CN115074751B - High-temperature electrolytic hydrogen production system and method capable of continuously and stably operating and application thereof - Google Patents
High-temperature electrolytic hydrogen production system and method capable of continuously and stably operating and application thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 195
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 195
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 110
- 230000002441 reversible effect Effects 0.000 claims abstract description 86
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 84
- 238000005338 heat storage Methods 0.000 claims abstract description 53
- 238000003860 storage Methods 0.000 claims abstract description 51
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000005485 electric heating Methods 0.000 claims abstract description 8
- 230000005855 radiation Effects 0.000 claims description 25
- 239000000446 fuel Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000010248 power generation Methods 0.000 description 18
- 230000005611 electricity Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
- C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/67—Heating or cooling means
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Abstract
The invention discloses a high-temperature electrolytic hydrogen production system and method capable of continuously and stably operating and application thereof. The system mainly comprises a photovoltaic cell array, a solar heat collector, a reversible solid oxide electrolysis hydrogen production unit, a storage battery, an electric steam generator, a ternary fused salt heat storage tank, a steam generator and a hydrogen storage unit. In the hydrogen production system, when sunlight is enough, the photovoltaic cell array provides electric energy for the reversible solid oxide electrolysis hydrogen production unit and the electric heating equipment, the residual electric energy is stored in the storage battery, and the heat storage tank stores heat absorbed by the solar heat collector and provides steam for the electrolysis hydrogen production process at any time; when the sunshine is insufficient, the storage battery and the heat storage tank device respectively provide electric energy and heat energy for the hydrogen production unit and the electric heating equipment, and the hydrogen production unit is maintained to work. The system integrates solar-driven high-temperature solid oxide electrolysis hydrogen production with ternary fused salt heat storage and storage battery technology in a coupling way, and realizes continuous and stable hydrogen production of the reversible solid oxide electrolysis hydrogen production unit under the drive of solar energy.
Description
Technical Field
The invention belongs to the field of high-temperature electrolytic hydrogen production and solar energy utilization, and particularly relates to a solar-driven high-temperature electrolytic hydrogen production system capable of continuously and stably running; in particular to a high-temperature electrolytic hydrogen production system and method capable of continuously and stably operating and application thereof.
Background
With the increasing serious problems of energy exhaustion, climate change, environmental pollution and the like caused by the use of fossil energy, the use of new energy is gradually promoted worldwide. The hydrogen energy is used as a high-efficiency and clean secondary energy source, and is widely developed. Electrolytic water hydrogen production is considered the cleanest hydrogen production method because of no pollutant emissions in the preparation process and the product. At present, the technology for producing hydrogen by electrolyzing water mainly adopts low-temperature water electrolysis, and has high energy consumption. The solid oxide electrolysis technology is operated in a high-temperature environment (600-1000 ℃), can accelerate the electrode reaction rate, effectively reduces the energy loss in the electrolysis process, has the electrolysis efficiency of a galvanic pile of more than 90 percent, and is an efficient energy conversion device. Under the double-carbon strategic goal of China, the technology for driving the electrolytic water to produce hydrogen by using the electric energy generated by renewable energy sources such as solar energy has great development potential, but the solar energy cannot be used as a stable electric energy and heat energy source because of the fluctuation and instability of sunlight, so that the technology is insufficient for supporting long-term, continuous and stable operation of hydrogen production equipment.
Currently, the prior art provides a partial solution to the above problems. In patent CN 112944697A published by 2021, 6 and 11, the invention relates to a solar photo-thermal/photovoltaic comprehensive energy cascade utilization system, solar photo-thermal converts solar energy into heat energy through a heliostat field and a heat absorber, and the heat energy is used for cascade utilization of photovoltaic cell arrays at different temperatures in a circulation process in a heat exchange medium heat energy mode through a heat exchange system to directly generate electricity and produce hydrogen through electrolysis of water for solar energy efficient conversion. The water electrolysis hydrogen production system is one or the composition of alkaline electrolysis, proton exchange membrane electrolysis, high-temperature electrolysis and the like. The solar photo-thermal/photovoltaic comprehensive energy system can realize continuous, stable and efficient step operation, and improves the energy utilization efficiency of solar energy. In the system, although the heat energy converted by solar energy is stored through the heat storage device, the electric energy generated by the photovoltaic cell array cannot be stored without the electric storage device and a corresponding control strategy, and the power supply for the electrolytic cell cannot be continuously and stably realized. When the solar radiation fluctuates or is not available, the high-temperature heat reservoir releases heat, and the photovoltaic cell array does not generate electricity and hydrogen any more. Meanwhile, the standby mode of the electrolytic hydrogen production system is not designed in the patent.
