Thermo-electron coupled electrolytic reaction system and operation method thereof

Abstract

The invention discloses a hot electron coupled electrolytic reaction system and an operation method thereof, and relates to the technical field of energy conversion and chemical engineering, the hot electron coupled electrolytic reaction system comprises an electrolytic tank reaction module, a hot electron emission module, an electric energy regulation and storage module and a heat energy regulation and utilization module; the electric energy regulation and storage module comprises an electric energy regulation device and an electricity storage device, the hot electron cathode is connected with the front end of the electric energy regulation device, the rear end of the electric energy regulation device is connected with the anode of the electrolytic tank, and the hot electron anode is connected with the cathode of the electrolytic tank; the electric energy regulation and control device regulates current and voltage input into the electrolytic tank; the heat energy regulation and utilization module comprises a heat energy regulation and storage assembly and a waste heat utilization device and is used for regulating heat input into the electrolytic tank or heat taken away from the electrolytic tank so as to regulate the reaction operation temperature of the electrolytic tank. The device can adapt to various external energy sources, supply electric energy and heat energy, meet different electrolytic reaction requirements and energy source characteristics, recover waste heat and waste electricity at the same time, and achieve efficient utilization of energy.

Description

Technical Field

[0001] This invention relates to the fields of energy conversion and chemical engineering, and in particular to a hot-electron coupled electrolytic reaction system and its operation method. Background Technology

[0002] Electrolyzers can efficiently convert non-steady-state renewable energy into storable and transportable chemical fuels, such as hydrogen and ammonia production, and further produce high-value-added chemicals like methanol, olefins, and aromatics. This is not only a key pathway for achieving large-scale energy storage and peak shaving, and for absorbing renewable energy, but also provides core support for building distributed energy systems. Furthermore, by coupling with technologies such as carbon capture and synthetic fuels, electrolyzers can convert captured greenhouse gases into resources for recycling, reducing emissions while achieving a low-carbon restructuring of energy production and consumption.

[0003] Furthermore, in the field of metal preparation, electrolytic cells are the core equipment for achieving efficient electrochemical reduction of high-purity, highly reactive metals. Compared with traditional pyrometallurgy, electrolytic cell technology can significantly reduce energy consumption and carbon emissions, making it a key technology for promoting the low-carbon upgrading of the metal preparation industry.

[0004] There are many types of existing electrolytic cells, such as alkaline electrolytic cells (AEC), proton exchange membrane electrolytic cells (PEMEC), solid oxide electrolytic cells (SOEC), anion exchange membrane electrolytic cells (AEMEC), and molten salt electrolytic cells (MSEC). The electrolysis process typically requires both electrical and thermal energy. However, traditional systems often require separate supply of electrical and thermal energy due to differences in the operating conditions of power transmission and heating devices, necessitating additional heating systems alongside the input electrical energy. Furthermore, because different types of electrolytic cells have varying requirements for the ratio and supply methods of electrical and thermal energy, the electro-thermal separation energy supply model is difficult to adapt to the differentiated energy needs of different electrolytic cells, thus limiting energy utilization. Summary of the Invention

[0005] To address the aforementioned problems, this invention proposes a thermionic coupling electrolysis reaction system and its operation method. The thermionic emission device serves as the power and heat supply for the electrolysis cell, adaptable to various external energy sources and capable of supplying both electrical and thermal energy to meet different electrolysis reactions and energy demands, while simultaneously achieving efficient energy utilization.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a thermionic coupling electrolytic reaction system, comprising: an electrolytic cell reaction module, a thermionic emission module, an electrical energy regulation and storage module, and a thermal energy regulation and utilization module; The electrolytic cell reaction module includes an electrolytic cell, which includes an electrolyte, an electrolytic cell cathode, and an electrolytic cell anode. Thermionic emission module includes one or more thermionic emission devices, each thermionic emission device including a thermionic cathode, a thermionic anode, and a gap between the two; The power regulation and energy storage module includes a power regulation device and an energy storage device connected to the power regulation device. The thermionic cathode is connected to the front end of the power regulation device, the rear end of the power regulation device is connected to the anode of the electrolytic cell, and the thermionic anode is connected to the cathode of the electrolytic cell. The power regulation device is used to regulate the current and voltage input to the electrolytic cell and to store excess electrical energy in the energy storage device. The thermal energy regulation and utilization module includes a thermal energy regulation and storage component and a waste heat utilization device connected to the thermal energy regulation and storage component. The thermal energy regulation and storage component is connected to the thermionic emission module and the electrolytic cell reaction module, and is used to regulate the operating temperature of the electrolytic cell and store or transfer excess heat to the waste heat utilization device.

[0007] As an alternative implementation, the thermionic anode is a transparent, opaque, or translucent material. An energy source excites electron-hole pairs in the thermionic cathode, so that the electrons have enough energy to overcome the potential barrier and pass through the gap to reach the thermionic anode. The electrons in the thermionic anode are then supplied to the cathode of the electrolytic cell.

[0008] As an alternative implementation, the thermionic cathode faces the energy source, and external energy directly reaches the thermionic cathode to excite electron-hole pairs. This method is called cathode incident. In this case, the thermionic anode is a transparent, opaque, or translucent material.

[0009] As an alternative implementation, the thermionic anode faces the energy source and is made of a transparent material. Concentrated solar energy passes through the thermionic anode and the gap, and after reaching the thermionic cathode, it excites the electron-hole pairs in the thermionic cathode. This method is called the anode-incident method.

