Thermocatalysis and electrolysis step-by-step hydrogen production system

Abstract

The invention discloses a thermocatalysis and electrolysis step-by-step hydrogen production system which comprises a flow battery and a thermocatalysis and electrolysis device, the thermocatalysis and electrolysis device comprises a thermocatalysis reactor, a first electrolytic bath, a first storage tank and a second storage tank, and the first storage tank is communicated with an inner cavity of the thermocatalysis reactor to form a circulation loop; the first electrolytic cell comprises a first positive electrode, a first negative electrode and a first ion exchange membrane, the first ion exchange membrane divides an inner cavity of the first electrolytic cell into a first chamber for arranging the first positive electrode and a second chamber for arranging the first negative electrode, and the first chamber is communicated with an inner cavity of the thermocatalytic reactor to form a circulation loop; the second chamber is communicated with the second storage tank to form a circulation loop, and the electrolyte in the second storage tank is reduced in the first electrolytic tank to generate hydrogen; the flow battery is used for being connected with a renewable energy system; and the thermocatalysis and electrolysis device is used for being connected with a renewable energy system and a flow battery. The system cost can be reduced, and the green electricity proportion can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogen production, and in particular relates to a thermal catalysis and electrolysis step-by-step hydrogen production system. Background Art

[0002] Hydrogen production from renewable energy power generation mainly includes alkaline hydrogen production, PEM hydrogen production, and green electricity hydrogen production coupled with energy storage systems. Due to the volatility and intermittency of renewable energy power generation, it is difficult to ensure the stable power consumption of green hydrogen synthesis load and the stability of the local area network. When renewable energy power generation is large, electricity may be abandoned, and when renewable energy power generation is short of electricity, it is necessary to connect electricity from the public grid, resulting in a lower proportion of green electricity for hydrogen production. In order to adapt to the technical difficulties of hydrogen production from renewable energy power generation, it is usually achieved by using renewable energy power generation power sources, configuring a higher proportion of energy storage, and connecting to the public grid to achieve stable hydrogen production, resulting in high overall system costs, high green hydrogen costs, and a low proportion of green electricity. Summary of the invention

[0003] The present invention aims to solve one of the technical problems in the related art at least to a certain extent.

[0004] To this end, an embodiment of the present invention proposes a thermal catalytic and electrolytic step-by-step hydrogen production system that can reduce system costs and increase the proportion of green electricity.

[0005] The thermal catalysis and electrolysis step-by-step hydrogen production system of the embodiment of the present invention comprises:

[0006] Flow batteries;

[0007] A thermal catalytic and electrolytic device, the thermal catalytic and electrolytic device comprising a thermal catalytic reactor, a first electrolyzer, a first storage tank for storing an organic hydrogen carrier, and a second storage tank for storing an electrolyte, the first storage tank being connected to the inner cavity of the thermal catalytic reactor to form a circulation loop, so that the organic hydrogen carrier is catalytically decomposed in the thermal catalytic reactor to generate hydrogen; the first electrolyzer comprising a first positive electrode, a first negative electrode, and a first ion exchange membrane, the first ion exchange membrane dividing the inner cavity of the first electrolyzer into a first chamber for arranging the first positive electrode and a second chamber for arranging the first negative electrode, the first chamber being connected to the inner cavity of the thermal catalytic reactor to form a circulation loop, the second chamber being connected to the second storage tank to form a circulation loop, and the electrolyte in the second storage tank being reduced in the first electrolyzer to generate hydrogen;

[0008] The liquid flow battery is used to be connected to a renewable energy system so that the liquid flow battery can be charged and stored with energy through the renewable energy system; the thermal catalytic and electrolytic device is used to be connected to a renewable energy system and the liquid flow battery so that the thermal catalytic and electrolytic device can be powered by the renewable energy system or the liquid flow battery.

[0009] The thermal catalytic and electrolytic step-by-step hydrogen production system of the embodiment of the present invention can directly power the thermal catalytic and electrolytic devices through the renewable energy system, which can reduce the system cost, and reasonably select the power supply according to the processing size of the renewable energy system to achieve stable hydrogen production, increase the proportion of green electricity hydrogen production, and reduce the cost of hydrogen production.

[0010] In some embodiments, the liquid flow battery includes a first battery stack, a third storage tank storing a positive electrolyte, and a fourth storage tank storing a negative electrolyte, the inner cavity of the first battery stack has a second positive electrode, a second negative electrode, and a second ion exchange membrane, the second ion exchange membrane divides the inner cavity of the first battery stack into a third chamber for arranging the second positive electrode and a fourth chamber for arranging the second negative electrode; the third storage tank is connected to the third chamber and forms a circulation loop so that the positive electrolyte circulates in the three tanks and the third chamber; the fourth storage tank is connected to the fourth chamber and forms a circulation loop so that the negative electrolyte circulates in the fourth storage tank and the fourth chamber.

[0011] In some embodiments, a second battery stack is further included, wherein the second battery stack has a third positive electrode, a third negative electrode and a third ion exchange membrane, wherein the third ion exchange membrane divides the inner cavity of the second battery stack into a fifth chamber for arranging the third positive electrode and a sixth chamber for arranging the third negative electrode, wherein the fifth chamber is connected to the first storage tank to form a circulation loop, and the sixth chamber is connected to the third storage tank to form a circulation loop;

[0012] The second fuel cell stack is used to be connected to a renewable energy system so as to supply power to the second fuel cell stack through the renewable energy system.

[0013] In some embodiments, it also includes:

[0014] An oxygen generator, the oxygen generator having an oxygen-generating catalytic layer and a first feed port, the first feed port being used to replenish the aqueous solution into the oxygen generator, the oxygen generator being connected to the third storage tank to form a circulation loop, the positive electrolyte being regenerated in the oxygen generator and generating oxygen in the oxygen generator;

[0015] A hydrogen generator, wherein the hydrogen generator has a hydrogen production catalytic layer and a second feed port, wherein the second feed port is used to replenish the aqueous solution into the hydrogen generator, the hydrogen generator is connected to the fourth storage tank to form a circulation loop, and the negative electrolyte is regenerated in the hydrogen generator to produce hydrogen in the hydrogen generator.

[0016] In some embodiments, the oxygen generator further comprises a first circulation pump, a first heater and a first agitator, and the hydrogen generator further comprises a second circulation pump, a second heater and a second agitator;

[0017] And / or, the oxygen generator is connected to a first pressure gauge and a first compressor, and the hydrogen generator is connected to a second pressure gauge and a second compressor;

[0018] And / or, the oxygen-generating catalytic layer comprises a first substrate layer and first catalytic particles, wherein the first substrate layer is carbon felt, graphite felt, titanium mesh, SiO 2 Any one of the particle fixed beds, wherein the first catalytic particles are IrO 2 or RuO 2 Particles; the hydrogen production catalytic layer includes a second substrate layer and a second catalytic particle, the second substrate layer is carbon felt, graphite felt, titanium mesh, SiO 2 Any one of the particle fixed beds, wherein the second catalytic particles are MoS 2 Or Mo 2 C particles.

[0019] In some embodiments, a hydrazine oxidation hydrogen production system is also included, the hydrazine oxidation hydrogen production system comprising a second electrolytic cell, a fifth storage tank storing a hydrazine solution, and a sixth storage tank storing an aqueous solution, the second electrolytic cell has a fourth positive electrode, a fourth negative electrode, and a fourth ion exchange membrane, the fourth ion exchange membrane divides the inner cavity of the second electrolytic cell into a seventh chamber for arranging the fourth positive electrode and an eighth chamber for arranging the fourth negative electrode; the fifth storage tank is connected to the seventh chamber and forms a circulation loop, so that the hydrazine solution circulates in the fifth storage tank and the seventh chamber; the sixth storage tank is connected to the eighth chamber and forms a circulation loop, so that the aqueous solution circulates in the sixth storage tank and the eighth chamber, and the aqueous solution is electrolyzed in the eighth chamber to generate hydrogen;

[0020] The hydrazine oxidation hydrogen production system is used to be connected to a renewable energy system and / or the liquid flow battery, so that the hydrazine oxidation hydrogen production system is powered by the renewable energy system, the liquid flow battery, or the hydrazine fuel cell.

[0021] In some embodiments, a hydrazine fuel cell is further included, wherein the inner cavity of the hydrazine fuel cell has a fifth positive electrode, a fifth negative electrode and a fifth ion exchange membrane, the fifth ion exchange membrane divides the inner cavity of the hydrazine fuel cell into a ninth chamber for arranging the fifth positive electrode and a tenth chamber for arranging the fifth negative electrode, the ninth chamber is connected to the third storage tank to form a circulation loop, and the tenth chamber is connected to the fifth storage tank to form a circulation loop;

[0022] The output end of the hydrazine fuel cell is connected to the first electrolyzer and the second electrolyzer to supply power to the first electrolyzer and the second electrolyzer.

[0023] In some embodiments, a seventh storage tank is further included, wherein the seventh storage tank is used to store H2 O 2 solution, the seventh storage tank is connected to the ninth chamber to form a circulation loop;

[0024] And / or, a heat exchanger is provided on the pipeline for allowing the hydrazine solution to flow from the seventh chamber to the fifth storage tank, and / or on the pipeline for allowing the aqueous solution to flow from the eighth chamber to the sixth storage tank, and the pipeline for allowing the positive electrolyte to flow from the third storage tank to the third chamber and the pipeline for allowing the negative electrolyte to flow from the fourth storage tank to the fourth chamber are both connected to the heat exchanger to perform heat exchange on the positive electrolyte and the negative electrolyte flowing to the first battery stack.