In patent CN 111139493A published in year 2020, 12, the invention relates to a solar photovoltaic photo-thermal high-temperature water electrolysis hydrogen production system and a hydrogen production method, and the produced high-temperature hydrogen and high-temperature oxygen are subjected to twice heat exchange, so that the heat of high-temperature gas generated by water electrolysis under high current in a high-temperature electrolytic cell is fully utilized, and the efficiency of the solar water electrolysis system is improved. The system is coupled with photovoltaic photo-thermal and high-temperature electrolysis, reasonably utilizes solar energy to produce hydrogen, and avoids instability of direct solar energy power generation. The problems of low efficiency, environmental protection and the like of the existing low-temperature hydrogen production are solved by reasonably utilizing the existing mature photo-thermal technology. In the system, the heat storage device is connected with the high-temperature steam generator, 800-degree high-temperature steam can be provided for the solid oxide electrolytic cell, so that the temperature of hydrogen and oxygen is reduced, but the electric energy generated by the photovoltaic cell array cannot be stored due to the fact that the electric energy source is not available when solar radiation is insufficient, continuous and stable power supply for the electrolytic cell cannot be realized, and then the electrolytic water hydrogen production system cannot continuously operate.
The invention patent CN 106884179A published on the 12 th year of the invention patent 2020 published on the 23 th month of 2017 relates to an electrolytic water vapor device based on trough solar energy. The water supply pump pumps water into the tank type solar heat utilization subsystem to heat the water into high-temperature water vapor, the high-temperature water vapor is obtained and sent to the electrolysis subsystem, and the electric energy required by the electrolysis cell and the auxiliary heater of the electrolysis subsystem is from the photovoltaic array or the storage battery. The water is heated into high-temperature steam by utilizing trough-type concentrating solar energy, then solar photovoltaic power generation is utilized, and the high-temperature steam is electrolyzed to obtain hydrogen and oxygen. The device has set up the battery and has stored the electric energy that photovoltaic array produced, but if guarantee long-term continuous operation, the capacity of required battery is great, leads to the cost too high. Compared with an electricity storage system, the heat storage system is lower in cost. This invention focuses on efficient conversion of water vapor and is not related in detail to continuous operation of the electrolysis system.
The invention patent CN 113357694A published in 9/17 of 2021 relates to a multi-energy coupling energy storage and supply system, which comprises a basic heat source area, a heat storage area, a photovoltaic power generation and supply area, a frequency modulation peak regulation energy storage area and an electrochemical power storage area, wherein the basic heat source area comprises a ground heat source and a heat pump, and the ground heat source, the heat pump and a heat energy pipe network are connected; the heat storage area comprises a low-temperature phase-change heat storage unit, the low-temperature phase-change heat storage unit is connected with a heat energy pipe network, and heat energy output by the heat pump through the heat energy pipe network is stored; the photovoltaic power generation and supply area comprises a solar power generation module, wherein the solar power generation module absorbs solar energy and converts the solar energy into electric energy, and the electric energy is connected with a power supply network; the frequency modulation peak regulation energy storage area comprises a reversible solid oxide fuel cell, the solid oxide fuel cell carries out electrolysis hydrogen production on electric energy from a power supply network and stores the electric energy into hydrogen energy, and outputs hydrogen generated by electrolysis and fuel of a natural gas pipe network to generate new electric energy, the new electric energy is connected with the power supply network, and frequency modulation and peak regulation are carried out on the power supply network; the electrochemical electricity storage area comprises a flow battery which is connected with the frequency modulation peak regulation energy storage area. When the photovoltaic power generation is insufficient in electric energy and the electricity price is high, the bidirectional solid oxide fuel cell/electrolyzer system is temporarily used as a standby energy source for power generation. Although the invention provides a liquid phase battery and a phase change heat storage device for storing electricity and heat, the invention does not relate to a continuous operation process control method of an electrolytic cell, and the continuous operation of the electrolytic cell and the possible starting and stopping problems of the electrolytic cell are not emphasized.
