LOHC coupled PEM electrolytic bath hydrogen production-hydrogen storage integrated system and control method

Abstract

According to the LOHC coupled PEM electrolytic cell hydrogen production-hydrogen storage integrated system and the control method, the back pressure valve is arranged, the control system controls the system to be started during hydrogenation reaction, the anode pressure of the electrolytic cell is increased, and therefore the resistance of a cathode hydrogen-poor organic carrier and hydrogen permeating into the anode is increased; therefore, the permeation amount of hydrogen and hydrogen-poor organic carriers at the proton exchange membrane is reduced, the influence on the hydrogenation efficiency is reduced, the resistance in a PEM hydrogenation system can be prevented from being increased, the influence on the current density in the hydrogenation process is reduced, and the hydrogenation efficiency of the organic liquid hydrogen storage carrier is more favorably improved.

Description

Technical Field

[0001] The present application relates to the technical field of water electrolysis hydrogen production and organic liquid hydrogen storage, and in particular to a LOHC coupled PEM electrolyzer hydrogen production-storage integrated system and control method. Background Art

[0002] The PEM water electrolysis hydrogen production coupled with LOHC hydrogen storage process has attracted much attention for its advantages of low temperature, low pressure and high conversion efficiency. Its principle is to couple the PEM water electrolysis hydrogen production and the organic liquid hydrogen storage carrier hydrogenation together, directly storing the hydrogen element in the water in the liquid organic hydrogen storage carrier in the form of a chemical reaction, so that the hydrogen-poor organic carrier becomes a hydrogen-rich organic carrier. The whole system is integrated and easy to operate, reducing the high temperature and high pressure required for conventional hydrogenation, and greatly improving the safety of the entire reaction.

[0003] However, the coupling of the two processes not only requires controlling the permeation of hydrogen, water, and hydrogen-poor organic carriers at the proton exchange membrane in the electrolyzer, but also takes into account the efficiency of hydrogenation of the hydrogen-poor organic carrier. Therefore, in order to reduce the permeation of hydrogen and hydrogen-poor organic carriers at the proton exchange membrane and affect the hydrogenation efficiency, the prior art usually chooses to increase the thickness of the proton exchange membrane. However, this will increase the resistance in the PEM hydrogenation system and affect the current density during the hydrogenation process, which is not conducive to improving the efficiency of hydrogenation of organic liquid hydrogen storage carriers. Summary of the invention

[0004] To solve the above problems, the present application provides a LOHC coupled PEM electrolyzer hydrogen production and storage integrated system and control method. By setting a back pressure valve, the control system controls it to start during the hydrogenation reaction, so that the anode pressure of the electrolyzer is increased to increase the resistance of the cathode hydrogen-poor organic carrier and hydrogen to penetrate into the anode, thereby reducing the permeation of hydrogen and hydrogen-poor organic carrier at the proton exchange membrane, reducing the impact on the hydrogenation efficiency, and avoiding increasing the resistance in the PEM hydrogenation system, reducing the impact on the current density during the hydrogenation process, which is more conducive to improving the hydrogenation efficiency of the organic liquid hydrogen storage carrier.

[0005] In a first aspect, the present application provides a LOHC coupled PEM electrolyzer hydrogen production and storage integrated system, the system comprising: an electrolyzer (1), a heat exchange system (2), a liquid organic matter circulation system (3) and a control system (4); The electrolytic cell (1) comprises an anode (11) and a cathode (12); a back pressure valve (111) is provided on a pipeline connected to a water outlet of the anode (11); the back pressure valve (111) is configured to increase the pressure of the anode (11) so that the pressure of the anode (11) is higher than the pressure of the cathode (12); The first end (21) of the heat exchange system (2) is connected to the pipeline connected to the back pressure valve (111), the second end (22) is connected to the liquid organic matter circulation system (3), and the third end (23) is connected to the liquid inlet of the cathode (12); The water-gas mixture discharged from the water outlet of the anode (11) enters the heat exchange system (2) via the first end (21); The hydrogen-poor organic carrier outputted from the liquid organic matter circulation system (3) enters the heat exchange system (2) via the second end (22) and performs heat exchange with the water-gas mixture. After the heat exchange, the hydrogen-poor organic carrier enters the cathode (12) via the third end (23) to perform a hydrogenation reaction in the cathode (12); The control system (4) is connected to the back pressure valve (111) and is configured to control the back pressure valve (111) to open or close.

[0006] Optionally, the back pressure valve (111) is configured to increase the pressure of the anode (11) to 0.3 MPa~1 MPa.

[0007] Optionally, the system further comprises a first temperature sensor (16); The first temperature sensor (16) is arranged on a connecting pipeline between the water outlet of the anode (11) and the back pressure valve (111); The first temperature sensor (16) is configured to transmit a first signal to the control system (4) in response to the temperature of the water-gas mixture; the control system (4) activates the back pressure valve (111) in response to the first signal to increase the pressure of the anode (11).

[0008] Optionally, the first temperature sensor (16) is configured to transmit a first signal to the control system (4) in response to the temperature of the water-gas mixture being between 45° C. and 55° C.

[0009] Optionally, the system further comprises a radiator (5) and a second temperature sensor (52); The radiator (5) has a liquid inlet end connected to the fourth end (24) of the heat exchange system (2), and a liquid outlet end connected to the water inlet of the pure water circulation system (51), and is configured to cool the water-gas mixture after heat exchange output from the fourth end (24) and then input it into the pure water circulation system (51) along the liquid outlet end of the radiator (5); The second temperature sensor (52) is disposed on a pipeline connecting the liquid inlet end of the radiator (5) and the fourth end (24), and is configured to transmit a second signal to the control system (4) in response to the temperature of the water-gas mixture after the heat exchange output by the fourth end (24); The control system (4) is connected to the radiator (5) and is configured to judge whether to activate the radiator (5) in response to the second signal, and the radiator (5) is used to cool the water-gas mixture after the heat exchange when it is activated; The water outlet of the pure water circulation system (51) is connected to the water inlet of the anode (11) so as to transport pure water to the anode (11).

[0010] Optionally, the control system (4) is specifically configured to activate the heat dissipation function of the radiator (5) in response to the second signal when the temperature value transmitted by the second signal is greater than 55°C; Furthermore, when the temperature value transmitted by the second signal is less than or equal to 55° C., the control system (4) responds to the second signal and disables the heat dissipation function of the radiator (5).

[0011] Optionally, the electrolytic cell (1) includes a cathode flow channel and an anode flow channel; Wherein, the depth of the cathode flow channel is smaller than the depth of the anode flow channel.

[0012] Optionally, the depth of the cathode flow channel is 0.2 mm to 0.4 mm, and the depth of the anode flow channel is 0.6 mm to 1.0 mm.

[0013] Optionally, the system further comprises a purge system (6); The first gas outlet end of the purge system (6) is connected to the water inlet of the anode (11) and is used to transport inert gas to blow out the water-gas mixture in the anode (11); The second gas outlet end is connected to the connecting pipeline of the liquid organic matter circulation system (3) and the second end (22) and is used to transport the inert gas to blow the hydrogen-poor organic carrier in the heat exchange system (2) and the cathode (12) out along the cathode (12) outlet.

[0014] In a second aspect, the present application provides a LOHC coupled PEM electrolyzer hydrogen production-storage integrated control method, the control method is applicable to the LOHC coupled PEM electrolyzer hydrogen production-storage integrated system described in the first aspect, the control method comprising: S1, heating the pure water in the pure water circulation system to 45°C to 55°C, and transporting the heated pure water to the electrolytic cell (1) along the water inlet of the anode (11); S2, the first temperature sensor (16) detects that the temperature of the water-gas mixture discharged from the water outlet of the anode (11) is 45°C to 55°C, and transmits a first signal to the control system (4). In response to the first signal, the control system (4) starts the power supply device to supply power to the electrolyzer (1), and starts the back pressure valve (111) to increase the pressure of the anode (11) to 0.3MPa to 1MPa, so that the pressure of the anode (11) is higher than the pressure of the cathode (12), so as to perform a hydrogen production reaction; S3, transporting the hydrogen-poor organic carrier in the liquid organic matter circulation system (3) to the heat exchange system (2), exchanging heat with the water-gas mixture discharged from the water outlet of the anode (11), and transporting the hydrogen-poor organic carrier after the heat exchange into the cathode (12) along the liquid inlet of the cathode (12) to perform a hydrogenation reaction to obtain a hydrogen-rich organic carrier; S4, the hydrogen-rich organic carrier and hydrogen enter the cooling device along the discharge port of the cathode (12), and are discharged after being cooled.

