11 and the carbon reaction chamber heat exchanger 13 respectively; the carbon reaction chamber 12 contains a large amount of coal, carbon dioxide gas is introduced into the carbon reaction chamber 12 and reacts to generate carbon monoxide in a high-temperature environment, the carbon reaction chamber 12 discharges the generated carbon monoxide and carbon dioxide mixed gas which does not participate in the reaction into the mixed gas separation device 6 through a gas discharge port, the carbon monoxide is separated by the mixed gas separation device 6 and then sent into the solid oxide fuel cell 8 to be used as fuel (the separated carbon monoxide is sent into the carbon monoxide storage tank 15 through a carbon monoxide conveying pipeline, the carbon monoxide in the storage tank 15 is sent into an anode gas inlet of the solid oxide fuel cell 8 through a gas pipe, an electric control valve 16 is arranged on the gas pipe), the solid oxide fuel cell 8 generates carbon dioxide and electric energy after reacting, the electric energy is changed into alternating current electric energy to be supplied to a load through the inverter 10, and the carbon dioxide generated by the solid oxide fuel cell 8 is fed back to the carbon reaction chamber 12 to be used for continuously Conversion to carbon monoxide; meanwhile, carbon dioxide separated by the mixed gas separation device 6 is discharged through a carbon dioxide conveying pipeline, the carbon dioxide conveying pipeline is divided into two branches, a branch I is connected with the carbon reaction chamber 12, a branch II is connected with the anode of the solid oxide fuel cell 8, and an electric control valve 7 is arranged on the branch II; when carbon dioxide needs to be used, the electronic control valve 7 is opened, the carbon dioxide is sent to an anode gas inlet of the solid oxide fuel cell 8 (at the moment, the electronic control valve 16 is in a closed state) and used for removing carbon deposition generated by an anode, the controller 9 detects voltages at two ends of the solid oxide fuel cell 8 in real time, carbon deposition conditions are judged, and the actions of the electronic control valve 7 and the electronic control valve 16 are controlled through the carbon deposition conditions. The electric control valve 7 and the electric control valve 16 are respectively connected with the controller 9 through cables, the acquisition module 17 acquires voltages at two ends of the solid oxide fuel cell 8 in real time and sends acquired signals to the controller 9 (the acquisition module 17 is a voltage sensor), namely, a cathode and an anode of the solid oxide fuel cell are respectively connected with the voltage sensor 17, and the voltage sensor 17 is connected with the controller 9 through cables.
The mixed gas separation device 6 comprises a molten carbonate fuel cell 16 and a steam-water separator 14 positioned at the gas outlet of the anode plate of the molten carbonate fuel cell 16; wherein the molten carbonate fuel cell 16 and the solid oxide fuel cell 8 are connected in parallel to supply power to an external load, namely, the cathode of the molten carbonate fuel cell 16 is connected in parallel with the cathode of the solid oxide fuel cell 8 through a wire, and the anode of the molten carbonate fuel cell 16 is connected in parallel with the anode of the solid oxide fuel cell 8 through a wire. The steam-water separator 14 is used for separating CO2、H2O and unreacted H2Unreacted H2And returning the molten carbonate fuel cell anode through the gas path through the anode plate gas inlet for reuse.
The molten carbonate fuel cell 16 of the present invention is a fuel cell composed of a porous lithium nickel oxide cathode 6-1, a porous electrolyte membrane 6-2, a porous metal anode 6-3 and a metal plate, wherein the electrolyte is molten carbonate. The metal polar plates are respectively an anode polar plate 18 and a cathode polar plate 21, the anode polar plate 18 is provided with an anode air inlet 20 and an anode air outlet 19, and the cathode polar plate 21 is provided with a cathode air inlet 23 and a cathode air outlet 22. Perforated current collecting plates 25 are also arranged between the cathode 6-1 and the cathode plate 21 and between the anode 6-3 and the anode plate 18.
The surface of the cathode plate 21, which is in contact with the cathode 6-1, is provided with a gas flowing channel 24, when the mixed gas flows in from the gas inlet 23 of the cathode plate 21, the gas capable of reacting on the surface of the cathode in the mixed gas gradually reacts with the surface of the cathode through the gas channel, the generated product enters the anode through the electrolyte layer 6-2, the cathode 6-1 and the anode 6-3 are porous materials, the mixed gas enters from the gas inlet 23 of the cathode plate 21, and after the reaction of the long gas channel, the gas which exits from the gas outlet 22 of the cathode plate 21 can be considered as the gas which is discharged from the gas outlet and is not reacted.