Lv Zewei, and the like, construct a sustainable power generation system combining photo-thermal steam generation, photovoltaic power generation, solid Oxide Electrolytic Cell (SOEC) water electrolysis hydrogen production and Solid Oxide Fuel Cell (SOFC) power generation complementation, and perform system parameter and energy efficiency optimization balance calculation. The system utilizes the high-temperature steam generated by the photo-thermal system to carry out high-temperature electrolysis, and can effectively reduce the electric energy consumption of the electric steam generator, thereby improving the energy storage efficiency. The energy storage mode of storing the surplus electric energy into the fuel chemical energy through high-temperature electrolysis can realize peak clipping and valley filling of the power grid, and reduces impact of fluctuation renewable energy sources on the power grid. The system generates electricity by the photovoltaic power generation system in the daytime, redundant electric energy is used for producing hydrogen by the SOEC system through electrolysis, and the SOEC power generation system generates electricity at night, so that the purpose of continuous power generation is realized. In order to maintain the stability of output power, the scales of the photo-thermal system, the photovoltaic system, the SOEC system and the SOFC system are required to be optimized and combined to be matched with each other, and the hydrogen produced by the SOEC system in the daytime is required to meet the power generation requirement of the SOEC system at night so as to ensure the all-weather continuous operation of the whole system. However, on the premise of ensuring stable output, the SOEC system can not ensure that redundant electric energy is used for producing hydrogen by electrolysis; meanwhile, high-temperature steam required for hydrogen production is provided by a photo-thermal system, and the heat energy requirement of the SOEC system for hydrogen production by electrolysis cannot be guaranteed at night because a heat storage system is not arranged, so that the problem of continuous hydrogen production of the SOEC system is not solved.
Because solar energy has the characteristics of volatility and intermittence, the prior art can not break through the technical bottleneck of continuous operation of the solar-driven electrolytic hydrogen production system. In the prior art, the solar heat collection device and the power generation device cannot be combined with the heat storage system and the power storage system at the same time, so that long-term stable and continuous heat energy and electric energy sources cannot be provided for the hydrogen production system. The invention provides a solar-driven high-temperature electrolytic hydrogen production system capable of continuously and stably running, which combines a solar-driven solid oxide electrolytic cell hydrogen production technology with a single-tank molten salt heat storage technology and a storage battery, solves the problem of discontinuous heat energy and electric energy supply, realizes clean and continuous hydrogen production, and has wide application prospect.
Disclosure of Invention
In order to solve the problem that a solar-driven electrolytic hydrogen production system cannot continuously work, the invention aims to provide a continuous and stable high-temperature electrolytic hydrogen production system, a continuous and stable high-temperature electrolytic hydrogen production method and application thereof, and the technical scheme is as follows:
The utility model provides a but continuous steady operation's high temperature electrolysis hydrogen manufacturing system, includes photovoltaic cell square matrix, battery, solar collector, its characterized in that:
When the solar radiation is enough, the generated energy of the photovoltaic cell square matrix is enough, and the generated electric quantity is respectively supplied to an electric steam generator, a storage battery and a reversible solid oxide electrolysis hydrogen production unit;
The solar heat collector absorbs solar radiation energy, stores the solar energy through the ternary fused salt heat storage tank and is connected with the reversible solid oxide electrolysis hydrogen production unit through the steam generator;
The reversible solid oxide electrolysis hydrogen production unit (4) comprises a galvanic pile, a fuel side heat exchanger, a fuel side electric heater, an air side heat exchanger, an air side electric heater, a pump, a fan and other devices;
when the solar energy radiation is insufficient, the stored electric energy is released to the reversible solid oxide electrolysis hydrogen production unit and the electric steam generator through the storage battery;
When the solar radiation and the residual electric quantity of the storage battery are insufficient, the photovoltaic cell array and the storage battery are insufficient to support the operation of the reversible solid oxide electrolytic hydrogen production unit, and the reversible solid oxide electrolytic hydrogen production unit is in a thermal standby mode. In the hot standby mode, the reversible solid oxide electrolytic hydrogen production unit reversely operates in a fuel cell mode, converts the chemical energy of hydrogen into electric energy, maintains the operation of a solid oxide electrolytic system, and maintains the temperature of an electrolytic cell to be above 600 ℃, thereby ensuring that the reversible solid oxide electrolytic hydrogen production unit can be quickly switched to a hydrogen production mode and realizing the continuous operation of the reversible solid oxide electrolytic hydrogen production unit.