[0015] In summary, the present application includes at least one of the following beneficial technical effects: 1. The present application provides a LOHC coupled PEM electrolyzer hydrogen production-storage integrated system, which realizes hydrogen production-storage integration by performing two reactions, hydrogen production and hydrogenation, in the electrolyzer, and then by setting a back pressure valve, using a control system to start the back pressure valve during the hydrogenation reaction, the pressure of the anode of the electrolyzer is increased, so that the pressure of the anode is higher than the pressure of the cathode, thereby increasing the resistance of hydrogen and hydrogen-poor organic carriers to penetrate from the cathode to the anode, reducing the penetration of hydrogen and hydrogen-poor organic carriers, and reducing the impact on the efficiency of the hydrogenation reaction; not only that, it can also reduce the use of thick proton exchange membranes, so that the resistance in the PEM hydrogenation system remains stable, and the current density during the hydrogenation process remains stable, which is conducive to the smooth progress of the hydrogenation reaction of the organic liquid hydrogen storage carrier, thereby improving the hydrogenation efficiency; 2. The present application provides an integrated hydrogen production and storage system of a LOHC-coupled PEM electrolyzer. By setting up a heat exchange system, a high-temperature water-gas mixture (including water and oxygen) formed by electrolyzing water at the anode of the electrolyzer is transported to the heat exchange system, and then a hydrogen-poor organic carrier is transported to the heat exchange system, and the high-temperature water-gas mixture is used to heat the hydrogen-poor organic carrier. The heated hydrogen-poor organic carrier is then sent to the cathode of the electrolyzer for a hydrogenation reaction, thereby fully utilizing the thermal energy of the electrolyzed water product and reducing the amount of thermal utilities used in the hydrogenation reaction of the organic liquid hydrogen storage carrier, thereby enhancing the energy-saving effect of the system operation process. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the description of the embodiments of the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0017] Figure 1 The schematic diagram of the structure of the LOHC coupled PEM electrolyzer hydrogen production and storage integrated system proposed in the embodiment of the present application is shown; Figure 2 A schematic diagram of the electrolytic cell structure proposed in an embodiment of the present application is shown; Figure 3 A schematic diagram of a control system proposed in an embodiment of the present application is shown; Figure 4 A flow chart of the integrated control method for hydrogen production and storage of LOHC-coupled PEM electrolyzers proposed in an embodiment of the present application is shown.

[0018] Description of reference numerals: 1. Electrolyzer; 11. Anode; 111. Back pressure valve; 112. Anode titanium plate; 113. Anode sealing material; 114. Platinum-plated porous titanium foam; 12. cathode; 121. titanium felt; 122. cathode sealing material; 123. cathode titanium plate; 13. Insulation plate; 14. Membrane electrode; 15. Insulation fastening bolts; 16. First temperature sensor; 17. DC power supply; 18. Fifth temperature sensor; 2. heat exchange system; 21. first end; 22. second end; 23. third end; 24. fourth end; 25. third temperature sensor; 3. Liquid organic matter circulation system; 31. Liquid organic matter storage tank; 311. Primary cooling tank; 312. Secondary cooling tank; 313. Drying tube; 314. Gas mass flow meter; 32. First solenoid valve; 33. Second diaphragm metering pump; 34. Fourth temperature sensor; 35. Second one-way valve; 36. First liquid level gauge; 37. Second solenoid valve; 38. Third diaphragm metering pump; 4. Control system; 41. Signal control part; 42. Signal monitoring part; 43. Data recording part; 44. Safety protection part; 5. Radiator; 51. Pure water circulation system; 511. Pure water storage tank; 512. First diaphragm metering pump; 513. First one-way valve; 514. Temperature and pressure integrated sensor; 515. Deionizer; 516. Conductivity meter; 517. Supplement and drain outlet; 518. Second liquid level meter; 52. A second temperature sensor; 6. Purge system; 61. First gas mass flow controller; 62. Third one-way valve; 63. Second gas mass flow controller; 64. Fourth one-way valve; 65. Water supply tank; 651. Water supply pump; 652. Three-way solenoid valve; 653. First water supply end; 654. Second water supply end; 655. Third water supply end; 66. Third solenoid valve; 67. Fifth one-way valve. DETAILED DESCRIPTION

[0019] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0020] In the drawings, the size of the constituent elements, the thickness of the layer or the area may be exaggerated for the sake of clarity. Therefore, any implementation of the present disclosure is not necessarily limited to the size shown in the drawings, and the shapes and sizes of the components in the drawings do not reflect the true proportions. In addition, the drawings schematically show ideal examples, and any implementation of the present disclosure is not limited to the shapes or values ​​shown in the drawings.

[0021] In the related technology, in the PEM water electrolysis hydrogen production coupled with LOHC hydrogen storage process, it is necessary to consider the permeation of hydrogen, water, and hydrogen-poor organic carriers at the membrane, and also the efficiency of hydrogenation of the hydrogen-poor organic carriers. Therefore, in order to reduce the permeation of hydrogen and hydrogen-poor organic carriers at the proton exchange membrane and affect the hydrogenation efficiency, the prior art usually chooses to increase the thickness of the proton exchange membrane.

[0022] However, in actual application, a thick proton exchange membrane will increase the resistance in the PEM hydrogenation system. According to Ohm's law, the increase in resistance means that at the same current, the system needs to consume more electrical energy to overcome this resistance. Therefore, more energy will be lost in the form of heat energy during the transmission process, resulting in a decrease in hydrogenation efficiency. In addition, when the thickness of the proton exchange membrane increases, the increase in resistance will lead to a decrease in the number of hydrogen ions passing through the membrane per unit time, which will also lead to a decrease in the hydrogenation rate.

[0023] Based on the problems of the prior art, the present application provides an integrated hydrogen production and storage system for a LOHC-coupled PEM electrolyzer, which achieves the goal of reducing the permeation of hydrogen-poor organic carriers and hydrogen from the cathode to the anode by setting the cathode side of the electrolyzer to normal pressure and increasing the pressure on the anode side without increasing the thickness of the proton exchange membrane or the internal resistance of the PEM electrolyzer, thereby improving the stability of the PEM electrolyzer and the hydrogenation efficiency.

[0024] First, see Figure 1 , the embodiment of the present application provides a LOHC coupled PEM electrolyzer hydrogen production-storage integrated system, the system comprising: an electrolyzer 1, a heat exchange system 2, a liquid organic matter circulation system 3 and a control system 4; The electrolytic cell 1 comprises an anode 11 and a cathode 12. A back pressure valve 111 is provided on a pipeline connected to a water outlet of the anode 11. The back pressure valve 111 is configured to increase the pressure of the anode 11 so that the pressure of the anode 11 is higher than the pressure of the cathode 12. The first end 21 of the heat exchange system 2 is connected to the pipeline connected to the back pressure valve 111, the second end 22 is connected to the liquid organic matter circulation system 3, and the third end 23 is connected to the liquid inlet of the cathode 12; The water-gas mixture discharged from the water outlet of the anode 11 enters the heat exchange system 2 through the first end 21; The hydrogen-poor organic carrier outputted from the liquid organic matter circulation system 3 enters the heat exchange system 2 through the second end 22 and performs heat exchange with the water-gas mixture. The hydrogen-poor organic carrier after heat exchange enters the cathode 12 through the third end 23 to perform hydrogenation reaction in the cathode 12. The control system 4 is connected to the back pressure valve 111 and is configured to control the back pressure valve 111 to be opened or closed.

[0025] It should be noted that LOHC stands for organic liquid hydrogen storage technology; PEM stands for proton exchange membrane electrolyzer.

