CN115074751A - High-temperature electrolytic hydrogen production system capable of continuously and stably operating, method and application thereof - Google Patents
High-temperature electrolytic hydrogen production system capable of continuously and stably operating, method and application thereof Download PDFInfo
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- CN115074751A CN115074751A CN202210538355.0A CN202210538355A CN115074751A CN 115074751 A CN115074751 A CN 115074751A CN 202210538355 A CN202210538355 A CN 202210538355A CN 115074751 A CN115074751 A CN 115074751A
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- 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
Abstract
The invention discloses a high-temperature electrolytic hydrogen production system capable of continuously and stably operating, a method and application thereof. The system mainly comprises a photovoltaic cell array, a solar thermal collector, a reversible solid oxide electrolysis hydrogen production unit, a storage battery, an electric steam generator, a ternary molten salt heat storage tank, a steam generator and a hydrogen storage unit. In the hydrogen production system, when the sunlight is sufficient, the photovoltaic cell array provides electric energy for the reversible solid oxide electrolytic hydrogen production unit and the electric heating device, 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 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 to maintain the hydrogen production unit to work. The system integrates solar-driven high-temperature solid oxide hydrogen production by electrolysis with ternary molten salt heat storage and storage battery technologies in a coupling manner, and realizes continuous and stable hydrogen production by the reversible solid oxide 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 severity of 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 popularized worldwide. Among them, hydrogen energy has been widely developed as a high-efficiency, clean secondary energy. The hydrogen production by water electrolysis is considered as the cleanest hydrogen production method because of the preparation process and no pollutant emission in the product. At present, the water electrolysis hydrogen production technology mainly adopts low-temperature water electrolysis hydrogen production, and the energy consumption is high. 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 galvanic pile electrolysis efficiency of more than 90 percent, and is a high-efficiency energy conversion device. Under the strategic goal of double carbon in China, the technology of driving hydrogen production by electrolyzing water by using electric energy generated by renewable energy sources such as solar energy and the like as power has great development potential, but because sunlight has volatility and instability, the solar energy cannot be used as a stable source of electric energy and heat energy, and is not enough to support the long-term, continuous and stable operation of hydrogen production equipment.
Currently, the prior art provides partial solutions to the above problems. The invention patent CN 112944697A published in 2021, 6 and 11 relates to a solar photo-thermal/photovoltaic comprehensive energy cascade utilization system, wherein 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 a photovoltaic cell array 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 efficiently convert the solar energy in a hydrogen preparation mode through water electrolysis. The water electrolysis hydrogen production system is one or the components 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 improve the energy utilization efficiency of solar energy. In the system, although the heat energy converted from solar energy is stored through the heat storage device, the electric energy generated by the photovoltaic cell array cannot be stored and cannot be continuously and stably supplied to the electrolytic cell without the arrangement of the electric storage device and a corresponding control strategy. When solar irradiation fluctuates or no solar irradiation exists, the high-temperature heat reservoir releases heat, and the photovoltaic cell array does not generate electricity and produce hydrogen any more. Meanwhile, the standby mode of the electrolytic hydrogen production system is not designed in the patent.
In an invention patent CN 111139493A published in 5, 12 and 2020, a solar photovoltaic photo-thermal high-temperature water electrolysis hydrogen production system and a hydrogen production method are disclosed, the produced high-temperature hydrogen and high-temperature oxygen are subjected to twice heat exchange, the heat of high-temperature gas generated by water electrolysis of a high-temperature electrolytic cell under large current is fully utilized, and the efficiency of a solar water electrolysis system is improved. The system couples photovoltaic photo-thermal and high-temperature electrolysis, reasonably utilizes solar energy to produce hydrogen, and avoids instability of direct solar power generation. Reasonably utilizes the current mature photo-thermal technology to solve the problems of low-temperature hydrogen production efficiency, environmental pollution and the like. In the system, the heat storage device is connected with the high-temperature steam generator and can provide 800-degree high-temperature steam for the solid oxide electrolytic cell, so that the temperature of the hydrogen and the oxygen is reduced, but the heat storage device is not arranged, and the electric energy generated by the photovoltaic cell array cannot be stored.