The invention also discloses a solar-driven high-temperature electrolysis hydrogen production method capable of continuously and stably operating, which comprises the following steps:
When the solar radiation is enough, the photovoltaic cell array provides electric energy for the reversible solid oxide electrolytic hydrogen production unit and the electric heating equipment, the residual electric energy is stored in the storage battery, and the heat storage tank stores the heat absorbed by the solar heat collector and provides steam for the electrolytic hydrogen production process at any time;
When the solar radiation is insufficient, the storage battery and the heat storage tank device respectively provide electric energy and heat energy for the reversible solid oxide electrolytic hydrogen production unit and the electric heating equipment, and the reversible solid oxide electrolytic hydrogen production unit is maintained to work;
When the solar radiation and the residual electric quantity of the storage battery are insufficient, the photovoltaic cell array and the storage battery are insufficient to support the operation of the reversible solid oxide electrolytic hydrogen production unit, and the reversible solid oxide electrolytic hydrogen production unit is in a thermal standby mode. In the hot standby mode, the reversible solid oxide electrolytic hydrogen production unit reversely operates in a fuel cell mode, converts the chemical energy of hydrogen into electric energy, maintains the operation of a solid oxide electrolytic system, and maintains the temperature of the reversible solid oxide electrolytic hydrogen production unit above 600 ℃, thereby ensuring that the reversible solid oxide electrolytic hydrogen production unit can be quickly switched to a hydrogen production mode and realizing the continuous operation of the reversible solid oxide electrolytic hydrogen production unit.
The invention also discloses a high-temperature electrolytic hydrogen production system which is driven by the solar energy and can continuously and stably run, and the system is applied to the high-temperature electrolytic hydrogen production device.
Advantageous effects
The solar-driven high-temperature solid oxide electrolysis hydrogen production and ternary fused salt heat storage and storage battery technology are coupled and integrated, so that the reversible solid oxide electrolysis hydrogen production unit can continuously and stably produce hydrogen under intermittent solar drive, and has the following characteristics:
(1) The electric energy can be stored in the storage battery, and the electric energy can be released to equipment such as the reversible solid oxide electrolytic hydrogen production unit, the electric steam generator and the like when no photovoltaic power generation is performed, so that the continuous operation electric heating requirement of the reversible solid oxide electrolytic hydrogen production unit is ensured;
(2) The heat storage system is arranged, and the single-tank ternary molten salt heat storage tank stores heat absorbed by the solar heat collector, so that steam required by the operation of the reversible solid oxide electrolysis hydrogen production unit can be provided at any time, and the continuous operation heat requirement of the reversible solid oxide electrolysis hydrogen production unit is ensured;
(3) The reversible solid oxide electrolysis hydrogen production unit has two working modes, namely a hydrogen production mode and a hot standby mode; in the hot standby mode, the reversible solid oxide electrolytic hydrogen production unit converts hydrogen into the minimum power (blower, pump, etc.) and enough heat required for maintaining the system operation, so that the temperature of the reversible solid oxide electrolytic hydrogen production unit is maintained above 600 ℃, and the reversible solid oxide electrolytic hydrogen production unit can be quickly switched to a hydrogen production mode.