[0026] In specific implementation, by setting the back pressure valve 111, when the control system 4 opens the back pressure valve 111, the back pressure valve 111 allows the water-gas mixture discharged from the water outlet of the anode 11 to accumulate in the pipeline and form a certain pressure, which will push the hydrogen-poor organic carrier and hydrogen molecules on the proton exchange membrane to move toward the cathode 12 side, but because the proton exchange membrane has limited permeability to hydrogen and hydrogen-poor organic carriers, this driving effect will effectively reduce the permeation of hydrogen and hydrogen-poor organic carriers. By setting the back pressure valve 111 to increase the pressure of the anode 11, there is no need to change the thickness of the proton exchange membrane, nor to increase the resistance in the system, so it will not increase the power consumption and heat loss of the system, which helps to improve the stability of the PEM electrolyzer and thus improve the hydrogenation efficiency.

[0027] The present application also realizes heat exchange between the water-gas mixture discharged from the water outlet of the anode 11 and the hydrogen-poor organic carrier by setting up a heat exchange system 2, which not only improves the energy utilization efficiency of the system, but also enables the hydrogen-poor organic carrier to reach a suitable temperature before entering the cathode 12, making it easier to contact the catalytic site, thereby improving the hydrogenation efficiency.

[0028] In some embodiments, the back pressure valve 111 is configured to increase the pressure of the anode 11 to 0.3 MPa-1 MPa.

[0029] In specific implementation, by increasing the pressure on the anode 11 side to 0.3 MPa~1 MPa, the penetration of hydrogen-poor organic carriers and hydrogen from the cathode 12 to the anode 11 can be effectively reduced, and the water-gas mixture on the anode 11 side of the electrolytic cell 1 can be smoothly discharged along the water outlet of the anode 11.

[0030] In some embodiments, see Figure 1 , the system further comprises a first temperature sensor 16; The first temperature sensor 16 is disposed on the connecting pipeline between the water outlet of the anode 11 and the back pressure valve 111; The first temperature sensor 16 is configured to transmit a first signal to the control system 4 in response to the temperature of the water-gas mixture; the control system 4 activates the back pressure valve 111 in response to the first signal to increase the pressure of the anode 11 .

[0031] It should be noted that the first signal is an electrical signal instructing the control system 4 to start the back pressure valve 111 .

[0032] In specific implementation, by providing the first temperature sensor 16, intelligent control and automatic adjustment of the back pressure valve 111 are realized, which greatly improves the flexibility and response speed of the system, thereby reducing the operating difficulty and labor cost of the system.

[0033] In some embodiments, the first temperature sensor 16 is configured to transmit a first signal to the control system 4 in response to the temperature of the water-gas mixture being 45° C. to 55° C.

[0034] In specific implementation, when the temperature of the water-gas mixture at the outlet of the anode 11 reaches a preset value, the control system 4 responds to the first signal, starts the back pressure valve 111, and uses the back pressure valve 111 to increase the pressure on the side of the anode 11. The measured temperature of the water-gas mixture is the same as the internal temperature of the electrolytic cell 1. At this temperature, the conductivity of the proton exchange membrane of the electrolytic cell 1 will increase appropriately, which is helpful to improve the performance and efficiency of the electrolytic cell 1; at the same time, this temperature range is also helpful to accelerate the transmission rate of hydroxide ions, increase the reaction speed, and thus increase the hydrogen production.

[0035] In some embodiments, see Figure 2 The electrolytic cell 1 further includes an insulating plate 13, an anode titanium plate 112, an anode sealing material 113, a platinum-plated porous titanium foam 114, a membrane electrode 14, a titanium felt 121, a cathode sealing material 122, a cathode titanium plate 123 and an insulating fastening bolt 15; The insulating plate 13 is wrapped around the electrolytic cell 1 to isolate the electricity and prevent the current from directly passing through the cell body and causing a short circuit; The cathode sealing material 122 corresponds to the anode sealing material 113, including but not limited to any one of expanded polytetrafluoroethylene, rubber or ceramic fiber, and has the characteristics of corrosion resistance and high temperature resistance; Insulating fastening bolts 15 are respectively connected to the top and bottom of the electrolytic cell 1 to firmly connect the various layers of the electrolytic cell 1 together while maintaining electrical isolation.

[0036] In some embodiments, the water inlet of the anode 11 of the electrolytic cell 1 is arranged at the upper end of the electrolytic cell 1 , and the water outlet is arranged at the lower end of the electrolytic cell 1 .

[0037] During implementation, during the process of producing hydrogen by electrolysis of water, the anode 11 will produce oxygen and water vapor. Setting the water outlet at the lower end of the electrolyzer 1 helps these gases to be discharged from the electrolyzer 1 along with the water flow, reducing the accumulation of gas in the anode 11 area and avoiding the formation of bubbles that hinder the electrolysis reaction. This design also helps to reduce the stagnation time of the water flow inside the electrolyzer 1, thereby reducing the risk of hydrogen-poor organic carriers and hydrogen permeating from the cathode to the anode. Because permeation usually occurs in areas where the fluid is stagnant or flows poorly, the flow design at the upper and lower ends helps to avoid this situation.

[0038] In some embodiments, see Figure 1 The system also includes a power supply device, which is a DC power supply 17 to supply power to the electrolytic cell 1 and transmit current and voltage signals to the control system 4. The control system 4 is configured to receive and store the current and voltage signals.

[0039] In some embodiments, see Figure 2 , the electrolytic cell 1 includes a cathode flow channel and an anode flow channel; Wherein, the depth of the cathode flow channel is smaller than the depth of the anode flow channel.

[0040] In specific implementation, under the rated flow rate of the hydrogen-poor organic carrier, by setting the cathode flow channel depth to be smaller, the hydrogen-poor organic carrier can be fully dispersed to the cathode 12 side of the membrane electrode 14 after diffusing through the titanium felt 121, and quickly and evenly reach the catalyst surface, thereby increasing the contact probability between the hydrogen-poor organic carrier and the catalyst, thereby improving the hydrogenation efficiency of the hydrogen-poor organic carrier.

[0041] In some embodiments, the depth of the cathode flow channel is 0.2 mm to 0.4 mm, and the depth of the anode flow channel is 0.6 mm to 1.0 mm.

[0042] In specific implementation, the cathode flow channel depth is set to 0.2 mm~0.4 mm, which is beneficial to reducing the mass transfer resistance between hydrogen and electrolyte and improving the hydrogen transfer efficiency; the setting of the shallow flow channel on the cathode side helps to reduce the penetration of hydrogen-poor organic carriers and hydrogen into the anode, ensure the effective utilization of reactants at the cathode, and improve the hydrogenation efficiency; the design of the shallow cathode flow channel optimizes the contact interface between the hydrogen-poor organic carrier and hydrogen, promotes the rapid progress of the hydrogenation reaction, which not only improves the hydrogenation reaction rate, but also ensures the sufficiency and efficiency of the hydrogenation process.

[0043] By setting the anode flow channel depth to 0.6 mm~1.0 mm, a larger space can be provided to accommodate and quickly discharge oxygen, preventing oxygen bubbles from clogging the pores of the diffusion layer, and reducing mass transfer resistance and heat transfer resistance; at the same time, the increased pressure on the anode side combined with the deep flow channel design effectively reduces the permeation phenomenon, allowing more hydrogen to be retained on the cathode side to participate in the hydrogenation reaction, thereby further improving the hydrogenation efficiency.

[0044] In some embodiments, see Figure 1 , the system further comprises a radiator 5 and a second temperature sensor 52; The radiator 5 has a liquid inlet connected to the fourth end 24 of the heat exchange system 2 and a liquid outlet connected to the water inlet of the pure water circulation system 51, and is configured to cool the water-gas mixture after heat exchange output from the fourth end 24 and then input it into the pure water circulation system 51 along the liquid outlet of the radiator 5; The second temperature sensor 52 is disposed on a pipeline connecting the liquid inlet end of the radiator 5 and the fourth end 24, and is configured to transmit a second signal to the control system 4 in response to the temperature of the water-gas mixture after heat exchange outputted from the fourth end 24; The control system 4 is connected to the radiator 5 and is configured to determine whether to activate the radiator 5 in response to the second signal. When the radiator 5 is activated, it is used to cool the water-gas mixture after the heat exchange. The water outlet of the pure water circulation system 51 is connected to the water inlet of the anode 11 to transport pure water to the anode 11 .