[0025] In some embodiments, the organic hydrogen carrier is any one of formic acid, methanol, and acetic acid, and the catalyst in the thermal catalytic reactor is a metal catalyst or a composite metal catalyst, and the catalyst is used to thermally catalytically decompose the organic hydrogen carrier to produce hydrogen;

[0026] And / or, the thermocatalytic reactor comprises a thermocatalytic layer, a third circulation pump, a third heater and a third agitator;

[0027] And / or, the thermal catalytic reactor is connected to a third pressure gauge, and the hydrogen outlet of the thermal catalytic reactor and the hydrogen outlet of the first electrolyzer are connected to a third compressor, a gas-liquid separator and a hydrogen purification device.

[0028] In some embodiments, an energy management and control system is also included, and the energy management and control system is used to control the operation of each component in the thermal catalytic and electrolytic step-by-step hydrogen production system. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a schematic diagram of a thermal catalytic and electrolytic step-by-step hydrogen production system (omitting the oxygen generator) according to an embodiment of the present invention.

[0030] Figure 2 Schematic diagram of a liquid flow battery, a hydrogen generator and an oxygen generator in an embodiment of the present invention.

[0031] Reference numerals:

[0032] 1. Thermocatalytic and electrolytic device; 11. Thermocatalytic reactor; 12. First electrolytic cell; 121. First positive electrode; 122. First negative electrode; 123. First ion exchange membrane; 124. First chamber; 125. Second chamber; 13. First storage tank; 14. Second storage tank; 15. Second battery stack; 151. Third positive electrode; 152. Third negative electrode; 153. Third ion exchange membrane; 154. Fifth chamber; 155. Sixth chamber; 16. Thermocatalytic layer; 17. Third circulation pump; 18. Third heater; 19. Third agitator;

[0033] 2. Liquid flow battery; 21. First battery stack; 22. Second positive electrode; 23. Second negative electrode; 24. Second ion exchange membrane; 25. Third chamber; 26. Fourth chamber; 27. Third storage tank; 28. Fourth storage tank;

[0034] 31. driving pump; 32. control valve; 33. first feed inlet; 34. second feed inlet; 35. heat exchanger;

[0035] 4. oxygen generator; 41. oxygen catalyst layer; 42. first circulation pump; 43. first heater; 44. first agitator; 45. first pressure gauge; 46. first compressor;

[0036] 5. Hydrogen generator; 51. Hydrogen catalyst layer; 52. Second circulation pump; 53. Second heater; 54. Second stirrer; 55. Second pressure gauge; 56. Second compressor;

[0037] 61. third compressor; 62. gas-liquid separator; 63. hydrogen purification device; 64. fourth compressor; 65. dryer;

[0038] 71. Renewable energy system; 72. Energy management system;

[0039] 8. Hydrazine oxidation hydrogen production system; 81. Second electrolytic cell; 82. Fourth positive electrode; 83. Fourth negative electrode; 84. Fourth ion exchange membrane; 85. Seventh chamber; 86. Eighth chamber; 87. Fifth storage tank; 88. Sixth storage tank;

[0040] 9. Hydrazine fuel cell; 91. Fifth positive electrode; 92. Fifth negative electrode; 93. Fifth ion exchange membrane; 94. Ninth chamber; 95. Tenth chamber; 96. Seventh storage tank. DETAILED DESCRIPTION

[0041] Embodiments of the present invention are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.

[0042] The inventors realized that in the process of renewable energy power generation and hydrogen production, the load fluctuation range of green hydrogen preparation by renewable energy power generation is narrow, the load fluctuation operation is difficult to control, the hydrogen purity is difficult to control, the efficiency is low, and the power consumption is large. In addition, there are also problems such as a large amount of heat generated by the electrolysis hydrogen production process that is not recycled, the gas purity is reduced under load fluctuation conditions, and the energy consumption of the purification separation / compression process is high, resulting in high energy consumption for renewable energy power generation and hydrogen production, low overall system efficiency, and a narrow load fluctuation range.

[0043] like Figure 1 As described above, the thermal catalysis and electrolysis step-by-step hydrogen production system of the embodiment of the present invention includes a liquid flow battery 2 and a thermal catalysis and electrolysis device 1.

[0044] The liquid flow battery 2 is used to be connected to the renewable energy system 71 so as to charge and store energy for the liquid flow battery 2 through the renewable energy system 71; the thermal catalytic and electrolytic device 1 is used to be connected to the renewable energy system 71 and the liquid flow battery 2 so as to supply power to the thermal catalytic and electrolytic device 1 through the renewable energy system 71 or the liquid flow battery 2.

[0045] That is to say, when the output of the renewable energy system 71 is large, the renewable energy system 71 generates electricity to supply the liquid flow battery 2 for charging and energy storage, and supplies power to the thermal catalytic and electrolytic device 1 for hydrogen production. When the output of the renewable energy system 71 is small or the output is predicted to be small in the next period, the liquid flow battery 2 is started to discharge, and the liquid flow battery 2 and the renewable energy system 71 are used to jointly supply power to the thermal catalytic and electrolytic device 1, or the liquid flow battery 2 is used alone to supply power to the thermal catalytic and electrolytic device 1, so as to realize continuous and stable operation of the thermal catalytic and electrolytic device 1.

[0046] The thermal catalytic and electrolytic device 1 includes a thermal catalytic reactor 11, a first electrolytic cell 12, a first storage tank 13 for storing an organic hydrogen carrier, and a second storage tank 14 for storing an electrolyte. The first storage tank 13 is connected to the inner cavity of the thermal catalytic reactor 11 to form a circulation loop, so that the organic hydrogen carrier is catalytically decomposed in the thermal catalytic reactor 11 to generate hydrogen; the first electrolytic cell 12 includes a first positive electrode 121, a first negative electrode 122 and a first ion exchange membrane 123. The first ion exchange membrane 123 divides the inner cavity of the first electrolytic cell 12 into a first chamber 124 for arranging the first positive electrode 121 and a second chamber 125 for arranging the first negative electrode 122. The first chamber 124 is connected to the inner cavity of the thermal catalytic reactor 11 to form a circulation loop, and the second chamber 125 is connected to the second storage tank 14 to form a circulation loop. The electrolyte in the second storage tank 14 is reduced in the first electrolytic cell 12 to generate hydrogen.

[0047] After the organic hydrogen carrier flows out of the first storage tank 13, it is driven by the driving pump 31 and enters the thermal catalytic reactor 11. The organic hydrogen carrier in the thermal catalytic reactor 11 contacts and reacts with the catalyst layer. Under the catalytic reaction of the catalyst layer, the organic hydrogen carrier is thermally decomposed to produce hydrogen. The prepared hydrogen is discharged and delivered to hydrogen users.

[0048] When the pressure drop in the thermal catalytic reactor 11 is detected, the organic hydrogen carrier is driven into the first electrolyzer 12 by the driving pump 31 and is oxidized at the first positive electrode 121. Compared with the oxygen evolution reaction at the positive electrode of the electrolyzed water, the overpotential of the electrolysis reaction can be effectively reduced. The second storage tank 14 has a feed port to replenish the electrolyte lost by electrolysis. After being driven by the driving pump 31, the electrolyte stored in the second storage tank 14 enters the second chamber 125 of the first electrolyzer 12 to be reduced and generate hydrogen. The wiring terminals of the first electrolyzer 12 are connected to the renewable energy power generation power supply and the liquid flow battery 2; the renewable energy power supply serves as the main power supply and the liquid flow battery 2 serves as the backup power supply. When the renewable energy source is out of power, the liquid flow battery 2 is powered, which can realize a continuous, large-scale and controllable supply of hydrogen for the hydrogen production system.

[0049] The thermal catalytic and electrolytic step-by-step hydrogen production system of the embodiment of the present invention can directly power the thermal catalytic and electrolytic device 1 through the renewable energy system 71, which can reduce the system cost, and reasonably select the power supply according to the processing size of the renewable energy system 71 to achieve stable hydrogen production, increase the proportion of green electricity hydrogen production, and reduce the cost of hydrogen production.

[0050] In some embodiments, the liquid flow battery 2 includes a first battery stack 21, a third storage tank 27 storing a positive electrolyte, and a fourth storage tank 28 storing a negative electrolyte. The inner cavity of the first battery stack 21 has a second positive electrode 22, a second negative electrode 23, and a second ion exchange membrane 24. The second ion exchange membrane 24 divides the inner cavity of the first battery stack 21 into a third chamber 25 for arranging the second positive electrode 22 and a fourth chamber 26 for arranging the second negative electrode 23; the third storage tank 27 is connected to the third chamber 25 and forms a circulation loop so that the positive electrolyte circulates in the third tank and the third chamber 25; the fourth storage tank 28 is connected to the fourth chamber 26 and forms a circulation loop so that the negative electrolyte circulates in the fourth storage tank 28 and the fourth chamber 26.