Drawings
FIG. 1 is a system, method and application of continuous steady operation high temperature electrolytic hydrogen production.
FIG. 2 is a flow chart of a solar-driven continuous steady operation high-temperature electrolytic hydrogen production method.
In the figure: the solar energy heat storage device comprises a 1-photovoltaic cell square matrix, a 2-electric steam generator, a 3-storage battery, a 4-reversible solid oxide electrolytic hydrogen production unit, a 5-solar heat collector, a 6-ternary molten salt heat storage tank, a 7-steam generator and an 8-hydrogen storage unit.
Detailed Description
The invention provides a high-temperature electrolytic hydrogen production system capable of continuously and stably operating, a method and application thereof, and the system and the method are described below with reference to the accompanying drawings.
The solar-driven high-temperature electrolytic hydrogen production system capable of continuously and stably running is shown in fig. 1, one path of a photovoltaic cell matrix 1 is connected with an electric steam generator 2, and an air outlet of the electric steam generator 2 is connected with a reversible solid oxide electrolytic hydrogen production unit 4; the second path is directly connected with the reversible solid oxide electrolysis hydrogen production unit 4; the third path is connected with a storage battery 3, and the storage battery 3 can provide electric energy for the reversible solid oxide electrolysis hydrogen production unit 4; the solar heat collector 5 is connected with the ternary fused salt heat storage tank 6 to form a loop, the ternary fused salt heat storage tank 6 is connected with the steam generator 7, and the air outlet of the steam generator 7 is connected with the reversible solid oxide electrolysis hydrogen production unit 4; the reversible solid oxide electrolysis hydrogen production unit 4 is connected with the hydrogen storage unit 8.
According to the working principle of the solar-driven continuous and stable-operation high-temperature electrolytic hydrogen production system, when solar radiation is enough, the generated energy of the photovoltaic cell square matrix 1 is sufficient, and the reversible solid oxide electrolytic hydrogen production unit 4 is in a hydrogen production mode and supplies power to equipment such as a galvanic pile, a heat exchange module, a pump, a fan and the like in the hydrogen production unit; part of the electric energy generated by the photovoltaic cell array 1 is sent to the reversible solid oxide electrolysis hydrogen production unit 4, and the electric energy is provided for the reversible solid oxide electrolysis hydrogen production unit 4; part of the electric energy is sent into the electric steam generator 2, high-temperature steam generated by the electric steam generator 2 is sent into the reversible solid oxide electrolysis hydrogen production unit 4, and the high-temperature steam enters the reversible solid oxide electrolysis hydrogen production unit 4 to participate in chemical reaction; the rest electric energy is sent to the storage battery 3 for storage; the solar heat collector 5 absorbs solar radiation energy to convert the solar radiation energy into heat energy, and stores the solar energy through the heat storage device; the heat storage device adopts a single-tank ternary molten salt heat storage tank 6, and uses ternary molten salt as a heat storage medium, and energy is stored or emitted through conversion between heat energy collected by the solar heat collector and the internal energy of the molten salt. The molten salt is an inorganic phase-change heat storage material and has the characteristics of good heat storage performance, large phase-change latent heat, high heat conductivity coefficient, low production cost and the like; compared with single-component fused salt and binary fused salt, the ternary fused salt has low phase transition point and better thermal stability in a medium-high temperature environment; for the double-tank heat storage tank, the cold tank, the hot tank and the two heat exchangers of the single-tank heat storage tank are integrated in one unit, the tank body is reduced, the required heat storage medium molten salt is less, and the construction cost, the operation cost and the maintenance cost of the heat storage tank can be effectively reduced, so that the single-tank ternary molten salt heat storage tank is selected for the heat storage device. The heat storage tank cold section is provided with a heat absorption heat exchanger, the heat section is provided with a steam generator 7, water is heated into high-temperature steam by utilizing the heat energy of the heat storage tank 6, the steam generator 7 is connected with the reversible solid oxide electrolysis hydrogen production unit 4, steam can be provided for the reversible solid oxide electrolysis hydrogen production unit 4, and the generated hydrogen is stored in the hydrogen storage unit 8.