[0010] As an alternative implementation, the electrolysis reaction system further includes an external energy supply module that provides an energy source for the thermionic emission device. The external energy supply module includes a focusing device and / or a heating device. The focusing device is used to concentrate light onto the thermionic emission device, and the heating device is used to heat the thermionic cathode in the thermionic emission device.

[0011] As an alternative implementation, the thermal energy regulation and storage component is used to monitor the temperature of the electrolytic cell and regulate the heat input to the electrolytic cell or the heat absorbed from the thermionic emission device and the electrolytic cell, thereby maintaining the electrolytic cell temperature to meet the electrolysis reaction temperature requirements.

[0012] As an alternative implementation, the heat from the thermionic emission device is transferred to a thermal energy regulation and storage component, which stores or transfers the heat according to categories to a waste heat utilization device. The waste heat utilization device utilizes the heat energy or converts it into electrical energy, and the generated electrical energy is connected in parallel or in series with the thermionic emission device and then transferred to an electrical energy regulation device.

[0013] As an alternative implementation, the electrolysis reaction system further includes a raw material conveying module connected above the electrolysis cell reaction module. The raw material conveying module includes an electrolysis cell cathode raw material conveying device and an electrolysis cell anode raw material conveying device. The cathode material conveying device of the electrolytic cell is connected to the top of the cathode of the electrolytic cell and is used to convey the reaction raw materials required by the cathode of the electrolytic cell to the cathode of the electrolytic cell. The anode material conveying device of the electrolytic cell is connected to the top of the anode of the electrolytic cell and is used to transport the raw materials required for the anode of the electrolytic cell to the anode of the electrolytic cell.

[0014] As an alternative implementation, the electrolysis reaction system further includes a product collection module connected to the lower part of the electrolysis cell reaction module. The product collection module includes a reduction product collection device and an oxidation product collection device. The reduction product collection device is connected to the cathode of the electrolysis cell, and the oxidation product collection device is connected to the anode of the electrolysis cell.

[0015] In a second aspect, the present invention provides a method for operating a hot-electron coupled electrolytic reaction system, employing the hot-electron coupled electrolytic reaction system described in the first aspect, comprising: An external energy source excites electron-hole pairs in the thermionic cathode and gives the electrons enough energy to overcome the potential barrier, pass through the gap to reach the thermionic anode, and the electrons in the thermionic anode reach the cathode of the electrolytic cell. Reactants are selectively fed into the cathode and anode of the electrolytic cell through a raw material conveying device, or no additional reactants are fed in. The reactants at the cathode of the electrolytic cell combine with electrons to undergo a reduction reaction, producing reduction products or generating negative ions at the same time. The reduction products enter the reduction product collection device, and the generated negative ions reach the anode of the electrolytic cell through the electrolyte and participate in the oxidation reaction. In an electrolytic cell, the reactants at the anode undergo an oxidation reaction to produce oxidation products or simultaneously generate positive ions and release electrons. The oxidation products enter the oxidation product collection device, while the generated positive ions reach the cathode of the electrolytic cell through the electrolyte and participate in the reduction reaction. The electrons reach the thermionic cathode through the power regulation device, forming a closed loop. The power regulation device adjusts the current and voltage input to the electrolytic cell to ensure the normal electrolytic reaction in the cell, and inputs excess power into the energy storage device for storage. The heat generated by the electrolytic cell and the thermionic emission device is input into the thermal energy regulation and storage component. The thermal energy regulation and storage component monitors the temperature of the electrolytic cell and regulates the reaction operating temperature of the electrolytic cell by adjusting the heat input to the electrolytic cell or the heat absorbed from the electrolytic cell. Excess heat is stored or transported to the waste heat utilization device according to categories.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention proposes a thermionic coupling electrolysis reaction system and its operation method. The thermionic emission device serves as the power and heat supply for the electrolytic cell, utilizing an external energy source for both electrical and thermal energy supply, while also recovering and utilizing system waste heat and electrical energy. Particularly for high-temperature electrolytic cells, by fully utilizing the high-temperature waste heat provided by the thermionic emission device, the entropy increase requirement in the electrolysis reaction can be effectively compensated. Simultaneously, the Gibbs free energy required for higher temperatures is relatively small, reducing energy consumption. By exciting electron-hole pairs in the thermionic emission material through light or heat, and converting thermal energy into electron kinetic energy, the electrons inside the material gain sufficient energy to overcome the surface potential barrier, reaching the thermionic anode from the thermionic cathode. This forms a closed loop connected to the external electrolytic cell, simplifying the structure of traditional electrolytic cell systems. This system can be applied to various types of electrolytic cells, producing not only clean fuels but also metals such as Zn, Pt, and Fe.

[0017] This invention, through the integrated design of the thermionic emission device, eliminates the need for separate power supply and heating equipment, as well as complex connecting pipelines and control modules in traditional systems, significantly simplifying the overall structure of the electrolytic cell system. This reduces costs associated with component procurement and system assembly, lowers the probability of malfunctions due to the coordinated operation of multiple devices, and reduces maintenance workload and costs. Furthermore, the compact design minimizes the system's footprint and improves space utilization.

[0018] The thermionic emission device of this invention is adaptable to various external energy sources, significantly expanding the energy utilization range of the electrolytic cell system. Whether it's clean energy sources such as solar energy, geothermal energy, or industrial waste heat, or other forms of thermal and solar energy, all can serve as external energy sources to drive the thermionic emission process. The electrical energy regulation and storage module adjusts the voltage and current input to the electrolytic cell to meet the reaction requirements. Simultaneously, the thermal energy regulation and utilization module collects the heat generated by the electrolytic cell and the thermionic emission device to supply the electrolytic cell, regulates the operating temperature of the electrolytic cell, and utilizes waste heat, achieving efficient supply of electrical and thermal energy and high-efficiency energy utilization.