[0045] It should be noted that the heat exchange system 2 includes a plate heat exchanger; When the radiator 5 is not activated, the radiator 5 is only a device for conveying a water-gas mixture; The second signal is an electrical signal that instructs the control system 4 to activate or disable the heat dissipation function of the radiator 5; The water vapor mixture includes water and oxygen.

[0046] In specific implementation, the water-gas mixture discharged from the water outlet of the anode 11 flows to the first end 21 through the pipeline, and the water-gas mixture enters the heat exchange system 2 through the first end 21, and heat exchanges with the hydrogen-poor organic carrier in the heat exchange system 2. The water-gas mixture after heat exchange flows downward along the fourth end 24 into the radiator 5, and the second temperature sensor 52 detects its temperature and transmits a second signal to the control system 4. The control system 4 responds to the second signal and determines whether to activate the radiator 5. By setting the above device, on the one hand, the temperature of the water-gas mixture after heat exchange can be accurately measured, and on the other hand, the radiator 5 can be avoided from being activated for a long time, which helps to reduce the total energy consumption of the system.

[0047] In some embodiments, the control system 4 is specifically configured to activate the heat dissipation function of the radiator 5 in response to the second signal when the temperature value transmitted by the second signal is greater than 55°C; Furthermore, when the temperature value transmitted by the second signal is less than or equal to 55° C., the control system 4 prohibits the heat dissipation function of the radiator 5 in response to the second signal.

[0048] In specific implementation, if the temperature of the water-gas mixture after heat exchange is too high, it is easy to damage the proton exchange membrane and other components of the electrolytic cell 1 after entering the electrolytic cell 1. Therefore, by setting the second temperature sensor 52 and the radiator 5, the temperature of the water-gas mixture after heat exchange can be detected in time. If it is greater than 55°C, the heat can be dissipated in time through the radiator 5; if the temperature of the water-gas mixture after heat exchange is ≤55°C, there is no need to activate the heat dissipation function of the radiator 5, and the water-gas mixture after heat exchange can be transported to the pure water circulation system 51 through the radiator 5 to avoid unnecessary energy consumption.

[0049] In some embodiments, see Figure 1 , the heat exchange system 2 further includes a third temperature sensor 25; The third temperature sensor 25 is disposed on a connecting pipeline between the third end 23 of the heat exchange system 2 and the liquid inlet of the cathode 12 .

[0050] During specific implementation, after the hydrogen-poor organic carrier undergoes heat exchange in the heat exchange system 2, it flows into the cathode 12 of the electrolytic cell 1 along the third end 23 of the heat exchange system 2 and the liquid inlet of the cathode 12. The third temperature sensor 25 can detect the temperature of the hydrogen-poor organic carrier after the heat exchange in real time to ensure that the temperature of the hydrogen-poor organic carrier entering the cathode 12 is appropriate, thereby avoiding damage to the interior of the electrolytic cell 1.

[0051] In a specific implementation, a heat-insulating material is provided on the pipeline connecting the third end 23 of the heat exchange system 2 and the liquid inlet of the cathode 12 to keep the temperature of the hydrogen-poor organic carrier constant after the heat exchange.

[0052] In a specific implementation, the third temperature sensor 25 transmits the temperature signal of the hydrogen-poor organic carrier after heat exchange, that is, the third signal, to the control system 4 , and the control system 4 is configured to receive and store the third signal.

[0053] In some embodiments, see Figure 1 The pure water circulation system 51 includes: a pure water storage tank 511, an electric heating device, a first diaphragm metering pump 512, a first one-way valve 513, a temperature and pressure integrated sensor 514, a deionizer 515 and a conductivity meter 516.

[0054] The electric heating device is arranged outside the pure water storage tank 511, and is used to heat the pure water in the pure water storage tank 511 to 45°C~55°C to meet the temperature required for the electrolysis reaction; the electric heating device is connected to the control system 4, and the control system 4 is configured to start or shut down the electric heating device; The water outlet at the bottom of the pure water storage tank 511 is connected to the water inlet of the anode 11, and the first diaphragm metering pump 512 is connected to the pipeline between the pure water storage tank 511 and the anode 11, and is connected to the pipeline near one end of the pure water storage tank 511, and is used to transport the pure water in the pure water storage tank 511 to the anode 11 of the electrolytic cell 1; The first one-way valve 513 is connected to the pipeline of the first diaphragm metering pump 512 away from the end of the pure water storage tank 511 to limit the pure water to flow only along the bottom of the pure water storage tank 511 to the anode 11 of the electrolytic cell 1 to avoid the backflow of pure water; The integrated temperature and pressure sensor 514 is connected to the pipeline near the water inlet of the anode 11 to detect the temperature of the pure water entering the electrolytic cell 1 to ensure that the temperature of the pure water is suitable for electrolysis.

[0055] In a specific implementation, the temperature and pressure integrated sensor 514 is configured to transmit temperature and pressure signals to the control system 4; The control system 4 is connected to the first diaphragm metering pump 512, and is configured to adjust the rotation speed of the first diaphragm metering pump 512 in response to the temperature and pressure signal to change the flow rate of pure water entering the anode 11 of the electrolyzer 1. Since the electrolyzer 1 generates a large amount of heat when working at the rated current. Therefore, by setting the temperature and pressure integrated sensor 514, the control system 4 calculates the temperature difference between the received first signal and the temperature and pressure signal, and then adjusts the pure water flow rate to keep the temperature indication difference between the temperature and pressure signal and the first signal within 10 ° C, so that the temperature in the electrolyzer 1 is between 45 ° C and 55 ° C, which helps to ensure the safety of the reaction process and allows the hydrogenation reaction in the electrolyzer 1 to proceed continuously.

[0056] It should be noted that the temperature and pressure signal is an electrical signal that instructs the control system 4 to adjust the rotation speed of the first diaphragm metering pump 512 .

[0057] In specific implementation, the deionizer 515 is disposed on the connecting pipeline between the radiator 5 and the water inlet of the pure water storage tank 511, and is connected to the pipeline near one end of the water inlet of the pure water storage tank 511; The deionizer 515 can filter the ions in the water-gas mixture transported in the pipeline, reduce the conductivity of the water-gas mixture entering the pure water storage tank 511 , and avoid contamination of the water quality in the pure water storage tank 511 .

[0058] In specific implementation, the conductivity meter 516 is vertically inserted into the pure water storage tank 511 along the upper end of the pure water storage tank 511, and the lower end of the conductivity meter 516 extends below the pure water interface to detect the conductivity of the pure water in the pure water storage tank 511 and transmit the conductivity signal to the control system 4; The control system 4 is configured to respond to the conductivity signal and determine that when the conductivity value exceeds the set value, the control system 4 shuts down various parts of the system to stop the system from running. After the water in the pure water storage tank 511 is replaced, the control system 4 restarts various parts of the system to start the system running, so as to ensure the safety of the inside of the electrolytic cell 1 during the system operation.

[0059] In some implementations, the outside of the pure water storage tank 511 is wrapped with insulation material to ensure that the temperature of the pure water entering the electrolytic cell 1 is maintained between 45°C and 55°C.

[0060] In a specific implementation, the thermal insulation material includes but is not limited to any one of polyurethane, glass wool, extruded polystyrene, rock wool, aluminum silicate and perlite.

[0061] In some embodiments, see Figure 1 The liquid organic matter circulation system 3 includes: a liquid organic matter storage tank 31 , a first solenoid valve 32 , a second diaphragm metering pump 33 , a fourth temperature sensor 34 and a second one-way valve 35 .