[0051] The thermal catalytic and electrolytic device 1 of the embodiment of the present invention also includes a second fuel cell stack 15, which has a third positive electrode 151, a third negative electrode 152 and a third ion exchange membrane 153. The third ion exchange membrane 153 divides the inner cavity of the second fuel cell stack 15 into a fifth chamber 154 for arranging the third positive electrode 151 and a sixth chamber 155 for arranging the third negative electrode 152. The fifth chamber 154 is connected to the first storage tank 13 to form a circulation loop, and the sixth chamber 155 is connected to the third storage tank 27 to form a circulation loop; the second fuel cell stack 15 is used to be connected to the renewable energy system 71 to supply power to the second fuel cell stack 15 through the renewable energy system 71.

[0052] After the liquid flow battery 2 system has been running for a long time, the capacity is unbalanced and the capacity and performance are attenuated due to hydrogen evolution. After the discharge of the liquid flow battery 2 system is completed, the first storage tank 13 is started, and the organic hydrogen carrier enters the fifth chamber 154 of the second battery stack 15 through the driving pump 31. At the same time, the connection terminal of the second battery stack 15 is connected to the renewable energy system 71 to charge the second battery stack 15. The electrolyte in the third storage tank 27 of the liquid flow battery 2 enters the sixth chamber 155 of the second battery stack 15 through the driving pump 31, and the second battery stack 15 is used to restore the capacity and performance of the liquid flow battery 2 system.

[0053] The specific operation method is as follows: the organic hydrogen carrier is driven by the driving pump 31 into the fifth chamber 154 of the second stack 15 to be oxidized; the positive electrode electrolyte in the third tank 27 (shared with the liquid flow battery 2 system) is driven by the driving pump 31 into the sixth chamber 155 of the second stack 15, and the excess M in the positive electrode electrolyte is (n+1)+ Restored to M (n+) , and then flows back to the third storage tank 27, and is charged at a constant voltage (such as 1-1.5V) until the charging current is observed to drop below 10mAcm-2 and continues to drop, indicating that M (n+1)+ All are restored to M (n+) , the capacity and performance of the flow battery 2 system have been restored.

[0054] like Figure 2 As shown, in some embodiments, the thermal catalytic and electrolytic step-by-step hydrogen production system also includes an oxygen generator 4 and a hydrogen generator 5. The oxygen generator 4 has an oxygen production catalyst layer 41 and a first feed port 33. The first feed port 33 is used to add aqueous solution to the oxygen generator 4. The oxygen generator 4 is connected to the third storage tank 27 to form a circulation loop. The positive electrolyte is regenerated in the oxygen generator 4 and oxygen is generated in the oxygen generator 4. The hydrogen generator 5 has a hydrogen production catalyst layer 51 and a second feed port 34. The second feed port 34 is used to add aqueous solution to the hydrogen generator 5. The hydrogen generator 5 is connected to the fourth storage tank 28 to form a circulation loop. The negative electrolyte is regenerated in the hydrogen generator 5 and hydrogen is generated in the hydrogen generator 5.

[0055] The hydrogen and oxygen production circuit system composed of the hydrogen generator 5 and the oxygen generator 4 and the flow battery 2 can be operated jointly or separately.

[0056] Specifically, during the charging / discharging process of the liquid flow battery 2, the hydrogen and oxygen production circuit system can be started simultaneously or as needed to realize the dual-circuit joint operation of the liquid flow battery 2 (as a primary circuit) and the hydrogen and oxygen production circuit system. The independent operation of hydrogen production and oxygen production by the hydrogen and oxygen production circuit system increases the storage capacity of the liquid flow battery 2, realizes the flexible decoupling operation of hydrogen production and liquid flow battery 2 charging and discharging, and improves the stability of hydrogen production power supply from renewable energy.

[0057] In the embodiment of the present invention, hydrogen production and oxygen production through the hydrogen and oxygen production circuit system are independently operated, and can be operated in conjunction with the thermal catalysis and electrolysis device 1, thereby increasing the storage capacity of the liquid flow battery 2, achieving flexible decoupling operation of hydrogen production and charging and discharging of the liquid flow battery 2, and at the same time improving the power supply stability of renewable energy hydrogen production, hydrogen production response speed and hydrogen production amount.

[0058] In some embodiments, the thermal catalytic and electrolytic step-by-step hydrogen production system further includes a hydrazine oxidation hydrogen production system 8, which includes a second electrolytic cell 81, a fifth storage tank 87 storing a hydrazine solution, and a sixth storage tank 88 storing an aqueous solution. The second electrolytic cell 81 has a fourth positive electrode 82, a fourth negative electrode 83, and a fourth ion exchange membrane 84. The fourth ion exchange membrane 84 divides the inner cavity of the second electrolytic cell 81 into a seventh chamber 85 for arranging the fourth positive electrode 82 and an eighth chamber 86 for arranging the fourth negative electrode 83. The storage tank 87 is connected to the seventh chamber 85 to form a circulation loop, so that the hydrazine solution circulates in the fifth storage tank 87 and the seventh chamber 85; the sixth storage tank 88 is connected to the eighth chamber 86 to form a circulation loop, so that the aqueous solution circulates in the sixth storage tank 88 and the eighth chamber 86, and the aqueous solution is electrolyzed in the eighth chamber 86 to generate hydrogen; the hydrazine oxidation hydrogen production system 8 is used to be connected to the renewable energy system 71 and / or the liquid flow battery 2, so as to power the hydrazine oxidation hydrogen production system 8 through the renewable energy system 71, the liquid flow battery 2, or the hydrazine fuel cell 9.

[0059] The process of hydrazine oxidation to produce hydrogen is as follows: the second electrolyzer 81 is powered by the renewable energy system 71 or the flow battery 2 or the hydrazine fuel cell 9, the hydrazine solution stored in the fifth storage tank 87 enters the seventh chamber 85 of the second electrolyzer 81, and under the action of the fourth positive electrode 82, the hydrazine in the seventh chamber 85 is oxidized and converted into nitrogen and water, and then flows out with the hydrazine solution, and flows back to the fifth storage tank 87, wherein the nitrogen can be discharged into the atmosphere after passing through the gas-liquid separator 62, the treatment device and other equipment. The aqueous solution stored in the sixth storage tank 88 enters the eighth chamber 86 of the second electrolyzer 81, and under the action of the fourth negative plate, the water is electrolyzed (proton reduced) to generate hydrogen, which flows out with the aqueous solution and flows back to the sixth storage tank 88, wherein the hydrogen can be discharged after passing through the compressor, the gas-liquid separation device, the hydrogen purification device 63 and other equipment, and is stored or supplied to hydrogen users.

[0060] The positive electrode of the second electrolyzer 81 uses the hydrazine oxidation reaction (HzOR) to replace the water decomposition positive electrode reaction, i.e., the oxygen evolution reaction (OER), in the traditional water electrolysis hydrogen production process. Due to the slow reaction kinetics and high energy barrier of the oxygen evolution reaction, the water electrolysis hydrogen production has high voltage, high power consumption, and low efficiency. The overpotential of the hydrazine oxidation reaction (HzOR) is lower than that of the oxygen evolution reaction (OER). Therefore, the voltage and power consumption required for the electrolyzer using the hydrazine oxidation reaction (HzOR) at the positive electrode are reduced, and efficient water electrolysis can be achieved. The hydrazine at the positive electrode of the electrolyzer is oxidized and converted into nitrogen and water, which is pollution-free to the environment.

[0061] In some embodiments, the thermal catalytic and electrolytic step-by-step hydrogen production system also includes a hydrazine fuel cell 9, the inner cavity of the hydrazine fuel cell 9 has a fifth positive electrode 91, a fifth negative electrode 92 and a fifth ion exchange membrane 93, the fifth ion exchange membrane 93 divides the inner cavity of the hydrazine fuel cell 9 into a ninth chamber 94 for arranging the fifth positive electrode 91 and a tenth chamber 95 for arranging the fifth negative electrode 92, the ninth chamber 94 is connected to the third storage tank 27 to form a circulation loop, and the tenth chamber 95 is connected to the fifth storage tank 87 to form a circulation loop.

[0062] The output end of the hydrazine fuel cell 9 is connected to the first electrolyzer 12 and the second electrolyzer 81 to supply power to the first electrolyzer 12 and the second electrolyzer 81 .

[0063] The hydrazine fuel cell 9 discharges when hydrogen production is required. The hydrazine solution stored in the fifth tank 87 is driven by the driving pump 31 to enter the ninth chamber 94 of the hydrazine fuel cell 9. The hydrazine is discharged and converted into nitrogen and water, which flow out with the hydrazine solution and flow back to the fifth tank 87. The electrolyte in the third tank 27 is driven by the pump and enters the ninth chamber 94 of the hydrazine fuel cell 9 for discharge, and flows back to the third tank 27 after discharge. The hydrazine fuel cell 9 is connected to the positive and negative poles of the first electrolyzer 12 and the second electrolyzer 81 through the positive and negative poles, and is hydrazine (N 2 H 4 ) The oxidation hydrogen production system and the thermal catalysis and electrolysis device 1 provide power.

[0064] Furthermore, the thermal catalytic and electrolytic step-by-step hydrogen production system further includes a seventh storage tank 96, which is used to store H 2 O 2 Solution, the seventh storage tank 96 is connected with the ninth chamber 94 to form a circulation loop.