[0019] Compared to the limitations of some traditional electrolytic cell systems that produce only a single type of product, the electrolytic reaction system of this invention can stably provide sufficient electrical and thermal energy to various types of electrolytic cells. It can be used not only for the efficient production of clean fuels such as hydrogen and methanol, but also for the electrolytic preparation of metallic materials such as Zn, Pt, and Fe. This advantage significantly broadens the system's application scenarios. For example, in the energy sector, it can serve as a distributed hydrogen production device, providing a clean hydrogen source for hydrogen-powered vehicles and fuel cells; in the metallurgical sector, it can be used for the electrolytic refining or electrolytic preparation of metals, especially for metals that are difficult to prepare using traditional metallurgical processes or that generate significant pollution during preparation, providing a cleaner and more efficient alternative; in the chemical industry, it can be used for the electrolytic synthesis of various chemical raw materials, achieving green production of chemical products; simultaneously, the system is adaptable to various types of electrolytic cells without requiring significant modifications for different cell types, further enhancing its versatility and market application potential.

[0020] Advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0022] Figure 1 This is a structural diagram of the hot-electron coupled electrolytic reaction system provided in Embodiment 1 of the present invention; Figure 2 This is a schematic diagram of the energy flow at the cathode of the thermionic coupled electrolytic reaction system provided in Embodiment 1 of the present invention; wherein, the solid line represents the electron flow and the dashed line represents the heat flow. Figure 3 This is a schematic diagram of the anode incident state of the thermionic coupling electrolytic reaction system provided in Embodiment 1 of the present invention; wherein, the solid line represents the electron flow, the double line represents the flow direction of the heat exchange medium, and the dashed box represents the overall control device of the thermal energy regulation and storage component. Figure 4 This is a schematic diagram of the material flow in a solid oxide electrolysis cell of a thermionic coupled electrolysis reaction system for producing ethylene, as provided in Embodiment 2 of the present invention. Figure 5 This is a schematic diagram of the material flow of a solid oxide electrolytic cell for hydrogen production via water electrolysis in a thermionic coupling electrolysis reaction system provided in Embodiment 3 of the present invention. The components include: 1. Thermionic emission module; 2. Electrolytic cell reaction module; 3. Power regulation and energy storage module; 4. Thermal energy regulation and utilization module; 5. External energy supply module; 6. Raw material conveying module; 7. Product collection module; 8. Electrolyte; 9. Electrolytic cell cathode; 10. Electrolytic cell anode; 11. Thermionic cathode; 12. Thermionic anode; 13. Gap; 14. Power regulation device; 15. Energy storage device; 16. Thermal energy regulation and storage component; 16-1. Thermal energy regulation device; 16-2. Thermal medium storage tank; 16-3. Cold medium storage tank; 16-4. Valve; 16-5 and 16-6. Pump; 16-7. High-temperature thermal storage device; 16-8. Low-temperature thermal storage device; 17. Waste heat utilization device; 18. Electrode plate; 19. Reduction product collection device; 20. Oxidation product collection device. Detailed Implementation

[0023] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0024] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0025] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form as well. Furthermore, it should be understood that the terms “comprising” and “including”, and any variations thereof, are intended to cover non-exclusive inclusion, for example, a process, method, system, product, or apparatus that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0026] Where there is no conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0027] Example 1 This embodiment provides a thermionic coupling electrolytic reaction system that does not require separate supply of electrical and thermal energy, and does not need to consider the mutual limitations of electrical and thermal energy supply devices, thus achieving thermal and electrical decoupling.

[0028] like Figure 1As shown, it includes: a thermionic emission module 1, an electrolytic cell reaction module 2 in which an electrolytic reaction occurs, an external energy supply module 5 that provides an energy source for the thermionic emission module 1, an electrical energy regulation and storage module 3 that regulates the electrical energy input to the electrolytic cell reaction module 2 and stores excess electrical energy from the thermionic emission module 1, a thermal energy regulation and utilization module 4 that collects and utilizes the heat from the electrolytic cell reaction module 2 and the thermionic emission module 1, and a raw material conveying module 6 connected to the top of the electrolytic cell reaction module 2 and a product collection module 7 connected to the bottom of the electrolytic cell reaction module 2.

[0029] In this embodiment, the external energy supply module 5 includes, but is not limited to, a focusing device and / or a heating device; the focusing device is used to concentrate light onto the thermionic emission module 1, and the heating device is used to heat the thermionic emission material of the thermionic emission module 1.

[0030] like Figure 2 As shown, in this embodiment, the electrolytic cell reaction module 2 includes an electrolytic cell reactor. The electrolytic cell consists of an electrolytic cell cathode 9, an electrolytic cell anode 10, and an electrolyte 8. The electrolytic cell cathode 9 is used to generate reduction products, the electrolytic cell anode 10 is used to generate oxidation products, and the specific type of electrolyte 8 is determined according to the types of reduction products and oxidation products.

[0031] In this embodiment, the thermionic emission module 1 includes one or more thermionic emission devices, each including a thermionic cathode 11, a thermionic anode 12, and a gap 13 between them.