An invention patent CN 106884179A published in 6 and 23 in 2017 and published in 2020 and 12 in 5 and 2017 relates to an electrolytic water vapor device based on trough solar energy. The water pump pumps water into the groove type solar heat utilization subsystem, water is heated into high-temperature steam, the obtained high-temperature steam is sent to the electrolysis subsystem, and electric energy required by an electrolysis cell and an auxiliary heater of the electrolysis subsystem comes from a photovoltaic array or a storage battery. The water is heated into high-temperature steam by using the groove type concentrating solar energy, and then the high-temperature steam is electrolyzed by using the solar photovoltaic power generation to obtain hydrogen and oxygen. The device has set up the electric energy that the storage battery stored photovoltaic array produced, but if guarantee long-term continuous operation, the capacity of required storage battery is great, leads to the cost too high. Compared with an electricity storage system, the cost of arranging the heat storage system is lower. This invention focuses on the efficient conversion of water vapor and does not relate in detail to the continuous operation of the electrolysis system.
In an invention patent CN 113357694A published in 2021, 9, 17, a multi-energy coupling energy storage and supply system is related, comprising a basic heat source area, a heat storage area, a photovoltaic power generation power supply area, a frequency modulation and peak regulation energy storage area and an electrochemical energy storage area, wherein the basic heat source area comprises a geothermal source and a heat pump, and the geothermal 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 stores heat energy output by a heat pump through the heat energy pipe network; the photovoltaic power generation power supply area comprises a solar power generation module, 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 and peak regulation energy storage area comprises a reversible solid oxide fuel cell, the solid oxide fuel cell performs 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, and the new electric energy is connected with the power supply network and performs frequency modulation and peak regulation on the power supply network; the electrochemical energy storage area comprises a flow battery, and the flow battery is connected with the frequency modulation and peak regulation energy storage area. When the photovoltaic power generation is insufficient and the electricity price is expensive, a bidirectional solid oxide fuel cell/electrolytic cell system is temporarily used as a standby energy source for power generation. Although the patent of the invention is provided with the liquid-phase battery and the phase-change heat storage device for storing and storing electricity, the invention does not relate to a method for controlling the continuous operation process of the electrolytic cell, and does not emphasize the continuous operation of the electrolytic cell and the possible starting and stopping problems of the electrolytic cell.
The Luzewei and the like construct a sustainable power generation system which combines photo-thermal steam production, photovoltaic power generation, hydrogen production by water electrolysis of a Solid Oxide Electrolytic Cell (SOEC) and power generation complementation of a Solid Oxide Fuel Cell (SOFC), and system parameters and energy efficiency optimization balance calculation are carried out. The system utilizes 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 fuel chemical energy through high-temperature electrolysis can realize peak clipping and valley filling of a power grid and reduce the impact of fluctuation renewable energy on the power grid. The system generates power by a photovoltaic power generation system in the daytime, redundant electric energy is used for hydrogen production by electrolysis of the SOEC system, and the power is generated by the SOFC power generation system at night, so that the aim of continuous power generation is fulfilled. In order to maintain the stability of output power, the scale of a photo-thermal system, a photovoltaic system, an SOEC system and an SOFC system needs to be optimized and combined to be matched with each other, hydrogen produced by the SOEC system in the daytime needs to meet the power generation requirement of the SOFC system at night, and the whole system is ensured to operate continuously in all weather. But the power generation of the SOFC system at night can not ensure that redundant electric energy is used for the electrolysis hydrogen production of the SOEC system on the premise of ensuring the stable output; meanwhile, high-temperature steam required by hydrogen production is provided by the photo-thermal system, and the heat energy requirement of the SOEC system for hydrogen production by electrolysis cannot be met at night due to the fact that the 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 technical bottleneck that the solar energy drives the electrolytic hydrogen production system to continuously work cannot be broken through in the prior art. 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 a long-term stable and continuous heat energy and electric energy source 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 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 work continuously, the invention aims to provide a high-temperature electrolytic hydrogen production system capable of running continuously and stably, a method and application thereof, and the technical scheme is as follows:
the utility model provides a but high temperature electrolysis hydrogen manufacturing system of continuous stable operation, includes photovoltaic cell square matrix, battery, solar collector, its characterized in that:
when the solar radiation is enough, the power generation capacity of the photovoltaic cell array is sufficient, and the generated power supplies power for the electric steam generator, the storage battery and the reversible solid oxide electrolysis hydrogen production unit respectively;
the solar heat collector 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 through the steam generator;
the reversible solid oxide electrolysis hydrogen production unit (4) comprises an electric 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 the like;
when the solar 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 both the solar radiation and the residual electric quantity of the storage battery are insufficient, the photovoltaic cell matrix and the storage battery are insufficient to support the reversible solid oxide electrolysis hydrogen production unit to work, and the reversible solid oxide electrolysis hydrogen production unit is in a hot standby mode. In the thermal standby mode, the reversible solid oxide electrolysis hydrogen production unit reversely operates in the fuel cell mode, hydrogen chemical energy is converted into electric energy, the solid oxide electrolysis system is maintained to operate, and the temperature of the electrolytic cell is maintained to be more than 600 ℃, so that the reversible solid oxide electrolysis hydrogen production unit can be rapidly switched to the hydrogen production mode, and the continuous operation of the reversible solid oxide electrolysis hydrogen production unit is realized.
The invention also discloses a solar-driven high-temperature electrolytic hydrogen production method capable of continuously and stably running, which comprises the following steps:
when 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 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 to maintain the reversible solid oxide electrolytic hydrogen production unit to work;
when both the solar radiation and the residual electric quantity of the storage battery are insufficient, the photovoltaic cell matrix and the storage battery are insufficient to support the reversible solid oxide electrolysis hydrogen production unit to work, and the reversible solid oxide electrolysis hydrogen production unit is in a hot standby mode. In the thermal standby mode, the reversible solid oxide electrolysis hydrogen production unit reversely operates in the fuel cell mode, hydrogen chemical energy is converted into electric energy, the solid oxide electrolysis system is maintained to operate, and the temperature of the reversible solid oxide electrolysis hydrogen production unit is maintained to be more than 600 ℃, so that the reversible solid oxide electrolysis hydrogen production unit can be rapidly switched to the hydrogen production mode, and the continuous operation of the reversible solid oxide electrolysis hydrogen production unit is realized.
The invention also discloses a high-temperature electrolytic hydrogen production device applying the solar-driven high-temperature electrolytic hydrogen production system capable of continuously and stably running.
Advantageous effects
Solar energy drives the hydrogen production by high-temperature solid oxide electrolysis and is coupled and integrated with ternary molten salt heat storage and storage battery technology, so that the hydrogen production unit by reversible solid oxide electrolysis can continuously and stably produce hydrogen under intermittent solar energy drive, and the hydrogen production unit has the following characteristics:
(1) the electric energy storage system is arranged, the storage battery can store electric energy and release the electric energy to the reversible solid oxide electrolytic hydrogen production unit, the electric steam generator and other devices when photovoltaic power generation does not exist, and the electric heating requirement of the reversible solid oxide electrolytic hydrogen production unit in continuous operation is guaranteed;
(2) the single-tank ternary molten salt heat storage tank stores heat absorbed by the solar heat collector, can provide steam required by the operation of the reversible solid oxide electrolysis hydrogen production unit at any time, and guarantees the continuous operation heat requirement of the reversible solid oxide electrolysis hydrogen production unit;
(3) the reversible solid oxide electrolysis hydrogen production unit has two working modes, namely a hydrogen production mode and a thermal standby mode; in the hot standby mode, the reversible solid oxide electrolysis hydrogen production unit converts hydrogen into minimum power (such as a blower, a pump and the like) and enough heat required by the system operation, so that the temperature of the reversible solid oxide electrolysis hydrogen production unit is kept above 600 ℃, and the reversible solid oxide electrolysis hydrogen production unit can be quickly switched to the hydrogen production mode.