[0065] The backup method for the hydrazine fuel cell 9 to ensure continuous operation of hydrogen production is that when the power stored in the flow battery 2 is exhausted, that is, the electrolyte in the third storage tank 27 can no longer be discharged, and the renewable energy power generation source is out of power, the H stored in the seventh storage tank 96 is used to generate hydrogen. 2 O 2 The solution is used as the positive electrode fuel of the hydrazine fuel cell 9 system, and the hydrazine solution is used as the negative electrode fuel of the hydrazine fuel cell 9 system to continue to operate and discharge, thereby ensuring continuous hydrogen production.

[0066] The embodiment of the present invention can realize the joint operation of the flow battery 2, the hydrazine oxidation hydrogen production system 8, the thermal catalysis and electrolysis device 1, and the hydrazine fuel cell 9, realize the stable and continuous operation of hydrazine oxidation hydrogen production, thermal catalysis and electrolysis distributed hydrogen production, ensure the stability of the power supply and self-sustaining continuous operation of the hydrogen production system, and also reduce the energy consumption of hydrogen production and increase the proportion of green electricity hydrogen production. The voltage and power consumption required for the hydrazine oxidation reaction and thermal catalysis and electrolysis hydrogen production are reduced, and efficient water electrolysis can be achieved, and the converted nitrogen and water will not pollute the environment.

[0067] The following combination Figure 1 and Figure 2 As shown, a specific embodiment of the thermal catalytic and electrolytic step-by-step hydrogen production system of an embodiment of the present invention is described in detail.

[0068] The thermal catalytic and electrolytic step-by-step hydrogen production system of the embodiment of the present invention includes a liquid flow battery 2, an oxygen generator 4, a hydrogen generator 5, a hydrazine oxidation hydrogen production system 8, a hydrazine fuel cell 9, a thermal catalytic and electrolytic device 1 and an energy management system 72. The energy management system 72 is used to control the operation of each component in the thermal catalytic and electrolytic step-by-step hydrogen production system.

[0069] The liquid flow battery 2 is used to be connected to the renewable energy system 71 so as to charge and store energy in the liquid flow battery 2 through the renewable energy system 71 .

[0070] The liquid flow battery 2 includes a first battery stack 21, a third storage tank 27 storing a positive electrolyte, and a fourth storage tank 28 storing a negative electrolyte. The liquid flow battery 2 also includes a pipeline for transporting electrolyte, a driving pump 31 for driving the electrolyte to flow in the pipeline, a control valve 32 for controlling the on and off of the pipeline, and a heat exchanger 35 for heating the positive electrolyte and the negative electrolyte. The inner cavity of the first battery stack 21 has a second positive electrode 22, a second negative electrode 23 and a second ion exchange membrane 24. The second ion exchange membrane 24 divides the inner cavity of the first battery stack 21 into a third chamber 25 for arranging the second positive electrode 22 and a fourth chamber 26 for arranging the second negative electrode 23; the third storage tank 27 is connected to the third chamber 25 and forms a circulation loop so that the positive electrolyte circulates in the three storage tanks and the third chamber 25; the fourth storage tank 28 is connected to the fourth chamber 26 and forms a circulation loop so that the negative electrolyte circulates in the fourth storage tank 28 and the fourth chamber 26.

[0071] The flow battery 2 system and its operation method are as follows:

[0072] The positive and negative electrolytes in the flow battery 2 both include electrolyte active material M (n+) (or V 4+ , Fe 2+ , or other positive electrode active material ions) and N (n+1)+ (or V 3+ , or other negative electrode active material ions.

[0073] The positive electrode reaction is M (n+) / M (n+1)+ Oxidation reaction (positive electrode pair includes but is not limited to Fe 2+ / Fe 3+ ,M(n+) / C 4 + , V 4+ / V 5+ , where M represents a certain metal ion at the positive electrode as an active substance), and the negative electrode reaction is N (n+1) / N (n+) Reduction reaction (negative electrode pairs include but are not limited to N(n+1)+ / N(n+) reaction, V 3+ / V 2+ , where N represents, where N represents a certain metal ion in the negative electrode as an active substance), the above positive and negative electrode pairs are for illustrating the working principle.

[0074] The electrolyte consists of a positive and negative electrode pair and a supporting electrolyte. The supporting electrolyte is an acidic medium composed of HCl, H 2 SO 4 , perchloric acid, nitric acid, methanesulfonic acid or mixed acid, etc., methanesulfonic acid can increase the activity of active substances such as M (n+) and N (n+1)+ Solubility, in the present invention, a mixed acid of hydrochloric acid / sulfuric acid / nitric acid+methanesulfonic acid is preferred. And the positive and negative electrolytes in the initial state have the same composition (that is, the new electrolytes without charge and discharge have the same composition), and the positive electrode of the first battery stack 21 constructed is M (n+) / M (n+1)+ Reaction, the positive electrode can be synthesized by chemical vapor deposition (CVD) TiC / TiO 2 Coated carbon-based electrode (carbon felt or graphite felt), or carbon-based electrode (carbon felt or graphite felt) with boron-doped titanium dioxide coating. TiC / TiO 2 Coating and boron-doped titanium dioxide coating effectively reduce the direct contact reaction of carbon-based electrodes in highly oxidizing M-based electrolytes and improve the corrosion resistance of the electrodes.

[0075] The operation process of the flow battery 2 system is as follows:

[0076] The negative electrode electrolyte of the liquid flow battery 2 flows out from the fourth storage tank 28, is driven by the driving pump 31, and passes through the heat exchanger 35 to form the temperature required by the liquid flow battery 2 (for example, the operating temperature is 60°C). When the ambient temperature is low, the heat exchanger 35 heats the electrolyte, and when the battery temperature rises (such as high current density circulation causes the battery to heat up), the heat exchanger 35 cools the electrolyte. The negative electrode electrolyte flows into the first battery stack 21 to react.

[0077] The first battery stack 21 is the power unit of the flow battery 2, which serves as the core component of energy exchange. The battery stack has multiple battery cells, positive current collectors and negative current collectors, each battery cell has a second positive electrode 22, a second negative electrode 23 and a second ion exchange membrane 24, and the positive current collectors and negative current collectors connect multiple battery cells in series to form a battery stack. Specifically, the first battery stack 21 is composed of one or more battery cells (referred to as single cells) connected in series. The battery cell is composed of positive and negative electrodes, electrolytes and ion exchange membranes separating electrodes, and has a battery assembly with a pair of positive and negative output terminals (bipolar plates or current collectors). When the number of battery cells is ≥1, multiple groups of identical battery cells are connected in series through negative current collectors and positive current collectors to form a battery stack, and the negative current collectors and positive current collectors are negative bipolar plates and positive bipolar plates, respectively. The positive and negative electrolytes undergo electrochemical redox reactions in the battery stack. Electrons flow between the positive and negative electrodes in the first battery stack 21 of the liquid flow battery 2 in an external circuit. During the charging process, the renewable energy system 71 generates electricity and supplies power to the liquid flow battery 2, and electrons flow from the positive electrode to the negative electrode in the external circuit.

[0078] During the normal charging process of flow battery 2, constant current or constant power is used to charge from 0V to U 1 (For example, U 1 =1 to 1.9V), constant current density = j normal (Can be set from 10 to 300mAcm -2 ). The reactant ions of the positive and negative electrolytes flow inside the first battery stack 21 and undergo electrochemical redox reactions on the positive and negative electrodes. The electrochemical reactions of the active materials of the positive and negative half-cells of the battery unit and their energy storage occur simultaneously. During the charging process of the flow battery 2, the positive electrode M (n+) Oxidation M(n+1)+ , N (n+1)+ Restore to N (n+) , and flow into the third storage tank 27 and the fourth storage tank 28 for storage respectively.

[0079] During the charging process, the negative electrode electrolyte after the electrochemical reaction flows out of the first battery stack 21 and flows into the fourth storage tank 28 for storage.

[0080] The same is true for the positive electrode side of the first stack 21. The positive electrode electrolyte of the flow battery 2 flows out from the third storage tank 27, is driven by the drive pump 31, and passes through the heat exchanger 35 to form the temperature required by the flow battery 2 (for example, the operating temperature of the flow battery 2 is ~60°C). When the ambient temperature is low, the heat exchanger 35 heats the electrolyte, and when the battery temperature rises (such as high current density circulation causes the battery to heat up), the heat exchanger 35 cools the electrolyte. After passing through the heat exchanger 35, the positive electrode electrolyte flows into the first stack 21.

[0081] During the charging process, the positive electrode electrolyte after the electrochemical reaction flows out of the first battery stack 21 and flows into the third storage tank 27 for storage.

[0082] The discharge process is similar to the charging process, except that the flow battery 2 discharges to the power load. 3+ Reduction to Fe 2+ , N (n+) Oxidized to N (n+1)+ , and flow back to the third storage tank 27 and the fourth storage tank 28 respectively.

[0083] The first battery stack 21 undergoes electrochemical reactions of charging and discharging. At the same time, electrochemical side reactions will inevitably occur under normal operating conditions of the liquid flow battery 2. The side reactions will irreversibly consume electrons, resulting in an imbalance in the charge state of the positive electrode electrolyte and the negative electrode electrolyte (referred to as charge imbalance), and ultimately leading to an imbalance in the capacity of the positive and negative electrodes and a reduction in capacity.