[0032] In this embodiment, the power regulation and energy storage module 3 includes a power regulation device 14 and an energy storage device 15; The thermionic cathode 11 is connected to the front end of the power regulation device 14, the rear end of the power regulation device 14 is connected to the anode 10 of the electrolytic cell, the thermionic anode 12 is connected to the cathode 9 of the electrolytic cell, and the energy storage device 15 is connected to the power regulation device 14.

[0033] As an alternative implementation, the power regulation device 14, such as a DC-DC converter, is used to regulate the current and voltage input to the electrolytic cell, thereby meeting the voltage and current requirements of the electrolytic cell reaction module 2. Excess power is input into the energy storage device 15 for storage and backup. The energy storage device 15, such as a battery, is used to store excess power generated in the system and to supplement power when the thermionic emission module 1 is insufficient.

[0034] In this embodiment, the heat from the thermionic emission module 1 and the electrolytic cell reaction module 2 is transferred to the thermal energy regulation and utilization module 4. The thermal energy regulation and utilization module 4 includes a thermal energy regulation and storage component 16 and a waste heat utilization device 17. Among them, the thermal energy regulation and storage component 16 is connected to the thermionic emission module 1 and the electrolytic cell reaction module 2 to monitor the electrolytic cell temperature. At the same time, the thermal energy regulation device 16-1 coordinates and controls the high-temperature heat storage device 16-7 and the low-temperature heat storage device 16-8 to regulate the heat input to the electrolytic cell or the heat absorbed from the electrolytic cell and thermionic emission module 1, so as to regulate the operating temperature of the electrolytic cell reaction, and stores or transports the excess heat to the waste heat utilization device 17 according to categories. Waste heat utilization device 17, such as thermopile (including conductive sheet), waste heat boiler, etc., is connected to thermal energy regulation and storage component 16 to convert or supply the waste heat delivered by thermal energy regulation and storage component 16 to downstream thermal energy utilization, etc.

[0035] It should be noted that thermionic emission technology is based on the thermionic emission effect. Through methods such as solar concentrating, industrial waste heat or resistance heating, electrons inside the cathode gain enough energy to overcome the work function and escape from the surface to form a free electron flow. Waste heat is generated during the energy conversion process, and the usable temperature range is 150-1000℃ or even higher. Through the recovery system, this waste heat can be used to supplement other energy needs.

[0036] In this embodiment, the thermionic emission module 1 includes two incident modes: cathode incident and anode incident. When the thermionic emission module 1 is cathode incident, the thermionic anode 12 is made of transparent, opaque, or translucent material; the thermionic cathode 11 faces the external energy supply module 5, and the side of the thermionic anode 12 facing away from the thermionic cathode 11 is attached to the electrolytic cell cathode 9 through an electrode plate 18 or the two are connected by a wire to achieve current conduction; The anode 10 of the electrolytic cell is connected to the back end of the power regulation device 14 (such as a DC-DC converter), and the front end of the power regulation device 14 is connected to the thermionic cathode 11. The power regulation device 14 regulates the current and voltage input to the electrolytic cell and inputs the excess power into the energy storage device 15 (such as a battery).

[0037] In the cathode incident mode, external energy excites the electron-hole pairs in the thermionic cathode 11, making the electron energy sufficient to overcome the potential barrier and pass through the gap 13 to reach the thermionic anode 12. The electrons in the thermionic anode 12 reach the electrolytic cell cathode 9 through the electrode plate 18 or the wire.

[0038] The thermal energy of the thermionic emission device is transferred to the electrolytic cell through the heat conduction of the electrode plate 18; The thermal energy regulation and storage component 16 includes a high-temperature thermal energy storage device 16-7, a thermal energy regulation device 16-1, and a low-temperature thermal energy storage device 16-8. The high-temperature thermal energy of the thermionic emission module 1 is absorbed by the high-temperature thermal energy storage device 16-7, and the low-temperature thermal energy of the electrolytic cell reaction module 2 is absorbed by the low-temperature thermal energy storage device 16-8. The thermal energy regulation device 16-1 monitors the reaction temperature in the electrolytic cell, coordinates and controls the high-temperature thermal energy storage device 16-7 and the low-temperature thermal energy storage device 16-8, and adjusts the thermal energy absorbed from the electrolytic cell and the thermionic emission device or the thermal energy input to the electrolytic cell, thereby controlling the temperature of the electrolytic cell. The thermal energy regulation and storage component 16 transfers excess heat to the waste heat utilization device 17 (such as a thermopile) to generate electricity. The thermopile converts thermal energy into electrical energy, which is then input into the power regulation device 14 for utilization.

[0039] like Figure 3 As shown, in the anode incident mode, the thermionic anode 12 is made of transparent material and faces the external energy supply module 5. The thermionic anode 12 is connected to the electrolytic cell cathode 9 through a wire. The anode 10 of the electrolytic cell is connected to the rear end of the power regulation device 14, and the front end of the power regulation device 14 is connected to the thermionic cathode 11. The power regulation device 14 regulates the current and voltage input to the electrolytic cell and inputs the excess power into the energy storage device 15.

[0040] In the anodic incident mode, the external energy is concentrated solar energy, which passes through the transparent thermionic anode 12 and the gap 13 to reach the thermionic cathode 11, exciting the electron-hole pairs in the thermionic cathode 11 so that the electron energy is sufficient to overcome the potential barrier and pass through the gap 13 to reach the thermionic anode 12. The electrons in the thermionic anode 12 reach the electrolytic cell cathode 9.