[0062] The liquid outlet of the liquid organic matter storage tank 31 is connected to the second end 22 of the heat exchange system 2, and the first solenoid valve 32 is arranged on a pipeline close to the liquid outlet of the liquid organic matter storage tank 31; The first solenoid valve 32 is connected to the control system 4, and the control system 4 is configured to control the first solenoid valve 32 to start or close, and the first solenoid valve 32 is in a normally closed state; The second diaphragm metering pump 33 is disposed on a pipeline connecting the liquid outlet of the liquid organic matter storage tank 31 and the second end 22 of the heat exchange system 2; the second diaphragm metering pump 33 is connected to the control system 4, and the control system 4 is configured to control the second diaphragm metering pump 33 to start or shut down; The second one-way valve 35 is disposed on the connecting pipeline between the second diaphragm metering pump 33 and the second end 22 of the heat exchange system 2 to limit the hydrogen-poor organic carrier to flow only from the liquid organic storage tank 31 to the heat exchange system 2 to avoid nitrogen backflow during purging; The fourth temperature sensor 34 is arranged on the pipeline connecting the second one-way valve 35 and the second end 22 of the heat exchange system 2, and is used to detect the temperature of the hydrogen-poor organic carrier entering the heat exchange system 2 and transmit a fourth signal to the control system 4. The control system 4 is configured to receive and store the fourth signal.

[0063] During specific implementation, after the control system 4 starts the first solenoid valve 32 and the second diaphragm metering pump 33, the pipeline between the liquid outlet end of the liquid organic storage tank 31 and the second end 22 of the heat exchange system 2 is connected, and the second diaphragm metering pump 33 is used to transport the hydrogen-poor organic carrier in the liquid organic storage tank 31 along the second end 22 of the heat exchange system 2 to the inside of the heat exchange system 2 to perform heat exchange with the water-gas mixture inside the heat exchange system 2.

[0064] It should be noted that the control system 4 is configured to adjust the rotation speed of the second diaphragm metering pump 33 to adjust the quality of the hydrogen-poor organic carrier entering the heat exchange system 2 and the cathode 12 of the electrolyzer 1 .

[0065] In a specific implementation, the hydrogen-poor organic carrier stored in the liquid organic matter storage tank 31 includes one of toluene, N-ethylindole, N-methylindole, pyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2-methylpyrazine, pyridazine, cyclopentylpyrazine, pyridine and 3-methylpyridine, or at least two of them mixed in any proportion.

[0066] In some embodiments, see Figure 1 , the liquid organic matter circulation system 3 also includes: a first liquid level meter 36, a second solenoid valve 37 and a third diaphragm metering pump 38; The first liquid level meter 36 is disposed on the liquid organic matter storage tank 31, and is used to detect the water content in the liquid organic matter storage tank 31, and transmit a first water level signal to the control system 4; The second solenoid valve 37 is disposed on a pipeline connected to the water outlet at the bottom of the liquid organic matter storage tank 31. The second solenoid valve 37 is in a normally closed state. The third diaphragm metering pump 38 is connected to the pipeline at one end of the second solenoid valve 37 away from the liquid organic matter storage tank 31. The control system 4 is connected to the second solenoid valve 37 and the third diaphragm metering pump 38 respectively, and is configured to open the second solenoid valve 37 and the third diaphragm metering pump 38 in response to the first water level signal.

[0067] In specific implementation, the hydrogenation reaction product specifically includes gaseous hydrogen-poor organic carrier, water vapor and gaseous hydrogen-rich organic carrier. Therefore, when the hydrogenation reaction product is discharged into the liquid organic storage tank 31 through the cathode 12 outlet, the water vapor will condense and liquefy, and the formed water will be stored in the liquid organic storage tank 31. If the amount of water is too much, it is easy to flow back to the electrolyzer 1 with the hydrogen-poor organic carrier, affecting the hydrogenation reaction. Therefore, after the control system 4 opens the second solenoid valve 37 and the third diaphragm metering pump 38, the pipeline connected to the water outlet at the bottom of the liquid organic storage tank 31 is connected, and the third diaphragm metering pump 38 is used to discharge the excess water in the liquid organic storage tank 31 in time to avoid the excess water from flowing back to the electrolyzer 1, thereby reducing the impact on the hydrogenation reaction.

[0068] In some embodiments, see Figure 1 The system also includes: a fifth temperature sensor 18, a primary cooling tank 311, a secondary cooling tank 312 and a drying pipe 313.

[0069] The upper end of the primary cooling tank 311 is connected to the outlet of the cathode 12, and the lower end is connected to the upper end of the liquid organic matter storage tank 31. During implementation, the hydrogenation reaction product flows into the primary cooling tank 311 along the outlet of the cathode 12 for cooling treatment, wherein the gaseous hydrogen-poor organic carrier and the gaseous hydrogen-rich organic carrier are cooled and liquefied and then flow downward along the primary cooling tank 311 into the liquid organic matter storage tank 31 for storage.

[0070] In specific implementation, a metal coil is provided inside the primary cooling tank 311, which can significantly reduce the temperature of the hydrogenation reaction product and condense the gaseous hydrogen-poor organic carrier and the gaseous hydrogen-rich organic carrier into liquid.

[0071] During specific implementation, the primary cooling tank 311 is externally connected to cooling water, wherein the cooling water inlet is arranged at the bottom of the primary cooling tank 311 and the cooling water outlet is arranged at the top of the primary cooling tank 311 .

[0072] In specific implementation, the fifth temperature sensor 18 is arranged on the connecting pipeline between the primary cooling tank 311 and the cathode 12 outlet, and is close to the cathode 12 of the electrolyzer 1, so as to detect the temperature of the hydrogenation reaction product discharged from the cathode 12 outlet, and transmit the fifth signal to the control system 4, and the control system 4 is configured to receive and store the fifth signal.

[0073] In specific implementation, the upper end of the secondary cooling tank 312 is connected to the side of the upper end of the liquid organic storage tank 31 away from the primary cooling tank 311, and the lower end is connected to the bottom of the liquid organic storage tank 31. Since the hydrogenation reaction product flowing into the liquid organic storage tank 31 also includes hydrogen, when the hydrogen flows upward, it will drive a small amount of volatile hydrogen-poor organic carrier to escape. By setting up the secondary cooling tank 312, hydrogen and a small amount of hydrogen-poor organic carrier enter the secondary cooling tank 312 upward, and after cooling, the hydrogen-poor organic carrier is liquefied, and then enters the liquid organic storage tank 31 along the lower end of the secondary cooling tank 312 for storage, which helps to recover the hydrogen-poor organic carrier and reduce waste.

[0074] In specific implementation, a metal coil and a T-type filter are provided inside the secondary cooling tank 312 . The T-type filter is used for secondary filtration of the hydrogen-poor organic carrier carried in the hydrogen, so that the hydrogen-poor organic carrier is discharged from the bottom of the secondary cooling tank 312 and refluxed into the liquid organic storage tank 31 .

[0075] During specific implementation, the secondary cooling tank 312 is externally connected to cooling water, wherein the cooling water inlet is arranged at the bottom of the secondary cooling tank 312 and the outlet is arranged at the top of the secondary cooling tank 312 .

[0076] In specific implementation, the upper end of the drying pipe 313 is connected to the upper end of the secondary cooling tank 312. The hydrogen in the secondary cooling tank 312 is discharged upward and then flows into the drying pipe 313, where the residual moisture on the hydrogen is dried and removed, and the hydrogen is discharged after drying.

[0077] In some embodiments, see Figure 1 A gas mass flow meter 314 is connected to one side of the drying tube 313 to detect the flow rate of hydrogen discharged from the drying tube 313 and transmit a gas flow signal to the control system 4; The control system 4 is configured to respond to the gas flow signal. When the hydrogen flow value reaches more than 75% of the theoretical electrolytic hydrogen production value, the control system 4 shuts down the system and stops the system from running, indicating that the hydrogen production-hydrogenation reaction is finished.

[0078] It should be noted that the air flow signal is an electrical signal instructing the control system 4 to shut down the system.

[0079] In some embodiments, see Figure 1 , the system further comprises a purge system 6; The first gas outlet end of the purge system 6 is connected to the water inlet of the anode 11, and is used to transport inert gas to blow out the water-gas mixture in the anode 11; The second gas outlet is connected to the connecting pipeline of the liquid organic matter circulation system 3 and the second end 22 for conveying the inert gas to blow out the hydrogen-poor organic carrier in the heat exchange system 2 and the cathode 12 along the outlet of the cathode 12 .

[0080] In specific implementation, the inert gas is preferably nitrogen; the air inlet of the purge system 6 is externally connected to compressed nitrogen.