[0084] Liquid flow battery 2, the electrochemical reactions and side reactions of the positive and negative electrodes during the charging process are:

[0085] Positive electrode: M (n+) -e - =M (n+1)+ ,xV vs SHE;

[0086] Negative electrode: N (n+1)+ +e - =N (n+) ,yV vs SHE;

[0087] Hydrogen evolution side reaction: 2H + +2e - =H 2 , 0V vs SHE.

[0088] The hydrogen gas released by the hydrogen release side reaction flows into the hydrogen generator and flows out together with the hydrogen produced.

[0089] The electrochemical reactions of the positive and negative electrodes during the discharge process are:

[0090] Positive electrode: M (n+1) +e - =M (n+) ,xV vs SHE;

[0091] Negative electrode: N (n+) -e - =N (n+1)+ , yV vs SHE.

[0092] The oxygen generator 4 has an oxygen production catalytic layer 41 and a first feed port 33, the first feed port 33 is used to add aqueous solution to the oxygen generator 4, the oxygen generator 4 is connected to the third storage tank 27 to form a circulation loop, the positive electrolyte is regenerated in the oxygen generator 4 and oxygen is generated in the oxygen generator 4; the hydrogen generator 5 has a hydrogen production catalytic layer 51 and a second feed port 34, the second feed port 34 is used to add aqueous solution to the hydrogen generator 5, the hydrogen generator 5 is connected to the fourth storage tank 28 to form a circulation loop, the negative electrolyte is regenerated in the hydrogen generator 5 and hydrogen is generated in the hydrogen generator 5.

[0093] The hydrogen and oxygen production circuit system composed of the hydrogen generator 5 and the oxygen generator 4 and the flow battery 2 can be operated jointly or separately.

[0094] Pipelines for conveying electrolyte, a driving pump 31 for driving the electrolyte to flow in the pipeline, a control valve 32 for controlling the on-off of the pipeline, and other components are provided between the oxygen generator 4 and the third storage tank 27, and between the hydrogen generator 5 and the fourth storage tank 28.

[0095] Specifically, during the charging / discharging process of the liquid flow battery 2, the hydrogen and oxygen production circuit system can be started simultaneously or as needed to realize the dual-circuit joint operation of the liquid flow battery 2 (as a primary circuit) and the hydrogen and oxygen production circuit system. The independent operation of hydrogen production and oxygen production by the hydrogen and oxygen production circuit system increases the storage capacity of the liquid flow battery 2, realizes the flexible decoupling operation of hydrogen production and liquid flow battery 2 charging and discharging, and improves the stability of hydrogen production power supply from renewable energy.

[0096] In the embodiment of the present invention, hydrogen production and oxygen production by the hydrogen and oxygen production circuit system are independently operated, and can be operated in conjunction with the thermal catalysis and electrolysis device 1 and the hydrazine oxidation hydrogen production system 8, thereby increasing the storage capacity of the liquid flow battery 2, achieving flexible decoupling operation of hydrogen production and charging and discharging of the liquid flow battery 2, and at the same time improving the power supply stability of renewable energy hydrogen production, hydrogen production response speed and hydrogen production amount.

[0097] The operation method of the secondary circuit of the oxygen production system is as follows:

[0098] During the charging or discharging process of the flow battery 2, the M in the third storage tank 27 (n+1)+ The electrolyte enters the oxygen generator 4 and discharges to produce oxygen. The oxygen-producing catalytic layer 41 of the oxygen generator 4 includes a first substrate layer and first catalytic particles. The first substrate layer is carbon felt, graphite felt, titanium mesh, SiO 2 Any of the fixed bed of particles, the first catalytic particles are IrO 2 or RuO 2 Particles.

[0099] The oxygen generator 4 also has a first circulation pump 42, a first heater 43 and a first agitator 44. The oxygen generator 4 is connected to a first pressure gauge 45 and a first compressor 46. The oxygen production reaction rate can be increased by means of catalysis, self-circulation and heating. The pressure and accident overpressure discharge are monitored by the first pressure gauge 45.

[0100] Positive Electrolyte M (n+1)+ Oxygen production formula: 4M (n+1)+ +2H 2 O=O 2 +4H + +4 M(n+) , the newly generated M (n+) The electrolyte returns to the third storage tank 27 to continue charging the liquid flow battery 2, thereby increasing the storage capacity of the liquid flow battery 2.

[0101] The operation method of the secondary circuit of the hydrogen production system is as follows:

[0102] During the charging or discharging process of the flow battery 2, N in the fourth storage tank 28 (n+) The electrolyte is discharged in the hydrogen generator 5 to produce hydrogen. The hydrogen production catalytic layer 51 includes a second substrate layer and a second catalytic particle. The second substrate layer is carbon felt, graphite felt, titanium mesh, SiO 2 Any of the fixed bed of particles, the second catalytic particle is MoS 2 Or Mo 2 C particles; the hydrogen generator 5 also has a second circulation pump 52, a second heater 53 and a second agitator 54; the hydrogen generator 5 is connected to a second pressure gauge 55 and a second compressor 56; the hydrogen production reaction rate is improved by means of catalysis, self-circulation and heating, the pressure is monitored by the second pressure gauge 55 and accidental overpressure discharge is performed.

[0103] Negative electrolyte N (n+) Hydrogen production equation: 4N (n+) +4H + =2H 2 +4N (n+1)+ , hydrogen production reactant H + H obtained from the above oxygen production circuit + , diffuses across the membrane to the negative electrode of the first stack 21 during the charging process of the flow battery 2, H + The hydrogen flows into the hydrogen generator and is reduced to H 2 The newly generated N (n+1)+ The electrolyte returns to the fourth storage tank 28 to continue charging the liquid flow battery 2, thereby increasing the storage capacity of the liquid flow battery 2.

[0104] H in the hydrogen generator + Reduced to H 2, after passing through the second compressor 56 and the dryer 65, the hydrogen is supplied to the hydrogen users. In particular, the hydrogen generator 5 and the oxygen generator 4 are decoupled from the charge and discharge of the flow battery 2 system, and the hydrogen generator 5 can operate independently. Since the hydrogen production principle is the discharge of the negative electrode electrolyte, the generated hydrogen has no oxygen impurities and does not need to be purified. According to the needs of hydrogen users, continuous and instant supply can be achieved.

[0105] Due to the above combined operation, the reactive substances M ions, N ions and H+ are conserved, and the "two-circuit system consisting of independent hydrogen production and oxygen production systems" only needs to replenish the corresponding stoichiometric volume / mass of the consumed aqueous solution to the feed inlet of the oxygen generator and the feed inlet of the hydrogen generator of the oxygen production circuit.

[0106] The hydrazine oxidation hydrogen production system 8 is used to connect with the renewable energy system 71 , the liquid flow battery 2 and the hydrazine fuel cell 9 , so as to supply power to the hydrazine oxidation hydrogen production system 8 through the renewable energy system 71 , the liquid flow battery 2 or the hydrazine fuel cell 9 .

[0107] That is to say, when the output of the renewable energy system 71 is relatively large, the renewable energy system 71 generates electricity to charge the liquid flow battery 2 for energy storage, and supplies electricity to the hydrazine oxidation hydrogen production system 8 for hydrogen production. When the output of the renewable energy system 71 is relatively small or the output is predicted to be relatively small in the next period, the liquid flow battery 2 is started to discharge, and the liquid flow battery 2 and the renewable energy system 71 are used to jointly supply electricity to the hydrazine oxidation hydrogen production system 8, or the liquid flow battery 2 is used to supply electricity to the hydrazine oxidation hydrogen production system 8 alone, or the hydrazine fuel cell 9 is used to supply electricity to the hydrazine oxidation hydrogen production system 8 alone, so as to realize the continuous and stable operation of the hydrazine oxidation hydrogen production system 8.

[0108] The hydrazine oxidation hydrogen production system 8 includes a second electrolytic cell 81, a fifth storage tank 87 storing a hydrazine solution, and a sixth storage tank 88 storing an aqueous solution. The components in the hydrazine oxidation hydrogen production system 8 are connected by a pipeline for conveying electrolyte, a driving pump 31 for driving the electrolyte to flow in the pipeline, a control valve 32 for controlling the on-off of the pipeline, and other components. The second electrolytic cell 81 has a fourth positive electrode 82, a fourth negative electrode 83 and a fourth ion exchange membrane 84, and the fourth ion exchange membrane 84 divides the inner cavity of the second electrolytic cell 81 into a seventh chamber 85 for arranging the fourth positive electrode 82 and an eighth chamber 86 for arranging the fourth negative electrode 83; the fifth storage tank 87 is connected to the seventh chamber 85 to form a circulation loop, so that the hydrazine solution circulates in the fifth storage tank 87 and the seventh chamber 85; the sixth storage tank 88 is connected to the eighth chamber 86 to form a circulation loop, so that the aqueous solution circulates in the sixth storage tank 88 and the eighth chamber 86, and the aqueous solution is electrolyzed in the eighth chamber 86 to generate hydrogen; the hydrazine oxidation hydrogen production system 8 is used to be connected to the renewable energy system 71 and / or the liquid flow battery 2, so as to power the hydrazine oxidation hydrogen production system 8 through the renewable energy system 71, the liquid flow battery 2, or the hydrazine fuel cell 9.