The anode 6-3 of the molten carbonate fuel cell 16 is metallic nickel; the cathode 6-1 is lithium nickel oxide; the electrolyte layer 6-2 is made of carbonate Li2CO3And K2CO3Mixed (electrolyte layer 6-2 conducting CO)3 2-Ions); wherein Li2CO3Is 62% by mass, K2CO3Is 38 percent.
Wherein, the exhaust port of the carbon reaction chamber 12 is connected with the inlet 23 of the cathode plate 21 of the molten carbonate fuel cell 16, the inlet 23 of the cathode plate is also connected with the external oxygen tank through a branch pipe, the carbon dioxide in the mixed gas reacts with the oxygen at the cathode 6-1 of the molten carbonate fuel cell 16 to generate CO3 2-Ion, CO3 2-Ions pass through the electrolyte layer 6-2 at the anode 6-3 and H2Reaction to form H2O and CO2，H2O and CO2After being separated by a steam-water separator 14 at the air outlet 19 of the anode plate, CO is separated2Discharging through a carbon dioxide conveying pipeline; unreacted carbon monoxide in the mixed gas is discharged from the cathode plate gas outlet 22 of the molten carbonate fuel cell 16 through a gas outletThe carbon oxide transfer line feeds into the solid oxide fuel cell 8.
The heat energy of the device is from the heat utilization of solar energy, and the generation and transmission of the heat energy are specifically as follows: the solar reflector group 1 reflects solar rays and focuses the solar rays on the solar heat collector 2, working media in the solar heat collector 2 are heated to high temperature which is above 900 ℃, the working media in the solar heat collector 2 store heat energy in the heat reservoir 4 through the solar heat exchanger 3, the temperature of the heat reservoir 4 is higher than 800 ℃, the heat reservoir 4 provides heat energy for the mixed gas separation device 6 through the separation heat exchanger 5, and the working temperature of the mixed gas separation device 6 is 750 ℃; the heat reservoir 4 provides heat energy for the solid oxide fuel cell 8 through the fuel cell stack heat exchanger 11, and the working temperature of the solid oxide fuel cell 8 is 750 ℃; the heat reservoir 4 provides heat energy to the carbon reaction chamber 12 through the carbon reaction chamber heat exchanger 13, and the working temperature of the carbon reaction chamber 12 is 700 ℃.
The invention relates to a carbon deposition treatment method of a solar energy-based medium-temperature fuel cell carbon cycle power generation device, wherein a controller controls the opening and closing of an electric control valve 7 by adopting a fuzzy control method:
the controller 9 monitors voltage signals at two ends of the solid oxide fuel cell 8 in real time, if the voltage signals are smaller than a fixed value, the controller 9 controls the electric control valve 7 to be opened, the electric control valve 16 is closed, carbon dioxide is added to the anode of the solid oxide fuel cell 8 at the moment, carbon deposition of the anode is eliminated, after the carbon deposition is eliminated, the voltage signals at two ends of the solid oxide fuel cell 8 are restored to a set value, the controller 9 controls the electric control valve 7 to be closed, the supply of carbon dioxide to the anode is cut off, the electric control valve 16 is opened, and fuel carbon monoxide is continuously introduced to the anode;
the fuzzy control method specifically comprises the following steps:
the control structure of the fuzzy controller is a 2-input and 1-output structure:
input variable x 1: the difference between the positive and negative voltages of the solid oxide fuel cell 8 and the standard voltage transformation;
input variable x 2: a rate of change of the difference;
output variable u 1: opening time of the electric control valve 7;
input and output variable discourse domain
The basic domain of input variables x1 and x2 is designed to be (0, 1), then the two input variables are divided into 3 linguistic variables, namely positive large (PB), Zero (ZE) and negative large (NB), and the membership function of the 3 linguistic variables of the two input variables in the basic domain of discourse (0, 1) is a triangle and trapezoid combined membership function;
the basic domain of output variable U1 is (0, 1), and the output variable is divided into 3 linguistic variables U, namely positive large (PB), Zero (ZE) and negative large (NB);
the membership function of the output variable u1 in the basic discourse domain is (0, 1) is a triangle and trapezoid combined membership function;
designing a fuzzy control rule:
the principle of designing the fuzzy control rule is that when the error is large or large, the control quantity is selected to eliminate the error as soon as possible, and when the error is small or small, the control quantity is selected to control the overshoot, and the fuzzy control rule of the typical working condition is as follows:
rule 1: if x1 and x2 are PB, then u1 is PB;
rule 2: if x1 ═ PB, x2 ═ ZE, then u1 ═ ZE;
rule 3: if x1 is PB and x2 is NB, then u1 is NB;
rule 4: if x1 ═ ZE, x2 ═ PB, then u1 ═ ZE;
rule 5: if x1 ═ ZE, x2 ═ ZE, then u1 ═ ZE;
rule 6: if x1 ═ ZE, x2 ═ NB, then u1 ═ NB;
rule 7: if x 1-NB, x 2-PB, then u 1-NB;
rule 8: if x1 ═ NB, x2 ═ ZE, then u1 ═ NB;
rule 9: if x 1-NB, x 2-NB, then u 1-NB;
and (3) a fuzzy resolving process:
and the solution of the fuzzy is carried out by adopting a maximum membership method.