According to the working principle of the solar-driven continuous and stable-operation high-temperature electrolytic hydrogen production system, when solar radiation is insufficient, the storage battery 3 releases stored electric energy to the reversible solid oxide electrolytic hydrogen production unit 4 and the electric steam generator 2; the heat stored in the single-tank ternary molten salt heat storage tank 6 is provided for the steam generator 7, and high-temperature steam generated by the steam generator 7 enters the solid oxide reversible solid oxide electrolysis hydrogen production unit 4 to be converted into hydrogen and is stored in the hydrogen storage unit 8; when the solar radiation and the residual electricity of the storage battery 3 are insufficient, the photovoltaic cell square matrix 1 and the storage battery 3 are insufficient to support the operation of the reversible solid oxide electrolysis hydrogen production unit 4, and the reversible solid oxide electrolysis hydrogen production unit 4 is in a hot standby mode; in the hot standby mode, the reversible solid oxide electrolytic hydrogen production unit 4 reversely operates in a fuel cell mode, converts hydrogen chemical energy into electric energy, maintains the operation of a solid oxide electrolytic system, and maintains the temperature of the reversible solid oxide electrolytic hydrogen production unit 4 above 600 ℃, thereby ensuring that the reversible solid oxide electrolytic hydrogen production unit 4 can be quickly switched to a hydrogen production mode, and realizing continuous operation of the reversible solid oxide electrolytic hydrogen production unit 4.
The reversible solid oxide electrolysis hydrogen production unit (4) comprises a galvanic pile, a fuel side heat exchanger, a fuel side electric heater, an air side heat exchanger, an air side electric heater, a pump, a fan and other devices.
The structure of a solid oxide cell is typically composed of a three-part structure, namely an anode, a cathode and an electrolyte. The anode (air electrode) and the cathode (fuel electrode) are arranged on two sides, and a compact electrolyte layer is arranged in the middle. The working temperature of the solid oxide water electrolysis hydrogen production is higher, about 600-1000 ℃. During operation, water vapor is introduced into one side of the fuel electrode, a certain voltage is applied between the cathode and the anode of the electrolytic cell, under the driving, H 2 O is decomposed into H 2 and consumed electrons to generate O 2-,O2-, the O 2-,O2- is transmitted to the fuel electrode through a compact electrolyte, the water vapor generates electrons at the cathode to form H 2 and O 2-,O2-, and the electrons reach the anode through the electrolyte layer to generate O 2. The specific reaction formula is as follows:
Cathode reaction: h 2O+2e-→H2+O2-
Anode reaction:
Total reaction of electrolysis:
In the hot standby mode, the reversible solid oxide electrolysis hydrogen production unit is operated in the fuel cell mode in reverse. The anode of the solid oxide fuel cell is used for transporting electrons and simultaneously catalytically oxidizing the fuel on the anode side; the cathode is used for reducing O 2 to O 2-; the electrolyte is used for separating the negative electrode and the positive electrode and transmitting ions. When a traditional solid oxide fuel cell (an oxygen ion conductor SOFC) works, O 2- generated by a cathode penetrates through an electrolyte layer to reach an anode, H 2 O and electrons are generated by the reaction of the anode and H 2, and the electrons are conducted to the cathode through an external circuit to form loop current. The reaction equation is:
Anode reaction: h 2+O2-→H2O+2e-
Cathode reaction: o 2+4e-→2O2-
Total reaction: 2H 2+O2→2H2 O
The working principle of the proton conductor SOFC is that hydrogen is catalyzed at an anode to generate H + and electrons, H + penetrates through an electrolyte layer to reach a cathode, H 2 O is generated by reaction of the cathode and O 2, and meanwhile, the electrons are conducted to the cathode through an external circuit to form loop current. The equation for the reaction is:
Anode reaction: h 2→2H++2e-
Cathode reaction: 4H ++O2+4e-→2H2 O
Total reaction: 2H 2+O2→2H2 O
In the solid oxide electrolytic hydrogen production system, the operation of equipment such as the reversible solid oxide electrolytic hydrogen production unit 4, the electric steam generator 2 and the like needs electric energy support, and the process of generating steam by the equipment such as the steam generator 7, the electric steam generator 2 and the like needs heat energy support. Thus, the solid oxide electrolytic hydrogen production system requires sufficient electrical and thermal energy supply to maintain the normal operation of the electrolysis process of water vapor in a high temperature environment. Therefore, if the continuous and stable operation of the solid oxide electrolysis hydrogen production system is to be realized, the continuous and stable supply of electric energy and heat energy is required to be ensured at the same time. In the existing solar-driven high-temperature water electrolysis hydrogen production technology, the electricity storage device and the heat storage device are not arranged at the same time, so that under the condition of insufficient solar radiation, continuous and stable supply of electric energy and heat energy cannot be ensured at the same time, and further continuous and stable operation of the solid oxide electrolysis hydrogen production unit cannot be maintained. Meanwhile, the prior patent does not relate to two working modes of starting and stopping an electrolytic cell and a switching method between the two working modes.