[0109] The process of hydrazine oxidation hydrogen production is as follows: the second electrolyzer 81 is powered by the renewable energy system 71 or the flow battery 2 or the hydrazine fuel cell 9, the hydrazine solution stored in the fifth storage tank 87 enters the seventh chamber 85 of the second electrolyzer 81, and under the action of the fourth positive electrode 82, the hydrazine in the seventh chamber 85 is oxidized and converted into nitrogen and water, and then flows out with the hydrazine solution, and flows back to the fifth storage tank 87, wherein the nitrogen can be discharged into the atmosphere after passing through the gas-liquid separator 62, the treatment device and other equipment. The aqueous solution stored in the sixth storage tank 88 enters the eighth chamber 86 of the second electrolyzer 81, and under the action of the fourth negative plate, the water is electrolyzed (proton reduced) to generate hydrogen, which flows out with the aqueous solution and flows back to the sixth storage tank 88, wherein the hydrogen can be discharged after passing through the fourth compressor 64, the gas-liquid separation device, the hydrogen purification device 63 and other equipment, and is stored or supplied to hydrogen users.

[0110] The positive electrode of the second electrolyzer 81 uses the hydrazine oxidation reaction (HzOR) to replace the water decomposition positive electrode reaction, i.e., the oxygen evolution reaction (OER), in the traditional water electrolysis hydrogen production process. Due to the slow reaction kinetics and high energy barrier of the oxygen evolution reaction, the water electrolysis hydrogen production has high voltage, high power consumption, and low efficiency. The overpotential of the hydrazine oxidation reaction (HzOR) is lower than that of the oxygen evolution reaction (OER). Therefore, the voltage and power consumption required for the electrolyzer using the hydrazine oxidation reaction (HzOR) at the positive electrode are reduced, and efficient water electrolysis can be achieved. The hydrazine at the positive electrode of the electrolyzer is oxidized and converted into nitrogen and water, which is pollution-free to the environment.

[0111] A heater is also arranged in the hydrazine oxidation hydrogen production system 8. Specifically, a heat exchanger 35 is provided on the pipeline for allowing the hydrazine solution to flow from the seventh chamber 85 to the fifth storage tank 87 and / or the pipeline for allowing the aqueous solution to flow from the eighth chamber 86 to the sixth storage tank 88. The pipeline for allowing the positive electrolyte to flow from the third storage tank 27 to the third chamber 25 and the pipeline for allowing the negative electrolyte to flow from the fourth storage tank 28 to the fourth chamber 26 are both connected to the heat exchanger 35 to perform heat exchange on the positive electrolyte and the negative electrolyte flowing to the first fuel cell stack 21.

[0112] That is, in the hydrazine oxidation hydrogen production system 8, the electrolysis reaction heat in the electrolyzer is transmitted to the heat exchanger 35 by the hydrazine solution flowing from the seventh chamber 85 to the fifth storage tank 87 and / or the aqueous solution flowing from the eighth chamber 86 to the sixth storage tank 88, and the positive electrode electrolyte flowing from the third storage tank 27 to the third chamber 25 and the negative electrode electrolyte flowing from the fourth storage tank 28 to the fourth chamber 26 in the liquid flow battery 2 are heated, the reaction rate of the liquid flow battery 2 is increased, and the reaction heat of the electrolyzer is recycled. The electrolysis reaction heat can be transferred through the heat exchanger 35 for heating the positive and negative electrolytes of the liquid flow battery 2, the reaction rate of the liquid flow battery 2 is increased, and the reaction heat of the electrolyzer is recycled.

[0113] For example, the pipeline for allowing the hydrazine solution to flow from the seventh chamber 85 to the fifth storage tank 87 and the pipeline for allowing the aqueous solution to flow from the eighth chamber 86 to the sixth storage tank 88 are both connected to the hot side medium flow channel of the corresponding first heat exchanger, the pipeline for allowing the positive electrode electrolyte to flow from the third storage tank 27 to the third chamber 25 and the pipeline for allowing the negative electrode electrolyte to flow from the fourth storage tank 28 to the fourth chamber 26 are both connected to the cold side medium flow channel of the corresponding second heat exchanger, and a connecting pipe is provided between the corresponding first heat exchanger and the second heat exchanger. The medium in the connecting pipe absorbs heat in the first heat exchanger and then flows to the second heat exchanger to release heat, thereby realizing heat transfer.

[0114] For another example, the pipeline for allowing the hydrazine solution to flow from the seventh chamber 85 to the fifth storage tank 87 and the pipeline for allowing the aqueous solution to flow from the eighth chamber 86 to the sixth storage tank 88 are both connected to the hot side medium flow channel of the corresponding first heat exchanger, and the pipeline for allowing the positive electrode electrolyte to flow from the third storage tank 27 to the third chamber 25 and the pipeline for allowing the negative electrode electrolyte to flow from the fourth storage tank 28 to the fourth chamber 26 are both connected to the cold side medium flow channel of the corresponding first heat exchanger, and the solution in the hot side medium flow channel and the solution in the cold side medium flow channel located in the same first heat exchanger are indirectly heat exchanged.

[0115] The inner cavity of the hydrazine fuel cell 9 has a fifth positive electrode 91, a fifth negative electrode 92, a fifth ion exchange membrane 93 and a seventh storage tank 96. The fifth ion exchange membrane 93 divides the inner cavity of the hydrazine fuel cell 9 into a ninth chamber 94 for arranging the fifth positive electrode 91 and a tenth chamber 95 for arranging the fifth negative electrode 92. The ninth chamber 94 is connected to the third storage tank 27 to form a circulation loop, and the tenth chamber 95 is connected to the fifth storage tank 87 to form a circulation loop. The output end of the fuel cell is connected to the first electrolyzer 12 and the second electrolyzer 81 to supply power to the first electrolyzer 12 and the second electrolyzer 81. The seventh storage tank 96 is used to store H 2 O 2 Solution, the seventh storage tank 96 is connected with the ninth chamber 94 to form a circulation loop.

[0116] A pipeline for conveying electrolyte, a driving pump 31 for driving the electrolyte to flow in the pipeline, a control valve 32 for controlling the on-off of the pipeline and other components are arranged between the hydrazine fuel cell 9 and the third storage tank 27 and the fifth storage tank 87 .

[0117] Hydrazine fuel cell 9 and hydrazine (N 2 H 4 ) The oxidation hydrogen production system shares the fifth storage tank 87, which is used for the fuel cell and hydrazine (N 2 H 4 ) hydrazine solution is provided for hydrogen production by oxidation; the hydrazine fuel cell 9 system and the liquid flow battery 2 share a third storage tank 27 to provide positive electrode fuel for the fuel cell.

[0118] The hydrazine fuel cell 9 discharges when hydrogen production is required. The hydrazine solution stored in the fifth storage tank 87 is driven by the driving pump 31 to enter the ninth chamber 94 of the hydrazine fuel cell 9. The hydrazine is discharged and converted into nitrogen and water, which flow out with the hydrazine solution and flow back to the fifth storage tank 87. The third storage tank 27 contains M (n+1)+ After being driven by the pump, the electrolyte enters the ninth chamber 94 of the hydrazine fuel cell 9 for discharge, and then flows back to the third storage tank 27 after discharge. The hydrazine fuel cell 9 is connected to the positive and negative electrode connections of the first electrolyzer 12 and the second electrolyzer 81 through the positive and negative electrode connections, and is a hydrazine (N 2 H 4 ) The oxidation hydrogen production system and the thermal catalysis and electrolysis device 1 provide power.

[0119] The backup method for the hydrazine fuel cell 9 to ensure continuous operation of hydrogen production is that when the power stored in the flow battery 2 is exhausted, that is, the electrolyte in the third storage tank 27 can no longer be discharged, and the renewable energy power generation source is out of power, the H stored in the seventh storage tank 96 is used to generate hydrogen. 2 O 2 The solution is used as the positive electrode fuel of the hydrazine fuel cell 9 system, and the hydrazine solution is used as the negative electrode fuel of the hydrazine fuel cell 9 system to continue to operate and discharge, thereby ensuring continuous hydrogen production.

[0120] The embodiment of the present invention can realize the joint operation of the flow battery 2, the hydrazine oxidation hydrogen production system 8, the thermal catalysis and electrolysis device 1, and the hydrazine fuel cell 9, realize the stable and continuous operation of hydrazine oxidation hydrogen production, thermal catalysis and electrolysis distributed hydrogen production, ensure the stability of the power supply and self-sustaining continuous operation of the hydrogen production system, and also reduce the energy consumption of hydrogen production and increase the proportion of green electricity hydrogen production. The voltage and power consumption required for the hydrazine oxidation reaction and thermal catalysis and electrolysis hydrogen production are reduced, and efficient water electrolysis can be achieved, and the converted nitrogen and water will not pollute the environment.

[0121] The thermal catalytic and electrolytic device 1 is used to be connected to the renewable energy system 71 , the liquid flow battery 2 and the hydrazine fuel cell 9 , so that the thermal catalytic and electrolytic device 1 is powered by the renewable energy system 71 , the liquid flow battery 2 or the hydrazine fuel cell 9 .