[0041] The thermionic emission module 1 is connected to the thermal energy regulation and storage component 16 through a heat exchange tube, so as to transfer the thermal energy generated by the thermionic emission device to the thermal energy regulation and storage component 16 through the heat exchange medium in the heat exchange tube; wherein, the heat exchange medium includes heat transfer oil, molten salt, etc.

[0042] The thermal energy regulation and storage component 16 is connected to the electrolytic cell and includes a thermal energy regulation device 16-1, a hot medium storage tank 16-2, a cold medium storage tank 16-3, a valve 16-4, a pump 16-5, and a pump 16-6. The heat exchange medium flows from the cold medium storage tank 16-3 to the vicinity of the thermionic emission module 1 via pump 16-6. After flowing through the thermionic emission device, it generates a high-temperature medium. The thermal energy control device 16-1 monitors the temperature of the electrolytic cell and regulates the flow rate of the high-temperature medium input into the electrolytic cell by adjusting the opening of the valve 16-4, thereby controlling the temperature of the electrolytic cell. Excess high-temperature medium enters the hot medium storage tank 16-2 for storage. The heat of the high-temperature medium flowing through the electrolytic cell reaction module 2 is absorbed by the electrolytic cell, generating a low-temperature medium, which enters the cold medium storage tank 16-3 for storage.

[0043] When the thermal energy generated by the thermionic emission device is insufficient or does not generate heat, the thermal energy regulation device 16-1 shuts off pump 16-6 and turns on pump 16-5 to regulate the flow rate of the high-temperature medium input into the electrolytic cell. The high-temperature medium transfers heat energy to the electrolytic cell, thereby maintaining the temperature of the electrolytic cell and generating a low-temperature medium, which enters the cold medium storage tank 16-3 for storage.

[0044] In this embodiment, the raw material conveying module 6 includes an electrolytic cell cathode raw material conveying device and an electrolytic cell anode raw material conveying device; The cathode material conveying device of the electrolytic cell is connected to the top of the cathode 9 of the electrolytic cell and is used to convey the reaction raw materials required for the cathode 9 of the electrolytic cell to the cathode 9 of the electrolytic cell; the anode material conveying device of the electrolytic cell is connected to the top of the anode 10 of the electrolytic cell and is used to convey the raw materials required for the anode 10 of the electrolytic cell to the anode 10 of the electrolytic cell.

[0045] In this embodiment, the product collection module 7 includes a reduction product collection device 19 and an oxidation product collection device 20; the reduction product collection device 19 is connected to the cathode 9 of the electrolytic cell, and the oxidation product collection device 20 is connected to the anode 10 of the electrolytic cell; the design and materials of the reduction product collection device 19 and the oxidation product collection device 20 depend on the type of product stored.

[0046] Example 2 This embodiment provides a method for operating a hot-electron coupled electrolytic reaction system, based on the hot-electron coupled electrolytic reaction system described in Embodiment 1. It is suitable for the high-temperature (700-900℃) electrolytic preparation of ethylene in a solid oxide electrolytic cell, and includes the following steps: The incident method adopts the anodic incident type. The external energy supply module 5 includes a concentrator to transmit high-concentration solar energy to the thermionic anode 12. The energy passes through the transparent thermionic anode 12 and the gap 13 to reach the thermionic cathode 11, which excites the electron-hole pairs in the thermionic cathode 11 and makes the electrons have enough energy to overcome the potential barrier. The electrons pass through the gap 13 to reach the thermionic anode 12. The electrons in the thermionic anode 12 are transmitted to the fuel electrode through the wire. Meanwhile, in this embodiment, molten salt is used as the heat exchange medium. The molten salt flows from the cold medium storage tank 16-3 to the vicinity of the thermionic emission module 1 via pump 16-6. After flowing through the thermionic emission device, it generates high-temperature molten salt. The thermal energy control device 16-1 monitors the temperature of the solid oxide electrolysis cell and adjusts the flow rate of the high-temperature molten salt input into the solid oxide electrolysis cell by adjusting the opening of valve 16-4, thereby controlling the temperature of the solid oxide electrolysis cell. Excess high-temperature molten salt enters the heat medium storage tank 16-2 for storage. The heat of the high-temperature molten salt flowing through the solid oxide electrolysis cell is absorbed by the solid oxide electrolysis cell, generating low-temperature molten salt. The low-temperature medium enters the cold medium storage tank 16-3 for storage.

[0047] When the thermal energy generated by the thermionic emission device is insufficient or no heat is generated (i.e., during cloudy or rainy weather or at night), the thermal energy control device 16-1 shuts off pump 16-6 and turns on pump 16-5 to regulate the flow rate of high-temperature molten salt input to the solid oxide electrolytic cell. The high-temperature molten salt transfers heat energy to the solid oxide electrolytic cell, thereby maintaining the temperature of the solid oxide electrolytic cell and generating low-temperature molten salt, which enters the cold medium storage tank 16-3 for storage.

[0048] like Figure 4 As shown, CO2 reactant is input into the channel through the raw material conveying module 6. The CO2 in the channel diffuses into the fuel electrode and combines with electrons to undergo a reduction reaction at high temperature, producing CO and oxygen ions. The CO enters the reduction product collection device 19.

[0049] The raw material conveying module delivers the reactant methane to the oxygen electrode. The methane diffuses to the oxygen electrode through the channel. Oxygen ions reach the oxygen electrode through the electrolyte 8 and undergo an oxidation reaction with the methane at the oxygen electrode to produce ethylene, water vapor, and electrons. The ethylene and water vapor are discharged from the oxygen electrode under the action of the purging gas and reach the oxidation product collection device 20. The electrons enter the power regulation device 14 (such as a DC-DC converter) through the wire and then reach the thermionic cathode 11 to form a closed loop. The DC-DC converter regulates the current and voltage input to the solid oxide electrolytic cell and inputs the excess power into the storage battery for storage.