[0081] In a specific implementation, after the hydrogenation reaction is completed, the purge system 6 is started, and part of the inert gas is sent into the anode 11 along the first gas outlet end of the purge system 6 to blow out the remaining water-gas mixture in the anode 11. The water-gas mixture enters the heat exchange system 2 along the pipeline connected to the water outlet of the anode 11 and the first end 21 of the heat exchange system 2, and then flows into the pure water circulation system 51 along the fourth end 24 of the heat exchange system 2 and the radiator 5 for storage; Another part of the inert gas enters the heat exchange system 2 along the second gas outlet end of the purge system 6, and the hydrogen-poor organic carrier in the heat exchange system 2 is first blown along the pipeline to the cathode 12 of the electrolyzer 1, and then the hydrogen-poor organic carrier in the cathode 12 is blown along the outlet of the cathode 12 to the liquid organic circulation system 3 for storage, so as to avoid the hydrogen-poor organic carrier from corroding the heat exchange system 2, the electrolyzer 1 and the pipeline when the system is not running, which helps to protect the internal stability of the system and extend the service life of the system.

[0082] In some embodiments, see Figure 1 The purge system 6 includes: a first gas mass flow controller 61 , a third one-way valve 62 , a second gas mass flow controller 63 and a fourth one-way valve 64 .

[0083] The first gas mass flow controller 61 is disposed on a pipeline connecting the first gas outlet of the purge system 6 and the water inlet of the anode 11 , and is close to the water inlet of the anode 11 , and is used to control the flow of the inert gas for purging the anode 11 .

[0084] The third one-way valve 62 is disposed on the pipeline between the first gas mass flow controller 61 and the water inlet of the anode 11 to limit the inert gas to be blown only toward the anode 11 and avoid the backflow of pure water.

[0085] The second gas mass flow controller 63 is arranged on the connecting pipeline between the second gas outlet of the purge system 6 and the liquid organic matter storage tank 31 and the second end 22 of the heat exchange system 2, and is used to control the inert gas flow of the purge heat exchange system 2, the cathode 12 of the electrolytic cell 1 and the pipeline.

[0086] The fourth one-way valve 64 is disposed on the pipeline of the second gas mass flow controller 63 away from the second gas outlet of the purge system 6 to limit the backflow of the hydrogen-poor organic carrier and pure water.

[0087] In some embodiments, see Figure 1 The system also includes: a water replenishment tank 65, a third solenoid valve 66 and a fifth one-way valve 67.

[0088] The water outlet at the bottom of the water supply tank 65 is connected to the liquid outlet of the liquid organic matter storage tank 31 through a pipeline, and the third solenoid valve 66 is arranged on the pipeline between the water supply tank 65 and the liquid organic matter storage tank 31 and is in a normally closed state; The control system 4 is connected to the third solenoid valve 66 and is configured to start the third solenoid valve 66, conduct the pipeline between the water replenishment tank 65 and the liquid organic storage tank 31, and send the pure water in the water replenishment tank 65 along the pipeline into the pipeline connected to the liquid outlet of the liquid organic storage tank 31. At this time, the inert gas blown by the purge system 6 drives the pure water to flow into the heat exchange system 2, and washes the hydrogen-poor organic carrier on the inner wall of the heat exchange system 2. The inert gas then blows the mixture of water and hydrogen-poor organic carrier along the pipeline to the cathode 12 of the electrolyzer 1, and continues to wash the hydrogen-poor organic carrier on the inner wall of the electrolyzer 1, and finally discharges the mixture of water and hydrogen-poor organic carrier into the primary cooling tank 311 along the outlet of the cathode 12, and flows into the liquid organic storage tank 31 along the bottom of the primary cooling tank 311 after cooling, which helps to more thoroughly clean the heat exchange system 2 and the cathode 12 of the electrolyzer 1, avoid residual hydrogen-poor organic carriers, and also helps to recover the hydrogen-poor organic carriers and reduce waste.

[0089] The fifth one-way valve 67 is arranged on the pipeline between the third solenoid valve 66 and the liquid organic matter storage tank 31, and is used to limit the pure water in the water replenishment tank 65 to only flow out of the water replenishment tank 65, thereby preventing the mixture of water and liquid hydrogen-poor organic carrier from flowing back and contaminating the pure water in the water replenishment tank 65.

[0090] In some embodiments, see Figure 1 A water supply and drainage outlet 517 is provided at the bottom of the pure water storage tank 511, and the bottom of the water supply tank 65 is connected to the water supply and drainage outlet 517 of the pure water storage tank 511. A water supply pump 651 is provided on the pipeline connecting the water supply tank 65 and the pure water storage tank 511. The water supply pump 651 is used to transport the pure water in the water supply tank 65 to the pure water storage tank 511 for easy water replenishment.

[0091] In some embodiments, see Figure 1 , a second liquid level meter 518 is also provided on the pure water storage tank 511, which is used to detect the water level in the pure water storage tank 511 and transmit a second water level signal to the control system 4; A three-way solenoid valve 652 is provided on the connecting pipeline between the bottom of the water replenishment tank 65 and the replenishment and drainage outlet 517 of the pure water storage tank 511. The first water delivery end 653 of the three-way solenoid valve 652 is connected to the bottom of the water replenishment tank 65, the second end 22 is connected to the replenishment and drainage outlet 517 of the pure water storage tank 511, and the third end 23 is in a normally closed state; The control system 4 is electrically connected to the three-way solenoid valve 652 and is configured to determine whether to start the three-way solenoid valve 652 in response to the second water level signal; Specifically, when the second water level signal received by the control system 4 is lower than a preset value, the water supply pump 651 is started, the first water supply end 653 and the second water supply end 654 of the three-way solenoid valve 652 are opened, the pipeline between the water supply tank 65 and the pure water storage tank 511 is connected, and the water supply pump 651 is used to supply water to the pure water storage tank 511; When the second water level signal received by the control system 4 is greater than or equal to the preset value, the first water supply end 653, the second water supply end 654 and the water supply pump 651 of the three-way solenoid valve 652 are closed, the pipeline between the water supply tank 65 and the pure water storage tank 511 is blocked, and water supply to the pure water storage tank 511 is stopped.

[0092] In specific implementation, the conductivity meter 516 is used to detect the conductivity of water in the pure water storage tank 511 and transmit the conductivity signal to the control system 4; The control system 4 is configured to respond to the conductivity signal. When it is determined that the conductivity signal is greater than a preset value, the second water supply end 654 and the third water supply end 655 of the three-way solenoid valve 652 are started to discharge the waste water in the pure water storage tank 511 along the second water supply end 654 and the third water supply end 655 of the three-way solenoid valve 652 in sequence.

[0093] In some embodiments, see Figure 3 The control system 4 includes: a signal control part 41, a signal monitoring part 42, a data recording part 43 and a safety protection part 44.

[0094] Wherein, the signal control part 41 is configured to control the start or shut down of the first diaphragm metering pump 512, the back pressure valve 111, the first solenoid valve 32, the second diaphragm metering pump 33, the second solenoid valve 37, the third diaphragm metering pump 38, the third solenoid valve 66, the first gas mass flow controller 61, the second gas mass flow controller 63, the water supply pump 651, the three-way solenoid valve 652 and the DC power supply 17, and activate or disable the heat dissipation function of the radiator 55; The signal monitoring part 42 is configured to monitor the integrated temperature and pressure sensor 514, the first temperature sensor 16, the second temperature sensor 52, the third temperature sensor 25, the fourth temperature sensor 34, the fifth temperature sensor 18, the conductivity meter 516, the first liquid level meter 36, the gas mass flow meter 314, and the second liquid level meter 518; The data recording part 43 is configured to record the temperature and pressure signal value, the first signal value, the second signal value, the third signal value, the fourth signal value, the fifth signal value, the conductivity signal value, the first water level signal value, the air flow signal value, and the second water level signal value; The safety protection part 44 is configured to monitor the first temperature sensor 16, the conductivity meter 516, the fifth temperature sensor 18 and the DC power supply 17; In specific implementation, the data abnormality parking process is set in the safety protection part 44 of the control system 4, and the specific settings are: ① Since the first signal value is the same as the internal temperature of the anode 11 of the electrolytic cell 1, when the received first signal value exceeds 90°C, the control system 4 responds to the first signal and controls the entire system to stop, and restarts the system after the electrolytic cell 1 cools down; ② When the received conductivity signal value exceeds the set value, the control system 4 responds to the conductivity signal, controls the entire system to stop, replaces the water in the pure water storage tank 511, and then restarts the system; ③ Since the fifth signal value is the same as the internal temperature of the cathode 12 of the electrolytic cell 1, when the value of the received fifth signal exceeds 90°C, the control system 4 responds to the fifth signal and controls the entire system to stop, and restarts the system after the electrolytic cell 1 cools down; ④ When the received current and voltage signal values ​​are lower than the minimum protection value and greater than the maximum protection value, the control system 4 responds to the current and voltage signals to control the entire system to stop, and restart the system after adjustment.