Drawings
FIG. 1 is a high-temperature electrolytic hydrogen production system, method and application thereof capable of continuously and stably operating.
FIG. 2 is a flow chart of a solar-powered continuous and stable operation high-temperature electrolytic hydrogen production method.
In the figure: the system comprises a photovoltaic cell array 1, an electric steam generator 2, a storage battery 3, a reversible solid oxide electrolysis hydrogen production unit 4, a solar heat collector 5, a ternary fused salt heat storage tank 6, a steam generator 7 and a hydrogen storage unit 8.
Detailed Description
The invention provides a high-temperature electrolytic hydrogen production system capable of continuously and stably operating, a method and application thereof, which are described below by combining with the accompanying drawings.
As shown in fig. 1, in the solar-driven high-temperature electrolytic hydrogen production system capable of continuously and stably operating, one path of a photovoltaic cell array 1 is connected with an electric steam generator 2, and a gas 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 a 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 molten salt heat storage tank 6 to form a loop, the ternary molten salt heat storage tank 6 is connected with the steam generator 7, and 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.
According to the working principle of the solar-driven high-temperature electrolytic hydrogen production system capable of continuously and stably running, when solar radiation is enough, the power generation capacity of the photovoltaic cell array 1 is sufficient, and the reversible solid oxide electrolytic hydrogen production unit 4 is in a hydrogen production mode and supplies power to devices such as a galvanic pile, a heat exchange module, a pump, a fan and the like in the hydrogen production unit; a part of electric energy generated by the photovoltaic cell array 1 is sent to the reversible solid oxide electrolysis hydrogen production unit 4 to provide electric energy for the reversible solid oxide electrolysis hydrogen production unit 4; a part of 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 hydrogen production unit 4, and the high-temperature steam enters the reversible solid oxide 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 and converts the solar radiation energy into heat energy, and the heat storage device stores the solar energy; the heat storage device adopts a single-tank ternary molten salt heat storage tank 6, ternary molten salt is used as a heat storage medium, and energy is stored or generated by converting heat energy collected by a solar heat collector and internal energy of the molten salt. The fused 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 molten salt and binary molten salt, the ternary molten salt has low phase change point and better thermal stability in medium-high temperature environment; compared with a 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 quantity of heat storage medium molten salt needed is small, the construction cost, the operation cost and the maintenance cost of the heat storage tank can be effectively reduced, and therefore the single-tank ternary molten salt heat storage tank is selected as the heat storage device. The cold section of the heat storage tank is provided with a heat absorption heat exchanger, the hot 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 electrolytic hydrogen production unit 4 and can provide steam for the reversible solid oxide electrolytic 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 high-temperature electrolytic hydrogen production system capable of continuously and stably running, 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 the 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 stored in the hydrogen storage unit 8; when both 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 not enough to support the reversible solid oxide electrolysis hydrogen production unit 4 to work, and the reversible solid oxide electrolysis hydrogen production unit 4 is in a hot standby mode; in the thermal standby mode, the reversible solid oxide electrolysis hydrogen production unit 4 reversely operates in the fuel cell mode, hydrogen chemical energy is converted into electric energy, the solid oxide electrolysis system is maintained to operate, and the temperature of the reversible solid oxide electrolysis hydrogen production unit 4 is maintained above 600 ℃, so that the reversible solid oxide electrolysis hydrogen production unit 4 can be rapidly switched to the hydrogen production mode, and the continuous operation of the reversible solid oxide electrolysis hydrogen production unit 4 is realized.
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 the like.