[0050] Example 3 This embodiment provides a method for operating a hot-electron coupled electrolysis reaction system, based on the hot-electron coupled electrolysis reaction system described in Embodiment 1. It is suitable for high-temperature (700-900℃) water electrolysis to produce hydrogen in a solid oxide electrolysis cell, and includes the following steps: The incident method adopts cathode incident type. The external energy supply module 5 includes a concentrator to transmit high-concentration solar energy to the thermionic cathode 11, which excites electron-hole pairs in the thermionic cathode 11 and makes the electrons have enough energy to overcome the potential barrier, pass through the gap 13 and reach the thermionic anode 12. The electrons in the thermionic anode 12 are transferred to the fuel electrode through the electrode plate 18.

[0051] Simultaneously, the heat from the thermionic emission device is conducted to the solid oxide electrolytic cell. The thermal energy regulation and storage component 16 includes multiple small devices that collect and store the thermal energy from the solid oxide electrolytic cell and the thermionic emission device in categories. The thermal energy regulation device 16-1 monitors the temperature of the solid oxide electrolytic cell and calls upon the high-temperature thermal storage device 16-7 and the low-temperature thermal storage device 16-8 to regulate the heat conducted by the thermionic emission device or the heat absorbed from the thermionic emission device and the solid oxide electrolytic cell, thereby ensuring that the solid oxide electrolytic cell meets the electrolysis reaction temperature requirements. The thermal energy generated by the thermionic emission device is absorbed by the high-temperature thermal storage device 16-7, and the thermal energy generated by the solid oxide electrolytic cell is absorbed by the low-temperature thermal storage device 16-8.

[0052] The thermal energy regulation and storage component 16 transfers excess thermal energy to the waste heat utilization device 17. In this embodiment, the waste heat utilization device 17 adopts a waste heat boiler so that downstream thermal energy can be utilized.

[0053] like Figure 5 As shown, reactants H2O and H2 are input into the channel through the raw material conveying module 6. The H2O and H2 in the channel diffuse into the fuel electrode. A small amount of H2 is used to prevent the fuel electrode from oxidizing. H2O combines with electrons and undergoes a reduction reaction at high temperature to produce H2 and oxygen ions. H2 enters the reduction product collection device 19. Oxygen ions reach the oxygen electrode through the electrolyte 8 and undergo an oxidation reaction at the oxygen electrode to produce oxygen and electrons. Purge gas is conveyed to the oxygen electrode through the raw material conveying module 6 to discharge the oxygen in the oxygen electrode to the oxidation product collection device 20. Electrons enter the power regulation device 14 through the wire and then reach the thermionic cathode 11 to form a closed loop. The power regulation device 14 regulates the voltage and current input to the solid oxide electrolytic cell and stores the excess electrical energy in the energy storage device 15.

[0054] Example 4 This embodiment provides a method for operating a hot-electron coupled electrolysis reaction system, based on the hot-electron coupled electrolysis reaction system described in Embodiment 1. It is suitable for producing hydrogen by electrolyzing water in an alkaline electrolysis cell at low temperatures (60-80°C), and includes the following steps: The incident method adopts cathode incident type. The external energy supply module 5 includes a factory thermal energy regulation and utilization device, which transmits thermal energy to the thermionic cathode 11, excites the electron-hole pairs of the thermionic cathode 11, and makes the electron energy sufficient to overcome the potential barrier, pass through the gap 13 to reach the thermionic anode 12, and the electrons in the thermionic anode 12 reach the electrolytic cell cathode 9 through the wire.

[0055] The cathode 9 and anode 10 of the electrolytic cell are placed in a sodium hydroxide electrolyte with a mass fraction of 19%, and the reduction reaction and oxidation reaction are separated by a diaphragm that allows only negative ions and water molecules to pass through.

[0056] In the cathode 9 of the electrolytic cell, water and electrons combine to produce hydrogen and hydroxide ions. The hydrogen enters the reduction product collection device 19, and the hydroxide ions pass through the diaphragm to reach the anode 10 of the electrolytic cell. An oxidation reaction occurs at the anode 10, producing oxygen, water, and electrons. The oxygen enters the oxidation product collection device 20, and the electrons enter the power regulation device 14 (such as a DC-DC converter) through wires, and then reach the thermionic cathode 11, forming a closed loop. The DC-DC converter regulates the current and voltage input to the alkaline electrolytic cell and stores excess electrical energy in the energy storage device 15.

[0057] The heat energy from the thermionic emission device enters the thermal energy regulation and storage component 16. The heat from the thermal energy regulation and storage component 16 is transferred to the waste heat utilization device 17 (such as a thermopile). The thermopile converts the heat energy into electrical energy through thermoelectric power generation. The generated current is connected in parallel or in series with the thermionic emission device and fed back into the alkaline electrolytic cell.

[0058] Meanwhile, the heat flow process in this embodiment differs from that in Embodiment 2 in that the heat exchange medium is heat transfer oil (or hot water). The heat energy control device 16-1 monitors the temperature of the alkaline electrolysis cell and adjusts the flow rate of heat transfer oil (or hot water) input to the alkaline electrolysis cell by adjusting the opening degree of the valves between the various equipment passages in the heat energy control and storage components and the start / stop status (or operating parameters) of the pumps, thereby maintaining the temperature of the alkaline electrolysis cell.