[0095] In summary, by setting up the safety data abnormal shutdown processing in the safety protection part 44 of the control system 4, it is beneficial to ensure the safety of the system operation process and make the hydrogen production-hydrogenation process safer.

[0096] Second, see Figure 4 The present application provides a LOHC coupled PEM electrolyzer hydrogen production-storage integrated control method, the control method is applicable to the LOHC coupled PEM electrolyzer hydrogen production-storage integrated system described in the first aspect, the control method comprises: S1, heating the pure water in the pure water circulation system 51 to 45°C~55°C, and transporting the heated pure water to the electrolytic cell 1 along the water inlet of the anode 11; S2, the first temperature sensor 16 detects that the temperature of the water-gas mixture discharged from the water outlet of the anode 11 is 45°C~55°C, and transmits a first signal to the control system 4. In response to the first signal, the control system 4 starts the power supply device to supply power to the electrolyzer 1, and starts the back pressure valve 111 to increase the pressure of the anode 11 to 0.3 MPa~0.5 MPa, so that the pressure of the anode 11 is higher than the pressure of the cathode 12, and the hydrogen production reaction is carried out; S3, transporting the hydrogen-poor organic carrier in the liquid organic matter circulation system 3 to the heat exchange system 2, and performing heat exchange treatment with the water-gas mixture discharged from the water outlet of the anode 11, and the hydrogen-poor organic carrier after heat exchange is sent to the cathode 12 along the liquid inlet of the cathode 12 to perform hydrogenation reaction to obtain the hydrogen-rich organic carrier and hydrogen; S4, the hydrogen-rich organic carrier and hydrogen enter the cooling device along the discharge port of the cathode 12, and are discharged after being cooled.

[0097] During specific implementation, the method provided in the present application optimizes the working environment of the proton exchange membrane by precisely controlling the water temperature and pressure of the anode 11, reduces the penetration of hydrogen and hydrogen-poor organic carriers, and avoids the problem of increased resistance and reduced energy efficiency caused by simply increasing the thickness of the proton exchange membrane in the traditional method, so that the hydrogenation reaction proceeds smoothly. The waste heat of the water-gas mixture discharged from the outlet of the anode 11 is also fully utilized, and the hydrogen-poor organic carrier is preheated by the heat exchange system 2. After preheating, the hydrogen-poor organic carrier is more likely to contact with the active sites on the surface of the proton exchange membrane, thereby improving the efficiency and product quality of the hydrogenation reaction, and also saving the overall energy consumption of the system. The power supply of the electrolyzer 1 and the opening of the back pressure valve 111 are also precisely controlled by temperature, so as to maximize the utilization of energy and reduce the overall energy consumption and operating costs of the system.

[0098] In summary, the control method provided in this application not only improves the efficiency of hydrogen production and storage, but also contributes to environmental protection and sustainable development by optimizing energy utilization and reducing energy consumption. By reducing unnecessary energy loss and emissions, it helps to reduce the negative impact on the environment, which is in line with the current green and low-carbon development trend.

[0099] The following is a detailed description of a LOHC coupled PEM electrolyzer hydrogen production and storage integrated system and control method provided by the present application through specific embodiments.

[0100] Example 1 application Figure 1 The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system shown.

[0101] 1. The control system 4 starts the electric heating device to heat the pure water in the pure water storage tank 511, and sets the heating temperature to 50°C. Then the control system 4 starts the first diaphragm metering pump 512, and the heated pure water flows into the anode 11 through the pipeline, and circulates inside the anode 11 of the electrolytic cell 1; 2. The first temperature sensor 16 detects that the temperature of the water-gas mixture discharged from the water outlet of the anode 11 is between 50±5°C, and transmits a first signal to the control system 4. In response to the first signal, the control system 4 starts the DC power supply 17 to supply power to the electrolyzer 1. The current density loading mode is from small to large, and the upper limit is 400 mA / cm2. The back pressure valve 111 is started to increase the pressure of the anode 11 to 0.5 MPa, so that the pressure of the anode 11 is higher than the pressure of the cathode 12, and the hydrogen production reaction is carried out. The water-gas mixture discharged from the water outlet of the anode 11 passes through the pipeline and enters the plate heat exchanger along the first end 21 of the plate heat exchanger; 3. The control system 4 starts the second metering diaphragm pump, so that the hydrogen-poor organic carrier first flows into the plate heat exchanger through the pipeline to exchange heat with the water-gas mixture, and then flows into the cathode 12 of the electrolyzer 1 through the pipeline, and circulates inside the cathode 12 of the electrolyzer 1 to perform a hydrogenation reaction. The obtained hydrogenation reaction product enters the primary cooling tank 311 along the cathode 12 outlet for cooling, and the liquefied hydrogenation reaction product flows downward into the liquid organic storage tank 31, wherein hydrogen and a small amount of hydrogen-poor organic carrier upwardly enter the secondary cooling tank 312, and after condensation, they are filtered through a T-type filter to separate the hydrogen-poor organic carrier and hydrogen, and the hydrogen enters the drying pipe 313 upwardly for drying and discharge, and the hydrogen-poor organic carrier flows back to the liquid organic storage tank 31 for storage; 4. When the electrolytic cell 1 is working at rated current, a large amount of heat is generated. The control system 4 adjusts the rotation speed of the first diaphragm metering pump 512 to change the flow rate of circulating water entering the anode 11 of the electrolytic cell 1, so that the temperature reading difference between the temperature and pressure integrated sensor 514 and the first temperature sensor 16 is within 10°C; 5. After heat exchange, the water-gas mixture discharged from the water outlet of the anode 11 of the electrolytic cell 1 transfers part of the heat to the hydrogen-poor organic carrier. The second temperature sensor 52 detects the temperature of the water-gas mixture after heat exchange and transmits a second signal to the control system 4. When the second signal value T>55°C, the control system 4 responds to the second signal and activates the radiator 5 to cool the water-gas mixture after heat exchange. The cooled water-gas mixture flows into the pure water storage tank 511. 6. Due to the characteristics of the membrane electrode 14 in the electrolytic cell 1, during the hydrogenation reaction, some water penetrates from the anode 11 to the cathode 12, is discharged through the outlet of the cathode 12, and finally gathers inside the liquid organic storage tank 31. The water level in the liquid organic storage tank 31 is detected by the first liquid level meter 36, and a first water level signal is transmitted to the control system 4. When the value of the first water level signal exceeds the safety value, the control system 4 responds to the first water level signal, starts the second solenoid valve 37 and the third diaphragm metering pump 38, and discharges the excess water in the liquid organic storage tank 31; when the value of the first water level signal is lower than the safety value, the control system 4 responds to the first water level signal, closes the second solenoid valve 37 and the third diaphragm metering pump 38, and prevents the hydrogen-poor organic carrier from flowing out; 7. The gas mass flow meter 314 detects the real-time flow of hydrogen and transmits a gas flow signal to the control system 4. When the gas flow signal value reaches more than 75% of the theoretical electrolytic hydrogen production value, the control system 4 responds to the gas flow signal, first controls to turn off the DC power supply 17, gradually reduces the current density until it is zero, then reduces the pressure value of the back pressure valve 111 until it is zero, and finally turns off the first diaphragm metering pump 512, the second diaphragm pump metering, the radiator 5 and the electric heating device to stop the hydrogen production-hydrogenation reaction; 8. Finally, the control system 4 starts the third solenoid valve 66, connects the pipeline between the water replenishment tank 65 and the liquid organic matter storage tank 31, and sends the pure water in the water replenishment tank 65 along the pipeline into the pipeline connected to the liquid outlet of the liquid organic matter storage tank 31, and then starts the first gas mass flow controller 61 and the second gas mass flow controller 63. The first gas mass flow controller 61 blows nitrogen along the pipeline to the anode 11 of the electrolytic cell 1, blows out the water-gas mixture in the anode 11, and the water-gas mixture flows into the plate heat exchanger along the water outlet of the anode 11. Finally, Finally, it flows into the pure water storage tank 511 through the radiator 5 and the pipeline; the second gas mass flow controller 63 blows nitrogen into the pipeline connected to the liquid outlet of the liquid organic storage tank 31, and blows pure water to the plate heat exchanger and the cathode 12 of the electrolyzer 1 to wash the hydrogen-poor organic carrier on the inner wall thereof, and the final mixture of water and hydrogen-poor organic carrier is discharged along the outlet of the cathode 12, condensed by the primary cooling tank 311, and then refluxed to the liquid organic storage tank 31 for storage. After the purging is complete, the control system shuts down the entire system to stop the system from running.