The structure of a solid oxide electrolysis cell usually consists of a three-part structure, namely an anode, a cathode and an electrolyte. The anode (air electrode) and cathode (fuel electrode) are placed on both sides with a dense electrolyte layer in the middle. The working temperature of the solid oxide water electrolysis hydrogen production is higher, which is about 600-1000 ℃. When the electrolytic cell works, 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, and H is driven by the voltage 2 Decomposition of O to H 2 And consuming electrons to produce O 2- ，O 2- Through the transmission of dense electrolyte, water vapor gets electrons at the cathode to form H 2 And O 2- ，O 2- Loss of electron generation O through the electrolyte layer to the anode 2 . The specific reaction formula is as follows:
and (3) cathode reaction: h 2 O+2e - →H 2 +O 2-
And (3) anode reaction:
electrolysis total reaction:
in the hot standby mode, the reversible solid oxide electrolysis hydrogen production unit reversely operates in the fuel cell mode. The anode of the solid oxide fuel cell is used for transmitting electrons and simultaneously catalytically oxidizing fuel at the anode side; cathode for introducing O 2 Reduction to O 2- (ii) a The electrolyte is used for separating the negative electrode and the positive electrode and transmitting ions. When the traditional solid oxide fuel cell (oxygen ion conductor SOFC) works, O generated by the cathode 2- Penetrates the electrolyte layer to the anode, where it and H 2 Reaction to form H 2 O and electrons, the electrons are conducted to the cathode through an external circuit to form loop current. The reaction equation is as follows:
and (3) anode reaction: h 2 +O 2- →H 2 O+2e -
And (3) cathode reaction: o is 2 +4e - →2O 2-
And (3) total reaction: 2H 2 +O 2 →2H 2 O
The proton conductor SOFC has the working principle that hydrogen is catalytically generated into H at the anode + And electrons, H + Penetrates the electrolyte layer to the cathode, where it is connected with O 2 Reaction to form H 2 And O, meanwhile, the electrons are conducted to the cathode through an external circuit to form loop current. The equation for the reaction is:
and (3) anode reaction: h 2 →2H + +2e -
And (3) cathode reaction: 4H + +O 2 +4e - →2H 2 O
And (3) total reaction: 2H 2 +O 2 →2H 2 O
In the solid oxide electrolysis hydrogen production system, the operation of the reversible solid oxide electrolysis hydrogen production unit 4, the electric steam generator 2 and other devices needs electric energy support, and the process of generating water vapor by the steam generator 7, the electric steam generator 2 and other devices needs heat energy support. Therefore, the solid oxide electrolytic hydrogen production system needs enough electric energy and heat energy supply to maintain the normal operation of the electrolytic process of water vapor in a high-temperature environment. Therefore, if the continuous and stable operation of the solid oxide electrolytic 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, an electricity storage device and a heat storage device are not arranged at the same time, so that under the condition of insufficient solar radiation, the continuous and stable supply of electric energy and heat energy cannot be ensured at the same time, and the continuous and stable operation of a solid oxide electrolysis hydrogen production unit cannot be maintained. Meanwhile, the prior patent does not relate to two working modes of starting and stopping the electrolytic cell and a switching method between the two working modes.
The invention is also provided with an electric 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 the reversible solid oxide electrolysis hydrogen production unit 4, the electric steam generator 2 and other devices when photovoltaic power generation does not exist, so that the electric heating requirement of continuous operation of the reversible solid oxide electrolysis hydrogen production unit 4 is met; the single-tank ternary molten salt heat storage tank 6 stores heat absorbed by the solar heat collector 5, can provide steam required by the operation of the reversible solid oxide electrolysis hydrogen production unit 4 at any time, and guarantees the continuous operation heat requirement of the reversible solid oxide electrolysis hydrogen production unit 4. In addition, the reversible solid oxide electrolysis hydrogen production unit 4 has two working modes, namely a hydrogen production mode and a thermal standby mode; in the thermal standby mode, the reversible solid oxide electrolysis hydrogen production unit 4 converts hydrogen into minimum power (such as a blower, a pump and the like) and enough heat required by the system operation, so that the temperature of the reversible solid oxide electrolysis hydrogen production unit is kept above 600 ℃, the conversion time of the thermal standby mode and the hydrogen production mode can be greatly reduced, and the continuity of the operation of the solid oxide electrolysis hydrogen production system is improved.