[0122] That is to say, when the output of the renewable energy system 71 is large, the renewable energy system 71 generates electricity to supply the liquid flow battery 2 for charging and energy storage, and supplies power to the thermal catalytic and electrolytic device 1 for hydrogen production. When the output of the renewable energy system 71 is small or the output is predicted to be small in the next period, the liquid flow battery 2 is started to discharge, and the liquid flow battery 2 and the renewable energy system 71 are used to supply power to the thermal catalytic and electrolytic device 1 together, or the liquid flow battery 2 is used to supply power to the thermal catalytic and electrolytic device 1 alone, or the hydrazine fuel cell 9 is used to supply power to the thermal catalytic and electrolytic device 1, so as to realize the continuous and stable operation of the thermal catalytic and electrolytic device 1.

[0123] The thermal catalytic and electrolytic device 1 includes a thermal catalytic reactor 11, a first electrolytic cell 12, a first storage tank 13 for storing an organic hydrogen carrier, a second storage tank 14 for storing an electrolyte, and a second stack 15. The first storage tank 13 is connected to the inner cavity of the thermal catalytic reactor 11 to form a circulation loop, so that the organic hydrogen carrier is catalytically decomposed in the thermal catalytic reactor 11 to generate hydrogen; the first electrolytic cell 12 includes a first positive electrode 121, a first negative electrode 122 and a first ion exchange membrane 123. The first ion exchange membrane 123 divides the inner cavity of the first electrolytic cell 12 into a first chamber 124 for arranging the first positive electrode 121 and a second chamber 125 for arranging the first negative electrode 122. The first chamber 124 is connected to the inner cavity of the thermal catalytic reactor 11 to form a circulation loop, and the second chamber 125 is connected to the second storage tank 14 to form a circulation loop. The electrolyte in the second storage tank 14 is reduced in the first electrolytic cell 12 to generate hydrogen.

[0124] The second battery stack 15 has a third positive electrode 151, a third negative electrode 152 and a third ion exchange membrane 153. The third ion exchange membrane 153 divides the inner cavity of the second battery stack 15 into a fifth chamber 154 for arranging the third positive electrode 151 and a sixth chamber 155 for arranging the third negative electrode 152. The fifth chamber 154 is connected to the first storage tank 13 to form a circulation loop, and the sixth chamber 155 is connected to the third storage tank 27 to form a circulation loop. The second battery stack 15 is used to be connected to the renewable energy system 71 so as to supply power to the second battery stack 15 through the renewable energy system 71.

[0125] In the embodiment of the present invention, a combined circuit of a thermal catalytic and electrolytic device 1 of an organic hydrogen carrier, a liquid flow battery 2, and a hydrazine fuel cell 9 is utilized to mainly carry out thermal catalytic hydrogen production and electrolytic hydrogen production by the organic hydrogen carrier, and a renewable energy system 71, a liquid flow battery 2, and a hydrazine fuel cell 9 are used to supply power complementary to provide a continuous power supply for the organic hydrogen carrier system; the thermal catalytic and electrolytic hydrogen production of the organic hydrogen carrier and the liquid flow battery 2 system share a third storage tank 27 to provide the liquid flow battery 2 with energy storage battery capacity and performance recovery.

[0126] Among them, the organic hydrogen carrier can be selected from formic acid, methanol, acetic acid, etc. Preferably, formic acid is selected at medium and low temperatures and normal pressure, and methanol and acetic acid can be selected at high temperature and high pressure.

[0127] The thermal catalytic reactor 11 has a thermal catalytic layer 16, a third circulation pump 17, a third heater 18 and a third agitator 19. The catalyst in the thermal catalytic layer 16 in the thermal catalytic reactor 11 is a metal catalyst or a composite metal catalyst, and the catalyst is used to thermally catalytically decompose the organic hydrogen carrier to produce hydrogen.

[0128] Specifically, the catalyst in the thermal catalytic layer 16 includes, but is not limited to: metal or composite metal catalysts (e.g., Group VIII noble metal catalysts: palladium, platinum, ruthenium, rhodium, iridium, etc., Pd, Pt, Ru, Rh, Ir, or PtRu, RuIr and other noble metal complexes; non-noble metal catalysts: iron, copper, manganese, cobalt, Fe, Cu, Mn, Co, etc., or their complexes such as CoCu), the catalyst is loaded on a nitrogen-doped carbon carrier to form a PtRu / C, or CoCu-N / C structure catalyst. The thermal catalytic layer 16 uses a thermal catalytic reactor 11 under heating reaction conditions to accelerate the spontaneous thermal catalytic decomposition of organic hydrogen carriers (such as formic acid, methanol) to produce hydrogen and reduce the power consumption of electrolytic hydrogen production.

[0129] The thermocatalytic reactor 11 is connected to a third pressure gauge, and the hydrogen outlet of the thermocatalytic reactor 11 and the hydrogen outlet of the first electrolyzer 12 are connected to a third compressor 61, a gas-liquid separator 62 and a hydrogen purification device 63 for purifying and discharging the hydrogen.

[0130] The combined operation method of the organic hydrogen carrier thermal catalytic decomposition and electrolysis step-by-step hydrogen production system, the liquid flow battery 2, and the hydrazine fuel cell 9 is as follows:

[0131] After the organic hydrogen carrier flows out of the first storage tank 13, it is driven into the thermal catalytic reactor 11 by the driving pump 31, and is heated to the desired temperature (100-300 degrees Celsius) by the third heater 18. The organic hydrogen carrier can be driven to self-circulate in the thermal catalytic reactor 11 by the third circulation pump 17, thereby improving the full uniformity of the reaction. By starting the third agitator 19 to accelerate the contact reaction between the organic hydrogen carrier and the catalyst layer, the reaction rate can be further accelerated. Under the catalytic reaction of the thermal catalytic layer 16 (the catalyst selection is as described above), the organic hydrogen carrier is thermally decomposed to produce hydrogen. The thermal catalytic reactor 11 is equipped with a pressure gauge and can perform overpressure emission monitoring. The prepared hydrogen is connected to the third compressor 61 through a pipeline and is transported to the hydrogen user after passing through the gas-liquid separator 62 and the hydrogen purification device 63.

[0132] When the pressure drop is detected, the driving pump 31 drives the organic hydrogen carrier in the thermal catalytic reactor 11 into the first electrolyzer 12, and is oxidized in the first chamber 124 of the first electrolyzer 12. Compared with the oxygen evolution reaction of the positive electrode of the electrolyzed water, the overpotential of the electrolysis reaction can be effectively reduced. The second storage tank 14 has a feed port for replenishing the electrolyte lost by electrolysis in the first electrolyzer 12. After being driven by the driving pump 31, the electrolyte stored in the second storage tank 14 enters the second chamber 125 and is reduced to generate hydrogen. The first electrolyzer 12 can be connected to the power generation power supply of the renewable energy system 71; when the renewable energy source is short of electricity, it is connected to the liquid flow battery 2 for power supply or the hydrazine fuel cell 9. The renewable energy system 71 serves as the main power supply, and the liquid flow battery 2 and the hydrazine fuel cell 9 serve as backup power supplies, which can realize a continuous, large-scale and controllable supply of hydrogen for the hydrogen production system.

[0133] The hydrogen produced by the thermal catalytic decomposition of the organic hydrogen carrier and the hydrogen produced by the step-by-step electrolysis are driven by the third compressor 61, and after passing through the gas-liquid separation device and the hydrogen purification device 63 to remove water and carbon dioxide, they can be continuously and massively supplied to the outside.

[0134] At the same time, after the liquid flow battery 2 has been running for a long time, the capacity is unbalanced due to hydrogen evolution (the positive electrode M (n+1)+ If the increase leads to insufficient charging capacity), capacity and performance decay, then after the liquid flow battery 2 system is discharged, the organic hydrogen carrier in the first storage tank 13 is transported into the fifth chamber 154 of the second battery stack 15 through the driving pump 31, and the electrolyte in the third storage tank 27 is transported into the sixth chamber 155 of the second battery stack 15 through the driving pump 31, and the renewable energy system 71 charges the second battery stack 15 to restore the capacity and performance of the liquid flow battery 2 system.

[0135] The operation method is as follows: the organic hydrogen carrier is driven by the driving pump 31 into the fifth chamber 154 of the second stack 15 to be oxidized into carbon dioxide; the electrolyte in the third storage tank 27 (shared with the flow battery 2) is driven by the driving pump 31 into the sixth chamber 155 of the second stack 15, and the excess M in the electrolyte is (n+1)+ Restored to M (n+) , return to the third storage tank 27, and charge at a constant voltage (such as 1-1.5V) until the charging current is observed to drop below 10mAcm-2 and continue to decrease, indicating that M (n+1)+ All are restored to M (n+) , the capacity and performance of the flow battery 2 system have been restored.

[0136] In the embodiment of the present invention, the complementary power supply, hydrogen and oxygen production process, energy storage process and capacity and performance recovery process of renewable energy / liquid flow battery 2 / hydrazine fuel cell 9 are controlled by energy management and control system 72.