Claims (9)

1. The utility model provides an intermediate temperature fuel cell carbon cycle power generation facility based on solar energy which characterized in that: the device comprises a solar energy absorption and conversion device, a carbon reaction chamber, a mixed gas separation device and a solid oxide fuel cell; the solar energy absorption and conversion device supplies heat energy to the carbon reaction chamber, the mixed gas separation device and the solid oxide fuel cell through the heat exchangers respectively; the carbon reaction chamber generates carbon monoxide by utilizing heat energy after being charged with carbon dioxide, an exhaust port of the carbon reaction chamber is connected with a mixed gas separation device, the mixed gas separation device separates the carbon monoxide and the carbon dioxide discharged from the carbon reaction chamber, the separated carbon monoxide is sent into a solid oxide fuel cell through a carbon monoxide conveying pipeline, the separated carbon dioxide is discharged through a carbon dioxide conveying pipeline, the carbon dioxide conveying pipeline is divided into two branches, the branch I is connected with the carbon reaction chamber, the branch II is connected with the anode of the solid oxide fuel cell, and an electric control valve is arranged on the branch II; the solid oxide fuel cell utilizes carbon monoxide to generate carbon dioxide and electric energy, the generated carbon dioxide is sent into a carbon reaction chamber, and the generated electric energy is supplied to an external load; the solid oxide fuel cell system further comprises a controller, the electric control valve is connected with the controller through a cable, and the controller collects voltages at two ends of the solid oxide fuel cell through a voltage sensor.
2. A solar-based medium-temperature fuel cell carbon cycle power plant according to claim 1, characterized in that: the solar energy absorption and conversion device comprises a solar reflector group, a solar thermal collector, a solar heat exchanger and a heat reservoir, wherein solar rays are reflected by the solar reflector group and focused on the solar thermal collector, and heat energy in the solar thermal collector is stored in the heat reservoir through the solar heat exchanger.
3. A solar-based medium-temperature fuel cell carbon cycle power plant according to claim 2, characterized in that: the heat exchanger comprises a separation heat exchanger, a fuel cell stack heat exchanger and a carbon reaction chamber heat exchanger, the heat energy output end of the heat reservoir is respectively connected with the heat energy input ends of the separation heat exchanger, the fuel cell stack heat exchanger and the carbon reaction chamber heat exchanger, the heat energy output end of the separation heat exchanger is connected with the mixed gas separation device, the heat energy output end of the fuel cell stack heat exchanger is connected with the solid oxide fuel cell, and the heat energy output end of the carbon reaction chamber heat exchanger is connected with the carbon reaction chamber.
4. A solar-based medium-temperature fuel cell carbon cycle power plant according to claim 1, characterized in that: the carbon reaction chamber contains solid coal, and the filling amount of the coal is more than 3/4 of the volume of the cavity of the carbon reaction chamber.
5. A solar-based medium-temperature fuel cell carbon cycle power plant according to claim 1, characterized in that: the mixed gas separation device comprises a molten carbonate fuel cell and a steam-water separator positioned at the gas outlet of the anode plate of the molten carbonate fuel cell; wherein the molten carbonate fuel cell is in parallel with the solid oxide fuel cell to power an external load.