The invention is provided with a power storage system mainly comprising a storage battery 3 and a heat storage system mainly comprising a solar heat collector 5 and a single-tank ternary molten salt heat storage tank 6. The storage battery 3 can store electric energy and release the electric energy to equipment such as the reversible solid oxide electrolytic hydrogen production unit 4, the electric steam generator 2 and the like when no photovoltaic power generation is performed, so that the electric heating requirement of continuous operation of the reversible solid oxide electrolytic hydrogen production unit 4 is ensured; the single-tank ternary molten salt heat storage tank 6 stores the heat absorbed by the solar heat collector 5, so that steam required by the operation of the reversible solid oxide electrolysis hydrogen production unit 4 can be provided at any time, and the continuous operation heat requirement of the reversible solid oxide electrolysis hydrogen production unit 4 is ensured. In addition, the reversible solid oxide electrolysis hydrogen production unit 4 has two working modes, namely a hydrogen production mode and a hot standby mode; in the hot standby mode, the reversible solid oxide electrolytic hydrogen production unit 4 converts hydrogen into the minimum power (blower, pump, etc.) and enough heat required for maintaining the system to operate, so that the temperature of the reversible solid oxide electrolytic hydrogen production unit is maintained above 600 ℃, the conversion time of the hot standby mode and the hydrogen production mode can be greatly reduced, and the operation continuity of the solid oxide electrolytic hydrogen production system is increased.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The utility model provides a but continuous steady operation's high temperature electrolysis hydrogen manufacturing system, includes photovoltaic cell square matrix (1), battery (3), solar collector (5), its characterized in that:
When the solar radiation is enough, the generated energy of the photovoltaic cell square matrix (1) is enough, and the generated electric quantity is respectively supplied to the electric steam generator (2), the storage battery (3) and the reversible solid oxide electrolysis hydrogen production unit (4);
The solar heat collector (5) absorbs solar radiation energy, stores the solar energy through the ternary molten salt heat storage tank and is connected with the reversible solid oxide electrolysis hydrogen production unit (4) through the steam generator;
when the solar energy radiation is insufficient, the stored electric energy is released to the reversible solid oxide electrolysis hydrogen production unit (4) and the electric steam generator (2) through the storage battery (3);
when the solar radiation and the residual electric quantity of the storage battery (3) are insufficient, the photovoltaic cell square matrix (1) and the storage battery (3) are insufficient to support the operation of the reversible solid oxide electrolysis hydrogen production unit (4), and the reversible solid oxide electrolysis hydrogen production unit (4) is in a hot standby mode;
The hot standby mode is: the reversible solid oxide electrolytic hydrogen production unit (4) reversely operates in a fuel cell mode, converts hydrogen chemical energy into electric energy, maintains the operation of a solid oxide system, and maintains the temperature of the reversible solid oxide electrolytic hydrogen production unit (4) above 600 ℃, so that the reversible solid oxide electrolytic hydrogen production unit (4) can be rapidly switched to a hydrogen production mode, and continuous operation of the reversible solid oxide electrolytic hydrogen production unit (4) is realized;
when the solar energy radiation is insufficient, the heat stored in the ternary fused salt heat storage tank is provided for the steam generator (7), and high-temperature steam generated by the steam generator (7) enters the solid oxide reversible solid oxide electrolysis hydrogen production unit (4) to be converted into hydrogen.