[0137] Through the complementary power supply of renewable energy / liquid flow battery 2 system / fuel cell system, the hydrogen production and oxygen production processes are separated to ensure continuous large-scale controllable hydrogen; through the above thermal catalysis and electrolysis step-by-step hydrogen production, organic hydrogen carrier and catalyst design, thermal catalysis and electrolysis step-by-step hydrogen production design, compared with traditional electrolysis hydrogen production, the electrolysis overpotential and hydrogen production power consumption are reduced, the efficiency of the hydrogen production system is improved, energy consumption is reduced, and the cost of hydrogen production is reduced.

[0138] In the description of the present invention, it is to be understood that the terms “center”, “longitudinal”, “lateral”, “length”, “width”, “thickness”, “up”, “down”, “front”, “back”, “left”, “right”, “vertical”, “horizontal”, “top”, “bottom”, “inside”, “outside”, “clockwise”, “counterclockwise”, “axial”, “radial”, “circumferential”, etc., indicating orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0139] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0140] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral one; it can be a mechanical connection, an electrical connection, or communication with each other; it can be a direct connection, or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0141] In the present invention, unless otherwise clearly specified and limited, a first feature being "above" or "below" a second feature may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, a first feature being "above", "above" or "above" a second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. A first feature being "below", "below" or "below" a second feature may mean that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is lower in level than the second feature.

[0142] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" etc. mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0143] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A thermal catalytic and electrolytic step-by-step hydrogen production system, characterized in that: include: Flow batteries; A thermal catalytic and electrolytic device, the thermal catalytic and electrolytic device comprising a thermal catalytic reactor, a first electrolyzer, a first storage tank for storing an organic hydrogen carrier, and a second storage tank for storing an electrolyte, the first storage tank being connected to the inner cavity of the thermal catalytic reactor to form a circulation loop, so that the organic hydrogen carrier is catalytically decomposed in the thermal catalytic reactor to generate hydrogen; the first electrolyzer comprising a first positive electrode, a first negative electrode, and a first ion exchange membrane, the first ion exchange membrane dividing the inner cavity of the first electrolyzer into a first chamber for arranging the first positive electrode and a second chamber for arranging the first negative electrode, the first chamber being connected to the inner cavity of the thermal catalytic reactor to form a circulation loop, the second chamber being connected to the second storage tank to form a circulation loop, and the electrolyte in the second storage tank being reduced in the first electrolyzer to generate hydrogen; The liquid flow battery is used to be connected to a renewable energy system so that the liquid flow battery can be charged and stored with energy through the renewable energy system; the thermal catalytic and electrolytic device is used to be connected to a renewable energy system and the liquid flow battery so that the thermal catalytic and electrolytic device can be powered by the renewable energy system or the liquid flow battery.

2. The thermal catalysis and electrolysis step-by-step hydrogen production system according to claim 1 is characterized in that: The liquid flow battery includes a first battery stack, a third storage tank storing a positive electrolyte, and a fourth storage tank storing a negative electrolyte. The inner cavity of the first battery stack has a second positive electrode, a second negative electrode, and a second ion exchange membrane. The second ion exchange membrane divides the inner cavity of the first battery stack into a third chamber for arranging the second positive electrode and a fourth chamber for arranging the second negative electrode; the third storage tank is connected to the third chamber to form a circulation loop so that the positive electrolyte circulates in the three tanks and the third chamber; the fourth storage tank is connected to the fourth chamber to form a circulation loop so that the negative electrolyte circulates in the fourth tank and the fourth chamber.

3. The thermal catalysis and electrolysis step-by-step hydrogen production system according to claim 2 is characterized in that: Also includes a second battery stack, the second battery stack has a third positive electrode, a third negative electrode and a third ion exchange membrane, the third ion exchange membrane divides the inner cavity of the second battery stack into a fifth chamber for arranging the third positive electrode and a sixth chamber for arranging the third negative electrode, the fifth chamber is connected to the first storage tank to form a circulation loop, and the sixth chamber is connected to the third storage tank to form a circulation loop; The second fuel cell stack is used to be connected to a renewable energy system so as to supply power to the second fuel cell stack through the renewable energy system.

4. The thermal catalysis and electrolysis step-by-step hydrogen production system according to claim 2 is characterized in that: Also includes: An oxygen generator, the oxygen generator having an oxygen-generating catalytic layer and a first feed port, the first feed port being used to replenish the aqueous solution into the oxygen generator, the oxygen generator being connected to the third storage tank to form a circulation loop, the positive electrolyte being regenerated in the oxygen generator and generating oxygen in the oxygen generator; A hydrogen generator, wherein the hydrogen generator has a hydrogen production catalytic layer and a second feed port, wherein the second feed port is used to replenish the aqueous solution into the hydrogen generator, the hydrogen generator is connected to the fourth storage tank to form a circulation loop, and the negative electrolyte is regenerated in the hydrogen generator to produce hydrogen in the hydrogen generator.

5. The thermal catalysis and electrolysis step-by-step hydrogen production system according to claim 4 is characterized in that: The oxygen generator further comprises a first circulation pump, a first heater and a first agitator, and the hydrogen generator further comprises a second circulation pump, a second heater and a second agitator; And / or, the oxygen generator is connected to a first pressure gauge and a first compressor, and the hydrogen generator is connected to a second pressure gauge and a second compressor; And / or, the oxygen-producing catalytic layer comprises a first substrate layer and first catalytic particles, the first substrate layer is any one of carbon felt, graphite felt, titanium mesh, and a fixed bed of SiO2 particles, and the first catalytic particles are IrO2 or RuO2 particles; the hydrogen-producing catalytic layer comprises a second substrate layer and second catalytic particles, the second substrate layer is any one of carbon felt, graphite felt, titanium mesh, and a fixed bed of SiO2 particles, and the second catalytic particles are MoS2 or Mo2C particles.

6. The thermal catalysis and electrolysis step-by-step hydrogen production system according to claim 2, characterized in that: The invention also includes a hydrazine oxidation hydrogen production system, which includes a second electrolytic cell, a fifth storage tank storing a hydrazine solution, and a sixth storage tank storing an aqueous solution, wherein the second electrolytic cell has a fourth positive electrode, a fourth negative electrode, and a fourth ion exchange membrane, and the fourth ion exchange membrane divides the inner cavity of the second electrolytic cell into a seventh chamber for arranging the fourth positive electrode and an eighth chamber for arranging the fourth negative electrode; the fifth storage tank is connected to the seventh chamber and forms a circulation loop, so that the hydrazine solution circulates in the fifth storage tank and the seventh chamber; the sixth storage tank is connected to the eighth chamber and forms a circulation loop, so that the aqueous solution circulates in the sixth storage tank and the eighth chamber, and the aqueous solution is electrolyzed in the eighth chamber to generate hydrogen; The hydrazine oxidation hydrogen production system is used to be connected to a renewable energy system and / or the liquid flow battery, so that the hydrazine oxidation hydrogen production system is powered by the renewable energy system, the liquid flow battery, or the hydrazine fuel cell.

7. The thermal catalytic and electrolytic step-by-step hydrogen production system according to claim 6, characterized in that: Also included is a hydrazine fuel cell, wherein the inner cavity of the hydrazine fuel cell has a fifth positive electrode, a fifth negative electrode and a fifth ion exchange membrane, the fifth ion exchange membrane divides the inner cavity of the hydrazine fuel cell into a ninth chamber for arranging the fifth positive electrode and a tenth chamber for arranging the fifth negative electrode, the ninth chamber is connected to the third storage tank to form a circulation loop, and the tenth chamber is connected to the fifth storage tank to form a circulation loop; The output end of the hydrazine fuel cell is connected to the first electrolyzer and the second electrolyzer to supply power to the first electrolyzer and the second electrolyzer.

8. The thermal catalytic and electrolytic step-by-step hydrogen production system according to claim 7, characterized in that: Also includes a seventh storage tank, the seventh storage tank is used to store H2O2 solution, the seventh storage tank is connected with the ninth chamber to form a circulation loop; And / or, a heat exchanger is provided on the pipeline for allowing the hydrazine solution to flow from the seventh chamber to the fifth storage tank, and / or on the pipeline for allowing the aqueous solution to flow from the eighth chamber to the sixth storage tank, and the pipeline for allowing the positive electrolyte to flow from the third storage tank to the third chamber and the pipeline for allowing the negative electrolyte to flow from the fourth storage tank to the fourth chamber are both connected to the heat exchanger to perform heat exchange on the positive electrolyte and the negative electrolyte flowing to the first battery stack.

9. The thermal catalysis and electrolysis step-by-step hydrogen production system according to claim 1, characterized in that: The organic hydrogen carrier is any one of formic acid, methanol and acetic acid, the catalyst in the thermal catalytic reactor is a metal catalyst or a composite metal catalyst, and the catalyst is used to thermally catalytically decompose the organic hydrogen carrier to generate hydrogen; And / or, the thermocatalytic reactor comprises a thermocatalytic layer, a third circulation pump, a third heater and a third agitator; And / or, the thermal catalytic reactor is connected to a third pressure gauge, and the hydrogen outlet of the thermal catalytic reactor and the hydrogen outlet of the first electrolyzer are connected to a third compressor, a gas-liquid separator and a hydrogen purification device.

10. The thermal catalytic and electrolytic stepwise hydrogen production system according to any one of claims 1 to 9, characterized in that: It also includes an energy management and control system, which is used to control the operation of various components in the thermal catalytic and electrolytic step-by-step hydrogen production system.

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