6. A solar-based medium-temperature fuel cell carbon cycle power plant according to claim 5, characterized in that: the anode of the molten carbonate fuel cell is metallic nickel; the cathode is lithium nickel oxide; the electrolyte layer is made of carbonate Li2CO3And K2CO3Mixing and preparing; wherein Li2CO3Is 62% by mass, K2CO3Is 38 percent.
7. A solar-based medium-temperature fuel cell carbon cycle power plant according to claim 5, characterized in that: the exhaust port of the carbon reaction chamber is connected with the cathode plate air inlet of the molten carbonate fuel cell, the cathode plate air inlet is also connected with an external oxygen tank through a branch pipe, and carbon dioxide reacts with oxygen at the cathode of the molten carbonate fuel cell to generate CO3 2-Ion, CO3 2-Ions pass through the electrolyte layer at the anode and H2Reaction to form H2O and CO2，H2O and CO2After being separated by a steam-water separator at the air outlet of the anode plate, CO is separated2Through a carbon dioxide conveying pipeDischarging; and unreacted carbon monoxide is discharged from the outlet of the cathode plate of the molten carbonate fuel cell and is conveyed into the anode of the solid oxide fuel cell through a carbon monoxide conveying pipeline.
8. A carbon deposition treatment method for a solar-based medium-temperature fuel cell carbon cycle power generation device according to claim 1, characterized in that: the carbon deposition treatment method comprises the following steps: the controller monitors voltage signals at two ends of the solid oxide fuel cell in real time, and controls the electric control valve to be opened if the voltage signals are smaller than a fixed value, so that carbon dioxide is added to the anode of the solid oxide fuel cell, and carbon deposition of the anode is eliminated; after carbon deposition is eliminated, voltage signals at two ends of the solid oxide fuel cell recover to set values, the controller controls the electric control valve to be closed, carbon dioxide supply of the anode of the solid oxide fuel cell is cut off, and carbon monoxide fuel continues to be introduced into the anode of the solid oxide fuel cell.
9. The carbon deposition treatment method of the solar-based medium-temperature fuel cell carbon cycle power generation device according to claim 8, characterized in that: specifically, a fuzzy control method is adopted for control:
the control structure of the fuzzy controller is a 2-input and 1-output structure:
input variable x 1: the difference value of the anode and cathode voltages of the solid oxide fuel cell and the standard transformation voltage;
input variable x 2: a rate of change of the difference;
output variable u 1: opening time of the electric control valve;
input and output variable discourse domain
The basic domain of input variables x1 and x2 is designed to be (0, 1), then the two input variables are divided into 3 linguistic variables, namely positive large (PB), Zero (ZE) and negative large (NB), and the membership function of the 3 linguistic variables of the two input variables in the basic domain of discourse (0, 1) is a triangle and trapezoid combined membership function;
the basic domain of output variable U1 is (0, 1), and the output variable is divided into 3 linguistic variables U, namely positive large (PB), Zero (ZE) and negative large (NB);
the membership function of the output variable u1 in the basic discourse domain is (0, 1) is a triangle and trapezoid combined membership function;
designing a fuzzy control rule:
the principle of designing the fuzzy control rule is that when the error is large or large, the control quantity is selected to eliminate the error as soon as possible, and when the error is small or small, the control quantity is selected to control the overshoot, and the fuzzy control rule of the typical working condition is as follows:
rule 1: if x1 and x2 are PB, then u1 is PB;
rule 2: if x1 ═ PB, x2 ═ ZE, then u1 ═ ZE;
rule 3: if x1 is PB and x2 is NB, then u1 is NB;
rule 4: if x1 ═ ZE, x2 ═ PB, then u1 ═ ZE;
rule 5: if x1 ═ ZE, x2 ═ ZE, then u1 ═ ZE;
rule 6: if x1 ═ ZE, x2 ═ NB, then u1 ═ NB;
rule 7: if x 1-NB, x 2-PB, then u 1-NB;
rule 8: if x1 ═ NB, x2 ═ ZE, then u1 ═ NB;
rule 9: if x 1-NB, x 2-NB, then u 1-NB;
and (3) a fuzzy resolving process:
and the solution of the fuzzy is carried out by adopting a maximum membership method.
CN202010527161.1A 2020-06-10 2020-06-10 Solar energy-based medium-temperature fuel cell carbon cycle power generation device and carbon deposition treatment method thereof Pending CN111584907A (en)

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