[0102] In summary, the present application provides a LOHC coupled PEM electrolyzer hydrogen production-storage integrated system and control method, which can realize hydrogen production-hydrogenation in one step. The whole system has high integration, is easy to operate, and can greatly reduce the total energy consumption of the system. And compared with thermochemical hydrogenation, the temperature and pressure of hydrogenation are greatly reduced, and the safety is higher. Then, by setting the back pressure valve 111, the control system 4 controls it to start during the hydrogenation reaction, so that the pressure of the anode 11 of the electrolyzer 1 increases, so as to increase the resistance of the hydrogen-poor organic carrier of the cathode 12 and the hydrogen to penetrate into the anode 11, thereby reducing the permeation amount of hydrogen and hydrogen-poor organic carrier at the proton exchange membrane, and effectively improving the hydrogen storage efficiency per unit time.

[0103] Although the preferred embodiments of the present application have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present application.

[0104] Finally, it should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or terminal device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or terminal device. In the absence of further restrictions, the elements defined by the sentence "including one..." do not exclude the existence of other identical elements in the process, method, article or terminal device including the elements.

[0105] The above is a detailed introduction to a LOHC coupled PEM electrolyzer hydrogen production-storage integrated system and control method provided by the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for general technicians in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A LOHC coupled PEM electrolyzer hydrogen production and storage integrated system, characterized in that: The system comprises: an electrolytic cell (1), a heat exchange system (2), a liquid organic matter circulation system (3) and a control system (4); The electrolytic cell (1) comprises an anode (11) and a cathode (12); a back pressure valve (111) is provided on a pipeline connected to a water outlet of the anode (11); the back pressure valve (111) is configured to increase the pressure of the anode (11) so that the pressure of the anode (11) is higher than the pressure of the cathode (12); The first end (21) of the heat exchange system (2) is connected to the pipeline connected to the back pressure valve (111), the second end (22) is connected to the liquid organic matter circulation system (3), and the third end (23) is connected to the liquid inlet of the cathode (12); The water-gas mixture discharged from the water outlet of the anode (11) enters the heat exchange system (2) via the first end (21); The hydrogen-poor organic carrier outputted from the liquid organic matter circulation system (3) enters the heat exchange system (2) via the second end (22) and performs heat exchange with the water-gas mixture. After the heat exchange, the hydrogen-poor organic carrier enters the cathode (12) via the third end (23) to perform a hydrogenation reaction in the cathode (12); The control system (4) is connected to the back pressure valve (111) and is configured to control the back pressure valve (111) to open or close.

2. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 1, characterized in that: The back pressure valve (111) is configured to increase the pressure of the anode (11) to 0.3 MPa-1 MPa.

3. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 1, characterized in that: The system also includes a first temperature sensor (16); The first temperature sensor (16) is arranged on a connecting pipeline between the water outlet of the anode (11) and the back pressure valve (111); The first temperature sensor (16) is configured to transmit a first signal to the control system (4) in response to the temperature of the water-gas mixture; the control system (4) activates the back pressure valve (111) in response to the first signal to increase the pressure of the anode (11).

4. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 3, characterized in that: The first temperature sensor (16) is configured to transmit a first signal to the control system (4) in response to the temperature of the water-gas mixture being between 45°C and 55°C.

5. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 3, characterized in that: The system also includes a heat sink (5) and a second temperature sensor (52); The radiator (5) has a liquid inlet end connected to the fourth end (24) of the heat exchange system (2), and a liquid outlet end connected to the water inlet of the pure water circulation system (51), and is configured to cool the water-gas mixture after heat exchange output from the fourth end (24) and then input it into the pure water circulation system (51) along the liquid outlet end of the radiator (5); The second temperature sensor (52) is disposed on a pipeline connecting the liquid inlet end of the radiator (5) and the fourth end (24), and is configured to transmit a second signal to the control system (4) in response to the temperature of the water-gas mixture after the heat exchange output by the fourth end (24); The control system (4) is connected to the radiator (5) and is configured to judge whether to activate the radiator (5) in response to the second signal, and the radiator (5) is used to cool the water-gas mixture after the heat exchange when it is activated; The water outlet of the pure water circulation system (51) is connected to the water inlet of the anode (11) so as to transport pure water to the anode (11).

6. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 5, characterized in that: The control system (4) is specifically configured to activate the heat dissipation function of the radiator (5) in response to the second signal when the temperature value transmitted by the second signal is greater than 55°C; Furthermore, when the temperature value transmitted by the second signal is less than or equal to 55° C., the control system (4) responds to the second signal and disables the heat dissipation function of the radiator (5).

7. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 1, characterized in that: The electrolytic cell (1) comprises a cathode flow channel and an anode flow channel; Wherein, the depth of the cathode flow channel is smaller than the depth of the anode flow channel.

8. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 7, characterized in that: The depth of the cathode flow channel is 0.2 mm to 0.4 mm, and the depth of the anode flow channel is 0.6 mm to 1.0 mm.

9. The LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to claim 1, characterized in that: The system also includes a purge system (6); The first gas outlet end of the purge system (6) is connected to the water inlet of the anode (11) and is used to transport inert gas to blow out the water-gas mixture in the anode (11); The second gas outlet end is connected to the connecting pipeline of the liquid organic matter circulation system (3) and the second end (22) and is used to transport the inert gas to blow the hydrogen-poor organic carrier in the heat exchange system (2) and the cathode (12) out along the cathode (12) outlet.

10. A LOHC coupled PEM electrolyzer hydrogen production and storage integrated control method, characterized in that: The control method is applicable to the LOHC coupled PEM electrolyzer hydrogen production and storage integrated system according to any one of claims 1 to 9, and the control method comprises: S1, heating the pure water in the pure water circulation system to 45°C to 55°C, and transporting the heated pure water to the electrolytic cell (1) along the water inlet of the anode (11); S2, the first temperature sensor (16) detects that the temperature of the water-gas mixture discharged from the water outlet of the anode (11) is 45°C to 55°C, and transmits a first signal to the control system (4). In response to the first signal, the control system (4) starts the power supply device to supply power to the electrolyzer (1), and starts the back pressure valve (111) to increase the pressure of the anode (11) to 0.3 MPa to 1 MPa, so that the pressure of the anode (11) is higher than the pressure of the cathode (12), so as to perform a hydrogen production reaction; S3, transporting the hydrogen-poor organic carrier in the liquid organic matter circulation system (3) to the heat exchange system (2), exchanging heat with the water-gas mixture discharged from the water outlet of the anode (11), and transporting the hydrogen-poor organic carrier after the heat exchange into the cathode (12) along the liquid inlet of the cathode (12) to perform a hydrogenation reaction to obtain a hydrogen-rich organic carrier; S4, the hydrogen-rich organic carrier and hydrogen enter the cooling device along the discharge port of the cathode (12), and are discharged after being cooled.

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