[0059] Example 5 This embodiment provides a method for operating a hot-electron coupled electrolysis reaction system, based on the hot-electron coupled electrolysis reaction system described in Embodiment 1. It is suitable for hydrogen production by water electrolysis at low temperatures (50-90℃) in a proton exchange membrane electrolyzer, and includes the following steps: The incident method adopts cathode incident type. The external energy supply module 5 includes a nuclear energy utilization device, which transfers thermal energy to the thermionic emission module 1, excites the electron-hole pairs of the thermionic cathode 11, and makes the electron energy sufficient to overcome the potential barrier, pass through the gap 13 to reach the thermionic anode 12, and the electrons in the thermionic anode 12 reach the electrolytic cell cathode 9 through the electrode plate 18.

[0060] Water is fed into the anode 10 of the electrolytic cell through the raw material conveying module 6. Under the action of the catalyst, the water undergoes an oxidation reaction to generate hydrogen ions, oxygen, and electrons. The oxygen enters the oxidation product collection device 20. The hydrogen ions pass through the proton exchange membrane to the cathode 9 of the electrolytic cell, where they combine with electrons to undergo a reduction reaction and produce hydrogen gas. The hydrogen gas enters the reduction product collection device 19. The electrons pass through the wires to the power regulation device 14 and then to the thermionic cathode 11, forming a closed loop. The power regulation device 14 adjusts the voltage and current input to the proton exchange membrane electrolytic cell to ensure that the reaction in the proton exchange membrane electrolytic cell proceeds normally and stores the excess electrical energy in the energy storage device 15 (such as a battery).

[0061] Simultaneously, the heat from the thermionic emission device is conducted to the proton exchange membrane electrolyzer. The thermal energy regulation and storage component 16 monitors the temperature of the proton exchange membrane electrolyzer. The thermal energy regulation device 16-1 coordinates and controls the high-temperature heat storage device 16-7 and the low-temperature heat storage device 16-8 to adjust the heat conducted by the thermionic emission device or the heat absorbed from the thermionic emission device and the proton exchange membrane electrolyzer, so that the proton exchange membrane electrolyzer meets the electrolysis reaction temperature requirements. The heat from the thermionic emission device enters the high-temperature heat storage device 16-7, and the heat energy from the proton exchange membrane electrolyzer enters the low-temperature heat storage device 16-8 for storage or to transfer excess heat energy to the waste heat utilization device 17 for heat energy utilization.

[0062] Example 6 This embodiment provides a method for operating a thermionic coupling electrolytic reaction system, based on the thermionic coupling electrolytic reaction system described in Embodiment 1, suitable for reducing iron at high temperature (800°C) in a molten salt electrolytic cell, including the following steps: The incident method adopts the anodic incident type. The external energy supply module 5 uses a concentrator to transmit high-concentration solar energy to the thermionic anode 12. The energy passes through the transparent thermionic anode 12 and the gap 13 to reach the thermionic cathode 11, which excites the electron-hole pairs in the thermionic cathode 11 and makes the electrons have enough energy to overcome the potential barrier. The electrons pass through the gap 13 to reach the thermionic anode 12. The electrons in the thermionic anode 12 are transmitted to the electrolytic cell cathode 9 through the wire.

[0063] The cathode material of the electrolytic cell is iron oxide, and the electrolyte 8 is molten calcium chloride. The heat from the thermionic cathode 11 is transferred to the molten salt electrolytic cell. At high temperature, iron oxide undergoes a reduction reaction with electrons to produce iron and oxygen ions. The oxygen ions pass through the calcium chloride electrolyte to the anode 10 of the electrolytic cell, where they undergo an oxidation reaction to produce oxygen and electrons. The oxygen enters the oxidation product collection device 20, and the electrons enter the power regulation device 14 through wires, and then reach the thermionic cathode 11 to form a closed loop. The power regulation device 14 regulates the voltage and current input to the molten salt electrolytic cell to ensure that the reaction in the electrolytic cell proceeds normally, and stores the excess electrical energy in the energy storage device 15 (such as a battery).

[0064] The heat generated by the molten salt electrolysis cell and the thermionic emission device is absorbed by the thermal energy regulation and storage component 16. The thermal energy regulation and storage component 16 monitors the temperature of the electrolysis cell. The thermal energy regulation device 16-1 coordinates and controls the high-temperature heat storage device 16-7 and the low-temperature heat storage device 16-8 to adjust the heat conducted by the thermionic emission device or the heat absorbed from the thermionic emission device and the electrolysis cell, so that the molten salt electrolysis cell meets the electrolysis reaction temperature requirements. The absorbed heat energy is stored or the excess heat energy is transferred to the waste heat utilization device 17 for heat energy utilization.

[0065] While the specific embodiments of the present invention have been described above in conjunction with the accompanying drawings, this is not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims

1. A hot-electron coupled electrolytic reaction system, characterized in that, include: Electrolytic cell reaction module, thermionic emission module, power regulation and energy storage module, and thermal energy regulation and utilization module; The electrolytic cell reaction module includes an electrolytic cell, which includes an electrolyte, an electrolytic cell cathode, and an electrolytic cell anode. Thermionic emission module includes one or more thermionic emission devices, each thermionic emission device including a thermionic cathode, a thermionic anode, and a gap between the two; The power regulation and energy storage module includes a power regulation device and an energy storage device connected to the power regulation device. The thermionic cathode is connected to the front end of the power regulation device, the rear end of the power regulation device is connected to the anode of the electrolytic cell, and the thermionic anode is connected to the cathode of the electrolytic cell. The power regulation device is used to regulate the current and voltage input to the electrolytic cell and input excess power to the energy storage device. The thermal energy regulation and utilization module includes a thermal energy regulation and storage component and a waste heat utilization device connected to the thermal energy regulation and storage component. The thermal energy regulation and storage component is connected to the thermionic emission module and the electrolytic cell reaction module, and is used to regulate the heat in the electrolytic cell and store or transfer excess heat to the waste heat utilization device.