2. The continuous steady operation high temperature electrolytic hydrogen production system according to claim 1, wherein: the ternary fused salt heat storage tank is a single-tank ternary fused salt heat storage tank (6), ternary fused salt is used as a heat storage medium, a cold tank, a hot tank and two heat exchangers are integrated in one unit, a heat absorption heat exchanger is arranged at a cold section, and a steam generator is arranged at a hot section.
3. The continuous steady operation high temperature electrolytic hydrogen production system according to claim 1, wherein: the reversible solid oxide electrolysis hydrogen production unit (4) comprises a galvanic pile, a fuel side heat exchanger, a fuel side electric heater, an air side heat exchanger, an air side electric heater, a pump and fan device.
4. The continuous steady operation high temperature electrolytic hydrogen production system according to claim 1, wherein: the air outlet of the electric steam generator (2) is respectively communicated with the reversible solid oxide electrolysis hydrogen production unit (4) and the steam generator (7); the output end of the solar heat collector (5) is sequentially connected with the input ends of the ternary molten salt heat storage tank (6) and the steam generator (7); the gas outlet of the steam generator (7) is connected with the reversible solid oxide electrolysis hydrogen production unit (4); the reversible solid oxide electrolysis hydrogen production unit (4) is connected with the hydrogen storage unit (8).
5. The continuous steady operation high temperature electrolytic hydrogen production system according to claim 1, wherein: when the solar radiation is enough, the generating capacity of the photovoltaic cell square matrix (1) is fully divided into three parts to be used: part of the electric energy is sent into a reversible solid oxide electrolysis hydrogen production unit (4) to supply power for a galvanic pile, an electric heater, a pump and fan equipment in the hydrogen production unit, so that the hydrogen production unit is in a hydrogen production state; part of the electric energy is sent into an electric steam generator (2), high-temperature steam generated by the electric steam generator (2) is sent into a reversible solid oxide electrolytic hydrogen production unit (4), and the high-temperature steam, hydrogen and air enter the reversible solid oxide electrolytic hydrogen production unit (4) to participate in chemical reaction; the rest electric energy is sent to a storage battery (3) for storage.
6. A continuously and stably operable high temperature electrolytic hydrogen production system according to claim 1, wherein the storage battery (3) releases the stored electric energy to the reversible solid oxide electrolytic hydrogen production unit (4) and the electric steam generator (2) when the solar radiation is insufficient; the heat stored in the ternary molten salt heat storage tank (6) is provided for the steam generator (7), high-temperature steam generated by the steam generator (7) enters the reversible solid oxide electrolysis hydrogen production unit (4) to be converted into hydrogen, and the hydrogen is stored in the hydrogen storage unit (8).
7. A solar-driven continuous steady operation high temperature electrolytic hydrogen production method, comprising the continuous steady operation high temperature electrolytic hydrogen production system as claimed in any one of claims 1-6, comprising the steps of:
When the solar radiation is enough, the photovoltaic cell array (1) provides electric energy for the reversible solid oxide electrolysis hydrogen production unit (4) and the electric heating equipment, the rest electric energy is stored in the storage battery (3), and the heat storage tank (6) stores the heat absorbed by the solar heat collector (5) and provides heat for the steam in the electrolysis hydrogen production process at any time;
When the solar radiation is insufficient, the storage battery (3) and the heat storage tank (6) respectively provide electric energy and heat energy for the reversible solid oxide electrolysis hydrogen production unit (4) and the electric heating equipment, and the reversible solid oxide electrolysis hydrogen production unit (4) is maintained to work;
when the solar radiation and the residual electric quantity of the storage battery (3) are insufficient, the photovoltaic cell array (1) and the storage battery (3) are insufficient to support the operation of the reversible solid oxide electrolysis hydrogen production unit (4), and the reversible solid oxide electrolysis hydrogen production unit (4) is in a thermal standby mode.
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