The foregoing shows and describes the general principles, essential 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, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The utility model provides a but high temperature electrolysis hydrogen manufacturing system of continuous stable operation, includes photovoltaic cell square matrix (1), battery (3), solar collector (5), its characterized in that:
when solar radiation is enough, the power generation amount of the photovoltaic cell array (1) is enough, and the generated power supplies power for the electric steam generator (2), the storage battery (3) and the reversible solid oxide electrolysis hydrogen production unit (4) respectively;
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 radiation is insufficient, the stored electric energy is released to a reversible solid oxide electrolytic hydrogen production unit (4) and an electric steam generator (2) through a storage battery (3);
when both 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 not enough to support the reversible solid oxide hydrogen production unit (4) to work, and the reversible solid oxide hydrogen production unit (4) is in a hot standby mode.
2. The high-temperature electrolytic hydrogen production system capable of continuously and stably operating according to claim 1, characterized in that: the ternary molten salt heat storage tank is a single-tank ternary molten salt heat storage tank (6) which takes ternary molten salt as a heat storage medium, a cold tank, a hot tank and two heat exchangers are integrated in one unit, a cold section is provided with a heat absorption heat exchanger, and a hot section is provided with a steam generator.
3. The high-temperature electrolytic hydrogen production system capable of continuously and stably operating according to claim 1, characterized in that: 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 a fan device.
4. The high-temperature electrolytic hydrogen production system capable of continuously and stably operating according to claim 1, characterized in that: the gas 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 high-temperature electrolytic hydrogen production system capable of continuously and stably operating according to claim 1, characterized in that: the hot standby mode is as follows: the reversible solid oxide electrolysis hydrogen production unit (4) reversely operates in a fuel cell mode, hydrogen chemical energy is converted into electric energy, a solid oxide system is maintained to operate, and the temperature of the reversible solid oxide electrolysis hydrogen production unit (4) is maintained to be more than 600 ℃, so that the reversible solid oxide electrolysis hydrogen production unit (4) can be rapidly switched to a hydrogen production mode, and the continuous operation of the reversible solid oxide electrolysis hydrogen production unit (4) is realized.
6. The high-temperature electrolytic hydrogen production system capable of continuously and stably operating according to claim 1, characterized in that: when solar radiation is enough, the power generation capacity of the photovoltaic cell square matrix (1) is enough to be used in three parts: a part of electric energy is sent into a reversible solid oxide electrolysis hydrogen production unit (4) to supply power to devices such as a galvanic pile, an electric heater, a pump, a fan and the like in the hydrogen production unit, so that the hydrogen production unit is in a hydrogen production state; part of 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 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 the storage battery (3) for storage.
7. A high temperature electrolytic hydrogen production system capable of continuous and stable operation according to claim 1, characterized in that 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 ternary molten salt heat storage tank (6) is provided for the steam generator (7), and the 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 is stored in the hydrogen storage unit (8).
8. A solar-driven high-temperature electrolytic hydrogen production method capable of continuously and stably operating, which comprises the high-temperature electrolytic hydrogen production system capable of continuously and stably operating according to any one of claims 1 to 7, and comprises the following steps:
when solar radiation is enough, the photovoltaic cell array (1) provides electric energy for the reversible solid oxide electrolytic hydrogen production unit (4) and the electric heating equipment, the residual electric energy is stored in the storage battery (3), and the heat storage tank (6) stores heat absorbed by the solar heat collector (5) and provides heat for steam in the electrolytic hydrogen production process at any time;
when 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 electrolytic hydrogen production unit (4) and the electric heating equipment, and the reversible solid oxide electrolytic hydrogen production unit (4) is maintained to work;
when both the solar radiation and the residual electricity of the storage battery (3) are insufficient, the photovoltaic cell array (1) and the storage battery (3) are not enough to support the reversible solid oxide electrolysis hydrogen production unit (4) to work, and the reversible solid oxide electrolysis hydrogen production unit (4) is in a hot standby mode.
9. The solar-driven high-temperature electrolytic hydrogen production system capable of continuously and stably operating as claimed in any one of claims 1 to 7 is applied to a high-temperature electrolytic hydrogen production device.
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| CN116121786B (en) * | 2023-02-21 | 2023-11-21 | 华北电力大学 | Solar-driven solid oxide electrolytic cell distributed poly-generation system and method |
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