2. The hot-electron coupled electrolytic reaction system as described in claim 1, characterized in that, The thermionic anode is made of a transparent, opaque, or semi-transparent material. An energy source excites electron-hole pairs in the thermionic cathode, so that the electrons have enough energy to overcome the potential barrier and pass through the gap to reach the thermionic anode. The electrons in the thermionic anode are then supplied to the cathode of the electrolytic cell.

3. The hot-electron coupled electrolytic reaction system as described in claim 2, characterized in that, The thermionic cathode faces the energy source, and external energy directly reaches the thermionic cathode to excite electron-hole pairs. This method is called cathode incident. In this case, the thermionic anode is a transparent, opaque, or translucent material.

4. The hot-electron coupled electrolytic reaction system as described in claim 2, characterized in that, In the anodic incident mode, the thermionic anode faces the energy source and is made of transparent material. Concentrated solar energy passes through the thermionic anode and the gap, and after reaching the thermionic cathode, it excites the electron-hole pairs in the thermionic cathode. This method is called the anodic incident mode.

5. The hot-electron coupled electrolytic reaction system according to any one of claims 2-4, characterized in that, The electrolysis reaction system also includes an external energy supply module that provides an energy source for the thermionic emission device. The external energy supply module includes a focusing device and / or a heating device. The focusing device is used to concentrate light onto the thermionic emission device, and the heating device is used to heat the thermionic cathode in the thermionic emission device.

6. The hot-electron coupled electrolytic reaction system as described in claim 1, characterized in that, The thermal energy regulation and storage component is used to monitor the temperature of the electrolytic cell and regulate the heat input to the electrolytic cell or the heat absorbed from the thermionic emission device and the electrolytic cell, so as to maintain the electrolytic cell temperature at the required electrolysis reaction temperature.

7. The hot-electron coupled electrolytic reaction system as described in claim 1, characterized in that, The heat from the thermionic emission device is transferred to the thermal energy regulation and storage component, which stores or transfers the heat according to its categories to the waste heat utilization device. The waste heat utilization device utilizes the heat energy or converts it into electrical energy, and the generated electrical energy is connected in parallel or in series with the thermionic emission device and then transferred to the electrical energy regulation device.

8. The hot-electron coupled electrolytic reaction system as described in claim 1, characterized in that, The electrolysis reaction system also includes a raw material conveying module connected to the top of the electrolysis cell reaction module. The raw material conveying module includes an electrolysis cell cathode raw material conveying device and an electrolysis cell anode raw material conveying device. The cathode material conveying device of the electrolytic cell is connected to the top of the cathode of the electrolytic cell and is used to convey the reaction raw materials required by the cathode of the electrolytic cell to the cathode of the electrolytic cell. The anode material conveying device of the electrolytic cell is connected to the top of the anode of the electrolytic cell and is used to transport the raw materials required for the anode of the electrolytic cell to the anode of the electrolytic cell.

9. The hot-electron coupled electrolytic reaction system as described in claim 1, characterized in that, The electrolysis reaction system also includes a product collection module connected to the bottom of the electrolysis cell reaction module. The product collection module includes a reduction product collection device and an oxidation product collection device. The reduction product collection device is connected to the cathode of the electrolytic cell, and the oxidation product collection device is connected to the anode of the electrolytic cell.

10. A method for operating a hot-electron coupled electrolytic reaction system, characterized in that, The electrolytic reaction system employing the hot electron coupling according to any one of claims 1-9 comprises: An external energy source excites electron-hole pairs in the thermionic cathode and gives the electrons enough energy to overcome the potential barrier, pass through the gap to reach the thermionic anode, and the electrons in the thermionic anode reach the cathode of the electrolytic cell. Reactants are selectively fed into the cathode and anode of the electrolytic cell through a raw material conveying device, or no additional reactants are fed in. The reactants at the cathode of the electrolytic cell combine with electrons to undergo a reduction reaction, producing reduction products or generating negative ions at the same time. The reduction products enter the reduction product collection device, and the generated negative ions reach the anode of the electrolytic cell through the electrolyte and participate in the oxidation reaction. In an electrolytic cell, the reactants at the anode undergo an oxidation reaction to produce oxidation products or simultaneously generate positive ions and release electrons. The oxidation products enter the oxidation product collection device, while the generated positive ions reach the cathode of the electrolytic cell through the electrolyte and participate in the reduction reaction. The electrons reach the thermionic cathode through the power regulation device, forming a closed loop. The power regulation device adjusts the current and voltage input to the electrolytic cell to ensure the normal electrolytic reaction in the cell, and inputs excess power into the energy storage device for storage. The heat generated by the electrolytic cell and the thermionic emission device is input into the thermal energy regulation and storage component. The thermal energy regulation and storage component monitors the temperature of the electrolytic cell and regulates the reaction operating temperature of the electrolytic cell by adjusting the heat input to the electrolytic cell or the heat absorbed from the electrolytic cell. Excess heat is stored or transported to the waste heat utilization device according to categories.

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